Seawater Fertilizer ( "Sea-Crop" )
SEA-CROP is an extension of the life's work of pioneer scientist
Dr. Maynard Murray.
His ground-breaking book "Sea Energy Agriculture" is well known
and loved by many.
Over a century of well documented research has shown that seawater
can have profound effects on both plant and animal life as long as
sodium chloride is not over-applied.
In the late nineteenth century Dr. Rene Quinton did experiments
showing that seawater could be used to replace blood in animals
and he went on to develop a seawater extract that was used for
transfusions in place of blood plasma during World War One.
During the twentieth century Dr. Maynard Murray spent decades
doing agricultural research with both plants and animals to
demonstrate the many benefits that can be obtained by using both
seawater and seawater concentrates.
In the twenty-first century Ambrosia Technology, LLC has continued
research based on the work of these pioneers and has developed the
product Sea-Crop. Sea-Crop is a concentrate that contains all of
the wonderful goodness of seawater in concentrated form but with
the sodium chloride 95% reduced.
It is believed that the 89 elements in seawater working together
with its contained organic content are responsible for its well
documented positive effects.
Leaves and raspberries from ordinary raspberry plant on left and
the plant on the right was treated with SEA-CROP for 3 consecutive
years. The 6 berries from the treated plant weighed 20.66 gm and
the 6 berries from the control weighed 8.53 gm.
SEA-CROP is a catalytic trigger that releases nature's
energy to give the full benefit of soil microflora symbiosis.
In all applications the root system of the treated plants was
In all instances soil tilth and microbial populations were
In all cases Sea-Crop improved the health and vigor of the treated
Using Sea-Crop on transplants of crucifers, melons and peppers
decreased the incidence of transplant loss by at least 50%.
In all applications the size, weight and shelf life of fruits and
vegetables was increased.
[ Click to enlarge ]
A METHOD OF PRODUCING USEFUL PRODUCTS FROM SEAWATER AND
Inventor: ZEIGLER Arthur
A process is provided for the recovery of useful products,
including fertilizers and nutritional supplements, from the
organic matter and minerals contained in seawater and other
brines. The dissolved organic carbon-based chemicals and suspended
particulate carbon-based organic matter are co-precipitated
together with the contained magnesium and/or calcium, along with
incidental trace minerals, entrained water and water of hydration.
Caustic soda (NaOH) and other alkali base or alkaline earth bases
and/or carbon dioxide (CO2) are added to the brine until pH of
10.75 to 11.0 is achieved. The settled or non-dry filtered or
centrifuged precipitate is utilized as a slurry and the
supernatant brine is discarded.
Background of the Invention
0001 This invention relates generally to the fields of chemical
extraction, fertilizers and nutritional supplements and more
specifically to a METHOD OF PRODUCING USEFUL PRODUCTS FROM
SEAWATER AND SIMILAR BRINES.
0002 For thousands of years mankind has utilized the minerals and
vegetable products of the oceans for both food and fertilizer.
0003 Even to this day sea salt is prized for its trace mineral
content and kelp products are used as both food and fertilizer in
many parts of the world.
0004 The present invention bonds both dissolved carbon-based
organic chemicals and suspended carbon-based organic particles to
hydroxide precipitates of marine minerals.
0005 They are bonded ionically, mechanically, electrostatically or
0006 For the bulk of dissolved organic carbon in the ocean,
chemical structure and basic biochemical parameters are largely
0007 FuIvic acid which is ubiquitous at low concentrations in all
parts of the ocean consists of many thousands of different organic
substances of both marine derived and terragenous origin.
0008 Not only are the compositions of these substances largely
unknown, so are their physical properties.
0009 It is known that some of these substances, especially
exopolysaccharides, are capable of spontaneous polymerization with
the production of jelly-like layers covering several square miles.
0010 Dimethylsulfoniopropionate, a substance produced by
phytoplankton for osmotic control, is generated in such quantities
that some of its decomposition products are considered to have a
major effect on planetary weather. It is known to have a
kosmotropic effect on water molecules.
0011 Other of the dissolved organic substances organize water
molecules into liquid and solid phase clathrates and
0012 A new class of highly abundant, nonliving organic marine
particles has recently been recognized.
0013 These colloidal particles consist primarily of exopolymers
released as exudates by phytoplankton and bacteria.These
exopolymer particles have been found to be present in seawater
ranging up to 5,000 particles per ml and varying in size from 3 to
0014 They are characterized as containing large amounts of water
which has been organized by the organic matter. It is postulated
that this ability of dissolved and particulate organic matter in
the oceans to organize and add structure to water molecules is, at
least in part, responsible for the observable and measurable
biological effects of the present invention on plant, animal and
0015 In the past, minerals have been extracted from seawater for
fertilizer and nutritional supplementation or the organic
chemicals have been extracted separately for the same purpose.
0016 To the best of the inventors knowledge, no one has
previously, intentionally extracted the two together for the
synergistic effect which they have in combination when used as a
0017 U.S. Patent #3,374,081 is a method of separating
minerals from seawater which are suitable for use as fertilizers
and animal feeds. It employs added proteinaceous materials to
precipitate minerals as chelated complexes.
The methods employed and precipitates obtained are of very
different nature than those of the present invention.
0018 U.S. Patent #2,606,839 employs methods similar to the
current invention for the purpose of producing a pure sodium
The patent shows no awareness of the valuable nature of the
byproduct for the applications claimed by the present invention.
0019 U.S. Patent #3,071,457 describes a method of
evaporating seawater to dryness for application of the resultant
solids as fertilizer.
This product very successfully increased crop yields but required
application rates of 550 to 2,200 pounds of sea solids per acre.
The first paragraph of this patent states that it relates only to
the inorganic salts contained in seawater.
0020 U.S. Patent #2,404,550 uses methods similar to the
current invention but uses them for the purpose of extraction and
purification of mineral salts from the waters of the Great Salt
Lake. One of its aims is the separation and exclusion of organic
content from the final product. Testing of the present invention
has demonstrated that purified minerals extracted from brines do
not have the desired effects.
0021 U.S. Patent #2,934,419 uses methods similar to the
current invention but differs in two very important respects. No
mention is made of organic content and the mineral precipitates
are dried. Testing of the current invention has shown that if the
precipitates are dried they can no longer significantly stimulate
0022 U.S. Patent #4,634,533 uses methods similar to the
current invention to recover useful products such as fertilizer,
animal feed supplements and mineral salts from brines. It differs
in two important respects.
It makes no mention of the organic chemical constituents of the
It requires the addition of a phosphorous source in order to have
the claimed benefit as a fertilizer.
0023 U.S. Patent #4,015,971 has the object of producing
fertilizers from seawater containing "microelements and active
This is accomplished by adding bivalent iron ions to the seawater
so that the organic substances are co-precipitated with the iron
hydroxides. It does not utilize the contained magnesium and
calcium brine constituents as does the present invention. The
5% to 10% increased crop yields with application rates of .5 to 3
kg of dried solids per hectare.
On this basis it is both less effective and less economical than
the present invention.
0024 U.S. Patent #5,074,901 is a method for producing a
liquor from seawater by achieving a 90% reduction of the original
volume through evaporation.
Although the patent states that this Liquor, when diluted, will
function as a fertilizer, its nature is very different from the
liquor produced by the current invention.
0025 U.S. Patent #6,147,229 describes a method of
producing magnesium fulvate from humus material.
It involves digesting the humus in a solution of sodium hydroxide,
then acidifying to precipitate humates followed by the addition of
magnesium hydroxide to the supernatent in order to precipitate
The current invention extracts magnesium fulvate from seawater in
a single step by the addition of sodium hydroxide, which
precipitates the contained magnesium as hydroxide that in turn
precipitates the contained fulvates as magnesium fulvate.
0026 These prior usages have not recognized the benefits,
economies and synergies that can be achieved by using the
magnesium and/or calcium constituents of the sea water and similar
brines to co-precipitate and recover in usable form, the organic
chemical and particulate orgai j content of said brines.
