CN117088801A - Refining method of N-methyl pyrrolidone - Google Patents
Refining method of N-methyl pyrrolidone Download PDFInfo
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- CN117088801A CN117088801A CN202310955187.XA CN202310955187A CN117088801A CN 117088801 A CN117088801 A CN 117088801A CN 202310955187 A CN202310955187 A CN 202310955187A CN 117088801 A CN117088801 A CN 117088801A
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- ball milling
- methylpyrrolidone
- nmp
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000007670 refining Methods 0.000 title claims abstract description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 239000012716 precipitator Substances 0.000 claims abstract 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 53
- 229920002530 polyetherether ketone Polymers 0.000 claims description 53
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 44
- 238000010438 heat treatment Methods 0.000 claims description 41
- 238000000498 ball milling Methods 0.000 claims description 35
- 239000012528 membrane Substances 0.000 claims description 29
- 238000005341 cation exchange Methods 0.000 claims description 26
- 239000002808 molecular sieve Substances 0.000 claims description 25
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 25
- 238000001354 calcination Methods 0.000 claims description 23
- 238000007873 sieving Methods 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000002033 PVDF binder Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000013049 sediment Substances 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 239000011812 mixed powder Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 239000003011 anion exchange membrane Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 7
- 238000001238 wet grinding Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- -1 ether ketone Chemical class 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000005292 vacuum distillation Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 19
- 239000011805 ball Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 206010029719 Nonspecific reaction Diseases 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a refining method of N-methyl pyrrolidone. Synthesizing N-methyl pyrrolidone by a catalyst under low temperature and low pressure, removing residual gamma-butyrolactone by a composite precipitator, removing impurity ions by an ion exchange membrane, and removing water by low temperature distillation to obtain refined N-methyl pyrrolidone.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a refining method of N-methylpyrrolidone.
Background
N-methyl pyrrolidone (NMP) is a common organic solvent, has the advantages of high solubility, high boiling point, low toxicity, high solvent performance, low surface tension and the like, and is widely applied to the fields of electronics, chemical industry, textile industry and pharmacy.
N-methylpyrrolidone is industrially produced by dehydration of monomethylamine and gamma-butyrolactone, and the production method thereof is roughly classified into a method using a catalyst and a method not using a catalyst.
Methods without using a catalyst a method for preparing N-methylpyrrolidone in 90 to 93% yield by reacting gamma-butyrolactone and monomethylamine at high temperature and high pressure in a batch reactor for 4 hours has been disclosed. In addition, there is also disclosed a method for preparing N-methylpyrrolidone in 94.3% yield by adding gamma-butyrolactone, water and monomethylamine to an autoclave and reacting them at high temperature and high pressure for 3 hours. These processes are relatively harsh in reaction conditions and relatively low in yields.
In the beginning of the 21 st century, germany BASF developed the preparation of N-methylpyrrolidone from mixed amine and gamma-butyrolactone at high temperature and high pressure, which solved the additional separation and purification steps using monomethylamine as a raw material, and was of higher purity. As a method for using the catalyst, a method is disclosed in which a compound catalyst is used for reaction of monomethylamine and gamma-butyrolactone as raw materials at high temperature and high pressure, and the conversion rate and selectivity of gamma-butyrolactone are greatly increased by means of the catalyst. The catalyst yields increase but the reaction conditions remain severe.
In the prior art, the method for producing the N-methyl pyrrolidone without using a catalyst has relatively low yield and severe reaction environment, the method using the catalyst improves the yield but cannot avoid the reaction condition requiring high temperature and high pressure, and the method for refining the N-methyl pyrrolidone with high conversion rate and high selectivity under low temperature and low pressure is researched.
Disclosure of Invention
The invention aims to solve the technical problems that: a process for purifying N-methylpyrrolidone by which a high conversion rate and a high selectivity can be achieved at a low temperature and a low pressure.
1) In order to solve the technical problems, the technical scheme provided by the invention comprises the following steps:
1. the mixed methyl amine is prepared under the catalysis of Ni-Pt by using the mol ratio of ammonia to methanol of 1:2.2;
2. adding gamma-butyrolactone (GBL for short), mixed methyl amine and water into a reactor, wherein the molar ratio of the gamma-butyrolactone to the mixed methyl amine to the water is 1:1-1.6:2-4, and adding 0.1-0.4 w% of catalyst of the mixed methyl amine;
3. the air pressure is kept at 1atm, the temperature of the reactor is raised to 125 ℃, and the temperature is kept for 25min;
4. continuously heating to 180 ℃ and preserving heat for 100min, continuously heating to 220 ℃ and preserving heat for 75min;
5. fractionating the obtained product after natural cooling, wherein the fraction at 20-50 ℃, 70-100 ℃ and 202-203 ℃ is separately recovered, the highest temperature cannot exceed 204 ℃, and the residual solution is crude N-methylpyrrolidone (NMP for short);
6. separating the residual GBL using a complex precipitant;
7. and separating GBL, and removing ionic impurities in NMP through an anion-cation exchange membrane to obtain refined NMP.
