CN114605336B - Post-treatment and waste water resource utilization method for synthesizing 4, 6-dihydroxypyrimidine - Google Patents
Post-treatment and waste water resource utilization method for synthesizing 4, 6-dihydroxypyrimidine Download PDFInfo
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- CN114605336B CN114605336B CN202210357909.7A CN202210357909A CN114605336B CN 114605336 B CN114605336 B CN 114605336B CN 202210357909 A CN202210357909 A CN 202210357909A CN 114605336 B CN114605336 B CN 114605336B
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- 239000002351 wastewater Substances 0.000 title claims abstract description 72
- DUFGYCAXVIUXIP-UHFFFAOYSA-N 4,6-dihydroxypyrimidine Chemical compound OC1=CC(O)=NC=N1 DUFGYCAXVIUXIP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 63
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 18
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 108
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 70
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 42
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims abstract description 38
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims abstract description 30
- 235000019254 sodium formate Nutrition 0.000 claims abstract description 30
- 239000004280 Sodium formate Substances 0.000 claims abstract description 28
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 claims abstract description 26
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 23
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 23
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 20
- 238000004064 recycling Methods 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 230000020477 pH reduction Effects 0.000 claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 90
- 239000000047 product Substances 0.000 claims description 30
- 159000000000 sodium salts Chemical class 0.000 claims description 25
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 239000012452 mother liquor Substances 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 150000003863 ammonium salts Chemical group 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- VDPSOCVUAXGQJD-UHFFFAOYSA-N [Na].OC1=CC(=NC=N1)O Chemical compound [Na].OC1=CC(=NC=N1)O VDPSOCVUAXGQJD-UHFFFAOYSA-N 0.000 claims description 7
- -1 ammonium ions Chemical class 0.000 claims description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 7
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 7
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 4
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 235000019253 formic acid Nutrition 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 5
- 239000001099 ammonium carbonate Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 235000012501 ammonium carbonate Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- 239000002535 acidifier Substances 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- LQAQMOIBXDELJX-UHFFFAOYSA-N 2-methoxyprop-2-enoic acid Chemical compound COC(=C)C(O)=O LQAQMOIBXDELJX-UHFFFAOYSA-N 0.000 description 1
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 1
- 229930003776 Vitamin B4 Natural products 0.000 description 1
- 229960000643 adenine Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000008979 vitamin B4 Nutrition 0.000 description 1
- 239000011579 vitamin B4 Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/52—Two oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/16—Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of organic chemical industry, and relates to a post-treatment method for synthesizing 4, 6-dihydroxypyrimidine and a method for recycling waste water thereof, which comprises the following steps: after the reaction for synthesizing 4, 6-dihydroxypyrimidine is finished, adding water for dissolution and sulfuric acid acidification to obtain a 4, 6-dihydroxypyrimidine product and waste water containing sodium sulfate and sodium formate; adding ammonium ion donor into the wastewater containing sodium sulfate and sodium formate, cooling and crystallizing to obtain sodium sulfate decahydrate and wastewater containing ammonium formate; distilling the wastewater containing ammonium formate to obtain ammonium formate and water; and (5) heating and decomposing ammonium formate to obtain formamide. The three wastes in the whole process are less, all resources of the whole system are fully utilized, the treatment energy consumption is low, the clean production of the 4, 6-dihydroxypyrimidine is realized, sodium sulfate and sodium formate in the wastewater are recycled, the sodium sulfate decahydrate and the formamide are obtained, the purity and the yield are both high, and the economic benefit is improved.
Description
Technical Field
The invention belongs to the technical field of organic chemical industry, and relates to a post-treatment and wastewater recycling method for synthesizing 4, 6-dihydroxypyrimidine.
Background
4, 6-Dihydroxypyrimidine (DHP) is widely used as a fine chemical raw material or an organic synthesis intermediate in the preparation of medicines, pesticides, bactericides and the like, and can be used for producing the intermediates of sulfamoxidec, vitamin B4, antitumor drugs, auxiliary drugs and the like in the pharmaceutical industry. In addition, the method can be also used for synthesizing intermediates of methoxy acrylic acid ester bactericides and the like.
At present, 4, 6-dihydroxypyrimidine is generally produced by taking malonate (mainly dimethyl malonate or diethyl malonate) and formamide as raw materials, reacting in sodium alkoxide (sodium methoxide or sodium ethoxide) solution to generate 4, 6-dihydroxypyrimidine sodium salt, dissolving the sodium salt in water, and acidifying with hydrochloric acid to obtain a 4, 6-dihydroxypyrimidine product. The above process has several disadvantages: the waste water amount is relatively large, about 10 tons of waste water is generated per ton of products, and the waste water contains sodium chloride and sodium formate, so that the separation is difficult, and the full utilization of the sodium chloride and the sodium formate cannot be realized.