Furthermore, they did not recognize that the resultant
precipitates are most bioactive in slurry form. That they did not
do so indicates that such usage is unobvious.
Brief Summary of the Invention
0027 The primary object of the invention is to extract, from
seawater and similar brines, its dissolved, carbon-based, organic
chemicals and particulate carbon-based organic matter together
with the contained bivalent minerals and incidental trace
minerals, entrained water and water of hydration, so that these
substances may be applied to beneficial use.
0028 Another objective of the invention is to produce from
seawater and similar brines an economical and efficacious
fertilizer and plant growth stimulant which would contain
microelements and active organic substances.
0029 Another objective of the invention is to produce a
nutritional supplement from seawater and similar brines that will
promote health and growth in animals and humans.
0030 An advantage of the invention is that it will produce
magnesium fulvate from seawater and similar brines in a single
0031 Other objects and advantages will become apparent from the
following descriptions, taken in connection with the accompanying
drawing, Figure 1, wherein by way of illustration and example, an
embodiment of the present invention is disclosed.
0032 In accordance with a preferred embodiment of the invention,
there is disclosed a method of co-precipitating the carbon-based
organic chemicals and carbon-based particulate matter contained in
seawater and similar brines together with its constituent,
bivalent magnesium and/or calcium and incidental trace minerals,
entrained water and water of hydration.
0033 In accordance with a preferred embodiment of the invention,
there is disclosed a method for producing from seawater and
similar brines, an economical and efficacious fertilizer and plant
growth stimulant, which utilizes both the organic substances and
constituent bivalent minerals which may be co-precipitated from
said brines together with trace minerals, water of hydration and
0034 In accordance with a preferred embodiment of the invention,
there is disclosed a method for producing from seawater and
similar brines, a health and growth promoting nutritional
supplement, which utilizes both the organic substances and
constituent bivalent minerals which may be co-precipitated from
said brines along with trace minerals, water of hydration and
Detailed Description of the Preferred Embodiments
0035 Detailed descriptions of the preferred embodiment are
provided herein. It is to be understood, however, that the present
invention may be embodied in various forms. Therefore, specific
details enclosed herein are not to be interpreted as limiting, but
rather as a basis for the claims and as a representative basis for
teaching one skilled in the art to employ the present invention in
virtually any appropriately detailed system, structure or manner.
0036 As illustrated in the drawing Figure 1, the seawater 10 is
treated in a reaction vessel 11, with caustic soda (NaOH), or any
other base or alkaline earth base that yields hydroxyl ions on
hydrolysis. The caustic soda is indicated in the drawing as being
fed through line 12, to the reaction vessel, 11. The concentration
of the caustic soda is such that the number of hydroxyl ions added
from line 12 is chemically equivalent to the total concentration
of the magnesium ions present in the seawater from the source, 10.
As a practical application, caustic soda is added until a pH of
10.75 to 11.0 is achieved. Soda ash (Na2CO3) or any other alkali
carbonate or alkaline earth carbonate is added to the seawater in
reaction vessel 11, in such concentration that the carbonate ions
are chemically equivalent to the calcium ions present in the
seawater. The soda ash is schematically indicated on the drawing
as being added to the reaction vessel 11, through line 14, and
such addition may be simultaneously with, or at different times
from, the addition of the caustic soda. Preferably, the seawater
with the caustic soda and soda ash added thereto is agitated in
the reaction vessel 11, to complete the dissolving and reaction of
0037 A precipitation occurs within a few minutes after the
addition of chemicals to the reaction vessel 11, from lines 12 and
14 and such precipitate is for the most part, magnesium hydroxide
and calcium carbonate. The surface area of such magnesium
hydroxide precipitates is tremendous, largely due to the fact that
it precipitates out in very small particles. The calcium carbonate
precipitate also has a very large surface area. The magnesium
hydroxide and calcium carbonate precipitates absorb trace elements
in the seawater on their large surface areas and thereby trace
elements are also separated from the seawater. Fulvates are
precipitated as magnesium fulvate. Most importantly, substantially
all of the dissolved organic carbon-based chemicals and
particulate carbon-based organic matter are co-precipitated
together with the magnesium hydroxide and calcium carbonate and
bonded to their surface either mechanically, ionically or
electrostatically. They can thus be separated from the seawater
together with their waters of hydration.
0038 Another preferred embodiment of the invention, which will
achieve the same result as the preceding description, would be as
illustrated in Figure 1, to treat the seawater 10, in reaction
vessel 11, with caustic soda or any other base or alkaline earth
base that yields hydroxyl ions on hydrolysis. The caustic soda
(NaOH) is indicated in the drawing as being fed through line 12,
to the reaction vessel 11. The concentration of the caustic soda
is such that the number of hydroxyl ions added from line 12, is
chemically equivalent to the total concentration of the magnesium
ions present in the seawater from the source, 10. As a practical
application, caustic soda is added until a pH of 10.75 to 11.0 is
achieved. Next, the liquor in reaction vessel 11, is agitated and
carbon dioxide gas is introduced through supply pipe 15, in an
amount sufficient to precipitate all of the contained calcium as
0039 Another preferred embodiment of the invention, which will
extract and recover all of the organic carbon contained in the
seawater, would be as illustrated in Figure 1, to treat the
seawater 10, in reaction vessel 11, with caustic soda (NaOH) as
indicated in the drawing as being supplied through line 12 to the
reaction vessel 11. The concentration of the caustic soda is such
that the number of hydroxyl ions added from line 12, is chemically
equivalent to the total concentration of magnesium ions present in
the seawater from the source, 10. Potassium hydroxide is also
added, as indicated in Figure 1, through supply line 13. The KOH
is supplied in sufficient quantity to convert all of the calcium
contained in the liquor being treated in reaction vessel 11, into
calcium hydroxide. As a practical application, but not limited to
this example, the sodium hydroxide can be supplied, together with
the potassium hydroxide, in a ratio of 95% sodium hydroxide to 5%
potassium hydroxide. This blend is supplied to the reaction vessel
11, until a pH of 10.75 to 11.0 is achieved.
0040 All of the examples given as preferred embodiment will
achieve substantially the same results, as far as co-precipitating
together with the magnesium and calcium, substantially all of the
dissolved carbon-based chemicals and carbon-based particulate
organic matter contained in the seawater feed illustrated as 10,
in Figure 1.
0041 Once the precipitation is achieved in the reaction vessel 11
by the chosen method, the liquor is allowed to stand quietly for a
period of time so that the precipitates may settle. In a preferred
embodiment of the invention as illustrated in Figure 1, the liquor
is allowed to rest in settling tank 16, for 48 hours and the
supernatant solution, 17, is then decanted and discarded. The
settled precipitates are the valuable product illustrated in
Figure 1, as 18, the slurry product.
0042 Seed germination tests done by the inventor have shown that
if the slurry is allowed to dry out, it losses its potency even if
rehydrated. Other tests have shown that it is the presence of the
organic content together with the bivalent marine minerals which
make the slurry product effective. A slurry of pure magnesium
and/or calcium hydroxide will not produce the beneficial effects
on plant and animal life that the slurry produced by the present
0043 If it is desired to alter the characteristics of the slurry
product identified as 18 in Figure 1, minerals or other substances
with the desired attributes may be added before and/or after
precipitation. For example, bivalent iron could be added to feed
10 and it would be precipitated along with the other minerals as
hydroxide. For special applications, any number of minerals or
other substances can be added before and/or after precipitation to
give desired characteristics to the slurry product.
0044 In a preferred embodiment of the invention, the precipitates
will contain from 10 to 50 grams per liter of total suspended
solids, although other proportions may be achieved if so desired.
0045 The slurry is stored in opaque containers away from direct
sunlight and strong electromagnetic fields, which may cause the
loss of potency.
0046 As a fertilizer and plant growth stimulant, in a preferred
embodiment the slurry is added to the growth medium at the rate of
one or more gallons per acre.
