CN114605336A - Method for post-treatment of synthesis of 4, 6-dihydroxypyrimidine and resource utilization of wastewater thereof - Google Patents
Method for post-treatment of synthesis of 4, 6-dihydroxypyrimidine and resource utilization of wastewater thereof Download PDFInfo
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- CN114605336A CN114605336A CN202210357909.7A CN202210357909A CN114605336A CN 114605336 A CN114605336 A CN 114605336A CN 202210357909 A CN202210357909 A CN 202210357909A CN 114605336 A CN114605336 A CN 114605336A
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- dihydroxypyrimidine
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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 59
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000003786 synthesis reaction Methods 0.000 title claims description 6
- 230000015572 biosynthetic process Effects 0.000 title claims description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 71
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 44
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims abstract description 40
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims abstract description 31
- 235000019254 sodium formate Nutrition 0.000 claims abstract description 31
- 239000004280 Sodium formate Substances 0.000 claims abstract description 29
- 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 25
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 25
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004064 recycling Methods 0.000 claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 93
- 159000000000 sodium salts Chemical class 0.000 claims description 24
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 16
- 239000012452 mother liquor Substances 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 230000020477 pH reduction Effects 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000012043 crude product Substances 0.000 claims description 10
- VDPSOCVUAXGQJD-UHFFFAOYSA-N [Na].OC1=CC(=NC=N1)O Chemical compound [Na].OC1=CC(=NC=N1)O VDPSOCVUAXGQJD-UHFFFAOYSA-N 0.000 claims description 9
- 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- -1 ammonium ions Chemical class 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- 150000003863 ammonium salts Chemical class 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
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 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
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 2
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000004519 manufacturing process 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 18
- 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 14
- 239000000243 solution Substances 0.000 description 11
- 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 9
- 235000019253 formic acid Nutrition 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000011780 sodium chloride Substances 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- 239000002535 acidifier Substances 0.000 description 2
- 230000009286 beneficial effect Effects 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
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 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
- 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
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 1
- 229930182692 Strobilurin Natural products 0.000 description 1
- 229930003776 Vitamin B4 Natural products 0.000 description 1
- 229960000643 adenine Drugs 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 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
- 239000003899 bactericide agent Substances 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
- 238000004090 dissolution Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000002360 preparation method 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
- 239000011734 sodium Substances 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
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 235000008979 vitamin B4 Nutrition 0.000 description 1
- 239000011579 vitamin B4 Substances 0.000 description 1
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- 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 wastewater thereof, which comprises the following steps: after the reaction for synthesizing the 4, 6-dihydroxypyrimidine is finished, adding water for dissolving, and acidifying with sulfuric acid to obtain a 4, 6-dihydroxypyrimidine product and wastewater containing sodium sulfate and sodium formate; adding ammonium ion donor into the wastewater containing sodium sulfate and sodium formate, and 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 heating and decomposing the ammonium formate to obtain the formamide. The three wastes are less generated in the whole process, 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, the sodium sulfate and the sodium formate in the wastewater are recovered to obtain the sodium sulfate decahydrate and the formamide, the purity and the yield are 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 method for synthesizing 4, 6-dihydroxypyrimidine and a method for recycling wastewater thereof.
Background
4, 6-Dihydroxypyrimidine (DHP) is generally used as a fine chemical raw material or an organic synthesis intermediate, is widely applied to the preparation of medicines, pesticides, bactericides and the like, and can be used for producing sulfonamides, such as sulfamosine, vitamin B4, antitumor drugs, auxiliary drug intermediates and the like in the pharmaceutical industry. In addition, the method can also be used for synthesizing intermediates of strobilurin fungicides and the like.
