CN110079864A - A kind of method that organic acid calcium salt prepares organic acid and calcium sulfate crystal whiskers by hydrochloric acid method - Google Patents
A kind of method that organic acid calcium salt prepares organic acid and calcium sulfate crystal whiskers by hydrochloric acid method Download PDFInfo
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- CN110079864A CN110079864A CN201910410118.4A CN201910410118A CN110079864A CN 110079864 A CN110079864 A CN 110079864A CN 201910410118 A CN201910410118 A CN 201910410118A CN 110079864 A CN110079864 A CN 110079864A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
Abstract
The present invention relates to the technical fields of organic acid separation and whisker synthesis, the method that specifically a kind of organic acid calcium salt prepares organic acid and calcium sulfate crystal whiskers by hydrochloric acid method, it is characterized in that steps are as follows for the preparation method: (one): raw material is organic acid calcium salt and hydrochloric acid, metathesis reaction is occurred into for organic acid calcium salt and mixed in hydrochloric acid, gained mainly contains the mixed solution of organic acid, organic acid calcium salt, calcium chloride and hydrochloric acid；(2): gained mixed solution carries out solvent extraction using organic solvent and obtains raffinate and load organic phases (I), load organic phases (I) washing obtains load organic phases (II), and load organic phases (II) back extraction obtains organic acid washing solutions and blank organic phase；(3): the organic acid washing solutions that step (2) obtains obtain organic acid production by concentration or crystallization；The raffinate and sulfuric acid or sulfuric acid reactant salt that step (2) obtains prepare calcium sulfate crystal whiskers, have many advantages, such as that no waste mine, at low cost, obtained calcium sulfate crystal whiskers draw ratio are high.
Description
Technical field
The present invention relates to the technical field of organic acid separation and whisker synthesis, specifically a kind of method is simple, without dirt
The high organic acid calcium salt of dye, no waste mine, at low cost, obtained calcium sulfate crystal whiskers draw ratio prepares organic acid and sulfuric acid by hydrochloric acid method
The method of calcium pyroborate.
Background technique
It is well known that calcium sulfate crystal whiskers be it is a kind of with single crystal form growth it is novel it is needle-shaped, there is uniform crosssection, complete
The complete fiber sub-nanometer material of shape, internal structure.Its form is since crystal is in the difference of axial direction and lateral growth rate
Caused by, the spiral of whisker mainly directed in the axial direction, which misplaces, to be grown, and side is low energy face, and growth is very slow, passes through surface
It spreads to screw feeding of appearing on the tip of whisker or basal plane, calcium sulfate crystal whiskers have high intensity, high-modulus, high tenacity, height absolutely
Edge, abrasion performance, high temperature resistant, acid and alkali-resistance, anticorrosive, infrared reflectivity is good, is easy to be surface-treated, is easily multiple with polymer
Many excellent physicochemical properties, the calcium sulfate crystal whiskers such as conjunction, nontoxic collect the advantage of both reinforcing fiber and ultra-fine inorganic filler in one
Body can be used in resin, plastics, rubber, coating, paint, papermaking, pitch, friction and sealing material making strengthening and toughening agent or function
It can type filler;It again can be directly as filtering material, thermal insulation material, fire-resistant heat insulating material, infrared light reflecting material and covered electric cable
High insulating materials.
Currently, preparing calcium sulfate calcium pyroborate is to be raw material through special process using gypsum and be formulated the ca sulphate fibre synthesized
Shape monocrystal, or prepared by other forms, still, the calcium sulfate that existing preparation method is formed is not whisker,
It is waste residue, utility value is low, and a large amount of waste material is generated during preparation, pollutes environment, increases production cost.
Summary of the invention
Present invention aim to address above-mentioned the deficiencies in the prior art, provide a kind of simple method, pollution-free, no waste mine,
The high organic acid calcium salt of at low cost, obtained calcium sulfate crystal whiskers draw ratio prepares the side of organic acid and calcium sulfate crystal whiskers by hydrochloric acid method
Method.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of method that organic acid calcium salt prepares organic acid and calcium sulfate crystal whiskers by hydrochloric acid method, it is characterised in that the preparation method
Steps are as follows:
(1): raw material is organic acid calcium salt and hydrochloric acid, metathesis reaction is occurred for organic acid calcium salt and mixed in hydrochloric acid, gained is main
Mixed solution containing organic acid, organic acid calcium salt, calcium chloride and hydrochloric acid；
(2): gained mixed solution carries out solvent extraction using organic solvent and obtains raffinate and load organic phases (I), and load has
Machine phase (I) washing obtains load organic phases (II), and load organic phases (II) back extraction obtains organic acid washing solutions and blank is organic
Phase；
(3): the organic acid washing solutions that step (2) obtains obtain organic acid production by decoloration, concentration or crystallization；Step (2)
Obtained raffinate and sulfuric acid or sulfuric acid reactant salt prepares calcium sulfate crystal whiskers.
