CN111807877A - DL-p-hydroxyphenylhydantoin and production process of urea sulfate/ammonium sulfate thereof - Google Patents
DL-p-hydroxyphenylhydantoin and production process of urea sulfate/ammonium sulfate thereof Download PDFInfo
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- CN111807877A CN111807877A CN202010677883.5A CN202010677883A CN111807877A CN 111807877 A CN111807877 A CN 111807877A CN 202010677883 A CN202010677883 A CN 202010677883A CN 111807877 A CN111807877 A CN 111807877A
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/02—Salts; Complexes; Addition compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/72—Two oxygen atoms, e.g. hydantoin
- C07D233/76—Two oxygen atoms, e.g. hydantoin with substituted hydrocarbon radicals attached to the third ring carbon atom
- C07D233/78—Radicals substituted by oxygen atoms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
Abstract
The invention discloses a production process of DL-p-hydroxyphenylhydantoin and urea sulfate/ammonium sulfate thereof, which comprises the following steps: step 1, adding phenol, urea and sulfuric acid into a reaction kettle according to a molar ratio, slowly heating, controlling the reaction temperature at 70-95 ℃, and preserving heat for 30 min; step 2, adding glyoxylic acid into the reaction liquid obtained in the step 1 dropwise, wherein the adding time is controlled to be 2-8 h; step 3, after the dropwise addition reaction is finished, controlling the temperature in the reaction kettle to be not lower than 85 ℃, and discharging after heat preservation for 2-5 hours; the invention has the beneficial effects that: compared with the DL-p-hydroxyphenylhydantoin synthesized by a hydrochloric acid method, the process has the advantages that the product quality and the yield are improved, and the problems that a large amount of HCL gas is released in a production field in the process of synthesizing the DL-p-hydroxyphenylhydantoin by the hydrochloric acid method, and other organic matters such as waste hydrochloric acid have influence on the production environment and production equipment are solved.
Description
Technical Field
The invention relates to the technical field of DL-p-hydroxyphenylhydantoin, in particular to a production process of DL-p-hydroxyphenylhydantoin and urea sulfate/ammonium sulfate thereof.
Background
At present, the domestic DL-p-hydroxyphenylhydantoin production process completely adopts a hydrochloric acid method synthesis process route, and the production process has the following defects: 1. a large amount of harmful HCL gas is generated in the production process, which affects the production environment and production equipment and needs to be purified by an adsorption tower: 2. produce a large amount of solid danger in the waste water treatment process and useless, need handle by special danger processing company, it is with high costs: 3. the production equipment is easy to corrode, and the maintenance cost is high: 4. the content of the by-products in the finished product is higher. The biggest defects of the synthetic process route adopting the hydrochloric acid method are that the generated solid waste is large in quantity, the waste water is difficult to treat, the cost is high, and especially, the large quantity of solid waste generated in the production process becomes the biggest obstacle influencing the normal production of enterprises.
Disclosure of Invention
The invention aims to overcome the process defects of producing DL-p-hydroxyphenylhydantoin by a hydrochloric acid method and solve the problems of difficult three-waste treatment, large solid waste generation amount and high cost in the production process. The invention takes glyoxylic acid, phenol, urea and sulfuric acid as raw materials, and obtains the DL-p-hydroxyphenylhydantoin product by condensation, suction filtration, centrifugal water washing and drying according to a certain molar ratio. The production mother liquor is treated through high temperature concentration and decomposition, pressure distillation to remove organic products, and then a certain amount of ammonia water is added for neutralization, and urea sulfate/ammonium sulfate products which are in line with the production of domestic compound fertilizers are produced through reaction, cooling, crystallization and separation.
