CN114436898A - Production process of guanidine sulfate - Google Patents
Production process of guanidine sulfate Download PDFInfo
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- CN114436898A CN114436898A CN202011203523.8A CN202011203523A CN114436898A CN 114436898 A CN114436898 A CN 114436898A CN 202011203523 A CN202011203523 A CN 202011203523A CN 114436898 A CN114436898 A CN 114436898A
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- guanidine
- guanidine sulfate
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- ZZTURJAZCMUWEP-UHFFFAOYSA-N diaminomethylideneazanium;hydrogen sulfate Chemical compound NC(N)=N.OS(O)(=O)=O ZZTURJAZCMUWEP-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 88
- 239000000047 product Substances 0.000 claims abstract description 66
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 54
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 46
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229960000789 guanidine hydrochloride Drugs 0.000 claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 42
- 238000001914 filtration Methods 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 23
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 23
- 239000012043 crude product Substances 0.000 claims abstract description 22
- 239000007789 gas Substances 0.000 claims abstract description 19
- 239000011780 sodium chloride Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 92
- 238000003756 stirring Methods 0.000 claims description 58
- 235000019270 ammonium chloride Nutrition 0.000 claims description 46
- 239000000706 filtrate Substances 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 40
- 238000000967 suction filtration Methods 0.000 claims description 34
- 230000008569 process Effects 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 19
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 18
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 18
- 235000011152 sodium sulphate Nutrition 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 9
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 9
- 238000001953 recrystallisation Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000012535 impurity Substances 0.000 abstract description 30
- 238000002360 preparation method Methods 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 48
- 230000000052 comparative effect Effects 0.000 description 39
- 239000000126 substance Substances 0.000 description 20
- 238000001514 detection method Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000012467 final product Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 229960004198 guanidine Drugs 0.000 description 3
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 description 3
- 150000002357 guanidines Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000010583 slow cooling Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- GARCJIQFHZTIFC-UHFFFAOYSA-N diaminomethylideneazanium;2,4,6-trinitrophenolate Chemical compound NC(N)=N.OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O GARCJIQFHZTIFC-UHFFFAOYSA-N 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 235000013547 stew Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- QXAITBQSYVNQDR-ZIOPAAQOSA-N amitraz Chemical compound C=1C=C(C)C=C(C)C=1/N=C/N(C)\C=N\C1=CC=C(C)C=C1C QXAITBQSYVNQDR-ZIOPAAQOSA-N 0.000 description 1
- 229960002587 amitraz Drugs 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002220 antihypertensive agent Substances 0.000 description 1
- 229940127088 antihypertensive drug Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000002795 guanidino group Chemical group C(N)(=N)N* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000008558 metabolic pathway by substance Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 nitrogen-containing organic compound Chemical class 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application relates to the field of preparation of guanidyl compounds, and particularly discloses a production process of guanidine sulfate, which comprises the following steps: s1, mixing guanidine hydrochloride and sulfuric acid with the molar ratio of 2 (1-2), and reacting for 1-48h at 30-100 ℃ to generate a reaction product and hydrogen chloride gas; s2, cooling and crystallizing the reaction product prepared in the S1, and filtering to prepare a crude product of guanidine sulfate; introducing hydrogen chloride gas into a sodium hydroxide aqueous solution to generate a sodium chloride solution and water; s3, recrystallizing the crude guanidine sulfate prepared in the S2 to prepare a finished product of guanidine sulfate; the prepared guanidine sulfate finished product has the advantages of less impurities and high purity.
Description
Technical Field
The application relates to the field of preparation of guanidine compounds, in particular to a production process of guanidine sulfate.
Background
Guanidine is a nitrogen-containing organic compound, also called "iminourea", "iminourea" or "amitraz", is a colorless crystal with strong hygroscopicity and is easily soluble in water; after being dissolved in water, the guanidyl carries positive charges, is easy to absorb and permeate into microorganisms, so that the metabolism of substances and energy is damaged, and the microorganisms are killed or inhibited; the guanidino group is easy to form hydrogen bond, has good stability and strong physiological activity, and can be used as antihypertensive drug.
Guanidine nitrate, guanidine hydrochloride, guanidine sulfate and guanidine carbonate are common guanidine compounds; guanidine sulfate is a white crystal substance, is safer and more environment-friendly than guanidine nitrate and other guanidine salts, and is commonly used as an intermediate of medicines, pesticides and dyes.
At present, the mature process for producing guanidine nitrate in the related technology utilizes the reaction of ammonium nitrate and dicyandiamide, and when guanidine sulfate is prepared, if the ammonium sulfate and dicyandiamide are used for reaction, because the sulfate ions are unstable, the side reaction is easily generated in the reaction process to generate impurities, so that the purity of the obtained product is low, and thus no mature process for producing guanidine sulfate exists at present.
Disclosure of Invention
In order to ensure that the chemical reaction for preparing the guanidine sulfate is simple and controllable, the impurities are less and the product purity is high, the application provides a production process of the guanidine sulfate.