Organic acid calcium salt in step (1) of the present invention in raw material is calcium lactate, calcium citrate, calcium malate, apple
Tartaric acid calcium monohydrogen phosphate, calcium gluconate, calcium succinate, succinic acid calcium monohydrogen phosphate, itaconic acid calcium, itaconic acid calcium monohydrogen phosphate, calcium tartrate, wine
Stone acid calcium monohydrogen phosphate, calcium fumarate, fumaric acid calcium monohydrogen phosphate or other monoacid calcium of organic acid, binary acid calcium of organic acid and ternary acid have
Machine acid calcium, the calcium citrate are citric acid calcium monohydrogen phosphate, dihydrogen citrate calcium and calcium citrate.
Organic solvent in step (2) of the present invention is in alcohols, ketone, ethers, esters, amides or amine
It is one or more, the alcohols be amylalcohol, hexanol, octanol, decyl alcohol, cyclohexanol, lauryl alcohol, tetradecyl alchohol or other alcohols are just
One of structure or isomery alcohol are a variety of；The ketone is methyl ethyl ketone, 2 pentanone, propione, methyln-hexyl ketone, 3- octanone, 3- decanone
With one of cyclohexanone or other ketones or a variety of；The ethers is isopropyl ether, butyl ether or other symmetrical structure ethers or non-right
Claim structure ether；The esters are P204 or TBP；The amine is TOA or N235；The amides are formamide, acetamide, third
Amide and caproamide.
Raffinate and sulfuric acid or sulfuric acid reactant salt in step (3) of the present invention prepare calcium sulfate crystal whiskers, wherein
Maintaining free calcium ions and sulfate concentration range in synthetic system is 0.001-2.0 mol/L；Reaction temperature is 10-160
DEG C,；Reaction time is 1-168 hours.
The concentration range of the optimization of free calcium ions and sulfate radical of the present invention is 0.01-0.05 mol/L, reaction
Temperature optimization is 50-120 DEG C.
The concentration of organic acid is 0.1-5.0 in the mixed solution as obtained by reaction in step (1) of the present invention
Mol/L, hydrogen ion concentration are 0.00001-10.0 mol/L.
It is born in step (2) of the present invention by the solvent extraction process of organic solvent and the mixed solution
It carries organic phase (I), load organic phases (I) wash to obtain the higher load organic phases of organic acid purity (II) by cleaning solution, bear
It carries organic phase (II) and obtains the strip liquor of the organic acid, being comparably during extraction, washing and back extraction by back extraction
1:50-50:1 is preferably comparably 1:1-30:1.
Extracting, wash and being stripped in step (2) of the present invention can be single-stage or multilevel process, the multistage
Process is counter-current extraction or fractional extraction, and series is greater than or equal to 1 grade, and extraction time is greater than or equal to 1min, and extraction temperature is
10-80 DEG C, revolving speed 50-1000r/min.
The detergent of washing process is pure water, the hydrochloric acid solution of various concentration or difference in step (2) of the present invention
The acylate solution of concentration, the water phase that detergent comes into full contact with generation with load organic phases (I) are expelled directly out or are incorporated into
Fractional extraction is formed to extraction process.
The present invention is since the calcium sulfate crystal whiskers purity that is obtained using above-mentioned preparation method is up to 99% or more, whiteness 90%-
95%, path length ratio is 80-200, has simple method, pollution-free, no waste mine, at low cost, obtained calcium sulfate crystal whiskers path length than high
Advantage.
Detailed description of the invention
Fig. 1 is reacting flow chart of the invention.