In order to achieve the purpose, the invention provides the following technical scheme: a production process of DL-p-hydroxyphenylhydantoin and urea sulfate/ammonium sulfate thereof comprises the following steps:
step 1, adding phenol, urea and sulfuric acid into a reaction kettle according to a molar ratio, slowly heating, controlling the reaction temperature at 70-95 ℃, and preserving heat for 30 min;
step 2, adding glyoxylic acid into the reaction liquid obtained in the step 1 dropwise, wherein the adding time is controlled to be 2-8 h;
step 3, after the dropwise addition reaction is finished, controlling the temperature in the reaction kettle to be not lower than 85 ℃, and discharging after heat preservation for 2-5 hours;
step 4, putting the materials in the reaction kettle into a prepared filter, performing suction filtration until no water drops visible to naked eyes exist on the surfaces of the materials, and then transferring the materials into a prepared centrifugal machine while the materials are hot;
step 5, putting prepared hot water with the temperature not lower than 85 ℃ into a centrifuge, overflowing the surface of the material, packaging the material after centrifugal washing for 3 times, drying the material until the water content is not higher than 0.5%, and packaging the material into a finished product;
step 6, filtering mother liquor, washing, hydrating and collecting, transferring part of the filtered mother liquor to the step 1 for use, transferring the rest of the filtered mother liquor to mother liquor for concentration, and recovering urea sulfate/ammonium sulfate products;
step 7, adding the recovered mother liquor into a concentration kettle, controlling the temperature in the concentration kettle to be not higher than 115 ℃, controlling the distillation time according to the actual condition, and then collecting distillate;
step 8, adding ammonia water into the mother liquor in an adjusting tank to adjust the pH value to 1-5.5, then adding the mother liquor into a concentration kettle for concentration, pumping the concentrated solution into an ammonium sulfate crystallization kettle at high temperature for cooling crystallization, and obtaining a crude product of ammonium sulfate through centrifugal separation; returning the separated liquid to a concentration system for concentration;
step 9, putting the cooling liquid in the concentration kettle into a cooling liquid centrifuge in a crystallization kettle for separation, separating out a by-product urea sulfate/ammonium sulfate product, and returning the separated liquid to the concentration kettle for continuous concentration;
step 10: when the concentration kettle is heated to 100 ℃, a large amount of water is evaporated, part of the water is separated into condensed water through the tower, the condensed water is sent to a wastewater treatment system for treatment, and part of the vapor is discharged.
Preferably, the molar ratio of the phenol to the urea to the sulfuric acid in the step 1 is (0.5-1.0) to (0.9-1.3).
Preferably, the catalyst in the step 1 is sulfuric acid with the concentration of 36-75%.
Preferably, the amount of the glyoxylic acid added dropwise in the step 2 at a concentration of 40 to 75 percent is 1.0 to 1.4 mol.
Preferably, after sulfuric acid is used as a catalyst in the steps 6 to 9, ammonia water is added to the concentrated solution for neutralization.
Preferably, in the step 8, the temperature in the concentration kettle is not higher than 115 ℃, and the reaction product is cooled to normal temperature.
Preferably, in the step 9, the separation liquid returns to the concentration kettle for continuous concentration treatment, and is discharged after being treated qualified.
Preferably, the content of the urea sulfate in the step 6 is 8-12%, and the content of the ammonium sulfate is 85-95%.
Compared with the prior art, the invention has the beneficial effects that: compared with the DL-p-hydroxyphenyl hydantoin synthesized by the hydrochloric acid method, the process has the advantages that the product quality and yield are improved, the problems that a large amount of HCL gas is discharged from a production site in the process of synthesizing the DL-p-hydroxyphenyl hydantoin by the hydrochloric acid method, and other organic matters such as waste hydrochloric acid have influence on production environment and production equipment are solved, the problems of large solid waste amount, difficult wastewater treatment and high cost in the production process of synthesizing the DL-p-hydroxyphenyl hydantoin by the hydrochloric acid method are effectively solved, and the generation of solid waste can be reduced by more than 90%; meanwhile, the urea sulfate/ammonium sulfate byproduct recovered by the method can be directly used for producing compound fertilizers, so that the wastewater treatment cost is reduced, and the economic benefit is increased; the wastewater generated in the production process can be discharged up to the standard after micro-electrolysis, resin filtration, rhizoma cyperi absorption, flocculation and decoloration and reverse osmosis membrane filtration.