The application provides a production process of guanidine sulfate, which adopts the following technical scheme:
a production process of guanidine sulfate comprises the following steps:
s1, mixing guanidine hydrochloride and sulfuric acid with the molar ratio of 2 (1-2), and reacting for 1-48h at 0-100 ℃ to generate reaction products and hydrogen chloride gas;
s2, cooling and crystallizing the reaction product prepared in the S1, and filtering to prepare a crude product of guanidine sulfate; introducing hydrogen chloride gas into a sodium hydroxide aqueous solution to generate a sodium chloride solution and water;
s3, recrystallizing the crude guanidine sulfate prepared in the S2 to prepare the finished product of guanidine sulfate.
By adopting the technical scheme, the guanidine sulfate and the hydrogen chloride gas are generated by the reaction of the guanidine hydrochloride and the sulfuric acid, and the chloride ions in the guanidine hydrochloride do not participate in the reaction, so that the reaction principle in the process of the prepared guanidine sulfate is simple and controllable, the impurities are few, and the purity of the generated guanidine sulfate is higher.
Guanidine hydrochloride reacts with sufficient sulfuric acid, the reaction speed can be increased by limiting the reaction temperature, and the guanidine hydrochloride can be fully reacted, so that the reaction can be efficiently and quickly carried out; but Cl in guanidine hydrochloride-Impurities easily affect the purity of the crude guanidine sulfate; the solubility of guanidine sulfate is greatly influenced by the change of temperature, and Cl-The solubility of the guanidine sulfate is less influenced along with the temperature change, insoluble substances and impurities in crude guanidine sulfate can be preliminarily removed by means of cooling crystallization, and the purposes of preliminarily removing impurities and improving purity are achievedIn (1).
The prepared crude guanidine sulfate is subjected to secondary impurity removal through recrystallization, so that the purity of the finished guanidine sulfate can be further improved; then this application utilizes the crystallization of cooling to tentatively get rid of large granule undissolved substance and impurity, then coordinates the recrystallization and carries out the secondary edulcoration, finally makes finished product guanidine sulfate have the advantage that impurity is few, purity is high.
Preferably, the guanidine hydrochloride in S1 is poured into the sulfuric acid at a constant speed within 60S, and the stirring is continuously carried out at a stirring speed of 300 r/min.
By adopting the technical scheme, the guanidine hydrochloride is poured into the sulfuric acid at a constant speed within 60s, so that the guanidine hydrochloride can better react with the sulfuric acid, the reaction is fully carried out, the side reaction can be avoided, and the purity of the crude guanidine sulfate is not easily influenced; the guanidine hydrochloride and the sulfuric acid can quickly dissipate the heat released by the guanidine hydrochloride and the sulfuric acid by continuously stirring in the process of pouring the guanidine hydrochloride into the sulfuric acid, and the side reaction is avoided under the condition of higher temperature, so that the purity of the crude guanidine sulfate is influenced.
Preferably, the mass fraction of sulfuric acid in S1 is 80% -115%.
By adopting the technical scheme, the high-concentration concentrated sulfuric acid has low impurity content and few side reactions in the reaction process, so that the purity of the product is improved; and concentrated sulfuric acid with higher concentration can better react with guanidine hydrochloride to avoid the residual guanidine hydrochloride, thereby reducing impurity Cl-The generation of other side reactions is reduced, and the generated guanidine sulfate has the advantages of less impurities and high purity.
Preferably, the reaction temperature of the guanidine hydrochloride and the sulfuric acid in the S1 is 50-80 ℃, and the reaction time is 4-24 h.
By adopting the technical scheme, the reaction of the guanidine hydrochloride and the sulfuric acid at the temperature of 50-80 ℃ can greatly shorten the reaction time, thereby improving the reaction efficiency and leading the industrial preparation of the guanidine sulfate to have convenient production and high efficiency.
Preferably, the cooling crystallization in S2 comprises the following steps: and (3) carrying out hot suction filtration on the reaction product prepared in the step S1, cooling the filtrate to 10-20 ℃ at the cooling speed of 5 ℃/10min, standing for 2-5h after cooling, and filtering to obtain a crude product of guanidine sulfate.
By adopting the technical scheme, insoluble substances in a reaction product can be better extracted through the suction filtration operation, so that the insoluble substances are prevented from influencing the purity of the crude guanidine sulfate; and the guanidine sulfate crystal can be prevented from being separated out and lost by carrying out suction filtration under the hot condition, so that the generated crude guanidine sulfate has higher purity.
Utilize slow cooling crystallization cooperation to stew and make the crude guanidine sulfate who makes have impurity few, the high advantage of purity, the in-process of slow crystallization makes reaction product form gradually reunion, guarantees that the crystal nucleus volume that generates is great, the quality is higher, and the crystal nucleus forms the back, and the operation that the cooperation was stood makes the crystal nucleus grow up fast, avoids the crystal nucleus to receive destruction in the growth process, influences the purity of crystal nucleus, finally influences the purity of finished guanidine sulfate.
The cooling speed is limited, so that the reaction product prepared by S1 gradually forms crystals in the cooling process, the principle that the solubility is slowly reduced is utilized, the crude guanidine sulfate can separate out large single crystals with better quality and larger volume, the formation of the large single crystals can reduce the contents of sulfate ions and chloride ions on the surfaces of the large single crystals and in the large single crystals, and the crude guanidine sulfate has the advantages of less impurities and high purity.
Preferably, in the S2 temperature-reducing crystallization process, the reaction product prepared in S1 is continuously stirred at a rotation speed of 300-500r/min during the temperature reduction from the temperature reduction speed of 5 ℃/10min to 50 ℃.
