CN112574337A - Production process of calcium polycarbophil - Google Patents
Production process of calcium polycarbophil Download PDFInfo
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- CN112574337A CN112574337A CN202011236898.4A CN202011236898A CN112574337A CN 112574337 A CN112574337 A CN 112574337A CN 202011236898 A CN202011236898 A CN 202011236898A CN 112574337 A CN112574337 A CN 112574337A
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- magnesium sulfate
- polycarbophil
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- calcium
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- 229920000148 Polycarbophil calcium Polymers 0.000 title claims abstract description 73
- 229940095498 calcium polycarbophil Drugs 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 118
- 239000007788 liquid Substances 0.000 claims abstract description 66
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 59
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 59
- 239000000243 solution Substances 0.000 claims abstract description 52
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000047 product Substances 0.000 claims abstract description 30
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- 229950005134 polycarbophil Drugs 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002244 precipitate Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- ZVQXQPNJHRNGID-UHFFFAOYSA-N tetramethylsuccinonitrile Chemical compound N#CC(C)(C)C(C)(C)C#N ZVQXQPNJHRNGID-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229940059101 polycarbophil calcium Drugs 0.000 claims abstract description 11
- 239000002699 waste material Substances 0.000 claims abstract description 11
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 10
- 238000004064 recycling Methods 0.000 claims abstract description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 238000003860 storage Methods 0.000 claims description 13
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 9
- 239000000347 magnesium hydroxide Substances 0.000 claims description 9
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 7
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000007086 side reaction Methods 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 238000000605 extraction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 9
- 239000003999 initiator Substances 0.000 description 7
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 5
- 239000001095 magnesium carbonate Substances 0.000 description 5
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- -1 carbomer magnesium salt Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229960001631 carbomer Drugs 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- 206010010774 Constipation Diseases 0.000 description 1
- 206010012735 Diarrhoea Diseases 0.000 description 1
- 206010019280 Heart failures Diseases 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010030113 Oedema Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- UBYDSYHGCPVBEQ-UHFFFAOYSA-N chloroform;propan-1-ol Chemical compound CCCO.ClC(Cl)Cl UBYDSYHGCPVBEQ-UHFFFAOYSA-N 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229940031958 magnesium carbonate hydroxide Drugs 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/74—Synthetic polymeric materials
- A61K31/765—Polymers containing oxygen
- A61K31/78—Polymers containing oxygen of acrylic acid or derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P1/00—Drugs for disorders of the alimentary tract or the digestive system
- A61P1/12—Antidiarrhoeals
Abstract
The invention discloses a production process of calcium polycarbophil, and particularly belongs to the technical field of medicine manufacturing processes. The method mainly comprises the following steps: reacting a magnesium sulfate solution with a mixed solution of acrylic acid and azobisisobutyronitrile to obtain a first product; separating the first product to obtain a first solid and a first liquid, and recovering the first liquid to obtain a standard magnesium sulfate solution; adding the first solid into an organic solvent for extraction treatment to obtain a polycarbophil magnesium salt and a mixed solution containing azobisisobutyronitrile and tetramethylsuccinonitrile, adding a proper amount of acrylic acid into the mixed solution containing azobisisobutyronitrile and tetramethylsuccinonitrile, mixing, and then recycling; adding the polycarbophil magnesium salt into a calcium carbonate solution to react to obtain a second reaction product, cooling and centrifugally separating the obtained second product to obtain a precipitate, adding a proper amount of sulfuric acid into the precipitate, purifying, recycling waste liquid and the like to obtain a polycarbophil calcium product with extremely high purity.
Description
Technical Field
The invention relates to the technical field of medicine manufacturing processes, in particular to a production process of calcium polycarbophil.
Background
Calcium Polycarbophil, also known as Polycarbophil, is known under the English name of Calcium Polycarbophil, and has the CAS number of 9003-97-8, and the Calcium Polycarbophil has strong water absorption property, is suitable for patients who are not suitable for taking sodium, such as chronic constipation patients with edema, hypertension and heart failure, and can also be used for water-based diarrhea. Most of the existing processes for producing calcium polycarbophil adopt polymerization to generate intermediate products, then calcium is added for replacement to generate calcium polycarbophil, but the processes are all rough processing modes, so that more harmful water bodies are generated to influence the environment, and the purity of the obtained product is low, so that the operation cost is influenced.