Drawings
FIG. 1 is a flow chart of a production process for synthesizing DL-p-hydroxyphenylhydantoin by a sulfuric acid method;
FIG. 2 is the main reaction chemical formula of DL-p-hydroxyphenylhydantoin of the present invention;
FIG. 3 shows the chemical formula of the side reaction of DL-p-hydroxyphenylhydantoin in accordance with the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1-3, the present invention provides a technical solution: a production process of DL-p-hydroxyphenylhydantoin and urea sulfate/ammonium sulfate thereof comprises the following steps:
step 1, adding phenol, urea and sulfuric acid into a reaction kettle according to a molar ratio, slowly heating, controlling the reaction temperature at 70-95 ℃, and preserving heat for 30 min;
step 2, adding glyoxylic acid into the reaction liquid obtained in the step 1 dropwise, wherein the adding time is controlled to be 2-8 h;
step 3, after the dropwise addition reaction is finished, controlling the temperature in the reaction kettle to be not lower than 85 ℃, and discharging after heat preservation for 2-5 hours;
step 4, putting the materials in the reaction kettle into a prepared filter, performing suction filtration until no water drops visible to naked eyes exist on the surfaces of the materials, and then transferring the materials into a prepared centrifugal machine while the materials are hot;
step 5, putting prepared hot water with the temperature not lower than 85 ℃ into a centrifuge, overflowing the surface of the material, packaging the material after centrifugal washing for 3 times, drying the material until the water content is not higher than 0.5%, and packaging the material into a finished product;
step 6, filtering mother liquor, washing, hydrating and collecting, transferring part of the filtered mother liquor to the step 1 for use, transferring the rest of the filtered mother liquor to mother liquor for concentration, and recovering urea sulfate/ammonium sulfate products;
step 7, adding the recovered mother liquor into a concentration kettle, controlling the temperature in the concentration kettle to be not higher than 115 ℃, controlling the distillation time according to the actual condition, and then collecting distillate;
step 8, adding ammonia water into the mother liquor in an adjusting tank to adjust the pH value to 1-5.5, then adding the mother liquor into a concentration kettle for concentration, pumping the concentrated solution into an ammonium sulfate crystallization kettle at high temperature for cooling crystallization, and obtaining a crude product of ammonium sulfate through centrifugal separation; returning the separated liquid to a concentration system for concentration;
step 9, putting the cooling liquid in the concentration kettle into a cooling liquid centrifuge in a crystallization kettle for separation, separating out a by-product urea sulfate/ammonium sulfate product, and returning the separated liquid to the concentration kettle for continuous concentration;
step 10: when the concentration kettle is heated to 100 ℃, a large amount of water is evaporated, part of the water is separated into condensed water through the tower, the condensed water is sent to a wastewater treatment system for treatment, and part of the vapor is discharged.
Wherein the mol ratio of the phenol to the urea to the sulfuric acid in the step 1 is (0.5-1.0) to (0.9-1.3).
Wherein, the catalyst in the step 1 is sulfuric acid with the concentration of 36-75%.
Wherein, the quantity of the glyoxylic acid with the dropping concentration of 40-75 percent in the step 2 is 1.0-1.4 mol.
Wherein, after sulfuric acid is used as a catalyst in the steps 6 to 9, ammonia water is added into the concentrated solution for neutralization.
Wherein in the step 8, the temperature in the concentration kettle is not higher than 115 ℃, and the reaction kettle is cooled to normal temperature after reaction
And 9, returning the separation liquid to the concentration kettle to continue concentration treatment, and discharging after the treatment is qualified.
Wherein, the content of the urea sulfate in the step 6 is 8-12%, and the content of the ammonium sulfate is 85-95%.
Example 1:
adding 37g of urea, 20g of phenol and 40mL of 75% sulfuric acid into a 250mL four-neck flask provided with a mechanical stirring device, a reflux condenser tube, a thermometer and a dropping funnel in sequence, controlling the reaction temperature to be 80 ℃ under the stirring condition, slowly dropping 30g of weighed 40% glyoxylic acid solution, controlling the dropping time to be about 4 hours, and controlling the reaction temperature to be not lower than 85 ℃; after the dropwise addition reaction is finished, stirring for 30min under heat preservation, cooling the reaction liquid to room temperature, and separating out white crystals; and (2) performing suction filtration by using a Buchner funnel, washing the filter cake for 3 times by using 50mL of hot water with the temperature of not lower than 85 ℃, performing suction filtration until no free moisture exists on the surface of the filter cake, and then putting the filter cake into a drying oven to be dried until the water content is not higher than 0.5%, thereby obtaining 25g of DL-p-hydroxyphenyl hydantoin with the purity of more than 98.5% and the mass yield (calculated by phenol) of 85%.
Example 2:
in a 2000mL beaker provided with a mechanical stirrer, a thermometer and a dropping funnel, 200mL of reaction mother liquor is added, 150g of urea, 73g of phenol and 125mL of 36% sulfuric acid are sequentially added, under the stirring condition, the reaction temperature is controlled to be 85 ℃, 110g of weighed 40% glyoxylic acid solution is slowly dripped, the dripping time is controlled to be about 4 hours, and the reaction temperature is not lower than 85 ℃; after the dropwise addition reaction is finished, stirring for 30min under heat preservation, cooling the reaction liquid to room temperature, and separating out white crystals; and (2) performing suction filtration by using a Buchner funnel, washing the filter cake for 3 times by using 150mL hot water with the temperature of not lower than 85 ℃, performing suction filtration until no free moisture exists on the surface of the filter cake, and then putting the filter cake into a drying oven to be dried until the water content is not higher than 0.5%, thereby obtaining 92g of DL-p-hydroxyphenyl hydantoin with the purity of more than 98.5% and the mass yield (calculated by phenol) of 85%.