0047 In another preferred embodiment of a fertilizer prepared
under this invention, the slurry product illustrated in Figure 1,
as 18, and containing 20 grams of total suspended solids per
liter, would be diluted with 999 parts of water so that the final
solution contains .1% of the slurry, illustrated as 18. To this
solution, any soluble nitrate fertilizer may be added at its
recommended rate. The resultant solution may be added directly to
the growth medium or applied as a foliar spray.
0048 Wheat treated in this manner has yielded 36% more grain by
weight than the control, which received the nitrate fertilizer
only, hi this test the slurry 18, was applied at the rate of one
gallon per acre. Similar results have been achieved with a variety
of row and orchard crops. Typical results with fruit include
increased size, increased sugar content, increased overall yield
and better keeping quality. 0049 If it is desired to alter the
characteristics of the agricultural slurry product, minerals or
other substances with the desired attributes may be added before
and/or after precipitation. For example, bivalent iron could be
added to feed 10 and it would be precipitated along with the other
minerals as hydroxide. Ionic zinc is an example of a mineral that
might be added after precipitation. For special applications, any
number of minerals or other substances can be added before and/or
after precipitation to give desired characteristics to the
agricultural slurry product.
0050 As a preferred embodiment of a nutritional supplement for
animals prepared from the slurry product identified as 18 in
Figure 1, the slurry product containing 20 grams of total
suspended solids per liter is added to the drinking water or feed
so that the daily dosage is one tenth to one half milliliter per
kilogram of body weight.
0051 The daily dose of this preparation is used to describe a
daily dose for a primate having a body weight of 70 kgs, unless
0052 hi animal testing conducted by the inventor, the above
formula was used at the rate of .4 milliliters per kg of body
weight per day to supplement the diet of white mice for a period
of thirty days, after which they were subjected to forced swim
testing. During the test period of 30 days the control population,
consisting of 10 mice that did not receive the supplement,
experienced a 30% mortality while the test population, consisting
of 30 mice that received the supplementation, experienced no
0053 When subjected to swim testing, the mice that had received
the supplementation were able to endure for a period averaging
3.23 times greater than the control population.
The groups which had received the supplementation had a 3.8 %
greater body weight at the termination of the test than did the
0054 In a preferred embodiment of this invention to prepare a
nutritional supplement for humans, the seawater feed illustrated
as 10 in Figure 1, would be filtered before being placed in the
reaction vessel 11, in order to remove any extraneous material.
The final slurry product 18 would undergo additional processing to
become the food grade slurry product identified in Figure 1 as 19.
The slurry would be rinsed by diluting to five times its volume
with fresh water and allowed to settle. This is illustrated in
Figure 1 with the fresh water shown as being supplied by line 20.
0055 After 48 hours the supernatant would be discarded as shown in
Figure 1 by line 21 and sodium chloride would be added at the rate
of one gram per liter and this is illustrated in Figure 1 as being
supplied by line 23. The resultant liquor may be further
sterilized before bottling by boiling for 10 minutes and, after
boiling and being allowed to cool, an addition of 35% hydrogen
peroxide is made at the rate of 2 milliliters per gallon of
liquor. The H2O2 is shown in Figure 1 as being supplied by line
22. Total suspended solids in the food grade slurry will vary
between 7 and 20 grams per liter and may be otherwise concentrated
0056 This liquor may be used as a beverage or added to food to
promote health and vigor, hi a preferred embodiment of packaging,
after bottling, the food grade slurry would be over-packed in
metalized plastic film or anti-static protective bags such as is
used for shipment of computer parts. Alternatively a metalized
bottle could be used or metal foil could be utilized as an outer
cover. These measures allow the product to be stored and shipped
without loss of potency.
0057 If it is desired to alter the characteristics of the food
slurry product identified as 19 in Figure 1, minerals or other
substances with the desired attributes may be added before and/or
after precipitation. For example, bivalent iron could be added to
feed 10 and it would be precipitated along with the other minerals
as hydroxide. For special applications, any number of minerals or
other substances can be added before and/or after precipitation to
give desired characteristics to the slurry product. Ionic cobalt
and iodine are examples of minerals that might be added after
0058 With respect to all methods disclosed herein, all steps,
procedures or processes may be considered to be done without
regard to the priority unless specified, or dictated by necessity
or force of logic. The identification of steps or products in any
priority is done only for the purpose of introducing them and
distinguishing them from one another, unless otherwise dictated by
necessity or force of logic.
0059 The foregoing is offered primarily for purposes of
illustration. It will be readily apparent to those skilled in the
art that the proportions, material, formulation procedures,
administration protocols and other parameters of this invention
may be further modified or substituted in various ways without
departing from the spirit and scope of the invention.
0060 While the invention has been described in connection with a
preferred embodiment, it is not intended to limit the scope of the
invention to the particular form set forth, but on the contrary,
it is intended to cover such alternative, modifications, and
equivalents as may be included within the spirit and scope of the
invention as defined by the appended claims. Table 1 Experimental
Our agricultural research has established the following data:
1. Seeds treated with the invention and germinated in a closed
container consumed 118% more oxygen in the first 24 hours than did
the control. This test of aerobic cellular respiration shows that
independent of all other factors, cellular respiration of the
plant is increased.
2. Yeast introduced to the invention in sugar water and placed in
a sealed container generated one third more CO2 in the first 24
hours than the untreated control. This test of anaerobic cellular
respiration shows that independent of what is happening in the
plant; increased cellular respiration will take place in
microorganisms in treated soil.
3. Treated soil in which wheat was germinated and grown out for 20
days was analyzed by a soil laboratory. The test showed that the
invention gave an increase of total bacterial biomass 32% greater
than fertilizer alone did. The test also showed that the treated
soil had an increase of total fungal biomass. The increase over
baseline was 264% greater with the invention than fertilizer alone
4. Brix refractometer testing of the sap from all of the various
species being trialed has shown at least a 30% greater content of
dissolved solids, primarily sugars, in the sap of the treated
plants when compared to the controls. This can only be achieved
through increased photosynthesis.
Taken together the data indicate the following:
A. All species of plants, when treated with the invention, will
gain the benefit of more energy through increased cellular
respiration and increased photosynthesis.
B. Soil health and vitality of the treated soil will be greatly
increased due to greater microorganism growth and content.
C. As a consequence of points A. and B., those species of plants
that have a symbiotic relationship with mycorrhizal fungi should
experience increased yields in direct proportion to each species
degree of dependence upon the mycorrhizal relationship.
This hypothesis is validated by the following test data: Potato
trials indicate Table 1 Experimental Proofs
achievable yield increases in the vicinity of 100% over and above
what fertilizer alone can produce. Wheat trials show increases of
25% to 45%. Other species show a similar pattern.
The fungi obtain carbohydrates and growth factors from the roots
of the plants. As the invention increases these carbohydrates in
the sap by over 30%, and at the same time increases the cellular
respiration of the soil microorganisms, a previously unattainable
synergy is achieved. This accounts for much of the enhanced yields
and plant health that we have observed.
Four week old white mice were obtained and split into two
populations. The control population consisted often mice and the
other group consisted of thirty mice.
AU populations were given measured amounts of the same food and
measured amounts of water daily. The mice in the test population
were also each given five drops of the formula in their water
every day for thirty days.
During the first week of the test there was a 30% mortality for
the control population but no deaths occurred in the group
receiving supplemention with the invention.
At the end of 30 days the mice were subjected to forced swim
testing to the point of terminal exhaustion and death.
1. The control group, that had not received supplementation,
endured for an average of 257 minutes, or 4 hours and 17 minutes.
2. The test population, that had received the invention endured
for an average of 830 minutes, or 13 hours and 49 minutes.
The test population, that received supplementation exhibited more
stamina than the control group by enduring the forced swim testing
for a much greater duration.
Supplementation with the invention as performed in this study
greatly enhances stamina.
Method of producing fertilizers from sea-like waters
The present invention relates to the production of fertiizers for
agriculture and, more specifically to fertilizers produced from
sea-like waters. The term "sea-like waters" means any natural
water featuring chlorine factors of individual components and
elements of the water which are characteristic of ocean water. The
chlorine factor is calculated from the formula: Kel = % el .times.