Specific embodiment
The following further describes the present invention with reference to the drawings:
As shown in the picture, a kind of method that organic acid calcium salt prepares organic acid and calcium sulfate crystal whiskers by hydrochloric acid method, feature exist
In the preparation method, steps are as follows: (one): raw material is organic acid calcium salt and hydrochloric acid, organic acid calcium salt and mixed in hydrochloric acid is occurred multiple
Decomposition reaction, gained mainly contain the mixed solution of organic acid, organic acid calcium salt, calcium chloride and hydrochloric acid；(2): gained mixing is molten
Liquid carries out solvent extraction using organic solvent and obtains raffinate and load organic phases (I), and load organic phases (I) washing is loaded
Organic phase (II), load organic phases (II) back extraction obtain organic acid washing solutions and blank organic phase；(3): step (2) obtains
Organic acid washing solutions by decoloration, concentration or crystallization obtain organic acid production；Raffinate that step (2) obtains and sulfuric acid or
Sulfuric acid reactant salt prepares calcium sulfate crystal whiskers, and the organic acid calcium salt in the step (one) in raw material is calcium lactate, citric acid
Calcium, calcium malate, malic acid calcium monohydrogen phosphate, calcium gluconate, calcium succinate, succinic acid calcium monohydrogen phosphate, itaconic acid calcium, one hydrogen of itaconic acid
Calcium, calcium tartrate, tartaric acid calcium monohydrogen phosphate, calcium fumarate, fumaric acid calcium monohydrogen phosphate or other monoacid calcium of organic acid, binary acid are organic
Sour calcium and ternary acid calcium of organic acid, the calcium citrate be citric acid calcium monohydrogen phosphate, dihydrogen citrate calcium and calcium citrate, it is described
The step of (two) in organic solvent be one of alcohols, ketone, ethers, esters, amides or amine or a variety of, the alcohol
Class is amylalcohol, hexanol, octanol, decyl alcohol, cyclohexanol, lauryl alcohol, one of the positive structure or isomery alcohol of tetradecyl alchohol or other alcohols
Or it is a variety of；The ketone is methyl ethyl ketone, 2 pentanone, propione, methyln-hexyl ketone, 3- octanone, 3- decanone and cyclohexanone or other ketones
One of or it is a variety of；The ethers is isopropyl ether, butyl ether or other symmetrical structure ethers or unsymmetric structure ether；The esters are
P204 or TBP；The amine is TOA or N235；The amides are formamide, acetamide, propionamide and caproamide；Described
Raffinate and sulfuric acid or sulfuric acid reactant salt in step (3) prepare calcium sulfate crystal whiskers, wherein maintaining free calcium in synthetic system
Ion and sulfate concentration range are 0.001-2.0 mol/L；Reaction temperature is 10-160 DEG C,；Reaction time is 1-168
Hour, the concentration range of the optimization of the free calcium ions and sulfate radical is 0.01-0.05 mol/L, and reaction temperature is optimized for
50-120 DEG C, as the concentration of organic acid in reaction gained mixed solution be 0.1-5.0 mol/L in the step (one),
Hydrogen ion concentration is 0.00001-10.0 mol/L, passes through the molten of organic solvent and the mixed solution in the step (two)
Agent extraction process obtains load organic phases (I), and it is higher negative that load organic phases (I) by cleaning solution wash to obtain organic acid purity
It carries organic phase (II), load organic phases (II) obtain the strip liquor of the organic acid, extraction, washing and back extraction by back extraction
In the process be comparably 1:50-50:1, be preferably comparably 1:1-30:1, extraction, washing and back extraction in the step (two)
Taking can be single-stage or multilevel process, and the multilevel process is counter-current extraction or fractional extraction, and series is greater than or equal to 1 grade, extraction
The time is taken to be greater than or equal to 1min, extraction temperature is 10-80 DEG C, revolving speed 50-1000r/min, is washed in the step (two)
The detergent for washing process is the acylate solution of pure water, the hydrochloric acid solution of various concentration or various concentration, detergent and load
The water phase that organic phase (I) comes into full contact with generation is expelled directly out or is incorporated into extraction process and forms fractional extraction.
The present invention is since the calcium sulfate crystal whiskers purity that is obtained using above-mentioned preparation method is up to 99% or more, whiteness 90%-
95%, draw ratio 80-200 have simple method, pollution-free, no waste mine, at low cost, obtained calcium sulfate crystal whiskers path length than high
Advantage.
Embodiment 1
When calcium citrate and hydrochloric acid being taken to carry out metathesis reaction, calcium ion concentration and hydrogen ion concentration ratio 1:6, temperature is 60 DEG C,
It generates calcium chloride and citric acid, the solution for reacting generation is extracted by organic solvent, obtain the raffinate containing calcium ion
With the load organic phases (I) containing citric acid, load organic phases (I) are obtained load organic phases (II) by washing, are loaded organic
Phase (II) back extraction obtains citric acid and blank organic phase, and blank organic phase can re-use extraction process, and citric acid passes through decoloration
Be concentrated to get citric acid product, sulfuric acid or sulfuric acid reactant salt are added in the raffinate containing calcium ion, wherein maintaining
Free calcium ions and sulfate concentration range are 1.0mol/L in synthetic system；Reaction temperature is 80 DEG C, the reaction time 60
Calcium sulfate crystal whiskers are prepared after hour, obtained calcium sulfate crystal whiskers purity is up to 99% or more, whiteness 94%, draw ratio 110.