CN111689908A discloses a post-treatment method for synthesizing 4, 6-dihydroxypyrimidine, which comprises the steps of firstly removing solvent of a system after the synthesis reaction is finished, then adding water for dissolution, cooling for crystallization, and separating out sodium salt of 4, 6-dihydroxypyrimidine and then carrying out solid-liquid separation; dissolving the solid in water, and then acidifying with hydrochloric acid to obtain a product 4, 6-dihydroxypyrimidine; acidifying the liquid with formic acid, separating solid and liquid again to obtain the product 4, 6-dihydroxypyrimidine, and concentrating the solid and liquid separated liquid after two times of acidification to obtain the products sodium chloride and sodium formate respectively. Although the method can separate sodium formate and sodium chloride, the amount of the sodium 4, 6-dihydroxypyrimidine salt separated out by cooling crystallization is small, the rest sodium 4, 6-dihydroxypyrimidine salt is still dissolved in water, expensive formic acid is needed to neutralize the sodium salt, a crude 4, 6-dihydroxypyrimidine product and sodium formate are obtained, the crude 4, 6-dihydroxypyrimidine product needs to be returned for refining again, the recycling frequency is more, the efficiency is low, and the treatment cost is high.
CN112979561a discloses a post-treatment method for synthesizing 4, 6-dihydroxypyrimidine, which comprises the steps of adding water for dissolution after the synthesis reaction is finished, adding active carbon for decolorization, acidizing by hydrochloric acid, and carrying out solid-liquid separation to obtain 4, 6-dihydroxypyrimidine and mother liquor (the 4, 6-dihydroxypyrimidine mother liquor contains complex components including water, methanol, hydrochloric acid, sodium chloride, formic acid and the like). Adding hydrochloric acid into the mother solution, heating, and performing esterification reaction to obtain methyl formate. Introducing ammonia gas into methyl formate for amination reaction to obtain formamide. And (5) evaporating methanol from the residual mother liquor, and adding alkali to dehydrate to obtain sodium chloride. The method can recycle formic acid in the wastewater, namely, methyl formate is generated by formate esterification, and formamide is generated by methyl formate amination, but the whole process has more complicated steps, the esterification reaction effect of formic acid and methanol in aqueous solution is poor, and the conversion rate is low. The distilled methyl formate takes away part of water, methanol and formic acid, and needs to be rectified again. Methyl formate obtained by rectification is required to react with ammonia again to generate formamide and methanol, and then the product formamide is obtained by rectification again. The whole process flow has complicated steps, low esterification reaction efficiency and higher cost for recovering the formamide.
CN106397337a discloses a post-treatment method for synthesizing 4, 6-dihydroxypyrimidine, which comprises the steps of cooling after the reaction is finished, carrying out negative pressure suction filtration, removing a part of methanol from filtrate, and recycling alkali; dissolving the filter cake in water, acidifying, crystallizing, carrying out negative pressure suction filtration and drying to obtain a product; and (3) decoloring the acidified mother liquor, concentrating under negative pressure, cooling, crystallizing, performing suction filtration under negative pressure to obtain a recovered product, and neutralizing and dehydrating filtrate alkali to obtain byproduct salt. The method can recycle a part of alkali, but the materials are quite viscous after the reaction is finished, the negative pressure suction filtration is also quite difficult in actual production, and sodium formate and formic acid generated in the reaction process are not effectively treated in the whole process. In the specific embodiment, the alkali is continuously recovered and reused for 3 times, the total yield can reach 90%, and the energy consumption is larger in the process of concentrating and reusing the alkali.
Disclosure of Invention
Problems to be solved by the invention
The invention aims to provide a method for post-treatment of synthetic 4, 6-dihydroxypyrimidine and resource utilization of waste water thereof, which has the advantages of less generation of three wastes, high resource utilization efficiency, simple steps and low treatment energy consumption.