100/% Cl, where % el is the percentage of a component, elements; %
Cl is the percentage of chloride ions.
Known in the art are fertilizers produced from sea water. These
fertilizers may be exemplified by, for example, potassium salts.
Potassium salts are prepared from sea water by addition of
phosphate ions to water containing potassium and magnesium,
increasing its pH to 7.5-9.5 by means of an ammonium-free base,
and separation of a residue the water by filtration, decantation
or centrifugation. Potassium salt is separated from the resulting
residue of a double slt of potassium-magnesium according to the
MgKPO4 + NH4 A .fwdarw. MgNH4 PO4 + KA
where A is an anion (cf. U.S. Pat. No. 3,195,978).
Another process (U.S. Pat. No. 3,382,038) contemplates recovery of
potassium from sea water by the addition of an alkali to increase
its pH to 10.5-12 and elevation of the water temperature from 25
DEG to 100 DEG C. Potassium along with other components is
precipitated. Finally, potassium may be recovered from sea water
by contact with a naturally-occurring zeolite, viz-glauconite,
from which it is partially removed by treating with a solution of
an ammonium salt the thus-regenerated zeolite or glauconite is
again contacted with sea water, followed by treating with a
solution of an ammonium salt to produce a potassium salt (U.S.
Pat. No. 3,497,314). Potassium salts pertain to the class of
microfertilizers and it is necessary to introduce into soil
several hundred kilograms of said salts per one hectare. If
potassium is recovered from sea water by the above-said processes,
losses of such valuable components as ions of ammonium,
phosphate-ions, caustic soda are possible as a result of
increasing the pH of sea water. Moreover, said salts neither
contain microelements and organic substances. Potassium salts
recovered from sea water correspond to similar fertilizers, in
their efficiency and purpose, produced in various countries from
salt deposits on dry land. The only advantage of the
above-mentioned fertilizers is that they may be produced by any
conuntry with an access to sea water. The main disadvantage of
potassium fertilizers produced from sea water resides in a
relatively high loss of ammonium and phosphorus ions and a high
alkali consumption, whereby production of potassium fertilizers
from sea water is limited.
It is an object of the present invention to produce fertilizers
from sea water which would contain microelements and active
Another object of the present invention is to select such a
composition of the fertilizers which would selectively stimulate
the growth and evolution of agricultural plants.
Still another object of the present invention is to provide such a
composition of the fertilizers which could be used in combination
with other type fertilizers.
A further object of the present invention is to provide such a
method of producing fertilizers from sea water which would be
easily reproduced on a commercial scale on the basis of cheap and
readily-available raw materials.
The method of producing fertilizers, according to the present
invention comprises introduction, into the sea-like water, of ions
of bivalent iron in an amount within the range of from 10 to 100
mg of iron per liter of said water at a pH = 5 to 9; therewith,
bivalent iron ions are oxidized and transformed into trivalent
iron ions with the formation of iron hydroxide; sorption of
microelements and organic substances being present in said water
by iron hydroxide at said pH values without sorption of sodium
chloride; separation of the resulting precipitate; drying of the
separated precipitate to the air-dry state containing
predominantly iron in an amount of from 23.4 to 31.5%, total
carbon 2.3 to 3.0%, total amount of microelements 0.1 to 0.3%.
As has been mentioned hereinbefore, concentration of hydrogen ions
in sea water should be within the pH range of from 5 to 9. If the
pH of water is below 5, then the rate of oxidation of Fe@2@+ ions
into Fe@3@+ becomes strongly retarded and the fertilizer yield
becomes substantially reduced, while at a pH of water above 9 the
resulting product becomes diluted with potassium and magnesium
hydroxides, wherefore its effectiveness, as a fertilizer, is
When iron is added to sea water in an amount of less than 10 mg
Fe/1, it is necessary to separate too large amounts of water from
the precipitate and the fertilizer production cost is
substantially increased; if iron is introduced into sea water in
an amount of more than 100 mg Fe/1, the resulting product has a
small content of organic substances, wherefore its efficiency is
As a source of bivalent iron ions it is advisable to use ferrous
salts both in a solid and liquid state. It is preferred, however,
to spent solutions from etching ferrous metals with hydrochloride
acid; these solutions are available in considerable amounts from
plants of mechanical engineering and ship-building industries.
Said solutions are toxic production wastes and great sums of money
are allocated to eliminate them, wherefore the use of spent
etching solutions for the production of fertilizers is
economically efficient and, furthermore, large areas of land and
sea are not polluted and, hence, environment pollution is reduced.
Solutions from etching of ferrous metals usually contain 120-160 g
of iron per liter of a solution and 30 to 60 g/1 of hydrochloric
acid; occasionally in such solutions there may be present
corrosion inhibitors in an amount of from 0.8 to 1.2% such as a
product of copolymerization of urotropin and aniline. Our
investigations in vegetation tests under field conditions have
shown that corrosion inhibitors being present in the fertilizer do
not exert any noticeable effect on the fertilizer efficiency.
In the practice of the present invention, the method according
thereto is effected as follows. Sea water is poured into a vessel
and ferrous chloride is introduced thereinto in the form of a
solid salt, aqueous solution, or spent etching solution at a rate
of 10 to 100 mg Fe/1 of water. The pH of the water is maintained
within the range of from 5 to 9. Ions of bivalent iron introduced
into sea water are oxidized according to the following scheme:
4Fe@2@+ + O2 + 2H2 O .fwdarw. 4Fe@3@+ + 4OH@-
the resulting ions are hydrolyzed:
Fe@3@+ + H2 O .fwdarw. Fe(OH)@2@+ + H@+
with the formation of hydroxide Fe(OH)@2@+ = H2 O.fwdarw.[Fe(OH)2
]@+ + H@+, containing active positively charged centers capable of
recovering, according to the ion-exchange mechanism, valuable
metals such as copper, zinc, molybdenum as well as amine complexes
and other components from sea water. The resulting precipitates of
ferrous hydroxide possess a particular property, i.e. they result
in no sorption of sodium ions. This phenomenon is favorable for
the fertilizer quality as will be shown hereinbelow. Sorption time
is 0.1 to 6.0 hours. Solid particles of iron hydroxide with
co-precipitated thereon microelements and organic substances are
separated from sea water by decantation with subsequent filtration
of the precipitate. The filtered precipitate contains about 70% of
This precipitate is dried to the air-dry state, i.e. such a state
when the precipitate contains an equilibric amount of humidity
under normal conditions. To this end, the precipitate is poured
over the ground and dried under environmental conditions or in
special drying chambers at a temperature of from 0 DEG to 50 DEG
C. When dried at a temperature of above 50 DEG C, the fertilizer
may have its activity lost, wherefore the use of such temperatures
is not advisable. As a result of these operations, a fertilizer of
the above-mentioned composition is obtained.
The present invention has the following advantages: the process of
its preparation is rather simple and commercially efficient
sources of the starting material, i.e. sea-like waters, are
practically unlimited and each country has vast resources of
ferrous salts. Taking into account the fact of utilization, with
equal success, of waste products containing ferrous salts,
economic efficiency is substantially increased. In addition, the
method of the present invention contributes to preventing
pollution of the environment with poisonous production wastes. The
fertilizer according to the present invention has an additional
advantage residing in that it steadily increases the yield
capacity of numerous agricultural plants by at least 5-10% at an
insignificant rate of 0.5 to 3 kg of one hectare. Another feature
of the present invention resides in its ability to stimulate the
growth of grape vines and increasing the yield capacity of not
only pulse plants but other type plants as well.
For a better understanding of the present invention some specific
Examples illustrating the method of producing fertilizers as well
as the use of the thus-produced fertilizers in with respect to
particular agricultural plants.