Embodiment 2
When citric acid calcium monohydrogen phosphate and hydrochloric acid being taken to carry out metathesis reaction, calcium ion concentration and hydrogen ion concentration ratio 1:2, temperature 60
DEG C, it generates calcium chloride and citric acid, the solution for reacting generation is extracted by organic solvent, obtain the raffinate containing calcium ion
Liquid and load organic phases (I) containing citric acid, load organic phases (I) obtain load organic phases (II) by washing, and load has
Machine phase (II) back extraction obtains citric acid and blank organic phase, and blank organic phase can re-use extraction process, and citric acid passes through de-
It color and is concentrated to get citric acid product, sulfuric acid or sulfuric acid reactant salt is added in the raffinate containing calcium ion, wherein tieing up
Holding free calcium ions and sulfate concentration range in synthetic system is 0.03 mol/L, and reaction temperature is optimized for 60 DEG C, when reaction
Between to prepare calcium sulfate crystal whiskers after 30 hours, obtained calcium sulfate crystal whiskers purity is up to 99% or more, whiteness 95%, and draw ratio is
160。
Embodiment 2
When dihydrogen citrate calcium and hydrochloric acid being taken to carry out metathesis reaction, calcium ion concentration and hydrogen ion concentration ratio 1:2, temperature 60
DEG C, it generates calcium chloride and citric acid, the solution for reacting generation is extracted by organic solvent, obtain the raffinate containing calcium ion
Liquid and load organic phases (I) containing citric acid, load organic phases (I) obtain load organic phases (II) by washing, and load has
Machine phase (II) back extraction obtains citric acid and blank organic phase, and blank organic phase can re-use extraction process, and citric acid passes through de-
It color and is concentrated to get citric acid product, sulfuric acid or sulfuric acid reactant salt is added in the raffinate containing calcium ion, wherein tieing up
Holding free calcium ions and sulfate concentration range in synthetic system is 0.02mol/L, and reaction temperature is optimized for 100 DEG C, when reaction
Between to prepare calcium sulfate crystal whiskers after 60 hours, obtained calcium sulfate crystal whiskers purity is up to 99% or more, whiteness 92%, and draw ratio is
130。
Embodiment 3
Calcium succinate and hydrochloric acid is taken to carry out metathesis reaction, temperature is 60 DEG C, generates calcium chloride and succinic acid, reacts the molten of generation
Liquid is extracted by organic solvent, obtains the raffinate containing calcium ion and the load organic phases (I) containing succinic acid, load
Organic phase (I) is obtained load organic phases (II) by washing, and load organic phases (II) back extraction obtains citric acid and blank organic phase,
Blank organic phase can re-use extraction process, and succinic acid is by decoloration and is concentrated to get succinic acid product, and described contains calcium
Sulfuric acid or sulfuric acid reactant salt are added in the raffinate of ion, wherein maintaining free calcium ions and sulfate concentration model in synthetic system
It encloses for 0.04mol/L, reaction temperature is optimized for 130 DEG C, and the reaction time is to prepare calcium sulfate crystal whiskers after 66 hours, obtains
Calcium sulfate crystal whiskers purity is up to 99% or more, whiteness 93%, draw ratio 90.
Embodiment 4
Calcium lactate and hydrochloric acid is taken to carry out metathesis reaction, temperature is 60 DEG C, generates calcium chloride and lactic acid, and the solution for reacting generation is logical
It crosses organic solvent to be extracted, obtains the raffinate containing calcium ion and the load organic phases (I) containing lactic acid, load organic phases
(I) it is obtained load organic phases (II) by washing, load organic phases (II) back extraction obtains lactic acid and blank organic phase, and blank is organic
Extraction process can be mutually re-used, lactic acid is by decoloration and is concentrated to get lactic product, the raffinate containing calcium ion
Middle addition sulfuric acid or sulfuric acid reactant salt, wherein maintaining free calcium ions and sulfate concentration range in synthetic system is 0.05mol/
L, reaction temperature are optimized for 140 DEG C, and the reaction time is to prepare calcium sulfate crystal whiskers after 80 hours, and obtained calcium sulfate crystal whiskers are pure
Degree is up to 99% or more, whiteness 93%, draw ratio 160.