Solution for solving the problem
In order to solve the problems, the invention provides a post-treatment method for synthesizing 4, 6-dihydroxypyrimidine and a method for recycling waste water thereof, which comprises the following steps:
step a: synthesizing 4, 6-dihydroxypyrimidine sodium salt by taking dimethyl malonate, formamide and sodium methoxide as raw materials, and after the reaction is finished: 1) Cooling, adding water to dissolve precipitate, distilling to obtain sodium salt mother liquor and aqueous methanol; or 2) distilling to obtain sodium salt solid and anhydrous methanol/hydrous methanol, and dissolving the sodium salt solid in water to obtain sodium salt mother liquor;
step b: acidifying the sodium salt mother liquor obtained in the step a by using sulfuric acid solution, carrying out solid-liquid separation to obtain a crude 4, 6-dihydroxypyrimidine product and waste water containing sodium sulfate and sodium formate, and carrying out post-treatment on the crude 4, 6-dihydroxypyrimidine product to obtain a 4, 6-dihydroxypyrimidine product;
step c: adding an ammonium ion donor into the wastewater obtained in the step b, cooling and crystallizing, and carrying out solid-liquid separation to obtain a sodium sulfate decahydrate crude product and wastewater containing ammonium formate;
2 HCOONa+(NH 4 ) 2 SO 4 →Na 2 SO 4 +2 HCOONH 4
step d: and c), distilling the wastewater containing ammonium formate obtained in the step c to obtain ammonium formate and water, heating and decomposing the ammonium formate to obtain a mixture of formamide and water, and rectifying the obtained mixture of formamide and water to obtain formamide and water.
HCOONH 4 →HCONH 2 +H 2 O
Preferably, in the step a, the sodium methoxide is a methanol solution of sodium methoxide.
Preferably, step a further comprises the steps of: and d, rectifying the aqueous methanol to obtain anhydrous methanol and water, and sleeving the obtained anhydrous methanol into the step a for recycling.
Preferably, in the step b, the post-treatment is water addition and drying.
Preferably, step c further comprises the steps of: and (3) washing the crude sodium sulfate decahydrate product with water, and drying to obtain a sodium sulfate decahydrate product.
Preferably, in step d, the resulting formamide is recycled to step a.
Preferably, in step a and/or step d, the resulting water jacket is reused in at least one of step a, step b and step c.
Preferably, the reaction temperature of the reaction in step a is from 60 to 65 ℃.
Preferably, the target temperature of the temperature reduction in step a is 0-25 ℃.
More preferably, the target temperature of the cooling in step a is 10-15 ℃.
Preferably, the distillation in step a is distillation under negative pressure.
More preferably, the distillation in step a is a distillation under negative pressure with a vacuum of-0.07 to-0.10 MPa.
Preferably, the amount of water used in step a is 3-5 times the theoretical yield of the sodium salt of 4, 6-dihydroxypyrimidine.
Preferably, the concentration of the sulfuric acid solution in step b is 20wt% to 40wt%.
Preferably, the amount of sulfuric acid in the sulfuric acid solution in step b is 1.2-1.5 times the theoretical number of moles of the sodium salt of 4, 6-dihydroxypyrimidine.
Preferably, the target pH of the acidification in step b is between 3.0 and 4.0.
More preferably, the target pH of the acidification in step b is between 3.0 and 3.5.
Preferably, the temperature of the acidification in step b is between 25 and 40 ℃.
Preferably, the acidification in step b is carried out simultaneously with stirring for a period of 1-3 hours.
Preferably, the ammonium ion donor in the step c is at least one of ammonium salt, ammonia water and ammonia gas.
More preferably, the ammonium salt is at least one of ammonium sulfate, ammonium bisulfate, ammonium carbonate and ammonium bicarbonate.
Further preferably, the ammonium salt is ammonium sulfate.
More preferably, the ammonium ion donor is aqueous ammonia.
Preferably, the concentration of the ammonia water is 20wt% to 30wt%.
More preferably, the concentration of the ammonia water is 22wt% to 38wt%.
Preferably, in step c, a sulfate ion donor is added to the wastewater.
Preferably, the sulfate ion donor is preferably sulfuric acid.
Preferably, the amount of the ammonium ion donor or the amount of the ammonium ion donor and the sulfate ion donor in step c satisfies the following condition: the mole number of sulfate ions in the wastewater containing sodium sulfate and sodium formate is equal to half of the mole number of sodium ions, and the mole number of ammonium ions is larger than the mole number of formate ions.
More preferably, the amount of the ammonium ion donor or the amount of the ammonium ion donor and the sulfate ion donor in step c further satisfies the following condition: the pH value of the wastewater containing sodium sulfate and sodium formate is 6.5-7.5.
Preferably, the target temperature of the temperature reduction in the step c is-5-10 ℃.
Preferably, the time of crystallization in step c is 0.5-3.0h.
More preferably, the time of crystallization in step c is 1.5-3.0h.
Preferably, the solid-liquid separation in step b and step c is each independently centrifugation or filtration.
Preferably, the drying in step b and step c is each independently heat drying (e.g. oven drying) or vacuum drying.
Preferably, the target temperature for heating in step d is 120-150 ℃.
More preferably, the target temperature for heating in step d is 120-135 ℃.