At present, malonate (mainly dimethyl malonate or diethyl malonate) and formamide are generally used as raw materials in industrial production of 4, 6-dihydroxypyrimidine, sodium alkoxide (sodium methoxide or sodium ethoxide) is reacted to generate 4, 6-dihydroxypyrimidine sodium salt, and the 4, 6-dihydroxypyrimidine product is obtained by adding water to dissolve the sodium salt and then acidifying the sodium salt with hydrochloric acid. The above process has several disadvantages as follows: the waste water amount is relatively large, about 10 tons of waste water is generated in each 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 removing a solvent of a system after the synthesis reaction is finished, adding water for dissolving, cooling for crystallization, separating out 4, 6-dihydroxypyrimidine sodium salt, and then carrying out solid-liquid separation; dissolving the solid in water, and acidifying with hydrochloric acid to obtain 4, 6-dihydroxypyrimidine; acidifying the liquid with formic acid, carrying out solid-liquid separation again to obtain the product 4, 6-dihydroxypyrimidine, and respectively concentrating the liquid obtained after the solid-liquid separation after the acidification for two times to obtain the products sodium chloride and sodium formate. Although the method can separate sodium formate and sodium chloride, the amount of 4, 6-dihydroxypyrimidine sodium salt separated out by cooling crystallization is small, the residual 4, 6-dihydroxypyrimidine sodium salt is still dissolved in water, the sodium salt needs to be neutralized by expensive formic acid to obtain a 4, 6-dihydroxypyrimidine crude product and sodium formate, and the 4, 6-dihydroxypyrimidine crude product needs to be returned for re-refining, so that the recycling times are large, 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 activated carbon for decolorization, acidifying with hydrochloric acid, and carrying out solid-liquid separation to obtain 4, 6-dihydroxypyrimidine and mother liquor (the 4, 6-dihydroxypyrimidine mother liquor contains complicated components such as water, methanol, hydrochloric acid, sodium chloride, formic acid and the like). Adding hydrochloric acid into the mother liquor, heating, and carrying out esterification reaction to obtain methyl formate. Introducing ammonia gas into the methyl formate to carry out amination reaction to obtain formamide. Methanol is distilled out from the residual mother liquor, and sodium chloride is obtained by adding alkali for dehydration. Although the method can recycle formic acid in the wastewater, namely formic acid is esterified to generate methyl formate, and the methyl formate is aminated to generate formamide, the steps of the whole process are more complicated, the esterification reaction effect of the formic acid and the methanol in the aqueous solution is poorer, and the conversion rate is lower. The distilled methyl formate can carry away part of water, methanol and formic acid and needs to be rectified again. And (3) the methyl formate obtained by rectification needs to react with ammonia gas again to generate formamide and methanol, and then the methyl formate is rectified again to obtain a formamide product. The whole process flow has complex steps, low esterification reaction efficiency and higher cost for recovering 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 suction filtration under negative pressure, removing a part of methanol from filtrate, and recycling alkali; adding water to the filter cake for dissolving, then acidifying, crystallizing, then 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 performing alkali neutralization and dehydration on the filtrate to obtain a byproduct salt. The method can recover a part of alkali, but the materials are quite sticky after the reaction is finished, the negative pressure suction filtration is quite difficult in the 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 recycled and reused for 3 times, the total yield can reach 90 percent, and the energy consumption is higher in the process of concentrating and using the alkali.
Disclosure of Invention
Problems to be solved by the invention
The invention aims to provide a post-treatment method for synthesizing 4, 6-dihydroxypyrimidine and a method for recycling wastewater thereof, wherein the post-treatment method has the advantages of less generation of three wastes, high recycling efficiency, simple steps and low treatment energy consumption.
Means for solving the problems
In order to solve the problems, the invention provides a post-treatment method for synthesizing 4, 6-dihydroxypyrimidine and a method for recycling wastewater thereof, which comprises the following steps:
step a: dimethyl malonate, formamide and sodium methoxide are used as raw materials to synthesize 4, 6-dihydroxypyrimidine sodium salt, and after the reaction is finished: 1) cooling, adding water to dissolve precipitate, and 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 a sulfuric acid solution, carrying out solid-liquid separation to obtain a 4, 6-dihydroxypyrimidine crude product and wastewater containing sodium sulfate and sodium formate, and carrying out post-treatment on the 4, 6-dihydroxypyrimidine crude product to obtain a 4, 6-dihydroxypyrimidine product;
step c: adding an ammonium ion donor into the wastewater obtained in the step b, cooling, crystallizing, and performing solid-liquid separation to obtain a crude sodium sulfate decahydrate product and wastewater containing ammonium formate;
2 HCOONa+(NH4)2SO4→Na2SO4+2 HCOONH4
step d: and d, distilling the waste water 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 the formamide and the water to obtain the formamide and the water.
HCOONH4→HCONH2+H2O
Preferably, in step a, the sodium methoxide is a solution of sodium methoxide in methanol.
Preferably, step a further comprises the steps of: and (b) rectifying the water-containing methanol to obtain anhydrous methanol and water, and sleeving the obtained anhydrous methanol in the step (a) for reuse.