Into a pool there was poured Black Sea water with a salinity of
1.83% and composition (percentage of the salt mass): NaCl--77.29;
KCl--2.11; MgCl2 -- 8.92; MgSO4 -- 6.33; MgBr2 -- 0.20; CaSO4 --
3.64; Ca(HCO3)2 -- 1.52.
the water also contained 3.5 mg/1 organic substances, 3.10@-@6 g
Cu/1, 4.10@-@6 g Mo/1, 8.10@-@6 g Zn/1. It was added with a spent
solution from etching of iron containing 120 g/1 of Fe, 30 g/1 of
HCl, and 1% of an inhibitor. Concentration of hydrogen ions in the
solution was adjusted to a predetermined value by means of a 36%
hydrochloric acid or solid soda; the solution was mixed by means
of air bubbling. After settling of the solution for 24 hours,
water was decanted. The resulting precipitate was filtered through
a dense tissue and dried in the air at a temperature within the
range of from 20 DEG to 35 DEG C.
Conditions of the process and results obtained are given, for six
texts in Table 1 hereinbelow.
Chemical characteristics of the products obtained in tests a, b,
c, d, e are given in Table 2.
It may be seen from Table 2 that the fertilizers produced at a
higher concentration of hydrogen ions in the solution contain
greater amounts of organic substances, while at a lower
concentration of hydrogen ions in the solution fertilizers with a
greater content of microelements are produced.
It has been found that a pH within the range of from 6.9 to 7.2
was the most advantageous for the process. This pH range was
selected due to the fact that practically no hydrochloric acid or
sodium carbonate need to be added to the sea water, whereby
fertilizers with a minimal production cost could be obtained.
Vegetation tests of the fertilizers for growth and development of
various agricultural plants have shown a high efficiency thereof.
Effect of the fertilizers produced from sea water in tests a and d
was determined in vegetation field experiments according to the
1. Control - seeds not treated with the fertilizers
2. Seeds treated with the fertilizes
3. Fertilizers were introduced into soil.
The tests were performed on soils of Ucraine and Moldavia. In
vegetation experiments the effect of a pre-seeding treatment of
seeds as well as the soil dressing effect on the productivity of
sugar beet and corn were studied. Seeds of sugar beet and corn
were treated at the rate of 0.125 kg of the fertilizer per 100 kg
of seeds of corn and 1.0 kg. of the fertilizer per 100 kg. of
seeds of sugar beet. The solid was dressed, for sugar beet, at the
rate of 1.5 kg of the fertilizers, and for corn at the rate of 0.5
kg of the fertilizers per 10 kg of commercial fertilizer mixture
based on nitrogen, phosphorus and potassium (referred to
hereinafter as NPK for the sake of brevity). Each experiment was
repeated 5 times. Soil humidity in the experiments was 70% of the
total moisture-absorbing capacity of the soil. The results of the
vegetation tests of sugar beet and corn are given in Table 3
It follows from Table 3 that the use of the fertilizer according
to the present invention increases the total mass of beet, its
sugar content, reduces the content of harmful nitrogen. For corn
there is an increase in total mass and grain. According to the
visual observations, beets to which the fertilizers of the present
invention were used in combination with pre-seeding enrichment of
seeds and with its introducing into soil, showed a more developed
In 1972 under field conditions the influence of pre-seeding
enrichment of seeds with the fertilizer of the present invention
on yield and sugar content on podzolic soils was studied.
Meteorological conditions of that year were unfavorable for sugar
beet. In the beginning of the vegetation period there was an
insufficient amount of humidity in the soil, poor precipitation,
while at the end of the period there was an abundant precipitation
which made the soil more dense thus imparing its aeration.
According to the data provided by the meteorological station of
the region where the experiments were performed, stock of humidity
in a one-meter soil layer was 22 mm during the test period at the
relative humidity of air of 62%. Only in July and August in a
meter soil layer the stock of humidity increased to 104-176 mm at
a relative humidity of air 70-75% while in September there was a
Efficiency of the fertilizers under these conditions is shown in
Table 4 illustrates unquestionable improvement of said
characteristics by using the fertilizer according to the present
It should be noted that the fertilizer introduced into soil is
located in places of root spreading. This phenomenon was noticed
both in laboratory and nature; it probably exerts a favorable
action on the plant growth.
The fertilizer of the present invention produced in test d was
tested during a two years' period for soil dressing of two strains
of grapes "Risling" "Rkatsiteli" and cabbage "Mozharskaja".
Dressing was effected by means of a 1% aqueous solution of the
fertilizer suspension simultaneously with nitrous fertilizers in
the amount of 400 l of the suspension per one hectare. The soil
for cabbage was dressed with a 0.5% aqueous solution of the
fertilizer suspension in the amount of 400 l per one hectare. The
test results are given in Table 5.
As seen from the data of this Table, the use of the fertilizer of
the present invention increases the yield of grapes and, to some
extent, its sugar content; yield of cabbage is substantially
In addition to said plants, we have performed vegetation and field
tests of the fertilizer of the present invention on such plants as
pea and millet. These test also provide the efficiency of the
fertilizers according to the present invention, since the results
of four field tests on gray podzol soils and grassland chernozems
showed an increased, by 21-62 c/ha, yield of sugar beet, improved
sugar content by 0.4-0.8%; sugar output was increased by 4.7-5.0
Soil dressing with the fertilizer of the present invention along
with NPK, as determined by the results of one experiment on gray
polzol soils, increased the yield of sugar beet roots by 51 c/ha
with simultaneous increase in the root sugar content by 1.1%.
The yield of corn silage mass in one experiment on
solonetz-chestnut soils was increased, as compared to the control
value, by 40 c/ha and yield of corn grain - by 4.4 c/ha.
The yield of corn silage mass in three experiments on
calcareous-chestnut, solonetz-chestnut and grassland-chernozemic
soils was increased by 20 to 40 c/ha.
The yield of winter wheat in two experiments on gray podzol and
calcareous-chestnut soils was increased by 3.0-3.6 c/ha; yield of
corn grain under the same conditions as for wheat was increased by
The yield of millet, according to the data of a two-years' test
period, on grassland-chernozems was increased by 6.8-8.8 c/ha.
Method of converting brines to useful products
SOMERVILLE, R., et al.
A process is provided for the recovery of one or more useful
products including fertilizer, animal feed supplements, iron
oxide, magnesia, salt, purified brine, and purified water from
brines. The source of the brines can be oil and gas field wastes,
seawater or effluent from a seawater desalination plant, or other
inland brine sources. Iron and magnesium are initially
precipitated from the brine. Then phosphoric acid is added to the
brine followed by an alkaline agent to produce precipitates useful
as fertilizer and animal feed supplements. The remaining salt in
the brine may then be removed and recovered along with purified
BACKGROUND OF THE INVENTION
This invention relates to a process for converting brines into
useful products, and more particularly to converting saline waters
such as oil and gas field brine wastes, seawater or effluent from
a seawater desalination plant, or other inland saline waters into
animal feed supplements, fertilizer, salt, purified brine and
Oil and gas field operations generate waste products in the
production and handling of crude oil and natural gas. These waste
products include drilling mud pit waters and oil and gas field
brines. The quantities of brines produced in oil and gas fields
can be substantial, with brine fractions accounting for from 4 to
96 percent of the total liquid volume produced. Brines from other
inland or seawater sources also present disposal problems.
Various method of disposal of these brines have been attempted
including solar evaporation, thermal evaporation, controlled
release of brines into surface water, and injection of brines into
subterranean formations. However, in areas of high annual rainfall
and/or high relative humidity, such as much of the midwestern and
eastern portions of the United States, solar evaporation becomes
impractical. Moreover, with increasing state and federal
regulatory pressures, diversion of large volumes of brine into
surface waters is not an environmentally acceptable solution.
While evaporation as a means of recovering fresh water from these
saline sources has been attempted, the presence in such brines of
a large proportion of divalent metal chlorides such as calcium and
magnesium chloride have greatly complicated recovery efforts.