ADVANTAGEOUS EFFECTS OF INVENTION
By adopting the technical scheme, the invention has the beneficial effects that:
(1) The method uses sulfuric acid as an acidifying reagent to obtain the 4, 6-dihydroxypyrimidine and sodium sulfate decahydrate, and the sulfuric acid has good acidifying effect, and can obtain the 4, 6-dihydroxypyrimidine with the purity of more than 99 percent. Compared with hydrochloric acid as an acidifying agent, sodium sulfate produced by sulfuric acid is easier to purify than sodium chloride produced by hydrochloric acid. Sulfuric acid is also cheaper than formic acid as an acidifying agent.
(2) Ammonium ion donor is added into the wastewater containing sodium sulfate and sodium formate, the temperature is reduced, sodium sulfate is crystallized to obtain sodium sulfate decahydrate, a large amount of water in the wastewater is taken away, the wastewater amount is reduced, and the energy consumption is greatly reduced. Sodium sulfate decahydrate has purity over 99% and yield of 90-95%.
(3) In the reaction system of the step a, the dosage of formamide is excessive, the excessive formamide is favorable for reaction, and the excessive formamide generates ammonium formate when meeting water in an alkaline environment; the generated ammonium formate and the ammonium formate obtained by converting sodium formate in the step c are heated and decomposed in the step d to generate formamide, the purity of the formamide is more than 98 percent, and the formamide can be reused for synthesizing the 4, 6-dihydroxypyrimidine in the step a.
(4) And (c) partially sleeving water distilled from the step a and the step d into the step a for dissolving the reaction product, partially sleeving the water into the step b for washing the crude 4, 6-dihydroxypyrimidine product, and partially sleeving the water into the step c for washing the crude sodium sulfate decahydrate product, so that most of the water is recycled, and resources are saved.
The post-treatment method for synthesizing the 4, 6-dihydroxypyrimidine provided by the invention makes full use of all resources, takes away a large amount of water in the wastewater in the sodium sulfate crystallization process, solves the problem of large wastewater production amount, and greatly reduces energy consumption. The byproduct formamide can recycle sodium formate in the wastewater, and the excessive formamide is recovered, so that the obtained formamide can be synthesized into the 4, 6-dihydroxypyrimidine again. The three wastes in the whole process are less, all resources of the whole system are fully utilized, the treatment energy consumption is low, the clean production of 4, 6-dihydroxypyrimidine is realized, sodium sulfate and sodium formate in the wastewater are recycled, sodium sulfate decahydrate and formamide with high purity and yield are obtained, and the economic benefit is improved.
Drawings
Fig. 1 is a process flow diagram of example 1.
Detailed Description
The invention provides a post-treatment method for synthesizing 4, 6-dihydroxypyrimidine and a method for recycling waste water thereof, which comprises the following four steps:
step a: synthesizing 4, 6-dihydroxypyrimidine sodium salt by taking dimethyl malonate, formamide and sodium methoxide as raw materials, and after the reaction is finished: 1) Cooling, adding water to dissolve precipitate, distilling to obtain sodium salt mother liquor and aqueous methanol; or 2) distilling to obtain sodium salt solid and anhydrous methanol/hydrous methanol, and dissolving the sodium salt solid in water to obtain sodium salt mother liquor;
step b: acidifying the sodium salt mother liquor obtained in the step a by using sulfuric acid solution, carrying out solid-liquid separation to obtain a crude 4, 6-dihydroxypyrimidine product and waste water containing sodium sulfate and sodium formate, and carrying out post-treatment on the crude 4, 6-dihydroxypyrimidine product to obtain a 4, 6-dihydroxypyrimidine product;
step c: adding an ammonium ion donor into the wastewater obtained in the step b, cooling and crystallizing, and carrying out solid-liquid separation to obtain a sodium sulfate decahydrate crude product and wastewater containing ammonium formate;
2 HCOONa+(NH 4 ) 2 SO 4 →Na 2 SO 4 +2 HCOONH 4
step d: and c), distilling the wastewater containing ammonium formate obtained in the step c to obtain ammonium formate and water, heating and decomposing the ammonium formate to obtain a mixture of formamide and water, and rectifying the obtained mixture of formamide and water to obtain formamide and water.
HCOONH 4 →HCONH 2 +H 2 O
In one embodiment, in step a, the sodium methoxide is a methanolic solution of sodium methoxide.
In one embodiment, step a further comprises the steps of: and d, rectifying the aqueous methanol to obtain anhydrous methanol and water, and sleeving the obtained anhydrous methanol into the step a for recycling.
In one embodiment, in step b, the post-treatment is water addition and drying.