For example, the Chinese patent with the publication number of CN105131159A discloses a production process of calcium polycarbophil, which comprises the following steps: the configuration: preparing a magnesium sulfate solution and preparing a mixed solution of acrylic acid and azoethylbutyronitrile; (ii) polymerization: mixing the two solutions in the step I, heating to 50-90 ℃, and reacting for 2-4 hours to generate a reaction mixture; filtering: filtering the reaction mixture obtained in the step II to obtain polycarbophil; calcium addition reaction: mixing polycarbophil and an aqueous solution of calcium carbonate, and carrying out heat preservation reaction for 4-8 hours at 80-100 ℃; separating: separating the reacted liquid to obtain a product; drying and crushing: drying and crushing the product to obtain a finished product. The yield of the calcium polycarbophil synthesized by the process is high. The scheme of the present disclosure has the following disadvantages: firstly, the wastewater containing the raw materials of the production process is not reasonably treated in the scheme, so that the process is simple, but the cost is high, and the current requirement on the environment is not facilitated; secondly, heating the mixed liquid containing the azobisisobutyronitrile in the scheme to decompose the azobisisobutyronitrile, so that liquid 2,3, 5-tricyano-2, 3, 5-trimethylethane, waxy succinonitrile at normal temperature and solid tetramethyl succinonitrile are generated, but the purity of the product is affected because the solid tetramethyl succinonitrile and the generated polycarbophil calcium are solid; thirdly, in the scheme, the polycarbophil is mixed with the aqueous solution of calcium carbonate and reacts in a heat preservation way at the temperature of 80-100 ℃, so that the polycarbophil calcium can be obtained and Mg (OH) can be generated2So that the purity of the obtained calcium polycarbophil is lower; fourthly, the waste materials generated in the scheme can be recycled by simple recovery or processing, so that the cost can be saved, but the scheme adoptsThe extraction process is not only not beneficial to saving cost, but also can cause the process to produce solution which is harmful to the environment.
Disclosure of Invention
The invention aims to solve the technical problems and provides a production process of polycarbophil calcium, which adopts the technical schemes of controlling temperature, recycling generated waste liquid, further purifying generated polycarbophil calcium products and the like, and can solve the problems of high process cost, incapability of recycling waste materials, generation of hazardous water bodies and low purity of obtained products.
The invention solves the problems and adopts the following technical scheme.
A process for producing calcium polycarbophil comprises the following steps:
s1, respectively injecting the magnesium sulfate solution in the first storage tank and the mixed solution of acrylic acid and azodiisobutyronitrile in the second storage tank into a reaction kettle, fully and uniformly mixing, heating, reacting to obtain a first product, and injecting an excessive magnesium sulfate solution;
s2, filtering and separating the first product through a filter to obtain a first solid and a first liquid, collecting the first liquid by using a first collecting tank, standing the first liquid, layering the first liquid, separating the upper layer liquid, the lower layer liquid and the upper layer liquid, wherein the upper layer liquid is a side reaction product and a reaction remainder of an oil phase, and the lower layer liquid is a side reaction product and a reaction remainder of a water phase;
s3, adding a proper amount of magnesium powder into the lower layer liquid for reaction, then detecting, and if the concentration of the magnesium sulfate is higher than the concentration standard in the step S1, adding a proper amount of pure water for dilution and adjustment to obtain a magnesium sulfate solution meeting the concentration standard in the step S1; if the concentration of the magnesium sulfate is smaller than the concentration standard in the step S1, adding a proper amount of high-concentration magnesium sulfate solution for regulation to obtain a magnesium sulfate solution meeting the concentration standard in the step S1; injecting the magnesium sulfate solution obtained in the step into a first storage tank;