2) Further, the reaction catalyst in the step 2 is ZMS-5 molecular sieve and Ce x Nb 2-x O 3 The mass ratio is 20:1, and the preparation method is as follows:
1. with Ce 2 O 3 With Nb 2 O 3 Mixing the raw materials in a molar ratio of 1:38 by utilizing a wet grinding process, wherein the mass ratio of the used materials to balls to ethanol is 1:1.5:1.2, the rotating speed of a ball mill is 200r/min, and the ball milling time is 12h;
2. sieving the mixture after ball milling with a 40-mesh sieve, and drying in a dryer;
3. performing secondary ball milling, wherein the rotating speed of the ball mill is 200r/min, and the ball milling time is 12h;
4. sieving the mixture after secondary ball milling with a 60-mesh sieve, and drying;
5. calcining in a high temperature furnace at a maximum temperature of 1860 ℃, heating up at a rate of 30 ℃/min, and preserving heat at the maximum temperature for 3 hours;
6. after the calcination is finished, slowly cooling to room temperature at 20 ℃/min;
7. mixing ZMS-5 molecular sieve with the obtained product, pulverizing, and sieving with 60 mesh sieve;
8. to ZMS-5 molecular sieve and Ce x Nb 2-x O 3 Adding PVA into the mixed powder for granulating;
9. calcining the particles at 500 ℃ to obtain catalyst particles;
3) Further, the steps for separating GBL impurities after fractionation of NMP are as follows:
1. taking 1L of deionized water, adding 0.01-0.05 g of CaO into the deionized water, and heating to 50 ℃;
2. maintaining the temperature of the aqueous solution at 50 ℃, adding 5 to 10g Co to the crude NMP 3 O 4 Slowly dripping the aqueous solution and continuously stirring;
3. stopping dripping the aqueous solution until no sediment is generated within 3min, and removing the sediment in the mixture by suction filtration to obtain NMP;
4. heating NMP to 110 ℃, continuing until no weight change exists, and filtering to obtain liquid;
4) Further, the preparation steps of the anion-cation exchange membrane are as follows:
1. polyether ether ketone (PEEK), PVDF/SiO is taken 2 -6 cation exchange membranes, 100g each of quaternized polyetheretherketone (qppek-OH) anion exchange membranes;
2. heating PEEK to 160 ℃ and converting the PEEK to a glassy state;
3. PVDF/SiO 1-5 cm thick 2 -6, paving 1mm glass state PEEK on the surface of a cation exchange membrane;
4. heating QPPEEK-OH to 160 ℃ to partially convert the QPPEEK-OH into a glassy state;
5. paving 1-5 cm vitrified QPPEEK-OH on the surface of the PEEK cooled and separated from the vitrified PEEK;
6. after cooling, an ion exchange membrane is obtained.
The invention has the beneficial effects that:
1) The method provided by the invention is used for carrying out the reaction at the low temperature and the low pressure of about 200 ℃ and 1atm, thereby realizing high conversion rate and high selectivity of N-methyl pyrrolidone. Compared with the high-temperature and high-pressure conditions in the traditional method, the refining method has milder reaction environment, high production efficiency and reduced energy consumption and cost, and is a more environment-friendly and economic production method.
2)Nb 3+ And Ce (Ce) 3+ Has excellent chemical catalytic activity, can obviously increase the conversion rate of GBL and the selectivity of NMP, and is doped with Nb by Ce 2 O 3 Formed Ce x Nb 2-x O 3 Has perovskite structure, and the crystal structure and lattice defect thereof provide abundant active sites for catalysis, make up for Nb 2 O 3 The problem of insufficient reaction speed under catalysis increases the conversion rate of reactants under the catalysis effect, the selectivity of Ce doped reaction can be freely regulated, the ZMS-5 molecular sieve has a pore channel structure which can assist the adsorption capacity of the ZMS-5 molecular sieve to the reactants, and the service life of the catalyst can be prolonged due to the stable chemical property of the ZMS-5 molecular sieve.