In one embodiment, step c further comprises the steps of: and (3) washing the crude sodium sulfate decahydrate product with water, and drying to obtain a sodium sulfate decahydrate product.
In one embodiment, in step d, the resulting formamide is jacketed to step a for reuse.
In one embodiment, in step a and/or step d, the resulting water jacket is reused in at least one of step a, step b and step c.
In one embodiment, the reaction temperature of the reaction described in step a is in the range of 60 to 65 ℃.
In one embodiment, the target temperature of the cooling in step a is between 0 and 25 ℃.
In a preferred embodiment, the target temperature of the cooling in step a is between 10 and 15 ℃.
In one embodiment, the distillation in step a is distillation under negative pressure.
In a preferred embodiment, the distillation in step a is a distillation under negative pressure at a vacuum level of-0.07 to-0.10 MPa.
In one embodiment, the amount of water used in step a is 3 to 5 times the theoretical yield of the sodium salt of 4, 6-dihydroxypyrimidine.
In one embodiment, the concentration of the sulfuric acid solution in step b is 20wt% to 40wt%.
In one embodiment, the amount of sulfuric acid in the sulfuric acid solution in step b is 1.2 to 1.5 times the theoretical moles of the sodium salt of 4, 6-dihydroxypyrimidine.
In one embodiment, the target pH of the acidification in step b is between 3.0 and 4.0.
In a preferred embodiment, the target pH of the acidification in step b is between 3.0 and 3.5.
In one embodiment, the temperature of the acidification in step b is between 25 and 40 ℃.
In one embodiment, the acidification in step b is performed with stirring for a period of 1h to 3h.
In one embodiment, the ammonium ion donor in step c is at least one of ammonium salt, ammonia water and ammonia gas.
In a preferred embodiment, the ammonium salt is at least one of ammonium sulfate, ammonium bisulfate, ammonium carbonate and ammonium bicarbonate, preferably ammonium sulfate.
In one embodiment, the ammonium ion donor is aqueous ammonia having a concentration of 20wt% to 30wt%, preferably 22wt% to 38wt%.
In one embodiment, in step c, a sulfate ion donor is added to the wastewater.
In one embodiment, the sulfate ion donor is sulfuric acid.
In one embodiment, the amount of the ammonium ion donor or the amount of the ammonium ion donor and the sulfate ion donor in step c satisfies the following condition: the mole number of sulfate ions in the wastewater containing sodium sulfate and sodium formate is equal to half of the mole number of sodium ions, and the mole number of ammonium ions is larger than the mole number of formate ions.
In a preferred embodiment, the amount of the ammonium ion donor or the amount of the ammonium ion donor and the sulfate ion donor in step c also satisfies the following conditions in order to make the sodium sulfate decahydrate more susceptible to crystallization: the pH value of the wastewater containing sodium sulfate and sodium formate is 6.5-7.5.
In one embodiment, the target temperature for the cooling in step c is from-5 to 10 ℃.
In one embodiment, the time of crystallization in step c is from 0.5 to 3.0 hours.
In a preferred embodiment, the time of crystallization in step c is from 1.5 to 3.0h.
In one embodiment, the solid-liquid separation in step b and step c is each independently centrifugation or filtration.
In one embodiment, the drying in step b and step c is each independently heat drying (e.g., oven drying) or vacuum drying.
In one embodiment, the target temperature for heating in step d is 120-150 ℃.
In a preferred embodiment, the target temperature for heating in step d is 120-135 ℃.
The technical scheme of the invention will be further described below with reference to specific examples. It should be understood that the following examples are illustrative and not intended to limit the scope of the present invention. Unless otherwise indicated, the instruments, materials, reagents, and the like used in the following examples are all available by conventional commercial means.
Example 1
Step a: 5942.2kg of 30wt% sodium methoxide methanol solution is put into a reaction kettle, the temperature is raised to 60-65 ℃, then 1080.9kg of mixture of formamide and 1321.1kg of dimethyl malonate is dripped, and after the dripping is finished, the reaction is carried out for 2 hours under heat preservation and stirring. After the reaction is finished, the temperature is reduced to 10-15 ℃, and 5043.7kg of water is added. Distilling to remove methanol under negative pressure of-0.07 to-0.10 MPa to obtain sodium salt mother liquor. The water-containing methanol is continuously rectified to obtain anhydrous methanol, and the anhydrous methanol can be used for synthesizing sodium methoxide methanol solution.
Step b: acidifying the sodium salt mother solution obtained in the step a by 4704.5kg of 25wt% sulfuric acid at the acidification temperature of 25-30 ℃ until the pH value is 3.0-3.5, centrifuging to obtain a crude 4, 6-dihydroxypyrimidine product and waste water containing sodium sulfate and sodium formate, washing the crude 4, 6-dihydroxypyrimidine product by adding 1681.4kg of water, and drying to obtain 1031.2kg of the product 4, 6-dihydroxypyrimidine with the content of 99.1% and the yield of 92.0%.
