CN108975361A - A kind of magnesium hydroxide soil conditioner prepared using magnesium elements in seawater - Google Patents
A kind of magnesium hydroxide soil conditioner prepared using magnesium elements in seawater Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/14—Magnesium hydroxide
- C01F5/22—Magnesium hydroxide from magnesium compounds with alkali hydroxides or alkaline- earth oxides or hydroxides
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
- A23K20/24—Compounds of alkaline earth metals, e.g. magnesium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/02—Magnesia
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/24—Magnesium carbonates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/26—Magnesium halides
- C01F5/30—Chlorides
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D5/00—Fertilisers containing magnesium
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2101/00—Agricultural use
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
The invention discloses a kind of methods using the magnesium in seawater, comprising the following steps: seawater is passed through the ion exchange column equipped with sodium form ion exchange resin；Using calcium chloride water as eluant, eluent, elution treated ion exchange column collects eluent；Lime is mixed with eluent, is sufficiently reacted, precipitation and separation and liquid；Drying precipitating.The present invention is raw material production main component as the alkaline matter of magnesium hydroxide using seawater, recycle the magnesium in seawater, this alkaline matter can be used as the use of calcium carbonate class acidic soil conditioner, the raw materials for production that can also be used as the calcium-magnesium-containings such as feed and calcium magnesium phosphate use, on the basis of ion-exchange-resin process extracts sea water magnesia, using calcium chloride solution as eluant, eluent, using lime as precipitating reagent and regenerative agent, it realizes ion exchange resin and eluant circulation utilizes, the rate of recovery of magnesium elements is up to 85% or more in seawater, and reach with seawater magnesium resource low energy consumption, low cost, the pollution-free purpose extracted magnesium hydroxide and prepare acidic soil conditioner.
Description
Technical field
The present invention relates to seawater utilization technical fields, prepare hydrogen-oxygen using magnesium elements in seawater more particularly, to a kind of
Change magnesium soil conditioner.
Background technique
South China rainfall is more, and soil passes through rainwater for a long time or acid rain washes away, and the alkalinity base cation such as calcium and magnesium largely drenches
Molten leaching loss, and the hydrogen of exchangeability and aluminium etc. cause acid ion to be released in soil, result in soil in acidity.China's soil in recent years
For earth in accelerating acidification trend or even part northern area soil acidification phenomenon also occur, it is big for a long time that this is mainly due to China
Amount mugineic acid and the chemical fertilizer of physiological phenomenon cause soil acidification to aggravate.Soil acidification can aggravate aluminium ion activation, plant absorption
It can be poisoned after aluminium, it is even dead to generate the harm of aluminium poison；And then accelerate the loss of soil mineral nutrient；Change simultaneously soil
Structure leads to soil leanness, influences plant normal development；Acid rain can also inducing plant pest and disease damage, make crop failure, reduce soil
Ground productivity.Therefore soil acidification has seriously affected China's agricultural production and development.
In recent years, gradually serious with China's soil acidification problem, the soil acid-base regulator of calcium and magnesium alkali ion obtains
The concern and application of more and more people are arrived.More commonly used at present and effective alkaline Auto-regulator is produced by raw material of alkaline residue
Soil acidity regulator and lime containing alkaline calcium ion.
Alkaline residue is the waste material of alkaline factory, and main component is the calcics magnesium salts such as magnesium hydroxide, calcium sulfate, calcium carbonate
Class, pH value are 9~12, can effectively improve the pH value of soil, and containing beneficial needed for the plant growths such as calcium, magnesium, sulphur, selenium
Element, but also can introduce heavy metal into soil containing impurity such as heavy metal elements, lead to soil secondary pollution.
Lime similarly can effectively improve soil pH value, and main component is by quick lime (CaO) and white lime (Ca
(OH)2).Lime is by raw material lime stone (CaCO3) generated after calcining and decomposing, low production cost, therefore in acid soil
The universal liming in territory area adjusts soil acidity, but long-term a large amount of limings will lead to soil and be acidified again, and a large amount of
Calcium ion can in soil or fertilizer sulfate radical and carbanion be combined into calcium sulfate and calcium carbonate, it is tight that this will lead to soil
Weight is hardened.Therefore production higher alkaline matter containing magnesium elements is as acid soil regulator with regard to particularly important.