s4, adding the obtained first solid into an organic solvent, and separating to obtain a polycarbophil magnesium salt and a mixed solution containing azodiisobutyronitrile and tetramethylsuccinonitrile; adding a certain amount of acrylic acid into the obtained mixed solution, mixing, and directly recycling the mixed solution into the reaction kettle in the step S1;
s5, washing the polycarbophil magnesium salt with distilled water to obtain pure polycarbophil magnesium salt and second liquid; collecting the second liquid by using a second collecting tank, extracting and separating the second liquid to obtain a mixed solution containing azobisisobutyronitrile and tetramethylsuccinonitrile, adding a certain amount of acrylic acid into the obtained mixed solution for mixing, and directly placing the mixed solution into the reaction kettle in the step S1;
s6, adding the washed polycarbophil magnesium salt into a calcium carbonate solution, fully and uniformly mixing, heating for reaction, and generating a second reaction product after the reaction;
s7, cooling the second product, and injecting the second product into a centrifuge for centrifugal separation to obtain a precipitate containing calcium polycarbophil and magnesium hydroxide; adding a proper amount of dilute sulfuric acid into the precipitate to obtain polycarbophil calcium precipitate and a magnesium sulfate solution;
s8, detecting the concentration of the magnesium sulfate solution obtained in the step S7, and if the concentration of the magnesium sulfate is larger than the concentration standard in the step S1, adding a proper amount of pure water for dilution adjustment to obtain the magnesium sulfate solution meeting the concentration standard in the step S1; if the concentration of the magnesium sulfate is smaller than the concentration standard in the step S1, adding a proper amount of high-concentration magnesium sulfate solution for regulation to obtain a magnesium sulfate solution meeting the concentration standard in the step S1; injecting the magnesium sulfate solution obtained in the step into a first storage tank;
s9, washing the calcium polycarbophil obtained in the step S7 with pure water to obtain pure calcium polycarbophil, and then drying, crushing and molding the pure calcium polycarbophil to obtain a calcium polycarbophil product with high purity.
Preferably, the production processes from step S1 to step S5 are all carried out in a thermostatic chamber with the temperature of 55-63 ℃. Can improve the solubility of the metal solution, and can also accelerate the reaction speed and improve the production efficiency.
Furthermore, the thermostatic chamber is a closed space which is closed, has no oxygen and is filled with nitrogen. The intermediate product in the production process can be protected, and the production yield of the target product is improved; meanwhile, the explosion caused by the quick cracking of the initiator can be prevented, and the production safety is further ensured.
Preferably, the temperature range in the reaction kettle in the step S1 is controlled to be 63-99 ℃. In order to allow for the initiation and more efficient cleavage while preventing the temperature from being so high that the initiator rapidly cleaves and thus explodes.
Preferably, the concentration of the azobisisobutyronitrile is 4 mol/L.
Further, the waste liquid separation in step S2 is to separate the waste liquid through a separation funnel, and sequentially collect the bottom liquid, liquid succinonitrile, and liquid 2,3, 5-tricyano-2, 3, 5-trimethylethane.
Preferably, the temperature range after the temperature reduction in the step S7 is 20 to 23 ℃.
Preferably, the waste water generated by washing the calcium polycarbophil in the step S9 may be utilized by adjusting the density of magnesium sulfate in the step S3 or the step S8.
Remarking:
azobisisobutyronitrile is a white crystal or crystalline powder, is insoluble in water, is soluble in diethyl ether, methanol, ethanol, propanol chloroform, dichloroethane, ethyl acetate, benzene, etc., and is often an oil-soluble initiator. The material is decomposed by heat, and the melting point is 100-104 ℃. It should be stored in a dry place at 20 ℃. Decomposing in water to release nitrogen and containing- (CH2)2-C-CN organic cyanide. The decomposition temperature is 64 ℃, the decomposition is slow at room temperature, and the decomposition is rapid at 100 ℃, so that explosion and ignition can be caused, and the material is flammable and toxic. Nitrogen and organic cyanide are discharged, and the latter is harmful to human bodies.