By adopting the technical scheme, the reaction product is continuously stirred at the cooling speed of 5 ℃/10min to 50 ℃, so that the heat of the reaction product can be rapidly dissipated in the early stage of cooling, the time for cooling and crystallizing is shortened, and the cooling efficiency is improved; stopping stirring after 50 ℃, and avoiding the stirring operation from damaging the formation and growth of crystal nuclei, thereby ensuring that the reaction product forms large single crystals with higher quality and larger volume and ensuring the purity of crude guanidine sulfate.
Preferably, S21 is included between S2 and S3;
s21, mixing the sodium chloride solution prepared in the S2 and ammonium sulfate according to the molar ratio of 2:1 to generate a mixed solution of ammonium chloride and sodium sulfate; and S22, heating the mixed solution of ammonium chloride and sodium sulfate generated in the step S21 to 80 ℃, filtering, taking the filtrate, cooling the filtrate, and performing suction filtration to obtain the finished product of ammonium chloride.
By adopting the technical scheme, the sodium chloride and the ammonium sulfate react to generate the ammonium chloride and the sodium sulfate, the ammonium chloride is one of raw materials for preparing the guanidine hydrochloride, the guanidine hydrochloride is one of raw materials for preparing the guanidine sulfate, and the hydrogen chloride waste gas can indirectly prepare the guanidine sulfate by treating the hydrogen chloride waste gas, so that the recycling of the raw materials is realized, and the production cost of industrial production of the guanidine sulfate is reduced.
The sodium chloride solution and the ammonium sulfate react under the condition of temperature rise, the reaction rate can be accelerated, a mixed solution of the ammonium chloride and the sodium sulfate is generated, the solubility of the sodium sulfate is reduced along with the rise of the temperature under the condition of higher temperature, so that the sodium sulfate can be separated out and crystallized, the sodium sulfate crystal is taken out from the mixed solution through the operation of filtration, and water-insoluble impurities in the mixed solution are filtered out, so that the purity of the ammonium chloride crystal is ensured; then cooling the filtrate, gradually precipitating ammonium chloride crystals along with the reduction of the temperature, and obtaining the high-yield ammonium chloride crystals through suction filtration.
Preferably, the filtration in S22 is a hot filtration.
Through adopting above-mentioned technical scheme, under the lower condition of temperature, ammonium chloride crystal can be appeared gradually, adopts and filters when hot, and what guarantee that filtration operation is filterable only is the water insoluble substance in ammonium chloride and the sodium sulfate mixed solution, and the ammonium chloride crystal of avoiding appearing is filtered to guarantee the yield of ammonium chloride crystal.
Preferably, the S22 filtrate is cooled to 30-40 ℃ and filtered with suction.
Through adopting above-mentioned technical scheme, through the temperature when injecing the suction filtration, guarantee that ammonium chloride has better crystallization effect when 30-40 ℃, avoid the suction filtration when the ammonium chloride crystal nucleus is not complete shaping yet, influence the yield of ammonium chloride crystal.
Preferably, the recrystallization process in S3 is as follows:
s31, placing the crude guanidine sulfate prepared in S2 in water, stirring and dissolving for 15-25min under the condition of 400-600r/min to prepare a stirring solution;
s32, heating the stirring liquid prepared in the S31 to 70-80 ℃, carrying out suction filtration while the stirring liquid is hot, and cooling and filtering the filtrate to obtain the finished product of guanidine sulfate.
By adopting the technical scheme, the crude guanidine sulfate is dissolved in water to prepare a stirring solution, and then the stirring solution is heated to improve the solubility of the crude guanidine sulfate; the water-insoluble impurities in the stirring solution are pumped out of the stirring solution by matching with hot suction filtration, so that the water-soluble substances in the stirring solution are ensured, and the purity of the finished product guanidine sulfate is influenced by the anhydrous insoluble impurities; the filtrate after suction filtration contains dissolved crude guanidine sulfate and impurity Cl-The crude guanidine sulfate is recrystallized by cooling, and Cl-When the concentration of (B) is not saturated, Cl is present-Will remain in the solution, and the crystals and impurities are separated by filtration; this application uses guanidine hydrochloride as the raw materials, utilizes cooling crystallization cooperation recrystallization, makes finished product guanidine sulfate have impurity few, the high advantage of purity.
In summary, the present application has the following beneficial effects:
1. the method utilizes the reaction of guanidine hydrochloride and concentrated sulfuric acid to generate the guanidine sulfate and the hydrogen chloride gas, and Cl is generated because chloride ions in the guanidine hydrochloride do not participate in the reaction-In the reaction solution due to Cl-The solution can not reach a saturated state, but the solubility of the guanidine sulfate changes along with the temperature change, and the impurities and water-insoluble substances in the product guanidine sulfate can be efficiently removed by utilizing cooling crystallization in combination with recrystallization, so that the reaction principle in the process of preparing the guanidine sulfate is simple and controllable, and the generated guanidine sulfate finished product has the advantages of less impurities and high purity.