Meanwhile the exploitation of China's magnesium elements relies on always the smelting production of ore resource (magnesite), disappears in production process
Mass energy is consumed, and is caused serious environmental pollution.Also contain a large amount of magnesium elements in seawater, be that content is only second in seawater
The metal ion of sodium ion, average content 1.29kg/m3, mainly exist in the form of magnesium chloride, but China is not yet at present
Make full use of the magnesium elements in seawater.
The principle for extracting magnesium elements in seawater at present mainly puts into alkali into seawater, makes the magnesium elements in seawater with Mg
(OH)2Form be precipitated out post-processing utilization, main method has soda processes, calcium method and three kinds of ammonia process.(1) calcium method is with stone
Ash direct plunges into seawater as precipitating reagent, although raw material is cheap, impurity is more during extracting magnesium, and filter progress is multiple
The miscellaneous, energy and material consumption are larger, and should not be used as acid soil containing foreign ions such as heavy metals from seawater in magnesium products
Earth regulator uses；(2) ammonia process is to add it in seawater using ammonia or ammonium hydroxide as precipitating reagent and remove precipitating magnesium elements, this
The magnesium hydroxide products content of method production is higher, but utilization rate of raw materials and production rate are lower, and material ammonium hydroxide and
Ammonia can generate pollution to environment；(3) soda processes are using the magnesium elements in sodium hydroxide pellets seawater, although the method technique
Simply, product will not contain more impurity, but cost of material is not low, and sodium hydroxide has corrosivity, there is peace in production process
Full hidden danger, if while the sodium ion that contains of product the saline and alkaline of soil can be improved into soil, salt damage is caused to plant.
Summary of the invention
The purpose of the invention is to overcome, there are high energy consumptions, high cost, height in the process for production alkaline matter containing magnesium at present
The deficiency of the problem of pollution provides a kind of magnesium hydroxide soil conditioner prepared using magnesium elements in seawater.
The first purpose of the invention is to provide a kind of methods of magnesium using seawater.
A second object of the present invention is to provide the substances containing magnesium that the preparation method is prepared.
Third object of the present invention is that the substance containing magnesium prepares magnesium metal, magnesium-containing compound, and/or combines containing magnesium salts
Application in object and soil conditioner, feed and/or fertilizer.
To achieve the goals above, the present invention is achieved by the following technical programs:
The present invention is using in the method concentrated seawater of inorganic ions exchanger resin absorption enrichment and calcium chloride solution elution release
Magnesium ion, then it is settled out the magnesium ion in calcium and magnesium concentrate by precipitating reagent of lime, it collects calcium chloride filtrate and is followed as eluant, eluent
Ring utilizes, and is prepared into acid soil instrumentality, process such as Fig. 1 after high-content magnesium hydroxide (containing a small amount of calcium) drying filtered out
It is shown.
Therefore a kind of claimed method of the magnesium using seawater, comprising the following steps:
S1. seawater is passed through into the ion exchange column equipped with sodium form ion exchange resin；
S2. using calcium chloride water as eluant, eluent, elution S1 treated ion exchange column collects eluent；
S3. lime is mixed with eluent, is sufficiently reacted, precipitation and separation and liquid；
S4. drying precipitating.
Preferably, in step S1, the temperature of seawater is 5 DEG C~45 DEG C.
Preferably, in step S1, the ion exchange column is bed ion exchange resin column.
Preferably, in step S1, the ratio of the packing volume of the volume and sodium form ion exchange resin of ion exchange column is 1:
(0.6~0.7).
Preferably, in step S1, the flow velocity of seawater is the packing volume with (7~10) per hour again.
Calcium and magnesium in sodium form ion exchange resin (NaR) adsorbing seawater forms calcium and magnesium type ion exchange resin (CaMgR), then
Calcium ions and magnesium ions in seawater obtain initial gross separation enrichment.Exchange process is as follows:
Seawater (adsorbing for the first time) after NaR+seawater → CaMgR+absorption.
By the seawater of sodium form ion exchange resin treatment, can be directly discharged into seawater, can also be used as evaporate brine with it is cold
But the raw materials for production such as seawater.
Preferably, in step S2, the concentration of calcium chloride is 30~45g/L.
Preferably, in step S2, eluting temperature is 5 DEG C~45 DEG C.
Preferably, in step S2, packing volume of the elution flow rate for (4~7) per hour again.