These metal chlorides are highly corrosive to process equipment
surfaces and deposit hard to remove mineral scales. This scale
deposition becomes an even greater problem when the brines are
Presently, brine treatment using dissolved air flotation methods
to remove suspended oil, followed by deep well injection of the
brine is regarded by the United States Environmental Protection
Agency as the best practicable technology for disposal. However,
deep well injectin is expensive, difficult to design to a given
level of capacity, and requires careful conditioning of the brine
prior to injection. Also, deep well injection of brines may
present a contamination hazard to fresh water aquifers. Economies
of scale favor deep well injection systems having capacities of
millions of gallons of brines per month. However, in oil and gas
fields in the midwestern and eastern United States where less
brine wastes are produced than in western oil fields, and where
the oil and gas fields themselves are smaller, deep well injection
may not, in many instances, be an economically feasible disposal
Some attempts have been made in the past to separate useful
byproducts from brines or other industrial waste waters. For
example, Miller, U.S. Pat. No. 3,374,081, teaches a method of
precipitating minerals from saline waters using lignin compounds,
proteinaceous compounds, and tannins. The saline waters are
initially concentrated by evaporation and the resultant salt
precipitate removed. Then an organic precipitating agent such as a
lignin or tannin is added to form an organic fertilizer containing
other inorganic minerals.
Baldassari, U.S. Pat. No. 4,069,033, teaches the extraction of
fertilizer salts and organic substances from a variety of
industrial waste waters including sugar mill, distillery, and
fermentation wastes. Baldassari teaches the use of strong acids or
bases to form precipitates from such waste waters which
precipitates are taught to be useful as fertilizers. However,
neither of these particular procedures is believed to have gained
Accordingly, the need exists for a cost effective and
environmentally acceptable method for the disposal of oil and gas
field waste brines and other saline water sources.
SUMMARY OF THE INVENTION
The present invention provides for the recovery of valuable
products such as animal feed supplements, fertilizers, magnesia,
iron oxide, salt, purified brine, and purified water from saline
water sources such as oil and gas field waste brines and seawater.
These products are useful materials having economic value.
According to one aspect of the present invention, a method is
provided in which an oxidizing agent is initially added to the
brine to remove iron from the brine as a precipitate. An alkaline
agent is then added to the brine to adjust the pH of the brine to
the range of 7.5 to 9.0 to cause magnesium ions present in the
brine to precipitate and be removed. Sufficiently phosphoric acid
is then added to the brine to provide a substantially
stoicheometric ratio of phosphoric acid to divalent cations,
principally calcium, in the brine. An alkaline agent is then added
to the brine to form calcium phosphate precipitates which are
useful as an animal feed supplements or fertilizers.
Optionally, the remaining dissolved salts in the brine solution,
which is now substantially free of divalent metal compounds, can
be readily separated and recovered by the use of a vapor
compression evaporator crystallizer of multiple effect evaporator
crystallizer. The recovered salt is principally sodium chloride.
This salt is a highly purified product which is useful for
practically all commercial purposes. The water which is recovered
from the separation process is substantially free of dissolved
solids and deleterious metal cations and can be disposed of
directly or can be sold as purified water to industrial and
Accordingly, it is an object of the present invention to provide a
process for the recovery of one or more useful products incuding
animal feed supplements, fertilizer, iron oxides, magnesia, salt,
purified brine, and purified water from brines. This and other
objects and advantages of the invention will be apparent from the
following detailed desription, the accompanying drawing, and the
BRIEF DESCRIPTION OF THE DRAWINGS
The single drawing FIGURE illustrates, in the form of a schematic
diagram, the process of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In accordance with the practice of the present invention, and with
reference to the drawing FIGURE, a saline water source such as an
oil field waste brine, seawater, or other inland saline water is
initially stored in a large pit, tank, or storage chamber 10. The
pit, tank, or storage chamber 10 is preferably lined or otherwise
formed to be substantially water tight. If an oil or gas field
waste brine is used as the saline water source, it may be
necessary to remove traces of oil which are present in the brine.
Typically, there is approximately one-half pint of oil per barrel
of brine as received from oil field operations. This oil removal
is accomplished through the use of a surface skimmer 12 which
collects oil floating on the surface of the brine and pumps it via
line 14 and pump 16 to an oil storage tank 18.
Additionally, further oil may be removed from the brine in a
separation device such as heater treater 20 after removal of the
brine from pit 10 via line 22 and pump 24. Heater treater 20
typically comprises a holding tank or the like which provides
undisturbed residence time for separation of the oil and brine.
Heat is supplied to heater treater 20 to accelerate the separation
process, and, optionally, chemicals may be added to heater treater
20 which further enhance separation.
The brine is then filtered to remove suspended solids by pumping
it via line 26 through filter 28. Filter 28 may be any suitable
filtration device and is preferably a vacuum drum or plate and
frame type filter. Such filtration devices are commercially
available from a number of sources.
After filtration, the brine is sent to tank 30 where an oxidizing
agent is added to the brine to convert any ferrous ions present in
the brine to the ferric state. Suitable oxidizing agents include
hydrogen peroxide, or ozone. Preferably, this oxidizing reaction
is carried out at an acidic pH. Depending on the pH of the brine
entering tank 30, the pH of the solution may be adjusted by the
addition of an acid or base to bring it within the optimum range.
An additional advantage of the oxidation step of the process is
that it will destroy any traces of organic materials which may be
present in the brine.
After oxidization, an alkaline agent is added to tank 30 to raise
the pH of the brine to about 7.0 and cause all iron ions present
therein to precipitate as iron oxides. The brine is then sent to a
suitable filter 32 where the iron oxide precipitate is removed.
The brine is then pumped via pump 34 to a further holding tank 36.
At this point in the process, magnesium is removed from the brine.
The presence of magnesium ions in the brine at a later point in
the process will result in the production of products having a
lower ecomonic value. Additionally, purified magnesium compounds
have economic value. Magnesium is typically present in the brine
as magnesium chloride which can be reacted with an alkaline
material to form magnesium hydroxide as illustrated by equations I
and II below:
MgCl2 +2NaOH.fwdarw.Mg(OH)2 +2NaCl (I)
MgCl2 +Ca(OH)2 .fwdarw.Mg(OH)2 +CaCl2 (II)
To remove magnesium, the brine is pumped via pump 38 to reactor
40. A sufficient amount of an alkaline agent to adjust the pH of
the brine to the range of 7.5 to 9.0 is added to reactor 40. A pH
meter (not shown) may be used to monitor the pH of the brine
solution. After reaction, the brine may be sent to a thickener or
settling tank 42 where the precipitated magnesium hydroxide would
be concentrated. The precipitate is then filtered in filter 44,
washed free of soluble salts, and either dried or calcined in
dryer 46. The magnesia product is useful in making refractory
bricks and magnesium metal as well as an additive for cosmetics,
pharmaceuticals, and insulation.
As shown by equations I and II above, the alkaline agent may be
either calcium hydroxide (hydrated lime), hydrated lime from
burned dolomite, or sodium hydroxide. If burned dolomite is used,
the magnesium content of the dolomite is recovered with the
magnesium hydroxide precipitate. Sodium and/or calcium cations,
which replace the magnesium ions in solution, are recovered later
in the process as explained below.
The clear brine solution from settling tank or thickener 42 and/or
filtrated from filter 44 is then sent to a work tank 48 which
serves as a holding tank for the brine prior to reaction with
phosphoric acid. The brine in work tank 48 may be periodically
sampled and analyzed at analysis station 50 to determine the
concentration of divalent calcium and other metal cations
contained therein. This analysis is then utilized to meter the
proper amount of phosphoric acid into the brine from phosphoric
acid source 52 and metering pump 54. Preferably, the amount of
phosphoric acid added is in a substantially stoichiometric ratio
to the concentration of divalent metal cations, principally
calcium, in the brine, resulting in a chemical reaction which
causes substantially all of the divalent metal cations in the
brine to be removed as a precipitate as more fully explained
below. The addition of a substantially stoichiometric amount of
phosphoric acid to the brine will lower the pH of the brine to
less than 2.0. The flow rate of the brine into reactor 56 may be
controlled by pump 58 and flow rate valve 60, and is monitored
periodically by flow rate indicator 62.