Yield of 4, 6-dihydroxypyrimidine based on dimethyl malonate = actual weight of 4, 6-dihydroxypyrimidine product/theoretical weight of 4, 6-dihydroxypyrimidine x 100%.
The waste water containing sodium sulfate and sodium formate comprises the following components: 15.2wt% sodium sulfate, 6.1wt% sodium formate, 0.36wt%4, 6-dihydroxypyrimidine, 0.12wt% organic impurities.
Step c: 594.0kg of ammonium sulfate is added into the obtained wastewater containing sodium sulfate and sodium formate, and 27wt% of ammonia water is added after stirring and dissolving to adjust the pH value to 6.5-7.5. Maintaining the temperature at 30-35 ℃, stirring for 1h, and then cooling. Gradually cooling to-5 ℃, maintaining the temperature at-5 ℃ and continuously stirring for 0.5h, and centrifuging to obtain wastewater containing ammonium formate and sodium sulfate decahydrate. The sodium sulfate decahydrate is washed by cold water to obtain 4969.2kg of sodium sulfate decahydrate with the content of 99.3 percent and the yield of 93.5 percent.
Step d: and c, distilling the wastewater containing ammonium formate obtained in the step c to remove water to obtain ammonium formate solid, heating to 130-135 ℃, gradually melting the ammonium formate, slowly heating and decomposing the ammonium formate to generate formamide and water, and rectifying the aqueous formamide again to obtain 568.4kg of formamide with the content of 98.3% and the yield of 86.2%. The resulting formamide can be recycled by passing it to step a and the resulting water can be passed to step a and step b.
A flow chart of the above process is shown in fig. 1.
Example 2
Step a: the procedure was the same as in example 1.
Step b: the procedure is the same as in example 1, with the same waste water composition.
Step c: adding 441kg of concentrated sulfuric acid into the wastewater containing sodium sulfate and sodium formate, introducing ammonia gas, and adjusting the pH value to 6.5-7.5. After stirring for 1h at 30-35 ℃, cooling, gradually cooling to-5 ℃, continuously stirring for 0.5h at-5 ℃, centrifuging, separating solid from liquid to obtain ammonium formate-containing wastewater and sodium sulfate decahydrate, washing the sodium sulfate decahydrate with cold water to obtain 4926.7kg of sodium sulfate decahydrate, wherein the content is 99.2%, and the yield is 92.7%.
Step d: and distilling the ammonium formate-containing wastewater to remove water to obtain ammonium formate solid, heating to 130-135 ℃, gradually melting ammonium formate, slowly heating to decompose to generate formamide and water, and rectifying the aqueous formamide again to obtain 564.5kg of formamide with the content of 98.1% and the yield of 85.6%. The resulting formamide can be recycled by passing it to step a and the resulting water can be passed to step a and step b.
Example 3
Step a: the procedure was the same as in example 1.
Step b: the procedure is the same as in example 1, with the same waste water composition.
Step c: the procedure was the same as in example 2.
Step d: and distilling the ammonium formate-containing wastewater to remove water to obtain ammonium formate solid, heating to 120-125 ℃, gradually melting ammonium formate, slowly heating to decompose to generate formamide and water, and rectifying the aqueous formamide again to obtain 532.1kg of formamide with the content of 98.5% and the yield of 80.7%. The resulting formamide can be recycled by passing it to step a and the resulting water can be passed to step a and step b.
Example 4
Step a: the procedure was the same as in example 1.
Step b: the procedure is the same as in example 1, with the same waste water composition.
Step c: 441kg of concentrated sulfuric acid and 480.45kg of ammonium carbonate are added into the wastewater containing sodium sulfate and sodium formate. After stirring for 1h at 30-35 ℃, cooling, gradually cooling to-5 ℃, continuously stirring for 0.5h at-5 ℃, centrifuging, separating solid from liquid to obtain ammonium formate-containing wastewater and sodium sulfate decahydrate, washing the sodium sulfate decahydrate with cold water to obtain 4910.8kg of sodium sulfate decahydrate, wherein the content is 99.1%, and the yield is 92.4%.
Step d: and distilling the ammonium formate-containing wastewater to remove water to obtain ammonium formate solid, heating to 130-135 ℃, gradually melting the ammonium formate, slowly heating to decompose to generate formamide and water, and rectifying the aqueous formamide again to obtain 548.6kg of formamide with the content of 98.4% and the yield of 83.2%. The resulting formamide can be recycled by passing it to step a and the resulting water can be passed to step a and step b.