Example 3:
step 1, in a 2000L enamel reaction kettle, starting stirring 500L of reaction mother liquor, then sequentially adding 250Kg of urea, 170Kg of phenol and 180L of 60 percent sulfuric acid into the reaction kettle, slowly controlling the reaction temperature at 90 ℃, and preserving heat for 30 min;
step 2, after the heat preservation is finished, adding 255Kg of weighed 50% glyoxylic acid into the reaction kettle in a dropwise manner, controlling the reaction temperature in the kettle to be not more than 90 ℃ and the dropwise adding time to be not less than 4 hours;
step 3, after the dropwise addition reaction is finished, controlling the reaction temperature to be not lower than 85 ℃, and preserving the temperature for 30 min; then, cooling to 85 ℃, and preparing for discharging;
step 4, putting the materials in the reaction kettle into a prepared filter, performing suction filtration until no water drops visible to naked eyes exist on the surfaces of the materials, and then transferring the materials into a prepared centrifugal machine while the materials are hot;
step 5, putting prepared hot water with the temperature not lower than 85 ℃ into a centrifuge, overflowing the surface of the material, packaging the material after centrifugal washing for 3 times, drying the material until the water content is not higher than 0.5%, and packaging the material into a finished product;
step 6, filtering mother liquor, washing, hydrating and collecting, transferring one part of the filtered mother liquor to the step 1 for use, transferring the rest part of the filtered mother liquor to the mother liquor for concentration, and recovering urea sulfate/ammonium sulfate products;
step 7, adding the recovered mother liquor into a concentration kettle, controlling the temperature in the concentration kettle to be not lower than 115 ℃, distilling for 4 hours, and collecting distillate;
step 8, adding ammonia water into the mother liquor in an adjusting tank to adjust the pH value to 1-5.5, then adding the mother liquor into a concentration kettle for concentration, pumping the concentrated solution into an ammonium sulfate crystallization kettle at high temperature for cooling crystallization, and obtaining a crude product of ammonium sulfate through centrifugal separation; returning the separated liquid to a concentration system for concentration;
step 9, separating the cooling liquid in the crystallization kettle by a centrifugal machine to separate a byproduct urea sulfate/ammonium sulfate product, and returning the separated liquid to the concentration kettle for continuous concentration;
step 10: when the concentration kettle is heated to 100 ℃, a large amount of water is evaporated, part of the water is separated into condensed water through the tower, the condensed water is sent to a wastewater treatment system for treatment, and part of the vapor is discharged.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A production process of DL-p-hydroxyphenylhydantoin and urea sulfate/ammonium sulfate thereof is characterized in that: the method comprises the following steps:
step 1, adding phenol, urea and sulfuric acid into a reaction kettle according to a molar ratio, slowly heating, controlling the reaction temperature at 70-95 ℃, and preserving heat for 30 min;
step 2, adding glyoxylic acid into the reaction liquid obtained in the step 1 dropwise, wherein the adding time is controlled to be 2-8 h;
step 3, after the dropwise addition reaction is finished, controlling the temperature in the reaction kettle to be not lower than 85 ℃, and discharging after heat preservation for 2-5 hours;
step 4, putting the materials in the reaction kettle into a prepared filter, performing suction filtration until no water drops visible to naked eyes exist on the surfaces of the materials, and then transferring the materials into a prepared centrifugal machine while the materials are hot;
step 5, putting prepared hot water with the temperature not lower than 85 ℃ into a centrifuge, overflowing the surface of the material, packaging the material after centrifugal washing for 3 times, drying the material until the water content is not higher than 0.5%, and packaging the material into a finished product;
step 6, hydrating and collecting the filtered mother liquor and washing water, transferring part of the filtered mother liquor to the step 1 for use, transferring the rest of the filtered mother liquor to mother liquor for concentration, and recycling urea sulfate/ammonium sulfate products;
step 7, adding the recovered mother liquor into a concentration kettle, controlling the temperature in the concentration kettle to be not higher than 115 ℃, controlling the distillation time according to the actual condition, and then collecting distillate;
step 8, adding ammonia water into the mother liquor in an adjusting tank to adjust the pH value to 1-5.5, then adding the mother liquor into a concentration kettle for concentration, pumping the concentrated solution into an ammonium sulfate crystallization kettle at high temperature for cooling crystallization, and obtaining a crude product of ammonium sulfate through centrifugal separation; returning the separated liquid to a concentration system for concentration;
and step 9: when the concentration kettle is heated to 100 ℃, a large amount of water is evaporated, part of the water is separated into condensed water through the tower, the condensed water is sent to a wastewater treatment system for treatment, and part of the vapor is discharged.