Preferably, in step b, the post-treatment is washing with water and drying.
Preferably, step c further comprises the steps of: and adding water to wash the crude sodium sulfate decahydrate, and drying to obtain a sodium sulfate decahydrate product.
Preferably, in step d, the formamide obtained 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 60-65 ℃.
Preferably, the target temperature of said temperature reduction in step a is 0-25 ℃.
More preferably, the target temperature for said temperature reduction in step a is 10-15 ℃.
Preferably, the distillation in step a is distillation under negative pressure conditions.
More preferably, the distillation in step a is carried out under a negative pressure condition with a vacuum degree of-0.07 to-0.10 MPa.
Preferably, the amount of water used in step a is 3 to 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 20 wt% to 40 wt%.
Preferably, the amount of sulfuric acid in the sulfuric acid solution in step b is 1.2 to 1.5 times the theoretical molar amount of the sodium salt of 4, 6-dihydroxypyrimidine.
Preferably, the target pH for acidification in step b is between 3.0 and 4.0.
More preferably, the target pH for the acidification in step b is between 3.0 and 3.5.
Preferably, the temperature of acidification in step b is between 25 and 40 ℃.
Preferably, the acidification in step b is performed with stirring for a period of 1-3 h.
Preferably, the ammonium ion donor in 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 20 wt% to 30 wt%.
More preferably, the concentration of the ammonia water is 22 wt% to 38 wt%.
Preferably, in step c, a sulfate ion donor is added to the wastewater.
Preferably, the sulfate ion donor is sulfuric acid.
Preferably, the amount of the ammonium ion donor or 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 that of sodium ions, and the mole number of ammonium ions is larger than that of formate ions.
More preferably, the amount of the ammonium ion donor or the ammonium ion donor and the sulfate ion donor used 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 to 10 ℃.
Preferably, the crystallization time in step c is 0.5 to 3.0 h.
More preferably, the crystallization time in step c is 1.5 to 3.0 h.
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 of the heating in step d is 120-150 ℃.
More preferably, the target temperature for the 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 4, 6-dihydroxypyrimidine and sodium sulfate decahydrate, the sulfuric acid has a good acidifying effect, and 4, 6-dihydroxypyrimidine with the purity of more than 99% can be obtained. The sodium sulfate produced by sulfuric acid is more easily purified than the sodium chloride produced by hydrochloric acid, as compared to hydrochloric acid as the acidifying agent. Sulfuric acid is also cheaper than formic acid as an acidifying agent.
(2) Adding ammonium ion donor into waste water containing sodium sulfate and sodium formate, cooling, crystallizing sodium sulfate to obtain sodium sulfate decahydrate, taking away a large amount of water in the waste water, reducing the amount of waste water and greatly reducing energy consumption. The purity of the sodium sulfate decahydrate is more than 99 percent, and the yield is 90-95 percent.
(3) In the reaction system of the step a, the amount of formamide must be excessive, the excessive amount is beneficial to the 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 the sodium formate in the step c are heated and decomposed in the step d to generate formamide, the formamide has the purity of more than 98 percent and can be reused for synthesizing the 4, 6-dihydroxypyrimidine in the step a, the method enables the excessive formamide to be recycled, and the sodium formate in the wastewater is recycled.
(4) A part of water distilled out in the steps a and d can be used for dissolving the reaction product in the step a, a part of water can be used for washing the crude 4, 6-dihydroxypyrimidine in the step b, and a part of water can be used for washing the crude sodium sulfate decahydrate in the step c, so that most of water can be recycled, and resources are saved.
The post-treatment method for synthesizing 4, 6-dihydroxypyrimidine provided by the invention makes full use of all resources, and the sodium sulfate crystallization process takes away a large amount of water in wastewater, so that the problem of large wastewater generation amount is solved, and the energy consumption is greatly reduced. The byproduct formamide recycles sodium formate in the wastewater, and excessive formamide is recycled, and the obtained formamide can be used for synthesizing 4, 6-dihydroxypyrimidine again. The three wastes are less generated in the whole process, 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, the sodium sulfate and the sodium formate in the wastewater are recovered, the sodium sulfate decahydrate and the formamide with higher 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 wastewater thereof, which comprises the following four steps:
step a: dimethyl malonate, formamide and sodium methoxide are used as raw materials to synthesize 4, 6-dihydroxypyrimidine sodium salt, and after the reaction is finished: 1) cooling, adding water to dissolve precipitate, and 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 a sulfuric acid solution, carrying out solid-liquid separation to obtain a 4, 6-dihydroxypyrimidine crude product and wastewater containing sodium sulfate and sodium formate, and carrying out post-treatment on the 4, 6-dihydroxypyrimidine crude product to obtain a 4, 6-dihydroxypyrimidine product;
step c: adding an ammonium ion donor into the wastewater obtained in the step b, cooling, crystallizing, and performing solid-liquid separation to obtain a crude sodium sulfate decahydrate product and wastewater containing ammonium formate;
2 HCOONa+(NH4)2SO4→Na2SO4+2 HCOONH4
step d: and d, distilling the waste water 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 the formamide and the water to obtain the formamide and the water.