2. Insoluble substances in the reaction product can be better extracted through the suction filtration operation of the reaction product, so that the influence of the insoluble substances on the purity of the crude guanidine sulfate is avoided; and the guanidine sulfate crystal can be prevented from being separated out and lost by carrying out suction filtration under the hot condition, so that the purity of the generated crude guanidine sulfate is ensured.
3. Utilize slow cooling crystallization cooperation to stew the crude guanidine sulfate that makes and have impurity few, the high advantage of purity, the in-process of slow crystallization makes reaction product form gradually reunion, guarantees that the crystal nucleus volume that generates is great, the quality is higher, and the crystal nucleus forms the back, and the operation that the cooperation was stood makes the crystal nucleus grow up fast, avoids the crystal nucleus to receive destruction in the growth process, influences the purity of crystal nucleus, finally influences the purity of finished guanidine sulfate.
4. The method comprises the following steps of reacting sodium chloride and ammonium sulfate to generate ammonium chloride and sodium sulfate, wherein the ammonium chloride is one of raw materials for preparing guanidine hydrochloride, the guanidine hydrochloride is one of raw materials for preparing guanidine sulfate, and the hydrogen chloride waste gas can be used for indirectly preparing the guanidine sulfate by treating the hydrogen chloride waste gas, so that the recycling of the raw materials is realized, and the production cost of industrial production of the guanidine sulfate is reduced.
5. The reaction product is continuously stirred at the cooling speed of 5 ℃/10min to 50 ℃, so that the heat of the reaction product can be rapidly dissipated in the early stage of cooling, the time for cooling and crystallizing is shortened, and the cooling efficiency is improved; stopping stirring after 50 ℃, and avoiding the stirring operation from damaging the formation and growth of crystal nuclei, thereby ensuring that the reaction product forms large single crystals with higher quality and larger volume and ensuring the purity of crude guanidine sulfate.
Detailed Description
The present application will be described in further detail with reference to examples.
Examples
Guanidine hydrochloride in the following raw materials is purchased from Nanjing research biotechnology limited company, and the content is equal to or more than 99.5%.
Example 1: the guanidine sulfate is prepared by the following method:
s1, mixing guanidine hydrochloride with a mass fraction of 80% in a molar ratio of 2:1, placing the guanidine hydrochloride in sulfuric acid at a constant speed within 60S, continuously stirring at a stirring speed of 300r/min, and then reacting for 48h at a temperature of 0 ℃ to generate a reaction product and hydrogen chloride gas;
s2, carrying out suction filtration on the reaction product prepared in the step S1 while the reaction product is hot, taking the filtrate, cooling the filtrate to 10 ℃ at the cooling speed of 5 ℃/10min, standing for 2h, and filtering to obtain a crude product of guanidine sulfate; introducing hydrogen chloride gas into a sodium hydroxide aqueous solution to generate a sodium chloride solution and water;
s3, putting the crude guanidine sulfate prepared in the S2 into water, stirring and dissolving for 15min under the condition of 400r/min, and preparing a stirring solution; heating the stirred solution to 70 ℃, carrying out suction filtration while the stirred solution is hot, taking the filtrate, cooling the filtrate to 20 ℃ at the cooling speed of 5 ℃/10min, and standing for 3h to obtain a preformed product;
s4, filtering the preform obtained in the S3, and drying at room temperature to obtain the finished product of guanidine sulfate.
Example 2: the guanidine sulfate is prepared by the following method:
s1, mixing guanidine hydrochloride with a mass fraction of 88% in a molar ratio of 2:1.2, placing the guanidine hydrochloride in sulfuric acid at a constant speed within 60S, continuously stirring at a stirring speed of 300r/min during the process, and then reacting for 24 hours at 50 ℃ to generate a reaction product and hydrogen chloride gas;
s2, carrying out suction filtration on the reaction product prepared in the step S1 while the reaction product is hot, taking the filtrate, cooling the filtrate to 12 ℃ at the cooling speed of 5 ℃/10min, standing for 2.5h, and filtering to obtain a crude product of guanidine sulfate; introducing hydrogen chloride gas into a sodium hydroxide aqueous solution to generate a sodium chloride solution and water;
s3, putting the crude guanidine sulfate prepared in the S2 into water, stirring and dissolving for 18min under the condition of 450r/min, and preparing a stirring solution; heating the stirred solution to 72 ℃, carrying out suction filtration while the stirred solution is hot, taking the filtrate, cooling the filtrate to 20 ℃ at the cooling speed of 5 ℃/10min, and standing for 3h to obtain a preformed product;
s4, filtering the preform obtained in the S3, and drying at room temperature to obtain the finished product of guanidine sulfate.