Calcium ion in eluant, eluent displaces the magnesium ion on calcium and magnesium type ion exchange resin (CaMgR), calcium and magnesium type ion
Exchanger resin (CaMgR) becomes calcium type ion exchange resin (CaR), and calcium chloride eluant, eluent is changed into calcium chloride and magnesium chloride
Mixed concentrated liquid (eluent).Elution process is as follows:
CaMgR + CaCl2Eluant, eluent → CaR+contains CaCl2And MgCl2Eluent.
Preferably, the ion exchange column after step S2 eluent is re-used for step S1, repeat absorption enrichment magnesium from
Son.
Calcium type ion exchange resin is Ke Xunhuanliyong, repeats above-mentioned absorption and is enriched with magnesium ion technique, process is as follows:
Seawater (second and absorption later) after CaR+seawater → CaMgR+absorption
Afterchlorinate magnesium and calcium chloride mixed concentrated liquid, Mg is concentrated by resin2+Ion concentration compared to increase in seawater 3 times with
On.Seawater passes through resin adsorption, the rich magnesium mixed concentrated liquid Mg after eluent2+Content is in the g/L of 2.4g/L~4.5.Arrive this
Step handles the seawater of unit volume, Mg therein2+The rate of recovery can reach 88% or more.
Preferably, in step S3, the condition sufficiently reacted is 10 DEG C~40 DEG C, and 40~250r/min of revolving speed is uninterruptedly stirred
Mix lower reaction 0.5h~1h.
Preferably, in step S3, filter press precipitation and separation is used.
Preferably, in step S3, calcium ion and magnesium ion mole in eluent are 1:1.0~1.4 in lime.
It is highly preferred that calcium ion and magnesium ion mole in eluent are 1:1.2~1.3 in lime in step S3.
This precipitating filtration method is to Mg2+The rate of recovery 93% or more, the main component of precipitating is magnesium hydroxide, and containing a small amount of
The alkaline matters such as calcium hydroxide, the description according to GB/T 6274-1997 to soil conditioner, this precipitated products can be used as well
Calcium carbonate class acidic soil conditioner application.
Preferably, in step S3, after isolated liquid addition hydrochloric acid to pH value is 6~7, regeneration is completed, is re-used for walking
Rapid S2.
Regenerative elution agent recycling elution process is as follows:
CaMgR+regenerated CaCl2Eluant, eluent → CaR+contains CaCl2And MgCl2Eluent (recycling elution)
Preferably, in step S4, the condition for drying precipitating is 170 DEG C~220 DEG C, is dried to its water content below 5%.
Preferably, in step S4, in sediment after drying and using magnesium hydroxide professional standard HG/T 3607-2000
Magnesium hydroxide carry out quality analysis.
Preferably, in step S4, fineness measurement is carried out to magnesium hydroxide powder after drying, and is greater than with particle diameter or small
Screening pack is carried out in 0.25mm.
Preferably, it in step S4, is advised using woven bag lined with polyethylene bag film by every bag of 50 ± 1kg or 25 ± 0.5kg
Lattice carry out pack packaging.
The substance containing magnesium that the preparation method is prepared also belongs to protection scope of the present invention.
The substance containing magnesium prepares magnesium metal, magnesium-containing compound, and/or composition containing magnesium salts and soil conditioner, feeding
Application in material and/or fertilizer.
The magnesium-containing compound includes but is not limited to magnesium chloride, magnesium hydroxide, magnesia, magnesium carbonate.
The magnesium substance is carried out fineness measurement by a kind of preparation method for preparing the soil conditioner containing magnesium hydroxide, and
It is sieved and is packed with particle diameter；Pack packaging is carried out using woven bag lined with polyethylene bag film.
Preferably, the magnesium substance is subjected to fineness measurement, and 0.25mm is more than or less than with particle diameter and is sieved
Pack；Pack packaging is carried out by every bag of 50 ± 1kg or 25 ± 0.5kg specification using woven bag lined with polyethylene bag film.
Compared with prior art, the invention has the following beneficial effects:
The present invention is raw material production main component as the alkaline matter of magnesium hydroxide using seawater, this alkaline matter can be used as calcium carbonate
Class acidic soil conditioner uses, on the basis of ion-exchange-resin process extracts sea water magnesia, using calcium chloride solution as eluant, eluent,
Using lime as precipitating reagent and regenerative agent, located again using the enrichment of room temperature resin adsorption, eluent, lime method precipitating, eluant, eluent
Reason, the production technology of drying screening, realize ion exchange resin and eluant circulation utilize, the rate of recovery of magnesium elements in seawater
Up to 85% or more, and reach and acid soil tune is prepared with the low energy consumption of seawater magnesium resource, low cost, pollution-free extraction magnesium hydroxide
Manage the purpose of agent.