Embodiment 5
Calcium malate and hydrochloric acid is taken to carry out metathesis reaction, temperature is 60 DEG C, generates calcium chloride and malic acid, reacts the molten of generation
Liquid is extracted by organic solvent, obtains the raffinate containing calcium ion and the load organic phases (I) containing malic acid, load
Organic phase (I) is obtained load organic phases (II) by washing, and load organic phases (II) back extraction obtains malic acid and blank organic phase,
Blank organic phase can re-use extraction process, and malic acid is by decoloration and is concentrated to get apple acid product, and described contains calcium
Sulfuric acid or sulfuric acid reactant salt are added in the raffinate of ion, wherein maintaining free calcium ions and sulfate concentration model in synthetic system
It encloses for 0.01mol/L, reaction temperature is optimized for 135 DEG C, and the reaction time is to prepare calcium sulfate crystal whiskers after 90 hours, obtains
Calcium sulfate crystal whiskers purity is up to 99% or more, whiteness 94%, draw ratio 100.
Embodiment 6
Calcium gluconate and hydrochloric acid is taken to carry out metathesis reaction, temperature is 60 DEG C, generates calcium chloride and gluconic acid, and reaction generates
Solution extracted by organic solvent, obtain the raffinate containing calcium ion and the load organic phases containing gluconic acid
(I), load organic phases (I) by washing obtain load organic phases (II), load organic phases (II) back extraction obtain gluconic acid and
Blank organic phase, blank organic phase can re-use extraction process, and gluconic acid is by decoloration and is concentrated to get gluconic acid production
Sulfuric acid or sulfuric acid reactant salt are added in the raffinate containing calcium ion for product, wherein maintain in synthetic system free calcium from
Son and sulfate concentration range are 0.03mol/L, and reaction temperature is optimized for 115 DEG C, and the reaction time is to prepare after 130 hours
Calcium sulfate crystal whiskers, obtained calcium sulfate crystal whiskers purity is up to 99% or more, whiteness 93%, draw ratio 190.
Embodiment 7
Itaconic acid calcium and hydrochloric acid is taken to carry out metathesis reaction, temperature is 60 DEG C, generates calcium chloride and itaconic acid, reacts the molten of generation
Liquid is extracted by organic solvent, obtains the raffinate containing calcium ion and the load organic phases (I) containing itaconic acid, load
Organic phase (I) is obtained load organic phases (II) by washing, and load organic phases (II) back extraction obtains itaconic acid and blank organic phase,
Blank organic phase can re-use extraction process, and itaconic acid is by decoloration and is concentrated to get itaconic acid product, and described contains calcium
Sulfuric acid or sulfuric acid reactant salt are added in the raffinate of ion, wherein maintaining free calcium ions and sulfate concentration model in synthetic system
It encloses for 0.03mol/L, reaction temperature is optimized for 115 DEG C, and the reaction time is to prepare calcium sulfate crystal whiskers after 130 hours, obtains
Calcium sulfate crystal whiskers purity is up to 99% or more, whiteness 94%, draw ratio 180.
Embodiment 8
Calcium tartrate and hydrochloric acid is taken to carry out metathesis reaction, temperature is 60 DEG C, generates calcium chloride and tartaric acid, reacts generation
Solution is extracted by organic solvent, obtains the raffinate containing calcium ion and the load organic phases (I) containing tartaric acid,
Load organic phases (I) are obtained load organic phases (II) by washing, and load organic phases (II) back extraction, which obtains tartaric acid and blank, to be had
Machine phase, blank organic phase can re-use extraction process, and tartaric acid is by decoloration and is concentrated to get winestone acid product, described
Sulfuric acid or sulfuric acid reactant salt are added in raffinate containing calcium ion, wherein maintaining free calcium ions and sulfate radical in synthetic system
Concentration range is 0.03mol/L, and reaction temperature is optimized for 115 DEG C, and the reaction time is to prepare calcium sulfate crystal whiskers after 130 hours,
Obtained calcium sulfate crystal whiskers purity is up to 99% or more, whiteness 92%, draw ratio 170.