HCOONH4→HCONH2+H2O
In one embodiment, in step a, the sodium methoxide is a solution of sodium methoxide in methanol.
In one embodiment, step a further comprises the steps of: and (b) rectifying the water-containing methanol to obtain anhydrous methanol and water, and sleeving the obtained anhydrous methanol in the step (a) for reuse.
In one embodiment, in step b, the post-treatment is washing with water and drying.
In one embodiment, step c further comprises the steps of: and adding water to wash the crude sodium sulfate decahydrate, and drying to obtain a sodium sulfate decahydrate product.
In one embodiment, in step d, the formamide obtained is recycled to step a.
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 in step a is 60-65 ℃.
In one embodiment, the target temperature for said temperature reduction in step a is from 0 to 25 ℃.
In a preferred embodiment, the target temperature for said lowering of the temperature in step a is 10-15 ℃.
In one embodiment, the distillation in step a is distillation under negative pressure conditions.
In a preferred embodiment, the distillation in step a is carried out under a vacuum 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 from 20 wt% to 40 wt%.
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 for acidification in step b is from 3.0 to 4.0.
In a preferred embodiment, the target pH for acidification in step b is between 3.0 and 3.5.
In one embodiment, the temperature of the acidification in step b is from 25 to 40 ℃.
In one embodiment, the acidification in step b is performed with stirring for a period of time ranging from 1h to 3 h.
In one embodiment, the ammonium ion donor in step c is at least one of ammonium salt, aqueous ammonia, 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 20 wt% to 30 wt%, preferably 22 wt% to 38 wt%.
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 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 that of sodium ions, and the mole number of ammonium ions is larger than that of formate ions.
In a preferred embodiment, the amount of ammonium ion donor or the amount of ammonium ion donor and sulfate ion donor used in step c further satisfies the following condition in order to make the sodium sulfate decahydrate more readily crystallizable: 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 temperature reduction in step c is-5 to 10 ℃.
In one embodiment, the time for said crystallization in step c is 0.5 to 3.0 h.
In a preferred embodiment, the crystallization time in step c is 1.5 to 3.0 h.
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 the heating in step d is 120-.
In a preferred embodiment, the target temperature for the heating in step d is 120-135 ℃.
The technical solution of the present invention will be further described with reference to the following specific examples. It should be understood that the following examples are only for illustrating and explaining the present invention and are 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 30 wt% sodium methoxide methanol solution is put into a reaction kettle, the temperature is raised to 60-65 ℃, then a mixture of 1080.9kg of formamide and 1321.1kg of dimethyl malonate is dripped, and after the dripping is finished, the mixture is kept warm and stirred for reaction for 2 hours. After the reaction, the temperature was reduced to 10-15 ℃ and 5043.7kg of water was added. Distilling under the negative pressure condition of-0.07 to-0.10 MPa to remove methanol to obtain sodium salt mother liquor. And continuously rectifying the aqueous methanol to obtain anhydrous methanol, wherein the anhydrous methanol can be used for synthesizing a sodium methoxide methanol solution.
Step b: and (b) acidifying the sodium salt mother liquor obtained in the step (a) by using 4704.5kg of 25 wt% sulfuric acid, wherein the acidification temperature is 25-30 ℃, acidifying until the pH value is 3.0-3.5, centrifuging to obtain a crude product of 4, 6-dihydroxypyrimidine and wastewater containing sodium sulfate and sodium formate, adding 1681.4kg of water into the crude product of 4, 6-dihydroxypyrimidine, washing, and drying to obtain 1031.2kg of the product of 4, 6-dihydroxypyrimidine with the content of 99.1% and the yield of 92.0%.