Detailed description of the invention
Fig. 1 is process flow chart.
Specific embodiment
The present invention is made with specific embodiment with reference to the accompanying drawings of the specification and further being elaborated, the embodiment
It is served only for explaining the present invention, be not intended to limit the scope of the present invention.Test method as used in the following examples is such as without spy
Different explanation, is conventional method；Used material, reagent etc., unless otherwise specified, for the reagent commercially obtained
And material.
A kind of magnesium hydroxide soil conditioner using magnesium elements in seawater of embodiment 1
Preparation method the following steps are included:
(1) absorption enrichment magnesium ion
First in the ion exchange column made of organic glass, be packed into bed form ion exchange resin, charge weight according to from
The maximum that sub- exchange column can accommodate seawater determines that loadings are exchange column volume 70%, indicates filling amount with BV, i.e.,
If exchange column can accommodate 1m3Seawater, the BV of institute's loaded resin are 700L；The divalent metals such as this resin primary attachment Calcium in Seawater magnesium
The ion exchange resin of cation.
23 DEG C of seawater is passed through into sodium form ion exchange resin with the flow velocity of 7BV/h, the calcium and magnesium shape in resin adsorption seawater
At calcium and magnesium type ion exchange resin, then the calcium ions and magnesium ions in seawater obtain initial gross separation enrichment.Exchange process is as follows: NaR+sea
Seawater (adsorbing for the first time) after water → CaMgR+absorption
It by the seawater of ion exchange resin, can be directly discharged into seawater, can also be used as and evaporate brine and refrigerated sea water etc. produces
Raw material.
(2) elution concentration magnesium ion
The calcium chloride water of 30~45g/L is configured as eluant, eluent, by it under 35 DEG C of eluting temperature, with 4~7 BV/h
Flow velocity eluted by calcium and magnesium type ion exchange resin.Calcium ion in eluant, eluent displaces calcium and magnesium type ion exchange resin
On magnesium ion, calcium and magnesium type ion exchange resin becomes calcium type ion exchange resin, and calcium chloride eluant, eluent is changed into calcium chloride
With the mixed concentrated liquid of magnesium chloride.Elution process is as follows:
CaMgR + CaCl2Eluant, eluent → CaR+contains CaCl2And MgCl2Eluent
Wherein calcium type ion exchange resin is Ke Xunhuanliyong, repeats above-mentioned absorption and is enriched with magnesium ion technique, process is as follows: CaR+
Seawater (second and absorption later) after seawater → CaMgR+absorption
Afterchlorinate magnesium and calcium chloride mixed concentrated liquid, Mg is concentrated by resin2+Ion concentration compared to increase in seawater 3 times with
On.Seawater passes through resin adsorption, the rich magnesium mixed concentrated liquid Mg after eluent2+Content is 4.5g/L.To this step, processing
The seawater of unit volume, Mg therein2+The rate of recovery is 94%.
(3) precipitating filtering
Using lime as precipitating reagent, quantitative lime is put into calcium and magnesium mixed concentrated liquid, is settled out wherein in the form of magnesium hydroxide
Rich Mg2+, magnesium hydroxide is filtered, calcium chloride filtrate is recycled, carries out regeneration treatment.
Calcium and magnesium mixed concentrated liquid is fitted into reaction kettle first, then puts into lime precipitation agent, control temperature of reaction kettle is 40
DEG C, the speed that revolving speed is 250r/min carries out reacting 1h under uninterrupted stirring, is then separated by filtration reaction solution by filter press
Magnesium hydrate precipitate drying storage out, this precipitating filtration method is to Mg2+The rate of recovery be 95%；
The magnesium hydrate precipitate, main component are magnesium hydroxide, and containing alkaline matters such as a small amount of calcium hydroxides, according to GB/T
Description of the 6274-1997 to soil conditioner, this precipitated products can be used as good calcium carbonate class acidic soil conditioner application；
The lime consumption is the integral molar quantity determination according to its calcium ions, is concentrated by calcium ion mole ratio in lime mixed
It closes the ratio that magnesium ion mole in liquid is 1:1.2~1.3 and launches lime.