Embodiment 9
Calcium fumarate and hydrochloric acid is taken to carry out metathesis reaction, temperature is 60 DEG C, generates calcium chloride and fumaric acid, reacts the molten of generation
Liquid is extracted by organic solvent, obtains the raffinate containing calcium ion and the load organic phases (I) containing fumaric acid, load
Organic phase (I) is obtained load organic phases (II) by washing, and load organic phases (II) back extraction obtains fumaric acid and blank organic phase,
Blank organic phase can re-use extraction process, and fumaric acid is by decoloration and is concentrated to get fumaric acid product, and described contains calcium
Sulfuric acid or sulfuric acid reactant salt are added in the raffinate of ion, wherein maintaining free calcium ions and sulfate concentration model in synthetic system
It encloses for 0.03mol/L, reaction temperature is optimized for 115 DEG C, and the reaction time is to prepare calcium sulfate crystal whiskers after 130 hours, obtains
Calcium sulfate crystal whiskers purity is up to 99% or more, whiteness 94%, draw ratio 120.
Embodiment 10
Malic acid calcium monohydrogen phosphate and hydrochloric acid is taken to carry out metathesis reaction, temperature is 60 DEG C, generates calcium chloride and malic acid, and reaction generates
Solution extracted by organic solvent, obtain the raffinate containing calcium ion and the load organic phases (I) containing malic acid,
Load organic phases (I) are obtained load organic phases (II) by washing, and load organic phases (II) back extraction, which obtains fumaric acid and blank, to be had
Machine phase, blank organic phase can re-use extraction process, and malic acid is by decoloration and is concentrated to get apple acid product, and described contains
Have and sulfuric acid or sulfuric acid reactant salt are added in the raffinate of calcium ion, wherein maintaining free calcium ions and sulfate radical in synthetic system dense
Degree range is 0.03mol/L, and reaction temperature is optimized for 115 DEG C, and the reaction time is to prepare calcium sulfate crystal whiskers after 130 hours, is obtained
The calcium sulfate crystal whiskers purity arrived is up to 99% or more, whiteness 93%, draw ratio 160.
Embodiment 11
Succinic acid calcium monohydrogen phosphate and hydrochloric acid is taken to carry out metathesis reaction, temperature is 60 DEG C, generates calcium chloride and succinic acid, and reaction generates
Solution extracted by organic solvent, obtain the raffinate containing calcium ion and the load organic phases contained (I), load has
Machine phase (I) is obtained load organic phases (II) by washing, and load organic phases (II) back extraction obtains succinic acid and blank organic phase, empty
White organic phase can re-use extraction process, and succinic acid is by decoloration and is concentrated to get succinic acid product, it is described containing calcium from
Sulfuric acid or sulfuric acid reactant salt are added in the raffinate of son, wherein maintaining free calcium ions and sulfate concentration range in synthetic system
For 0.03mol/L, reaction temperature is optimized for 115 DEG C, and the reaction time is to prepare calcium sulfate crystal whiskers after 130 hours, obtained sulphur
Sour calcium pyroborate purity is up to 99% or more, whiteness 94%, draw ratio 165.
Embodiment 12
Itaconic acid calcium monohydrogen phosphate and hydrochloric acid is taken to carry out metathesis reaction, temperature is 60 DEG C, generates calcium chloride and fumaric acid, and reaction generates
Solution extracted by organic solvent, obtain the raffinate containing calcium ion and the load organic phases (I) containing fumaric acid,
Load organic phases (I) are obtained load organic phases (II) by washing, and load organic phases (II) back extraction, which obtains fumaric acid and blank, to be had
Machine phase, blank organic phase can re-use extraction process, and fumaric acid is by decoloration and is concentrated to get fumaric acid product, and described contains
Have and sulfuric acid or sulfuric acid reactant salt are added in the raffinate of calcium ion, wherein maintaining free calcium ions and sulfate radical in synthetic system dense
Degree range is 0.03mol/L, and reaction temperature is optimized for 115 DEG C, and the reaction time is to prepare calcium sulfate crystal whiskers after 130 hours, is obtained
The calcium sulfate crystal whiskers purity arrived is up to 99% or more, whiteness 95%, draw ratio 145.