2. The process for producing DL-p-hydroxyphenylhydantoin and urea sulfate/ammonium sulfate thereof according to claim 1, wherein the process comprises the following steps: in the step 1, the mol ratio of the phenol to the urea to the sulfuric acid is (0.5-1.0) to (0.9-1.3).
3. The process for producing DL-p-hydroxyphenylhydantoin and urea sulfate/ammonium sulfate thereof according to claim 2, wherein the process comprises the following steps: the catalyst in the step 1 is sulfuric acid with the concentration of 36-75%.
4. The process for producing DL-p-hydroxyphenylhydantoin and urea sulfate/ammonium sulfate thereof according to claim 3, wherein the process comprises the following steps: in the step 2, the amount of the glyoxylic acid with the dropwise concentration of 40-75 percent is 1.0-1.4 mol.
5. The process for producing DL-p-hydroxyphenylhydantoin and urea sulfate/ammonium sulfate thereof according to claim 4, wherein the process comprises the following steps: and 6, after sulfuric acid is used as a catalyst in the steps 6 to 9, adding ammonia water into the concentrated solution for neutralization.
6. The process for producing DL-p-hydroxyphenylhydantoin and urea sulfate/ammonium sulfate thereof according to claim 1, wherein the process comprises the following steps: in the step 8, the temperature in the concentration kettle is not higher than 115 ℃, and the reaction kettle is cooled to normal temperature after reaction.
7. The process for producing DL-p-hydroxyphenylhydantoin and urea sulfate/ammonium sulfate thereof according to claim 1, wherein the process comprises the following steps: and 9, returning the separation liquid to the concentration kettle to continue concentration treatment, and discharging after the treatment is qualified.
8. The process for producing DL-p-hydroxyphenylhydantoin and urea sulfate/ammonium sulfate thereof according to claim 1, wherein the process comprises the following steps: in the step 6, the content of the urea sulfate is 8-12%, and the content of the ammonium sulfate is 85-95%.
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| CN202010677883.5A CN111807877A (en) | 2020-07-09 | 2020-07-09 | DL-p-hydroxyphenylhydantoin and production process of urea sulfate/ammonium sulfate thereof |
| PCT/CN2020/128662 WO2022007288A1 (en) | 2020-07-09 | 2020-11-13 | Dl-p-hydroxybenzene hydantoin and urea sulfate/ammonium sulfate production process thereof |
| ES202090071A ES2895202R1 (en) | 2020-07-09 | 2020-11-13 | DL-HYDROXYPHENYL HYDANTOIN AND THE CONSEQUENT PROCEDURE FOR THE PRODUCTION OF UREA SULFATE/AMMONIUM SULFATE |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112457256A (en) * | 2020-11-20 | 2021-03-09 | 杭州新桂实业有限公司 | Preparation method of DL-p-hydroxyphenylhydantoin |
| WO2022007288A1 (en) * | 2020-07-09 | 2022-01-13 | 定陶三化药业有限公司 | Dl-p-hydroxybenzene hydantoin and urea sulfate/ammonium sulfate production process thereof |
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2020
- 2020-07-09 CN CN202010677883.5A patent/CN111807877A/en active Pending
- 2020-11-13 ES ES202090071A patent/ES2895202R1/en active Pending
- 2020-11-13 WO PCT/CN2020/128662 patent/WO2022007288A1/en active Application Filing
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| WO2022007288A1 (en) * | 2020-07-09 | 2022-01-13 | 定陶三化药业有限公司 | Dl-p-hydroxybenzene hydantoin and urea sulfate/ammonium sulfate production process thereof |
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| CN112457256B (en) * | 2020-11-20 | 2022-08-05 | 杭州新桂实业有限公司 | Preparation method of DL-p-hydroxyphenylhydantoin |
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| WO2022007288A1 (en) | 2022-01-13 |
| ES2895202A2 (en) | 2022-02-17 |
| ES2895202R1 (en) | 2022-04-12 |
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