The calcium chloride filtrate of recycling carries out regeneration treatment, adjusts filtrate pH value using a little hydrochloric acid and drops to above-mentioned configured
Calcium chloride eluant, eluent after regeneration is recycled the initial pH value 6.5 of calcium chloride eluant, eluent in above-mentioned elution process, regeneration
Eluant circulation elution process is as follows:
CaMgR+regeneration CaCl2Eluant, eluent → CaR+contains CaCl2And MgCl2Eluent (recycling elution)
(4) drying screening
It will filter out the alkaline powder that main component is magnesium hydroxide to dry in drying machine, temperature is controlled at 220 DEG C, is dried to
Its water content 5% hereinafter, and using magnesium hydroxide professional standard HG/T 3607-2000 to the magnesium hydroxide in sediment into
Row quality analysis.
According to the requirement of sieve method in GB/T 6003.1-1997, using electric vibrating sieving machine to magnesium hydroxide powder after drying
Fineness measurement is carried out, and 0.25mm is more than or less than with particle diameter and carries out screening pack；According to the regulation in GB 8569, originally
Invention carries out pack packaging by every bag of 50 ± 1kg, 25 ± 0.5kg specification using woven bag lined with polyethylene bag film.
A kind of magnesium hydroxide soil conditioner using magnesium elements in seawater of embodiment 2
Preparation method the following steps are included:
(1) absorption enrichment magnesium ion
First in the ion exchange column made of organic glass, be packed into bed form ion exchange resin, charge weight according to from
The maximum that sub- exchange column can accommodate seawater determines that loadings are exchange column volume 70%, indicates filling amount with BV, i.e.,
If exchange column can accommodate 1m3Seawater, the BV of institute's loaded resin are 700L；The divalent metals such as this resin primary attachment Calcium in Seawater magnesium
The ion exchange resin of cation.
5 DEG C of seawater is passed through into sodium form ion exchange resin with the flow velocity of 7 BV/h, the calcium and magnesium shape in resin adsorption seawater
At calcium and magnesium type ion exchange resin, then the calcium ions and magnesium ions in seawater obtain initial gross separation enrichment.Exchange process is as follows: NaR+sea
Seawater (adsorbing for the first time) after water → CaMgR+absorption
It by the seawater of ion exchange resin, can be directly discharged into seawater, can also be used as and evaporate brine and refrigerated sea water etc. produces
Raw material.
(2) elution concentration magnesium ion
The calcium chloride water of 30~45g/L is configured as eluant, eluent, by it under 5 DEG C of eluting temperature, with 4~7 BV/h
Flow velocity eluted by calcium and magnesium type ion exchange resin.Calcium ion in eluant, eluent displaces calcium and magnesium type ion exchange resin
On magnesium ion, calcium and magnesium type ion exchange resin becomes calcium type ion exchange resin, and calcium chloride eluant, eluent is changed into calcium chloride
With the mixed concentrated liquid of magnesium chloride.Elution process is as follows:
CaMgR + CaCl2Eluant, eluent → CaR+contains CaCl2And MgCl2Eluent
Wherein calcium type ion exchange resin is Ke Xunhuanliyong, repeats above-mentioned absorption and is enriched with magnesium ion technique, process is as follows: CaR+
Seawater (second and absorption later) after seawater → CaMgR+absorption
Afterchlorinate magnesium and calcium chloride mixed concentrated liquid, Mg is concentrated by resin2+Ion concentration compared to increase in seawater 3 times with
On.Seawater passes through resin adsorption, the rich magnesium mixed concentrated liquid Mg after eluent2+Content is 2.4g/L.To this step, processing
The seawater of unit volume, Mg therein2+The rate of recovery is 88%.
(3) precipitating filtering
Using lime as precipitating reagent, quantitative lime is put into calcium and magnesium mixed concentrated liquid, is settled out wherein in the form of magnesium hydroxide
Rich Mg2+, magnesium hydroxide is filtered, calcium chloride filtrate is recycled, carries out regeneration treatment.