Yield of 4, 6-dihydroxypyrimidine was calculated as dimethyl malonate, actual weight of 4, 6-dihydroxypyrimidine product/theoretical weight of 4, 6-dihydroxypyrimidine × 100%.
The wastewater containing sodium sulfate and sodium formate comprises the following components: 15.2% by weight of sodium sulfate, 6.1% by weight of sodium formate, 0.36% by weight of 4, 6-dihydroxypyrimidine, 0.12% by weight of organic impurities.
Step c: 594.0kg of ammonium sulfate is added into the obtained wastewater containing sodium sulfate and sodium formate, and 27 wt% of ammonia water is added after stirring and dissolving to adjust the pH value to 6.5-7.5. Keeping the temperature at 30-35 ℃, stirring for 1h, and then cooling. Gradually reducing the temperature to-5 ℃, keeping the temperature at-5 ℃ and continuing stirring for 0.5h, and then 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 the product sodium sulfate decahydrate, the content is 99.3 percent, and the yield is 93.5 percent.
Step d: and d, distilling the wastewater containing the ammonium formate obtained in the step c to remove water to obtain an ammonium formate solid, heating to 130-135 ℃, gradually melting the ammonium formate, slowly heating to decompose the ammonium formate to generate formamide and water, and rectifying the aqueous formamide again to obtain 568.4kg of a product formamide with the content of 98.3% and the yield of 86.2%. The formamide can be recycled in the step a, and the water can be recycled in the steps a and b.
The 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 was the same as in example 1, with the same waste water composition.
Step c: 441kg of concentrated sulfuric acid is added into the wastewater containing sodium sulfate and sodium formate, ammonia gas is introduced, and the pH value is adjusted to 6.5-7.5. Stirring at 30-35 ℃ for 1h, cooling, gradually cooling to-5 ℃, continuously stirring at-5 ℃ for 0.5h, centrifuging, separating solid from liquid to obtain ammonium formate-containing wastewater and sodium sulfate decahydrate, and washing the sodium sulfate decahydrate with cold water to obtain 4926.7kg of sodium sulfate decahydrate with the content of 99.2% and the yield of 92.7%.
Step d: and distilling the wastewater containing ammonium formate to remove water to obtain solid ammonium formate, heating to 130-135 ℃, gradually melting the ammonium formate, slowly heating to decompose to generate formamide and water, and rectifying the water-containing formamide again to obtain 564.5kg of formamide with the content of 98.1% and the yield of 85.6%. The formamide can be recycled in the step a, and the water can be recycled in the steps a and b.
Example 3
A, step a: the procedure was the same as in example 1.
Step b: the procedure was as in example 1, with the same waste water composition.
Step c: the procedure was the same as in example 2.
Step d: distilling the waste water containing ammonium formate to remove water to obtain solid ammonium formate, heating to the temperature of 120-. The formamide can be recycled in the step a, and the water can be recycled in the steps a and b.
Example 4
A, step a: the procedure was the same as in example 1.
Step b: the procedure was as in example 1, with the same waste water composition.
Step c: 441kg of concentrated sulfuric acid is added into the wastewater containing sodium sulfate and sodium formate, and 480.45kg of ammonium carbonate is added. Stirring at 30-35 ℃ for 1h, cooling, gradually cooling to-5 ℃, continuously stirring at-5 ℃ for 0.5h, centrifuging, separating solid from liquid to obtain ammonium formate-containing wastewater and sodium sulfate decahydrate, and washing the sodium sulfate decahydrate with cold water to obtain 4910.8kg of sodium sulfate decahydrate with the content of 99.1% and the yield of 92.4%.
Step d: and distilling the wastewater containing ammonium formate to remove water to obtain solid ammonium formate, heating to 130-135 ℃, gradually melting the ammonium formate, slowly heating to decompose to generate formamide and water, and rectifying the water-containing formamide again to obtain 548.6kg of formamide with the content of 98.4% and the yield of 83.2%. The formamide can be recycled in the step a, and the water can be recycled in the steps a and b.
Example 5
Step a: the procedure was the same as in example 1.
Step b: the procedure was 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 wastewater containing ammonium formate to remove water to obtain solid ammonium formate, heating to the temperature of 120-. The formamide can be recycled in the step a, and the water can be recycled in the steps a and b.