Example 5
Step a: the procedure was the same as in example 1.
Step b: the procedure is the same as in example 1, with the same waste water composition.
Step c: the procedure was the same as in example 4.
Step d: and distilling the ammonium formate-containing wastewater to remove water to obtain ammonium formate solid, heating to 120-125 ℃, gradually melting ammonium formate, slowly heating to decompose to generate formamide and water, and rectifying the aqueous formamide again to obtain 521.4kg of formamide with the content of 98.3% and the yield of 79.3%. The resulting formamide can be recycled by passing it to step a and the resulting water can be passed to step a and step b.
Claims (12)
1. A post-treatment method for synthesizing 4, 6-dihydroxypyrimidine and a method for recycling waste water thereof comprise the following steps:
step a: synthesizing 4, 6-dihydroxypyrimidine sodium salt by taking dimethyl malonate, formamide and sodium methoxide as raw materials, and after the reaction is finished: 1) Cooling, adding water to dissolve precipitate, distilling to obtain sodium salt mother liquor and aqueous methanol; or 2) distilling to obtain sodium salt solid and anhydrous methanol or hydrous methanol, and dissolving the sodium salt solid in water to obtain sodium salt mother liquor;
step b: acidifying the sodium salt mother liquor obtained in the step a by using sulfuric acid solution, carrying out solid-liquid separation to obtain a crude 4, 6-dihydroxypyrimidine product and waste water containing sodium sulfate and sodium formate, and carrying out post-treatment on the crude 4, 6-dihydroxypyrimidine product to obtain a 4, 6-dihydroxypyrimidine product;
step c: adding an ammonium ion donor into the wastewater obtained in the step b, cooling and crystallizing, and carrying out solid-liquid separation to obtain a sodium sulfate decahydrate crude product and wastewater containing ammonium formate;
step d: c, distilling the wastewater containing ammonium formate obtained in the step c to obtain ammonium formate and water, heating and decomposing the ammonium formate to obtain a mixture of formamide and water, and rectifying the obtained mixture of formamide and water to obtain formamide and water;
wherein the dosage of sulfuric acid in the sulfuric acid solution in the step b is 1.2-1.5 times of the theoretical mole number of the 4, 6-dihydroxypyrimidine sodium salt;
in the step c, the ammonium ion donor is ammonium salt; the ammonium salt is at least one of ammonium sulfate and ammonium bisulfate;
the amount of ammonium ion donor in step c satisfies the following conditions: making the mole number of sulfate ions in the wastewater containing sodium sulfate and sodium formate equal to half of the mole number of sodium ions, and making the mole number of ammonium ions larger than the mole number of formate ions;
the amount of ammonium ion donor in step c also satisfies the following conditions: the pH value of the wastewater containing sodium sulfate and sodium formate is 6.5-7.5;
in step d, the formamide obtained is sleeved in step a for reuse.
2. The method for post-treatment of synthetic 4, 6-dihydroxypyrimidine and recycling of waste water thereof according to claim 1, wherein the method is characterized by comprising the following steps:
in the step a, the sodium methoxide is a methanol solution of sodium methoxide;
step a further comprises the steps of: rectifying the aqueous methanol to obtain anhydrous methanol and water;
in the step a, the obtained anhydrous methanol is sleeved in the step a for reuse;
step c further comprises the steps of: washing the sodium sulfate decahydrate crude product with water, and drying to obtain a sodium sulfate decahydrate product;
in step a and/or step d, the water jacket obtained is reused in at least one of step a, step b and step c.
3. The method for post-treatment of synthetic 4, 6-dihydroxypyrimidine and recycling of waste water thereof according to claim 1 or 2, wherein the method is characterized by comprising the following steps:
the acidification temperature in step b is 25-40 ℃.
4. The method for post-treatment of synthetic 4, 6-dihydroxypyrimidine and recycling of waste water thereof according to claim 1 or 2, wherein the method is characterized by comprising the following steps:
the target temperature for cooling in the step a is 0-25 ℃;
the water is used in step a in an amount of 3 to 5 times the theoretical yield of the sodium salt of 4, 6-dihydroxypyrimidine.
5. The method for post-treatment of synthetic 4, 6-dihydroxypyrimidine and recycling of waste water thereof according to claim 4, wherein the method is characterized by comprising the following steps:
the target temperature of the temperature reduction in the step a is 10-15 ℃.
6. The method for post-treatment of synthetic 4, 6-dihydroxypyrimidine and recycling of waste water thereof according to claim 1 or 2, wherein the method is characterized by comprising the following steps:
the concentration of the sulfuric acid solution in the step b is 20wt percent to 40wt percent;
the target pH of the acidification in step b is 3.0-4.0.