A preferred source of phosphoric acid is agricultural grade
phosphoric acid containing 75% orthophosphoric acid (54% when
reported as phosphorous pentoxide). The brine and phosphoric acid
are thoroughly agitated in reactor 56 to form a reaction mixture.
Any suitable agitation device may be utilized including a stirred
tank reactor or motionless mixing device.
To the reaction mixture, an alkaline agent is added to adjust the
pH of the mixture to the range of 1.8 to 2.9. A metering pump and
pH meter may be used to control the addition of alkaline agent. As
the alkaline agent, either soda ash (Na2 CO3), caustic soda
(NaOH), potassium hydroxide, or potassium carbonate are preferred.
The addition of an alkaline agent causes the precipitation of a
mixture of fertilizer salts including principally dicalcium
phosphate (CaHPO4.2H2 O). Additionally, most trace impurities in
the brine such as strontium, iron, aluminum, flourine, and the
like, will also be precipitated at this stage as complex mineral
salts. This is because other ions will react with the phosphoric
acid at pH's lower than that which calcium will react. This first
stage of precipitation may not be necessary where impurity levels
in the brine are sufficiently low.
Such precipitated compounds are separated from the brine solution
by filtration, such as by belt filter 64. The precipitate is then
dried in dryer 66. The dried precipitate is a citrate soluble
fertilizer material having an approximate NPK analysis of 0-40-0.
The reaction mixture is then taken to a further agitated reactor
68 where more alkaline reagent is added to bring the pH of the
reaction mixture to the range of 3.5 to 6.0. This causes
essentially complete precipitation of all remaining dicalcium
phosphate from the brine solution. Because of the preliminary
precipitation step, the dicalcium phosphate precipitated at this
stage of the process is quite pure as is useful as a premium grade
animal feed supplement. The precipitated dicalcium phosphate is
removed via belt filter 70 and then dried in dryer 72.
By controlling the pH of the brine solution after the addition of
phosphoric acid, the ratio of calcium phosphates precipitated at
each stage (reactors 56 and 68) may be controlled. If impurity
levels are sufficient to warrant a two-stage precipitation then,
preferably, a minimum amount of calcium phosphates is initally
precipitated with the major portion being precipitated in reactor
68. In practice, this ratio is about 10-30% in the first stage and
70-90% in the second stage.
Additionally, the total amount of calcium phosphates produced by
the process may be modified somewhat by the selection of alkaline
agents at various stages of the process. The use of calcium
hydroxide as an alkaline agent at earlier stages of the recovery
process will place more calcium cations into solution for later
precipitation. In this manner, the process of the present
invention is flexible to market conditions for the need for more
or less calcium phosphate products. Additionally, while the
preferred process has been described above, it is within the scope
of the invention to add phosphoric acid and alkaline agent to the
brine to precipitate calcium phosphates in a single stage
procedure or a procedure with two or more successive states.
The remaining brine is now substantially free of all divalent
metal cations. The brine is pumped from storage tank 74 by pump 76
to an optional evaporation system 78. It may be desirable to
adjust the pH of the brine in storage tank 75 to minimize
corrosion problems in the evaporation equipment, and this may be
accomplished by further addition of an alkaline agent such as
sodium hydroxide to the brine. The brine itself is a useful
product which can be used as a raw material for chlor-alkali
plants. Optionally, it may be evaporated to recover crystallized
Evaporation system 78 is preferably a forced circulation
evaporator-crystallizer with vapor recompression. Such systems are
commercially available. The evaporation system provides both a
pure crystallized salt and purified process water.
The recovered salt is principally sodium chloride. Potassium,
lithium, and any remaining calcium and magnesium cations are
concentrated in the bitterns produced by the evaporation process
and may be recycled back to the beginning of the process. The
recovered salt is a highly purified product which can be marketed
for practically all commercial uses.
The recovered water from evaporation system 78 is itself highly
pure and contains less than 1 mg/l of total solids and an absence
of deleterious anions and divalent metal cations. The water can be
used as process and wash water in the process of the present
invention, can be discharged directly to rivers, lakes, and
streams with no environmental harm, or alternatively may be sold
to industries having large purified water requirements.
While the methods herein described constitute preferred
embodiments of this invention, it is to be understood that the
invention is not limited to these precise methods and that changes
may be made without departing from the scope of the invention,
which is defined in the appended claims.
Composition derived from sea water for the treatment of
vegetation and its method of production
There is disclosed a LIQUOR useful as a natural herbicide and
also, when diluted with water, useful as a plant micronutrient.
O does not guarantee that they are complete, up-to-date or fit for
The present invention relates to a LIQUOR, a method for making the
same, and its use as a herbicide and/or a plant micronutrient,
depending on dilution.
BACKGROUND OF THE INVENTION
Sea solids useful as fertilizer are known from U.S. Pat. No.
3,071,457 to Murray. In addition, the use of nutrient sea
solids in hydroponic farming is disclosed in Murray's U.S. Pat.
No. 3,250,606. According to the teachings of these patents,
precipitated sea solids are harvested and used as a plant nutrient
On the other hand, U.S. Pat. No. 3,770,410 discloses the
production of potassium polyphosphates from a phosphoric acid
sludge by heating the sludge to eliminate most of the water and
then adding a salt mixture thereto to make a fertilizer.
Soilless culture of plants using sea water which is chemically
modified with non-natural substances to change its composition is
disclosed in U.S. Pat. No. 2,713,741. U.S. Pat. No. 3,640,695
and U.S. Pat. No. 3,332,767 disclose processes for
converting mineralized water into irrigation water, by
distillation and similar treatment.
U.S. Pat. No. 2,934,419 deals with the conversion of sea
water into a solid fertilizer. U.S. Pat. No. 2,663,628
discloses a method of making a lignin fertilizer base using a
cooking liquor as a component thereof. U.S. Pat. Nos.
4,450,001; 4,334,910; 4,382,013; 4,508,559; and 4,125,392
disclose similar compositions to regulate plant growth.
All of these known methods and their products fall into one of two
categories. Firstly, sea solids are precipitated, removed and used
as such. Secondly, the water of the starting material is distilled
and used as fresh water. In the first instance, the resultant
product is nothing more than a mixture of chemicals derived from
sea water; in the second instance, the resultant product is pure
None of the prior art disclose the use of a LIQUOR containing
water and salts, in which the ratios of the mineral salts to each
other and to the remaining water are different from the ratios of
such salts in the initial natural sea water. The resultant LIQUOR
thus naturally altered from its initial state functions per se as
a natural herbicide and also, in dilute aqueous concentrations, as
a natural micronutrient. As used herein, the term "LIQUOR" defines
the resultant product in which the ratios of salt are modified as
disclosed and is to be distinguished from natural sea water as
well as from a merely concentrated solution.
As will be explained hereinafter, the undiluted LIQUOR of the
present invention is a swift, highly effective natural herbicide
even when used in small amounts and may be applied directly to
offending and deleterious growths without affecting any
surrounding desirable vegetation. On the other hand, when highly
diluted with fresh water, the LIQUOR of the present invention
provides a totally unexpected and unobviously effective nutrient,
by means of which the growth of desirable vegetation is enhanced
and increased with rapidity and substantive benefit to the size,
taste, appearance and the like of the vegetation. A further
unexpected and unobvious result lies in the fact that the LIQUOR
acts as a preservative in that the fruit of such vegetation lasts
for a longer time after being picked. Thus, having a longer shelf
life and transport life.
The noted benefits and advantages of the invention will be
apparent from the following disclosure.