It is not possible for magnesium carbonate and magnesium hydroxide to precipitate together at the same time. Since magnesium carbonate is a sparingly soluble substance, it is not present in precipitated form and is usually converted to magnesium hydroxide for precipitation. Magnesium carbonate is generally slightly soluble in water and readily reacts with water when heated (softening hard water) to form magnesium hydroxide (because magnesium hydroxide is less soluble than magnesium carbonate), and the equation: MgCO3+H2O=Mg(OH)2↓+CO2↑。
In conclusion, the scheme has the following beneficial effects:
1. the first liquid produced in the invention is separated to obtain liquid 2,3, 5-tricyano-2, 3, 5-trimethylethane, liquid succinonitrile and a lower liquid, wherein the lower liquid contains sulfuric acid and magnesium sulfate, the produced lower liquid is added to be regulated, and pure water or a high-concentration magnesium sulfate solution is added to be regulated to the obtained solution, so that metal ions and produced waste materials generate raw materials required in the technology, the cost is saved, and the waste of resources is avoided, thereby protecting the environment; the pure 2,3, 5-tricyano-2, 3, 5-trimethylethane and the liquid succinonitrile can bring economic benefits, thereby improving the comprehensive utilization rate of raw materials;
2. the first solid containing the polycarbophil magnesium salt is subjected to refining treatment by adding an organic solvent, so that water-insoluble unreacted azodiisobutyronitrile generated by the azodiisobutyronitrile as an initiator and a product, namely tetramethyl succinonitrile after reaction are separated from the carbomer magnesium salt, the carbomer magnesium salt is further purified, and meanwhile, a solution containing the azodiisobutyronitrile and the tetramethyl succinonitrile is added with a proper amount of acrylic acid to be used as a raw material, so that the utilization rate of the raw material is improved, and the polycarbophil azodicarbonamide magnesium salt-containing composite material has the advantages of low cost, high utilization rate of the raw material and environmental protection;
3. according to the invention, the product after the calcium adding reaction is cooled and then injected into a centrifuge for centrifugal separation, and the output ratio of calcium polycarbophil is improved by using the change of temperature, so that a higher product return rate is obtained; simultaneously, adding a proper amount of dilute sulfuric acid into the obtained crude polycarbophil calcium to enable magnesium hydroxide precipitate in the crude polycarbophil calcium to generate magnesium sulfate solution, so that the purity of the polycarbophil calcium is improved and is close to one hundred percent;
4. according to the method, the wastewater obtained after the calcium polycarbophil is washed by pure water is used for adjusting the concentration of the magnesium sulfate solution, so that the wastewater cannot be directly discharged, the reasonable utilization of water is promoted, and a water body containing chemical substances cannot pollute the environment;
5. according to the invention, the production processes in the steps S1 to S5 are all arranged in a thermostatic chamber with the temperature of 55-63 ℃, so that the initiator in the material storage tank b is protected, the raw materials have certain high temperature, and the reaction in the reaction kettle can be carried out efficiently; meanwhile, the efficiency can be improved when the materials are recycled, so that the time is saved, and the production efficiency is improved.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention will be described in further detail below.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Examples
A process for producing calcium polycarbophil comprises the following steps:
s1, respectively injecting the magnesium sulfate solution in the first storage tank and the mixed solution of acrylic acid and azodiisobutyronitrile in the second storage tank into a reaction kettle, fully and uniformly mixing, and heating to react to obtain a first product, wherein the injected magnesium sulfate solution is excessive;
s2, filtering and separating the first product through a filter to obtain a first solid and a first liquid, collecting the first liquid by using a first collecting tank, standing the first liquid, layering the first liquid, separating the upper layer liquid, the lower layer liquid and the upper layer liquid, wherein the upper layer liquid is a side reaction product and a reaction remainder of an oil phase, and the lower layer liquid is a side reaction product and a reaction remainder of a water phase;