Embodiment 13
Tartaric acid calcium monohydrogen phosphate and hydrochloric acid is taken to carry out metathesis reaction, temperature is 60 DEG C, generates calcium chloride and tartaric acid, and reaction generates
Solution extracted by organic solvent, obtain the raffinate containing calcium ion and the load organic phases (I) containing tartaric acid,
Load organic phases (I) are obtained load organic phases (II) by washing, and load organic phases (II) back extraction, which obtains tartaric acid and blank, to be had
Machine phase, blank organic phase can re-use extraction process, and tartaric acid is by decoloration and is concentrated to get winestone acid product, and described contains
Have and sulfuric acid or sulfuric acid reactant salt are added in the raffinate of calcium ion, wherein maintaining free calcium ions and sulfate radical in synthetic system dense
Degree range is 0.03mol/L, and reaction temperature is optimized for 115 DEG C, and the reaction time is to prepare calcium sulfate crystal whiskers after 130 hours, is obtained
The calcium sulfate crystal whiskers purity arrived is up to 99% or more, whiteness 93%, draw ratio 135.
Embodiment 14
Fumaric acid calcium monohydrogen phosphate and hydrochloric acid is taken to carry out metathesis reaction, temperature is 60 DEG C, generates calcium chloride and fumaric acid, and reaction generates
Solution extracted by organic solvent, obtain the raffinate containing calcium ion and the load organic phases (I) containing fumaric acid,
Load organic phases (I) are obtained load organic phases (II) by washing, and load organic phases (II) back extraction, which obtains fumaric acid and blank, to be had
Machine phase, blank organic phase can re-use extraction process, and fumaric acid is by decoloration and is concentrated to get fumaric acid product, and described contains
Have and sulfuric acid or sulfuric acid reactant salt are added in the raffinate of calcium ion, wherein maintaining free calcium ions and sulfate radical in synthetic system dense
Degree range is 0.03mol/L, and reaction temperature is optimized for 115 DEG C, and the reaction time is to prepare calcium sulfate crystal whiskers after 130 hours, is obtained
The calcium sulfate crystal whiskers purity arrived is up to 99% or more, whiteness 92%, draw ratio 156.
Claims (9)
1. a kind of method that organic acid calcium salt prepares organic acid and calcium sulfate crystal whiskers by hydrochloric acid method, it is characterised in that the preparation side
Steps are as follows for method:
(1): raw material is organic acid calcium salt and hydrochloric acid, metathesis reaction is occurred for organic acid calcium salt and mixed in hydrochloric acid, gained is main
Mixed solution containing organic acid, organic acid calcium salt, calcium chloride and hydrochloric acid；
(2): gained mixed solution carries out solvent extraction using organic solvent and obtains raffinate and load organic phases (I), and load has
Machine phase (I) washing obtains load organic phases (II), and load organic phases (II) back extraction obtains organic acid washing solutions and blank is organic
Phase；
(3): the organic acid washing solutions that step (2) obtains obtain organic acid production by decoloration, concentration or crystallization；Step (2)
Obtained raffinate and sulfuric acid or sulfuric acid reactant salt prepares calcium sulfate crystal whiskers.
2. the side that a kind of organic acid calcium salt according to claim 1 prepares organic acid and calcium sulfate crystal whiskers by hydrochloric acid method
Method, it is characterised in that the organic acid calcium salt in the step (one) in raw material is calcium lactate, calcium citrate, calcium malate, apple
Tartaric acid calcium monohydrogen phosphate, calcium gluconate, calcium succinate, succinic acid calcium monohydrogen phosphate, itaconic acid calcium, itaconic acid calcium monohydrogen phosphate, calcium tartrate,
Tartaric acid calcium monohydrogen phosphate, calcium fumarate, fumaric acid calcium monohydrogen phosphate or other monoacid calcium of organic acid, binary acid calcium of organic acid and ternary acid
Calcium of organic acid, the calcium citrate are citric acid calcium monohydrogen phosphate, dihydrogen citrate calcium and calcium citrate.
3. the side that a kind of organic acid calcium salt according to claim 1 prepares organic acid and calcium sulfate crystal whiskers by hydrochloric acid method
Method, it is characterised in that the organic solvent in the step (two) is in alcohols, ketone, ethers, esters, amides or amine
One or more, the alcohols is amylalcohol, hexanol, octanol, decyl alcohol, cyclohexanol, lauryl alcohol, the positive structure of tetradecyl alchohol or other alcohols
Or one of isomery alcohol or a variety of；The ketone be methyl ethyl ketone, 2 pentanone, propione, methyln-hexyl ketone, 3- octanone, 3- decanone and
One of cyclohexanone or other ketones are a variety of；The ethers is isopropyl ether, butyl ether or other symmetrical structure ethers or asymmetric
Structure ether；The esters are P204 or TBP；The amides are formamide, acetamide, propionamide and caproamide.