Calcium and magnesium mixed concentrated liquid is fitted into reaction kettle first, then puts into lime precipitation agent, control temperature of reaction kettle is 10
DEG C, the speed that revolving speed is 40r/min carries out reacting 1h under uninterrupted stirring, is then separated by filtration reaction solution by filter press
Magnesium hydrate precipitate drying storage out, this precipitating filtration method is to Mg2+The rate of recovery be 93%；
The magnesium hydrate precipitate, main component are magnesium hydroxide, and containing alkaline matters such as a small amount of calcium hydroxides, according to GB/T
Description of the 6274-1997 to soil conditioner, this precipitated products can be used as good calcium carbonate class acidic soil conditioner application；
The lime consumption is the integral molar quantity determination according to its calcium ions, is concentrated by calcium ion mole ratio in lime mixed
Closing magnesium ion mole in liquid is 1:1.0.
The calcium chloride filtrate of recycling carries out regeneration treatment, adjusts filtrate pH value using a little hydrochloric acid and drops to above-mentioned configured
Calcium chloride eluant, eluent after regeneration is recycled the initial pH value 7 of calcium chloride eluant, eluent in above-mentioned elution process, and regeneration is washed
De- agent recycling elution process is as follows:
CaMgR+regeneration CaCl2Eluant, eluent → CaR+contains CaCl2And MgCl2Eluent (recycling elution)
(4) drying screening
It will filter out the alkaline powder that main component is magnesium hydroxide to dry in drying machine, temperature is controlled at 220 DEG C, is dried to
Its water content 5% hereinafter, and using magnesium hydroxide professional standard HG/T 3607-2000 to the magnesium hydroxide in sediment into
Row quality analysis.
According to the requirement of sieve method in GB/T 6003.1-1997, using electric vibrating sieving machine to magnesium hydroxide powder after drying
Fineness measurement is carried out, and 0.25mm is more than or less than with particle diameter and carries out screening pack；According to the regulation in GB 8569, originally
Invention carries out pack packaging by every bag of 50 ± 1kg, 25 ± 0.5kg specification using woven bag lined with polyethylene bag film.
A kind of magnesium hydroxide soil conditioner using magnesium elements in seawater of embodiment 3
Preparation method the following steps are included:
(1) absorption enrichment magnesium ion
First in the ion exchange column made of organic glass, be packed into bed form ion exchange resin, charge weight according to from
The maximum that sub- exchange column can accommodate seawater determines that loadings are exchange column volume 60%, indicates filling amount with BV, i.e.,
If exchange column can accommodate 1m3Seawater, the BV of institute's loaded resin are 600L；The divalent metals such as this resin primary attachment Calcium in Seawater magnesium
The ion exchange resin of cation.
45 DEG C of seawater is passed through into sodium form ion exchange resin with the flow velocity of 10 BV/h, the calcium and magnesium in resin adsorption seawater
Calcium and magnesium type ion exchange resin is formed, then the calcium ions and magnesium ions in seawater obtain initial gross separation enrichment.Exchange process is as follows: NaR+
Seawater (adsorbing for the first time) after seawater → CaMgR+absorption
It by the seawater of ion exchange resin, can be directly discharged into seawater, can also be used as and evaporate brine and refrigerated sea water etc. produces
Raw material.
(2) elution concentration magnesium ion
The calcium chloride water of 30~45g/L is configured as eluant, eluent, by it under 45 DEG C of eluting temperature, with 4~7 BV/h
Flow velocity eluted by calcium and magnesium type ion exchange resin.Calcium ion in eluant, eluent displaces calcium and magnesium type ion exchange resin
On magnesium ion, calcium and magnesium type ion exchange resin becomes calcium type ion exchange resin, and calcium chloride eluant, eluent is changed into calcium chloride
With the mixed concentrated liquid of magnesium chloride.Elution process is as follows:
CaMgR + CaCl2Eluant, eluent → CaR+contains CaCl2And MgCl2Eluent
Wherein calcium type ion exchange resin is Ke Xunhuanliyong, repeats above-mentioned absorption and is enriched with magnesium ion technique, process is as follows: CaR+
Seawater (second and absorption later) after seawater → CaMgR+absorption
Afterchlorinate magnesium and calcium chloride mixed concentrated liquid, Mg is concentrated by resin2+Ion concentration compared to increase in seawater 3 times with
On.Seawater passes through resin adsorption, the rich magnesium mixed concentrated liquid Mg after eluent2+Content is 3.5g/L.To this step, processing
The seawater of unit volume, Mg therein2+The rate of recovery is 91%.