s3, adding a proper amount of magnesium powder into the lower layer liquid for reaction, then detecting, and if the concentration of the magnesium sulfate is higher than the concentration standard in the step S1, adding a proper amount of pure water for dilution and adjustment to obtain a magnesium sulfate solution meeting the concentration standard in the step S1; if the concentration of the magnesium sulfate is smaller than the concentration standard in the step S1, adding a proper amount of high-concentration magnesium sulfate solution for regulation to obtain a magnesium sulfate solution meeting the concentration standard in the step S1; injecting the magnesium sulfate solution obtained in the step into a first storage tank;
s4, adding the obtained first solid into an organic solvent, and separating to obtain a polycarbophil magnesium salt and a mixed solution containing azodiisobutyronitrile and tetramethylsuccinonitrile; adding a certain amount of acrylic acid into the obtained mixed solution, mixing, and directly recycling the mixed solution into the reaction kettle in the step S1;
s5, washing the polycarbophil magnesium salt with distilled water to obtain pure polycarbophil magnesium salt and second liquid; collecting the second liquid by using a second collecting tank, extracting and separating the second liquid to obtain a mixed solution containing azobisisobutyronitrile and tetramethylsuccinonitrile, adding a certain amount of acrylic acid into the obtained mixed solution for mixing, and directly placing the mixed solution into the reaction kettle in the step S1;
s6, adding the washed polycarbophil magnesium salt into a calcium carbonate solution, fully and uniformly mixing, heating for reacting, and obtaining a second reaction product after reaction;
s7, cooling the second product, and injecting the second product into a centrifuge for centrifugal separation to obtain a precipitate containing calcium polycarbophil and magnesium hydroxide; adding a proper amount of dilute sulfuric acid into the precipitate to obtain polycarbophil calcium precipitate and a magnesium sulfate solution;
s8, detecting the concentration of the magnesium sulfate solution obtained in the step S7, and if the concentration of the magnesium sulfate is larger than the concentration standard in the step S1, adding a proper amount of pure water for dilution adjustment to obtain the magnesium sulfate solution meeting the concentration standard in the step S1; if the concentration of the magnesium sulfate is smaller than the concentration standard in the step S1, adding a proper amount of high-concentration magnesium sulfate solution for regulation to obtain a magnesium sulfate solution meeting the concentration standard in the step S1; injecting the magnesium sulfate solution obtained in the step into a first storage tank;
and S9, washing the calcium polycarbophil obtained in the step S7 with pure water to obtain pure calcium polycarbophil, and drying, crushing and molding the pure calcium polycarbophil to obtain a calcium polycarbophil product with high purity.
In this embodiment, the production processes from step S1 to step S5 are all performed in a thermostatic chamber at a temperature of 55-63 ℃. Wherein the thermostatic chamber is a closed space which is closed, has no oxygen and is filled with nitrogen. The environment filled with nitrogen can slow down the decomposition of the initiator when the temperature is lower than 63 ℃, thereby ensuring that raw materials entering the reaction kettle have no other impurities and preventing the initiator from being exploded too fast and generating harmful gases. And the temperature range in the reaction kettle in the step S1 is controlled to be 63-99 ℃. The concentration of the azodiisobutyronitrile is 3.5-4.5 mol/L. And the waste liquid separation of the step S2 is to collect the waste liquid through a separating funnel to obtain a magnesium sulfate solution a1, liquid succinonitrile and liquid 2,3, 5-tricyano-2, 3, 5-trimethylethane. The pure 2,3, 5-tricyano-2, 3, 5-trimethylethane and the liquid succinonitrile can also bring economic benefits, thereby improving the comprehensive utilization rate of raw materials. The temperature range of the step S7 after temperature reduction is 20-23 ℃. The waste water generated by washing the calcium polycarbophil in the step S9 may be utilized by adjusting the density of magnesium sulfate in the step S3 or the step S8. Steps S1 to S5 are performed in an atmosphere filled with nitrogen gas.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (8)
1. The production process of calcium polycarbophil is characterized by comprising the following steps:
s1, respectively injecting the magnesium sulfate solution in the first storage tank and the mixed solution of acrylic acid and azodiisobutyronitrile in the second storage tank into a reaction kettle, fully and uniformly mixing, heating, reacting to obtain a first product, and injecting an excessive magnesium sulfate solution;