Example 3: the guanidine sulfate is prepared by the following method:
s1, mixing guanidine hydrochloride with mass fraction of 98% in a molar ratio of 2:1.5, placing the guanidine hydrochloride in concentrated sulfuric acid at a constant speed within 60S, continuously stirring at a stirring speed of 300r/min, and reacting at 72 ℃ for 8h to generate a reaction product and hydrogen chloride gas;
s2, carrying out suction filtration on the reaction product prepared in the step S1 while the reaction product is hot, cooling the filtrate to 50 ℃ at a cooling speed of 5 ℃/10min, continuously stirring at a rotating speed of 450r/min during the cooling, stopping stirring after the temperature is lower than 50 ℃, continuously cooling to 15 ℃ at a cooling speed of 5 ℃/10min, standing for 3h, and filtering to obtain a crude product of guanidine sulfate; introducing hydrogen chloride gas into a sodium hydroxide aqueous solution to generate a sodium chloride solution and water;
s21, mixing the sodium chloride and the ammonium sulfate prepared in the S2 according to the molar ratio of 2:1 to generate a mixed solution of ammonium chloride and sodium sulfate;
s22, heating the mixed solution of ammonium chloride and sodium sulfate generated in the S21 to 80 ℃, filtering while the mixed solution is hot, taking the filtrate, cooling the filtrate to 35 ℃, and performing suction filtration to obtain an ammonium chloride finished product;
s3, putting the crude guanidine sulfate prepared in the S2 into water, stirring and dissolving for 20min under the condition of 500r/min, and preparing a stirring solution; heating the stirred solution to 75 ℃, carrying out suction filtration while the stirred solution is hot, taking the filtrate, cooling the filtrate to 20 ℃ at the cooling speed of 5 ℃/10min, and standing for 3h to obtain a preformed product;
s4, filtering the preform obtained in the S3, and drying at room temperature to obtain the finished product of guanidine sulfate.
Example 4: the guanidine sulfate is prepared by the following method:
s1, mixing guanidine hydrochloride with a mass fraction of 108% in a molar ratio of 2:1.8, placing the guanidine hydrochloride in concentrated sulfuric acid at a constant speed within 60S, continuously stirring at a stirring speed of 300r/min, and reacting at 80 ℃ for 4 hours to generate a reaction product and hydrogen chloride gas;
s2, carrying out suction filtration on the reaction product prepared in the step S1 while the reaction product is hot, cooling the filtrate to 50 ℃ at a cooling speed of 5 ℃/10min, continuously stirring at a rotating speed of 400r/min during the cooling, stopping stirring after the temperature is lower than 50 ℃, continuously cooling to 18 ℃ at a cooling speed of 5 ℃/10min, standing for 4h, and filtering to obtain a crude product of guanidine sulfate; introducing hydrogen chloride gas into a sodium hydroxide aqueous solution to generate a sodium chloride solution and water;
s21, mixing the sodium chloride and the ammonium sulfate prepared in the S2 according to the molar ratio of 2:1 to generate a mixed solution of ammonium chloride and sodium sulfate;
s22, heating the mixed solution of ammonium chloride and sodium sulfate generated in the step S21 to 80 ℃, filtering while the mixed solution is hot, taking the filtrate, cooling the filtrate to 30 ℃, and performing suction filtration to obtain a finished product of ammonium chloride;
s3, putting the crude guanidine sulfate prepared in the S2 into water, stirring and dissolving for 22min under the condition of 550r/min, and preparing a stirring solution; heating the stirred solution to 78 ℃, carrying out suction filtration while the stirred solution is hot, taking the filtrate, cooling the filtrate to 20 ℃ at the cooling speed of 5 ℃/10min, and standing for 3h to obtain a preformed product;
s4, filtering the preform obtained in the S3, and drying at room temperature to obtain the finished product of guanidine sulfate.
Example 5: the guanidine sulfate is prepared by the following method:
s1, mixing guanidine hydrochloride with mass fraction of 115% in a molar ratio of 1:1, placing the guanidine hydrochloride in concentrated sulfuric acid at a constant speed within 60S, continuously stirring at a stirring speed of 300r/min, and then reacting for 1h at 100 ℃ to generate a reaction product and hydrogen chloride gas;
s2, carrying out suction filtration on the reaction product prepared in the step S1 while the reaction product is hot, cooling the filtrate to 50 ℃ at a cooling speed of 5 ℃/10min, continuously stirring at a rotating speed of 500r/min during the cooling, stopping stirring after the temperature is lower than 50 ℃, continuously cooling to 20 ℃ at a cooling speed of 5 ℃/10min, standing for 5h, and filtering to obtain a crude product of guanidine sulfate; introducing hydrogen chloride gas into a sodium hydroxide aqueous solution to generate a sodium chloride solution and water;
s21, mixing the sodium chloride and the ammonium sulfate prepared in the S2 according to the molar ratio of 2:1 to generate a mixed solution of ammonium chloride and sodium sulfate;
s22, heating the mixed solution of ammonium chloride and sodium sulfate generated in the step S21 to 80 ℃, filtering while the mixed solution is hot, taking the filtrate, cooling the filtrate to 40 ℃, and performing suction filtration to obtain an ammonium chloride finished product;
s3, putting the crude guanidine sulfate prepared in the S2 into water, stirring and dissolving for 25min under the condition of 600r/min, and preparing a stirring solution; heating the stirred solution to 80 ℃, carrying out suction filtration while the stirred solution is hot, taking the filtrate, cooling the filtrate to 20 ℃ at the cooling speed of 5 ℃/10min, and standing for 3h to obtain a preformed product;
s4, filtering the preform obtained in the S3, and drying at room temperature to obtain the finished product of guanidine sulfate.
Comparative example
Comparative example 1: the comparative example differs from example 3 in that:
and S2, cooling and crystallizing the reaction product prepared in the S1, and filtering to obtain the finished product of guanidine sulfate.