7. The method for post-treatment of synthetic 4, 6-dihydroxypyrimidine and recycling of waste water thereof according to claim 6, wherein the method is characterized by comprising the following steps:
the target pH of the acidification in step b is 3.0-3.5.
8. The method for post-treatment of synthetic 4, 6-dihydroxypyrimidine and recycling of waste water thereof according to claim 1 or 2, wherein the method is characterized by comprising the following steps:
the ammonium salt is ammonium sulfate.
9. The method for post-treatment of synthetic 4, 6-dihydroxypyrimidine and recycling of waste water thereof according to claim 1 or 2, wherein the method is characterized by comprising the following steps:
the target temperature for cooling in the step c is-5-10 ℃;
the time of crystallization in step c is 0.5-3.0h.
10. The method for post-treatment of synthetic 4, 6-dihydroxypyrimidine and recycling of waste water thereof according to claim 9, wherein the method is characterized by comprising the following steps:
the time for crystallization in step c is 1.5-3.0h.
11. The method for post-treatment of synthetic 4, 6-dihydroxypyrimidine and recycling of waste water thereof according to claim 1 or 2, wherein the method is characterized by comprising the following steps:
the target temperature for heating in step d is 120-150 ℃.
12. The method for post-treatment of synthetic 4, 6-dihydroxypyrimidine and recycling of waste water thereof according to claim 11, wherein the method is characterized by:
the target temperature for heating in step d is 120-135 ℃.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5847139A (en) * | 1996-07-03 | 1998-12-08 | Huels Aktiengesellschaft | Process for the preparation of 4, 6- dihydroxypyrimidine |
| CN102115382A (en) * | 2010-12-29 | 2011-07-06 | 王莉 | Method for producing co-product of pentaerythritol as well as ammonium formate and sodium sulfate by waste liquid generated by preparation of pentaerythritol |
| CN105601499A (en) * | 2016-01-04 | 2016-05-25 | 北京科技大学 | Method for separating sodium acetate solution containing sodium sulfate |
| CN106397337A (en) * | 2015-07-27 | 2017-02-15 | 江苏扬农化工集团有限公司 | Post-treatment method for 4,6-dihydroxypyrimidine synthesis |
| CN111689908A (en) * | 2020-07-16 | 2020-09-22 | 石家庄杰克化工有限公司 | Post-treatment method for synthesizing 4, 6-dihydroxypyrimidine |
| CN112979561A (en) * | 2021-04-29 | 2021-06-18 | 潍坊滨海石油化工有限公司 | Post-treatment method for synthesizing 4, 6-dihydroxypyrimidine |
| CN113444050A (en) * | 2021-08-30 | 2021-09-28 | 潍坊滨海石油化工有限公司 | Production method of 4, 6-dihydroxypyrimidine |
| CN113527214A (en) * | 2021-09-10 | 2021-10-22 | 潍坊滨海石油化工有限公司 | Method for preparing 4, 6-dihydroxypyrimidine |
-
2022
- 2022-04-06 CN CN202210357909.7A patent/CN114605336B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5847139A (en) * | 1996-07-03 | 1998-12-08 | Huels Aktiengesellschaft | Process for the preparation of 4, 6- dihydroxypyrimidine |
| CN102115382A (en) * | 2010-12-29 | 2011-07-06 | 王莉 | Method for producing co-product of pentaerythritol as well as ammonium formate and sodium sulfate by waste liquid generated by preparation of pentaerythritol |
| CN106397337A (en) * | 2015-07-27 | 2017-02-15 | 江苏扬农化工集团有限公司 | Post-treatment method for 4,6-dihydroxypyrimidine synthesis |
| CN105601499A (en) * | 2016-01-04 | 2016-05-25 | 北京科技大学 | Method for separating sodium acetate solution containing sodium sulfate |
| CN111689908A (en) * | 2020-07-16 | 2020-09-22 | 石家庄杰克化工有限公司 | Post-treatment method for synthesizing 4, 6-dihydroxypyrimidine |
| CN112979561A (en) * | 2021-04-29 | 2021-06-18 | 潍坊滨海石油化工有限公司 | Post-treatment method for synthesizing 4, 6-dihydroxypyrimidine |
| CN113444050A (en) * | 2021-08-30 | 2021-09-28 | 潍坊滨海石油化工有限公司 | Production method of 4, 6-dihydroxypyrimidine |
| CN113527214A (en) * | 2021-09-10 | 2021-10-22 | 潍坊滨海石油化工有限公司 | Method for preparing 4, 6-dihydroxypyrimidine |
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