(3) precipitating filtering
Using lime as precipitating reagent, quantitative lime is put into calcium and magnesium mixed concentrated liquid, is settled out wherein in the form of magnesium hydroxide
Rich Mg2+, magnesium hydroxide is filtered, calcium chloride filtrate is recycled, carries out regeneration treatment.
Calcium and magnesium mixed concentrated liquid is fitted into reaction kettle first, then puts into lime precipitation agent, control temperature of reaction kettle is 40
DEG C, the speed that revolving speed is 250r/min carries out reacting 0.5h under uninterrupted stirring, and reaction solution is then passed through filter press, filtering point
Magnesium hydrate precipitate drying storage is separated out, this precipitating filtration method is to Mg2+The rate of recovery be 94%；
The magnesium hydrate precipitate, main component are magnesium hydroxide, and containing alkaline matters such as a small amount of calcium hydroxides, according to GB/T
Description of the 6274-1997 to soil conditioner, this precipitated products can be used as good calcium carbonate class acidic soil conditioner application；
The lime consumption is the integral molar quantity determination according to its calcium ions, is concentrated by calcium ion mole ratio in lime mixed
It closes the ratio that magnesium ion mole in liquid is 1:1.4 and launches lime.
The calcium chloride filtrate of recycling carries out regeneration treatment, adjusts filtrate pH value using a little hydrochloric acid and drops to above-mentioned configured
Calcium chloride eluant, eluent after regeneration is recycled the initial pH value 6 of calcium chloride eluant, eluent in above-mentioned elution process, and regeneration is washed
De- agent recycling elution process is as follows:
CaMgR+regeneration CaCl2Eluant, eluent → CaR+contains CaCl2And MgCl2Eluent (recycling elution)
(4) drying screening
It will filter out the alkaline powder that main component is magnesium hydroxide to dry in drying machine, temperature is controlled at 170 DEG C, is dried to
Its water content 5% hereinafter, and using magnesium hydroxide professional standard HG/T 3607-2000 to the magnesium hydroxide in sediment into
Row quality analysis.
According to the requirement of sieve method in GB/T 6003.1-1997, using electric vibrating sieving machine to magnesium hydroxide powder after drying
Fineness measurement is carried out, and 0.25mm is more than or less than with particle diameter and carries out screening pack；According to the regulation in GB 8569, originally
Invention carries out pack packaging by every bag of 50 ± 1kg, 25 ± 0.5kg specification using woven bag lined with polyethylene bag film.
Claims (10)
1. a kind of method of the magnesium using seawater, which comprises the following steps:
S1. seawater is passed through into the ion exchange column equipped with sodium form ion exchange resin；
S2. using calcium chloride water as eluant, eluent, elution S1 treated ion exchange column collects eluent；
S3. lime is mixed with eluent, is sufficiently reacted, precipitation and separation and liquid；
S4. drying precipitating.
2. the method according to claim 1, wherein in step S1, the volume and sodium form ion of ion exchange column
The ratio of the packing volume of exchanger resin is 1:(0.6~0.7).
3. the method according to claim 1, wherein the concentration of calcium chloride is 30~45g/L in step S2.
4. the method according to claim 1, wherein in step S2, elution flow rate is per hour (4~7) times
Packing volume.
5. the method according to claim 1, wherein the ion exchange column after step S2 eluent is used again
In step S1, absorption enrichment magnesium ion is repeated.
6. the condition sufficiently reacted is 10 DEG C~40 DEG C the method according to claim 1, wherein in step S3,
40~250r/min of revolving speed, uninterrupted stirring is lower to react 0.5h~1h.
7. the method according to claim 1, wherein in step S3, in lime in calcium ion and eluent magnesium from
Sub- mole is 1:1.0~1.4.
8. the method according to claim 1, wherein it is 6 that hydrochloric acid to pH value, which is added, in isolated liquid in step S3
After~7, regeneration is completed, step S2 is re-used for.
9. the standby obtained substance containing magnesium of any the method for claim 1~8.
10. substance containing magnesium described in claim 1 prepares magnesium metal, magnesium-containing compound, and/or composition containing magnesium salts and soil
Application in conditioner, feed and/or fertilizer.
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| PL443254A1 (en) * | 2022-12-23 | 2024-06-24 | Uniwersytet Przyrodniczy we Wrocławiu | Liquid organic-mineral calcium fertilizer |
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