s2, filtering and separating the first product through a filter to obtain a first solid and a first liquid, collecting the first liquid by using a first collecting tank, standing the first liquid, layering the first liquid, separating the upper layer liquid, the lower layer liquid and the upper layer liquid, wherein the upper layer liquid is a side reaction product and a reaction remainder of an oil phase, and the lower layer liquid is a side reaction product and a reaction remainder of a water phase;
s3, adding a proper amount of magnesium powder into the lower layer liquid for reaction, then detecting, and if the concentration of the magnesium sulfate is higher than the concentration standard in the step S1, adding a proper amount of pure water for dilution and adjustment to obtain a magnesium sulfate solution meeting the concentration standard in the step S1; if the concentration of the magnesium sulfate is smaller than the concentration standard in the step S1, adding a proper amount of high-concentration magnesium sulfate solution for regulation to obtain a magnesium sulfate solution meeting the concentration standard in the step S1; injecting the magnesium sulfate solution obtained in the step into a first storage tank;
s4, adding the obtained first solid into an organic solvent, and separating to obtain a polycarbophil magnesium salt and a mixed solution containing azodiisobutyronitrile and tetramethylsuccinonitrile; adding a certain amount of acrylic acid into the obtained mixed solution, mixing, and directly recycling the mixed solution into the reaction kettle in the step S1;
s5, washing the polycarbophil magnesium salt with distilled water to obtain pure polycarbophil magnesium salt and second liquid; collecting the second liquid by using a second collecting tank, extracting and separating the second liquid to obtain a mixed solution containing azobisisobutyronitrile and tetramethylsuccinonitrile, adding a certain amount of acrylic acid into the obtained mixed solution for mixing, and directly placing the mixed solution into the reaction kettle in the step S1;
s6, adding the washed polycarbophil magnesium salt into a calcium carbonate solution, fully and uniformly mixing, heating for reaction, and generating a second reaction product after the reaction;
s7, cooling the second product, and injecting the second product into a centrifuge for centrifugal separation to obtain a precipitate containing calcium polycarbophil and magnesium hydroxide; adding a proper amount of dilute sulfuric acid into the precipitate to obtain polycarbophil calcium precipitate and a magnesium sulfate solution;
s8, detecting the concentration of the magnesium sulfate solution obtained in the step S7, and if the concentration of the magnesium sulfate is larger than the concentration standard in the step S1, adding a proper amount of pure water for dilution adjustment to obtain the magnesium sulfate solution meeting the concentration standard in the step S1; if the concentration of the magnesium sulfate is smaller than the concentration standard in the step S1, adding a proper amount of high-concentration magnesium sulfate solution for regulation to obtain a magnesium sulfate solution meeting the concentration standard in the step S1; injecting the magnesium sulfate solution obtained in the step into a first storage tank;
s9, washing the calcium polycarbophil obtained in the step S7 with pure water to obtain pure calcium polycarbophil, and then drying, crushing and molding the pure calcium polycarbophil to obtain a calcium polycarbophil product with high purity.
2. The process according to claim 1, wherein the calcium polycarbophil is prepared by the following steps: the production processes from the step S1 to the step S5 are all carried out in a constant temperature chamber with the temperature of 55-63 ℃.
3. The process according to claim 2, wherein the calcium polycarbophil is prepared by the following steps: the thermostatic chamber is a closed space which is closed, has no oxygen and is filled with nitrogen.
4. The process according to claim 1, wherein the calcium polycarbophil is prepared by the following steps: and the temperature range in the reaction kettle in the step S1 is controlled to be 63-99 ℃.
5. The process according to claim 1, wherein the calcium polycarbophil is prepared by the following steps: the concentration of the azodiisobutyronitrile is 4 mol/L.
6. The process according to claim 1, wherein the calcium polycarbophil is prepared by the following steps: and the step S2 is to separate the waste liquid by a separating funnel, and sequentially collect the subnatant, the liquid succinonitrile and the liquid 2,3, 5-tricyano-2, 3, 5-trimethylethane.
7. The process according to claim 1, wherein the calcium polycarbophil is prepared by the following steps: the temperature range of the step S7 after temperature reduction is 20-23 ℃.
8. The process according to claim 1, wherein the calcium polycarbophil is prepared by the following steps: the waste water generated by washing the calcium polycarbophil in the step S9 may be utilized by adjusting the density of magnesium sulfate in the step S3 or the step S8.
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