Comparative example 2: this comparative example differs from example 3 in that:
s1, putting guanidine hydrochloride into concentrated sulfuric acid at one time, and reacting for 8 hours at 72 ℃ to generate reaction products and hydrogen chloride gas.
Comparative example 3: this comparative example differs from example 3 in that:
s2, cooling the reaction product prepared in the step S1 to 50 ℃ at a cooling rate of 5 ℃/10min, continuously stirring at a rotating speed of 450r/min during the period, stopping stirring after the temperature is lower than 50 ℃, continuously cooling to 15 ℃ at a cooling rate of 5 ℃/10min, standing for 3h, and filtering to obtain a crude guanidine sulfate product.
Comparative example 4: this comparative example differs from example 3 in that:
s2, carrying out suction filtration on the reaction product prepared in the step S1 while the reaction product is hot, taking the filtrate, cooling the filtrate to 15 ℃ within 1min, standing the filtrate for 3h, and filtering the filtrate to obtain a crude product of guanidine sulfate.
Comparative example 5: this comparative example differs from example 3 in that:
s2, carrying out suction filtration on the reaction product prepared in the step S1 while the reaction product is hot, cooling the filtrate to 15 ℃ at a cooling speed of 5 ℃/10min, continuously stirring at a rotating speed of 450r/min during the cooling, standing for 3h, and filtering to obtain a crude product of guanidine sulfate.
Comparative example 6: this comparative example differs from example 3 in that:
and S22, heating the mixed solution of ammonium chloride and sodium sulfate generated in the step S21 to 80 ℃, cooling to room temperature, and performing suction filtration to obtain the finished product of ammonium chloride.
Performance test
1. Detection of percentage content of guanidine sulfate
Finished guanidine sulfate was prepared as samples by the preparation methods of examples 1 to 5 and comparative examples 1 to 5, respectively.
The detection method comprises the following steps: weighing 2.5g of sample (accurate to 0.0002g), placing the sample in a 250mL beaker, adding 200mL of distilled water, heating to dissolve the sample, cooling to room temperature, transferring the sample into a 250mL volumetric flask, adding water to dilute the sample to a scale, shaking up, filtering, sucking 25mL of filtrate, placing the filtrate in the 250mL beaker, adding 2mL of ammonia water solution and 75mL of picric acid solution, stirring for 2min at a rotating speed of 100r/min when yellow picuanidine precipitate is formed, placing the beaker in a cold water bath at 5-10 ℃ for 1h, filtering the beaker by using a No. 4 glass crucible with constant weight, washing the beaker and the precipitate by using 30mL portions of original filtrate, draining, and placing the glass crucible with the precipitate in an oven at 105 ℃ for drying to the constant weight.
The calculation formula is as follows:
percentage of guanidine sulfate
In the test, m1 is the mass of guanidine picrate, g;
m is sample mass, g;
0.7510 is the ratio of the relative molecular masses of guanidine sulfate to guanidine picrate.
2. Detection of water-insoluble substances in guanidine sulfate
Finished guanidine sulfate was prepared as samples by the preparation methods of examples 1 to 5 and comparative examples 1 to 5, respectively.
The detection method comprises the following steps: weighing 10g of sample (accurate to 0.01g), placing the sample into a 250mL beaker, adding 200mL of distilled water, heating to dissolve the sample, placing the sample in an ice water bath at 0 ℃ to cool the sample to 20 ℃, filtering the sample by using a No. 4 glass crucible with constant weight, washing the precipitate by using 150mL of 20 ℃ distilled water for 3 times, wherein each time is about 50mL, and drying the glass crucible with the precipitate at 105 ℃ to constant weight.
The calculation formula is as follows:
percentage of guanidine sulfate water-insoluble matter
In the test: m2 is the total mass, g, of the glass crucible and the water-insoluble substance;
m3 is the mass of the glass crucible, g;
m4 is sample mass, g.
3. Impurity Cl in guanidine sulfate-Content detection
Finished guanidine sulfate was prepared as samples by the preparation methods of examples 1 to 5 and comparative examples 1 to 5, respectively.
The detection method comprises the following steps: weighing 10g (accurate to 0.01g) of sample, putting the sample into a 250mL beaker, adding 200mL of distilled water, stirring and dissolving, adding 10mL of silver nitrate solution, continuing stirring for 10min, standing for 30min, observing the turbidity degree of the solution, scoring, and taking a score of 0-10 minutes when the solution is separated and precipitated until the solution is not turbid.
TABLE 1 guanidine sulfate Performance test Table
As can be seen by combining examples 1-2 and examples 3-5 with Table 1, the percentage of guanidine sulfate produced in examples 3-5, both crude and finished, was increased as compared to examples 1-2; the method is characterized in that in the preparation process of the guanidine sulfate finished product, the cooling temperature is controlled to be matched with the stirring operation, so that the reaction product accelerates the growth of a crystal nucleus of crude guanidine sulfate in the crystallization process, the crystal nucleus of crude guanidine sulfate has higher purity, and the prepared finished guanidine sulfate has higher purity; meanwhile, the percentage of water-insoluble matters in the finished products prepared in examples 3-5 was reduced compared to that in examples 1-2, and Cl in the finished products prepared in examples 3-5-The content score is increased compared with that of the example 1-2, which shows that the stirring operation in the cooling crystallization process can uniformly disperse the water-insoluble substances in the reaction product, thereby ensuring that the water-insoluble substances are separated from the crude guanidine sulfate, and the prepared crude guanidine sulfate has low water-insoluble substance content and Cl content-The content is less, so that the prepared guanidine sulfate finished product has the advantages of less impurities and high purity.