Claims (10)
1. A post-treatment method for synthesizing 4, 6-dihydroxypyrimidine and a method for recycling wastewater thereof comprise the following steps:
a, step a: dimethyl malonate, formamide and sodium methoxide are used as raw materials to synthesize 4, 6-dihydroxypyrimidine sodium salt, and after the reaction is finished: 1) cooling, adding water to dissolve precipitate, and 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 a sulfuric acid solution, carrying out solid-liquid separation to obtain a 4, 6-dihydroxypyrimidine crude product and wastewater containing sodium sulfate and sodium formate, and carrying out post-treatment on the 4, 6-dihydroxypyrimidine crude product to obtain a 4, 6-dihydroxypyrimidine product;
step c: adding an ammonium ion donor into the wastewater obtained in the step b, cooling, crystallizing, and performing solid-liquid separation to obtain a crude sodium sulfate decahydrate product and wastewater containing ammonium formate;
step d: and d, distilling the waste water 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 the formamide and the water to obtain the formamide and the water.
2. The method for post-treatment of synthesis of 4, 6-dihydroxypyrimidine and resource utilization of wastewater thereof according to claim 1, characterized in that:
in the step a, the sodium methoxide is a methanol solution of sodium methoxide;
step a also includes the following steps: 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 also includes the following steps: adding water to the crude sodium sulfate decahydrate, washing, and drying to obtain a sodium sulfate decahydrate product;
in the step d, the obtained formamide is sleeved in the step a for reuse;
in step a and/or step d, the obtained water jacket is reused in at least one of step a, step b and step c.
3. The post-treatment of synthetic 4, 6-dihydroxypyrimidine and the method for recycling wastewater thereof according to claim 1 or 2, characterized in that:
the temperature of acidification in step b is 25-40 ℃.
4. The post-treatment of synthetic 4, 6-dihydroxypyrimidine and its wastewater resource utilization method according to any one of claims 1 to 3, characterized in that:
the target temperature for cooling in the step a is 0-25 ℃, preferably 10-15 ℃;
the amount of the water used in the step a is 3-5 times of the theoretical yield of the 4, 6-dihydroxypyrimidine sodium salt.
5. The post-treatment of synthetic 4, 6-dihydroxypyrimidine and its wastewater resource utilization method according to any one of claims 1 to 4, characterized in that:
the concentration of the sulfuric acid solution in the step b is 20-40 wt%;
the dosage of the sulfuric acid in the sulfuric acid solution in the step b is 1.2 to 1.5 times of the theoretical mole number of the 4, 6-dihydroxypyrimidine sodium salt;
the target pH value for the acidification in step b is 3.0-4.0, preferably 3.0-3.5.
6. The post-treatment of synthetic 4, 6-dihydroxypyrimidine and its wastewater resource utilization method according to any one of claims 1 to 5, characterized in that:
in the step c, the ammonium ion donor is at least one of ammonium salt, ammonia water and ammonia gas;
the ammonium salt is at least one of ammonium sulfate, ammonium bisulfate, ammonium carbonate, ammonium chloride and ammonium bicarbonate, preferably ammonium sulfate.
7. The post-treatment of synthetic 4, 6-dihydroxypyrimidine and its wastewater resource utilization method according to any one of claims 1 to 6, characterized in that:
in the step c, adding a sulfate ion donor into the wastewater;
the sulfate ion donor is preferably sulfuric acid.
8. The post-treatment for synthesizing 4, 6-dihydroxypyrimidine and the method for recycling wastewater thereof according to any one of claims 1 to 7, characterized in that:
the dosage of the ammonium ion donor or the dosage of the ammonium ion donor and the sulfate ion donor in the step c meets the following conditions: enabling the mole number of sulfate ions in the wastewater containing sodium sulfate and sodium formate to be equal to half of the mole number of sodium ions, and enabling the mole number of ammonium ions to be larger than that of formate ions;
preferably, the dosage of the ammonium ion donor or the dosage 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.
9. The post-treatment for synthesizing 4, 6-dihydroxypyrimidine and the method for recycling wastewater thereof according to any one of claims 1 to 8, wherein:
the target temperature of the temperature reduction in the step c is-5-10 ℃;
the crystallization time in the step c is 0.5-3.0 h; preferably 1.5-3.0 h.
10. The post-treatment for synthesizing 4, 6-dihydroxypyrimidine and the method for recycling wastewater thereof according to any one of claims 1 to 9, characterized in that:
the target temperature for the heating in step d is 120-150 ℃, preferably 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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