SUMMARY OF THE INVENTION
According to the present invention, natural sea water is subjected
to conditions suitable to evaporate a portion of the water
therefrom and simultaneously to precipitate a portion of the
mineral salts dissolved therein so that the amount of such mineral
salts remaining in the resulting LIQUOR differs from the amount of
mineral salts contained in the natural sea water in proportion
both to itself and to the remaining water. Thus, after the
precipitate is removed, the resultant LIQUOR is not a mere
concentrate of the natural sea water, but an unexpected mixture of
water and salt capable of being used per se as a natural herbicide
or diluted sufficiently with fresh water as a natural
More specifically, the present invention provides a method
comprising the steps of subjecting a quantity of natural sea water
to evaporation for a period of time sufficient to drive off a
substantial portion of its water content and to precipitate a
portion of the mineral salts dissolved in such natural sea water,
thereby forming a LIQUOR containing dissolved mineral salts in
ratios to each other and to the water different from those in the
initial sea water; separating the remaining LIQUOR from the
precipitated solid material (mineral salts); and recovering the
Still further, in accordance with the present invention,
deleterious vegetation can be destroyed or eradicated by applying
to the same the LIQUOR described above in an amount effective to
accomplish such result. On the other hand, when the above
described LIQUOR is diluted sufficiently with fresh water, it may
be applied to vegetation as a natural plant micronutrient when
utilized in an amount effective to enhance in a significant and
unobvious manner, the growth, appearance, and the like of the
plant to which it is applied.
DESCRIPTION OF THE INVENTION
In general, the production of LIQUOR according to the present
invention can be simply performed by allowing natural sea water to
rest in a shallow pan or the like until a quantity of the water
evaporates and a layer of precipitate scum is produced on the
surface of the remaining natural sea water. The precipitate is
then removed, the remaining natural sea water decanted, and the
resultant used as the LIQUOR.
For example, shallow pans are filled to the brim with natural sea
water and allowed to stand under conditions so that the dissolved
mineral salts appear as a precipitate on the surface of the
remaining natural sea water. Such precipitate is separated from
the remaining natural sea water, which comprises the LIQUOR and
can be decanted and bottled. The LIQUOR may first be filtered to
remove any large particles and similar contaminants. In general, a
quantity of about 5680 ml. of such initial natural sea water in
two pans (e.g. shallow 3 quart, 13.times.9.times.2 inches) is
reduced to about 230 ml. (an actual reduction of between 90% to
95% of volume) to provide the LIQUOR. This LIQUOR contains
approximately 26% by weight of dissolved mineral salts in
comparison to about 3.5% of mineral salts dissolved in the natural
sea water, and has a substantially neutral pH.
The process may be enhanced by allowing the natural sea water to
be moderately heated, with a gas or electric heater to elevate its
temperature to induce evaporation, but not to boil the same. Also,
the natural sea water may be placed in a vacuum environment to
increase the rate of evaporation.
Because of the relatively constant rate of evaporation induced by
the low heat, or the ambient external heat and the different rates
of precipitation of the mineral salts contained in the natural sea
water, the remaining LIQUOR contains dissolved mineral salts in
ratios to each other, different from those in the original natural
sea water. Such LIQUOR comprises a natural herbicide per se and
exerts a herbicidal effect on vegetation when applied thereto in
an amount effective to eradicate undesired or unwanted specimens.
While natural sea waters throughout the world vary somewhat in the
amount of dissolved mineral salts, there is a relative similarity
among them. New York sea water is generally typical of ocean
waters. The analysis of sea water is well established, as
evidenced by the data set forth on Pages 176 and 177 of "The
Oceans" (1942) by Sverdrup, Johnson, and Fleming.
A LIQUOR made from New York sea water in accordance with the
present invention has the following analysis with respect to the
mineral salts dissolved therein:
Chromium Total 0.02
and had a pH of 6.87.
The present LIQUOR is effective, undiluted, as a natural
herbicide, as already indicated. It has also been found that the
addition of a slight amount of fresh water to the LIQUOR does not
reduce its effectiveness as a herbicide. A small amount of a
wetting agent may be used to enhance the spread of the same. This
LIQUOR may be applied directly to the root system and/or to the
leaf system of the plant or vegetation to be killed by spraying or
other suitable means.
As previously mentioned, the LIQUOR is also useful as a plant
nutrient when it is highly diluted with fresh water. Broadly, the
LIQUOR should be present in an aqueous diluent in an amount at
least sufficient to have a micronutrient effect on plant life,
i.e., up to about 3800 parts of fresh water to 1 part of LIQUOR by
volume. In general, however, the LIQUOR is present in the aqueous
diluent in a concentration of about 0.5 ml. to about 1.0 ml. per
gallon to be useful as a plant nutrient. It has been found that
for fruit plants the lower range of concentration is best, while
for green leaf plants and the like, the upper range of
concentration (i.e. 1.0 ml. per gallon) is generally preferred.
Application of such diluted LIQUOR may be made to the root and/or
the leaf systems by spraying or otherwise as desired.
EXAMPLES OF USE
In order to illustrate the present invention more fully, the
following examples are set forth. In the examples all values with
respect to amounts and ratios are the same as those set forth
above, unless otherwise indicated.
As a Herbicide
Dandelion plants in a New York suburb were treated by spraying the
base of the plants with undiluted LIQUOR. The spray was made to
wet the soil but not to saturate it. Within one day signs of
morbidity were observed; and within three days the dandelions were
Such LIQUOR was similarly applied to weeds known as Nut Grass and
"Torpedo grass" in Lake Worth, Florida, with similar results.
The foregoing procedures were respectively repeated 5 to 10 times
over a period of several days on similar patches of dandelions and
Torpedo grass, nut grass, crab grass and the like.
In each instance, the present LIQUOR herbicide was selective and
attacked only those plants to which it was applied and did not
spread or leach outwardly and cause harm to any surrounding
It must be noted that the LIQUOR is made from a product of nature
and does not injure or affect the aquifer as previously known
commercial herbicides or pesticides do. It is made from a natural
product and does not have a carcinogenic background.
As A Nutrient
The LIQUOR was diluted in a ratio of 1 ml. to 1 gallon of fresh
tap water, the diluted solution being applied to tomato and
strawberry plants on commercial farms in Lake Worth, Florida
during the months of January through April. The plants were only a
part of the entire field of plants and were located in a partially
shaded area. The diluted LIQUOR was applied by spraying directly
to the leaf portions of the plants and to the soil surrounding the
Within several days it became obvious that the plants exhibited
improved color and strength. The plants grew more rapidly than
plants not so treated. The treated crop was larger in size and
weight and better resisted insect blight; and the fruit, when
harvested, were sweeter and tasted better than those not so
treated. This occurred notwithstanding the partial shade and the
winter growth season. The results, i.e., fruit of this experiment
were taste tested in comparison to non-treated fruit (control) by
an impartial panel. Of the persons responding, about 70% liked the
experimental tomato best, and only 25% liked the control tomato
best, while the rest could not differentiate between the
experimental fruit or the control.
An unexpected and unanticipated result was observed during recent
testswith strawberries. A large number of the control strawberries
displayed extensive mold formation and softening and had to be
discarded nine to eleven days after picking even when kept under
refrigerated conditions. On the other hand, strawberries treated
with the LIQUOR of the present invention lasted over 3 weeks and
few if any, were lost to mold, etc. Therefore, a natural
preservative feature is apparent from the present invention.
The present invention presents many other advantages. For example,
the LIQUOR is made from readily available natural starting
materials; and the method for making the same is simple and
straightforward, requiring no special expensive equipment or the
use of non-material chemical components. Moreover, the LIQUOR so
prepared can be readily made useful as a plant nutrient by simple
dilution with water or the like; and whether used as a herbicide
or a plant nutrient, the LIQUOR may be applied in any convenient
manner. Numerous other advantages of the invention will be readily
apparent to those skilled in the art.
It is to be understood that numerous modifications and variations
of this invention may be made without departing from the spirit
and scope of the invention, and consequently this invention should
not be limited to the described embodiments except as defined in
the appended claims.
Precipitation of minerals from brines
Related : MURRAY, Maynard : Seawater Fertilizer
[ PDF ]
Method of obtaining magnesia and potash from the waters of
the great salt lake
[ PDF ]
Method of treating sea water
[ PDF ]
Process of applying sea solids as fertilizer
Maynard R. Murray
[ PDF ]
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