In the preparation process of the guanidine sulfate in the comparative example 1, the reaction product is directly cooled, crystallized and filtered to prepare a finished product of the guanidine sulfate; compared with the embodiment 3, the percentage content of the crude product and the percentage content of the finished product of the guanidine sulfate prepared in the comparative example 1 are both less than the percentage content of the crude product and the percentage content of the finished product corresponding to the guanidine sulfate prepared in the embodiment 3; and prepared in comparative example 1The percentage content of the water-insoluble substances of the finished product is increased compared with that of the finished product prepared in example 3; while Cl of the final product prepared in comparative example 1-Content rating compared to Cl for the finished product prepared in example 3-The content score is reduced; the cooling crystallization is matched with the recrystallization, so that the impurities in the finished guanidine sulfate product can be efficiently removed, and the content of water insoluble substances and Cl in the finished product can be effectively reduced-Content, etc., so that the prepared guanidine sulfate finished product has the advantages of less impurities and high purity.
In the preparation process of the guanidine sulfate of comparative example 2, the guanidine hydrochloride is completely placed in concentrated sulfuric acid at one time; compared with the embodiment 3, the percentage content of the crude product and the percentage content of the finished product of the guanidine sulfate prepared in the comparative example 2 are both less than the percentage content of the crude product and the percentage content of the finished product corresponding to the guanidine sulfate prepared in the embodiment 3; and the percentage of water insoluble content of the finished product prepared in comparative example 2 was increased compared to the percentage of water insoluble content of the finished product prepared in example 3; while Cl of the final product prepared in comparative example 2-Content rating compared to Cl for the finished product prepared in example 3-The content score is reduced; the method shows that the guanidine hydrochloride is added once, the reaction is easy to be incomplete, and the incomplete reaction of the guanidine hydrochloride is easy to cause the product to contain a large amount of Cl-Impurities, large amounts of Cl-Resulting in a lower purity of the crude guanidine sulfate and thereby affecting the purity of the finished guanidine sulfate.
In the preparation process of the guanidine sulfate of the comparative example 3, the reaction product is directly cooled without hot pumping filtration, the temperature is reduced to 50 ℃ at the cooling speed of 5 ℃/10min, stirring is continuously carried out at the rotating speed of 450r/min during the cooling, the stirring is stopped when the temperature is lower than 50 ℃, the temperature is continuously reduced to 15 ℃ at the cooling speed of 5 ℃/10min, then standing is carried out for 3h, and a crude guanidine sulfate is prepared after filtration; compared with the embodiment 3, the percentage content of the crude product and the percentage content of the finished product of the guanidine sulfate prepared in the comparative example 3 are both less than the percentage content of the crude product and the percentage content of the finished product of the guanidine sulfate prepared in the embodiment 3; and the percentage of water insoluble content of the finished product prepared in comparative example 3 was increased compared to the percentage of water insoluble content of the finished product prepared in example 3; while Cl of the final product prepared in comparative example 3-Content score vs. fruitCl of the final product prepared in example 3-The content score is reduced; the method has the advantages that the water-insoluble substances can be better extracted by carrying out suction filtration under the hot condition, the guanidine sulfate is prevented from separating out crystals in a low-temperature environment, and the guanidine sulfate crystals are easily extracted together while the water-insoluble substances are extracted, so that the yield of crude guanidine sulfate crystals is lowered, and the purity of the crude guanidine sulfate is finally influenced.
In the preparation process of the guanidine sulfate in the comparative example 4, after a reaction product is filtered while hot, directly taking the filtrate, quickly cooling to 15 ℃ within 1min, standing for 3h, and filtering to obtain a crude guanidine sulfate product; compared with the embodiment 3, the percentage content of the crude product and the percentage content of the finished product of the guanidine sulfate prepared in the comparative example 4 are both less than the percentage content of the crude product and the percentage content of the finished product of the guanidine sulfate prepared in the embodiment 3; and the percentage of water insoluble content of the finished product prepared in comparative example 4 was increased compared to the percentage of water insoluble content of the finished product prepared in example 3; while Cl of the final product prepared in comparative example 4-Content rating compared to Cl for the finished product prepared in example 3-The content score is reduced; the demonstration utilizes slow cooling crystallization cooperation to stand the advantage that the crude guanidine sulfate that makes that has impurity few, that purity is high, and the in-process of slow crystallization makes reaction product form gradually and reunites, guarantees that the crystal nucleus volume that generates is great, the quality is higher, and after the crystal nucleus formed, the operation that the cooperation was stood makes the crystal nucleus grow up fast, avoids the crystal nucleus to receive destruction in the growth-up process, influences the purity of crystal nucleus, finally influences the purity of finished guanidine sulfate.