4. the side that a kind of organic acid calcium salt according to claim 1 prepares organic acid and calcium sulfate crystal whiskers by hydrochloric acid method
Method, it is characterised in that raffinate and sulfuric acid or sulfuric acid reactant salt in the step (three) prepare calcium sulfate crystal whiskers, wherein
Maintaining free calcium ions and sulfate concentration range in synthetic system is 0.001-2.0 mol/L；Reaction temperature is 10-160
DEG C,；Reaction time is 1-168 hours.
5. the side that a kind of organic acid calcium salt according to claim 4 prepares organic acid and calcium sulfate crystal whiskers by hydrochloric acid method
Method, it is characterised in that the concentration range of the optimization of the free calcium ions and sulfate radical is 0.01-0.05 mol/L, reaction temperature
Degree is optimized for 50-120 DEG C.
6. the side that a kind of organic acid calcium salt according to claim 1 prepares organic acid and calcium sulfate crystal whiskers by hydrochloric acid method
Method, it is characterised in that the concentration of organic acid is 0.1-5.0 in the mixed solution as obtained by reaction in the step (one)
Mol/L, hydrogen ion concentration are 0.00001-10.0 mol/L.
7. the side that a kind of organic acid calcium salt according to claim 1 prepares organic acid and calcium sulfate crystal whiskers by hydrochloric acid method
Method, it is characterised in that loaded in the step (two) by the solvent extraction process of organic solvent and the mixed solution
Organic phase (I), load organic phases (I) wash to obtain the higher load organic phases of organic acid purity (II) by cleaning solution, load
Organic phase (II) obtains the strip liquor of the organic acid by back extraction, is comparably 1 during extraction, washing and back extraction:
50-50:1 is preferably comparably 1:1-30:1.
8. the side that a kind of organic acid calcium salt according to claim 1 prepares organic acid and calcium sulfate crystal whiskers by hydrochloric acid method
Method, it is characterised in that extraction, washing and back extraction can be single-stage or multilevel process, the multistage mistake in the step (two)
Journey is counter-current extraction or fractional extraction, and series is greater than or equal to 1 grade, and extraction time is greater than or equal to 5min, extraction temperature 10-
80 DEG C, revolving speed 50-1000r/min.
9. the side that a kind of organic acid calcium salt according to claim 1 prepares organic acid and calcium sulfate crystal whiskers by hydrochloric acid method
Method, it is characterised in that the detergent of washing process is pure water, the hydrochloric acid solution of various concentration or difference in the step (two)
The acylate solution of concentration, the water phase that detergent comes into full contact with generation with load organic phases (I) are expelled directly out or are incorporated into
Fractional extraction is formed to extraction process.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110606802A (en) * | 2018-06-16 | 2019-12-24 | 上海清研新材料科技有限公司 | Method for recovering tartaric acid from calcium tartrate by using interfacial reaction |
| CN110777269A (en) * | 2019-10-31 | 2020-02-11 | 湖南邦普循环科技有限公司 | Method for extracting calcium without saponification |
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| US3961105A (en) * | 1972-03-27 | 1976-06-01 | Certain-Teed Products Corporation | Method for the manufacture of coated calcium sulfate whisker fibers |
| CN1938257A (en) * | 2004-01-29 | 2007-03-28 | 齐凯姆公司 | Recovery of organic acids |
| CN101230483A (en) * | 2007-11-05 | 2008-07-30 | 安徽工业大学 | Method for preparing gypsum whisker by calcium citrate |
| CN101736404A (en) * | 2010-01-22 | 2010-06-16 | 四川大学 | Co-production method of calcium sulfate whisker and phosphoric acid |
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| US3961105A (en) * | 1972-03-27 | 1976-06-01 | Certain-Teed Products Corporation | Method for the manufacture of coated calcium sulfate whisker fibers |
| CN1938257A (en) * | 2004-01-29 | 2007-03-28 | 齐凯姆公司 | Recovery of organic acids |
| CN101230483A (en) * | 2007-11-05 | 2008-07-30 | 安徽工业大学 | Method for preparing gypsum whisker by calcium citrate |
| CN101736404A (en) * | 2010-01-22 | 2010-06-16 | 四川大学 | Co-production method of calcium sulfate whisker and phosphoric acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110606802A (en) * | 2018-06-16 | 2019-12-24 | 上海清研新材料科技有限公司 | Method for recovering tartaric acid from calcium tartrate by using interfacial reaction |
| CN110777269A (en) * | 2019-10-31 | 2020-02-11 | 湖南邦普循环科技有限公司 | Method for extracting calcium without saponification |
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