In the preparation process of the guanidine sulfate in the comparative example 5, the reaction product is filtered while hot, the filtrate is taken to be cooled to 15 ℃ at the cooling speed of 5 ℃/10min, the filtrate is continuously stirred at the rotating speed of 450r/min during the cooling, then the mixture is kept stand for 3h, and a crude guanidine sulfate is prepared after filtration; compared with the embodiment 3, the percentage content of the crude product and the percentage content of the finished product of the guanidine sulfate prepared in the comparative example 5 are both less than the percentage content of the crude product and the percentage content of the finished product of the guanidine sulfate prepared in the embodiment 3; and the percentage of water insoluble content of the finished product prepared in comparative example 5 was increased compared to the percentage of water insoluble content of the finished product prepared in example 3; while Cl of the final product prepared in comparative example 5-Content score compared to realCl of the final product prepared in example 3-The content score is reduced; the reaction product is cooled and crystallized, and the heat of the reaction product can be rapidly dissipated through proper stirring operation, so that the cooling and crystallizing time is shortened, the cooling efficiency is improved, and if the reaction product is continuously stirred in the whole cooling and crystallizing process, crystal nuclei are easily damaged in the forming and growing processes, the purity of crude guanidine sulfate is influenced, and the purity of the guanidine sulfate finished product is finally influenced.
4. Detection of ammonium chloride content
The preparation methods of examples 3 to 5 and comparative example 6 were respectively adopted to prepare finished ammonium chloride as a sample; the content of the ammonium chloride is detected by adopting a method for detecting the ammonium chloride in GB/T2946-2018.
According to the detection, the mass fractions of the ammonium chloride in the examples 3 to 5 are 99.4%, 99.3% and 99.3% respectively, and the mass fraction of the ammonium chloride prepared in the comparative example 6 is 92.8%, compared with the ammonium chloride prepared in the examples 3 to 5, the purity of the ammonium chloride prepared in the comparative example 6 is lower than that of the ammonium chloride prepared in the examples 3 to 5, which shows that the operation of hot filtration can effectively remove the water insoluble substances in the mixed solution, and prevent the precipitated ammonium chloride crystals from being filtered, thereby ensuring the purity of the ammonium chloride crystals; meanwhile, the temperature during suction filtration is limited, so that the ammonium chloride has a good crystallization effect at 30-40 ℃, and the suction filtration is avoided when ammonium chloride crystal nuclei are not completely formed, thereby influencing the purity of ammonium chloride crystals.
The present embodiment is only for explaining the present application, and it is not limited to the present application, 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 application.
Claims (10)
1. The production process of guanidine sulfate is characterized by comprising the following steps
S1, mixing guanidine hydrochloride and sulfuric acid with the molar ratio of 2 (1-2), and reacting for 1-48h at 0-100 ℃ to generate reaction products and hydrogen chloride gas;
s2, cooling and crystallizing the reaction product prepared in the S1, and filtering to prepare a crude product of guanidine sulfate; introducing hydrogen chloride gas into a sodium hydroxide aqueous solution to generate a sodium chloride solution and water;
s3, recrystallizing the crude guanidine sulfate prepared in the S2 to prepare the finished product of guanidine sulfate.
2. The process for producing guanidine sulfate according to claim 1, wherein: the guanidine hydrochloride in S1 is poured into the sulfuric acid at a constant speed within 60S, and is continuously stirred at a stirring speed of 300 r/min.
3. The process for producing guanidine sulfate according to claim 1, wherein the mass fraction of sulfuric acid in S1 is 80-115%.
4. The process for producing guanidine sulfate according to claim 1, wherein the reaction temperature of guanidine hydrochloride and sulfuric acid in S1 is 50-80 ℃ and the reaction time is 4-24 h.
5. The process for producing guanidine sulfate according to claim 1, wherein the cooling crystallization in S2 comprises the following steps: and (3) carrying out hot suction filtration on the reaction product prepared in the step S1, cooling the filtrate to 10-20 ℃ at the cooling speed of 5 ℃/10min, standing for 2-5h after cooling, and filtering to obtain a crude product of guanidine sulfate.
6. The process for producing guanidine sulfate according to claim 5, wherein in the step of S2 cooling crystallization, the reaction product obtained in S1 is continuously stirred at a rotation speed of 300-500r/min during the period of cooling from 5 ℃/10min to 50 ℃.
7. The process for producing guanidine sulfate according to claim 1, wherein S21 is included between S2 and S3;
s21, mixing the sodium chloride solution prepared in the S2 and ammonium sulfate according to the molar ratio of 2:1 to generate a mixed solution of ammonium chloride and sodium sulfate;
and S22, heating the mixed solution of ammonium chloride and sodium sulfate generated in the step S21 to 80 ℃, filtering, taking the filtrate, cooling the filtrate, and performing suction filtration to obtain the finished product of ammonium chloride.
8. The process for producing a guanidine sulfate according to claim 7, wherein the filtration in S22 is a hot filtration.
9. The process for producing guanidine sulfate according to claim 7, wherein the S22 filtrate is cooled to 30-40 ℃ and filtered.
10. The process for producing guanidine sulfate according to claim 1, wherein the recrystallization process in S3 is as follows:
s31, placing the crude guanidine sulfate prepared in S2 in water, stirring and dissolving for 15-25min under the condition of 400-600r/min to prepare a stirring solution;
s32, heating the stirring liquid prepared in the S31 to 70-80 ℃, carrying out suction filtration while the stirring liquid is hot, and cooling and filtering the filtrate to obtain the finished product of guanidine sulfate.
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