3) After granulation, ce is wrapped in the ZMS-5 molecular sieve x Nb 2-x O 3 Forms a sphere, ce and Nb with different atomic sizes can regulate and control the pore canal structure, and meanwhile, ce x Nb 2-x O 3 Adjustable watchThe surface acid and alkali can be regulated to enhance the adsorption capacity of the pore channel surface to GBL and enhance the reaction capacity to improve the conversion rate, the pore channel structure is regulated to slow down the passing rate of GBL and the inside of the pore channel, so that the GBL is in full contact with the catalyst to improve the conversion rate, and meanwhile, the regulation and control can be carried out on GBL reaction products, so that the NMP selectivity can be increased.
4) The common NMP synthesis process at present is mostly carried out in a high-temperature and high-pressure environment, the catalytic process is relatively free from catalysis, the temperature and the pressure of the catalytic process are relatively low, the high-efficiency catalyst can reduce the temperature and the pressure required by converting GBL into NMP, and the side reaction is prevented while the energy is saved and the emission is reduced.
5) The GBL can be catalyzed and hydrolyzed to generate gamma-hydroxybutyric acid after the hot calcium hydroxide solution is dripped into contact with GBL, insoluble substances of gamma-hydroxybutyric acid calcium can be separated from NMP after the GBL reacts with the calcium hydroxide, and strong alkali Ca (OH) with low solubility is obtained 2 Catalyzing GBL hydrolysis, simultaneously reacting with the generated gamma-hydroxybutyric acid to generate insoluble substances of gamma-hydroxybutyric acid calcium in NMP to precipitate out, and consuming OH in time - Preventing NMP from hydrolyzing in contact with NMP for a long time.
6) Calcium hydroxide and Co 3 O 4 Meanwhile, the catalyst has extremely high catalytic activity, the hydrolysis reaction rate of GBL is greatly improved, slow hydrolysis caused by long-time contact of NMP and alkali solution is avoided, and the conversion rate of GBL is further increased and the GBL removal efficiency is maximized by adjusting the pH value and the characteristic of specific active sites through two-phase combination.
7)Co 3 O 4 The spinel structure has higher stability and longer service life than other catalysts, and the structure has high specific surface area, rich active sites and higher catalytic efficiency than other catalysts, and can well improve the conversion rate and conversion rate of GBL hydrolysis, so that GBL is quickly hydrolyzed and consumed OH - NMP is prevented from hydrolysis.
8) NMP is often applied to dissolve other organic matters to be used as a solvent, anions contained in NMP possibly reduce the dissolving capacity of NMP, so that the use of NMP is not favored due to the fact that the solubility of NMP to certain matters is reduced, metal cations are catalyzed in NMP to inhibit nonspecific reactions, and synthesis reactions taking NMP as a raw material are not favored, so that adsorption by an ion exchange membrane is removed to the greatest extent. Therefore, the ion exchange membrane is used for adsorption removal.
9) The PEEK and PVDF are used in a combined mode, the strength and toughness of the exchange membrane can be improved, the ion adsorption is conducted under the pressure difference condition, the stability of the ion exchange membrane is improved, the service life of the ion exchange membrane is prolonged, the QPPEEK-OH membrane and the PVDF/SiO2 membrane are respectively high in adsorption efficiency on magazine metal ions and acid radical ions stored in NMP, and a small amount of ion impurities in NMP can be removed efficiently and rapidly.
Detailed Description
The present invention will be described in further detail with reference to examples.
The starting materials or chemical reagents for the examples of the present invention, unless otherwise specified, were obtained by conventional commercial means.
Example 1
(1) Preparation of ZMS-5/Ce x Nb 2-x O 3 The composite catalyst comprises the following steps:
1. with Ce 2 O 3 With Nb 2 O 3 Mixing the raw materials in a molar ratio of 1:38 by utilizing a wet grinding process, wherein the mass ratio of the used materials to balls to ethanol is 1:1.5:1.2, the rotating speed of a ball mill is 200r/min, and the ball milling time is 12h;
2. sieving the mixture after ball milling with a 40-mesh sieve, and drying in a dryer;
3. performing secondary ball milling, wherein the rotating speed of the ball mill is 200r/min, and the ball milling time is 12h;
4. sieving the mixture after secondary ball milling with a 60-mesh sieve, and drying;
5. calcining in a high temperature furnace at a maximum temperature of 1860 ℃, heating up at a rate of 30 ℃/min, and preserving heat at the maximum temperature for 3 hours;
6. after the calcination is finished, slowly cooling to room temperature at 20 ℃/min;
7. mixing the ZMS-5 molecular sieve with the obtained product according to the mass ratio of 20:1, crushing, and sieving with a 60-mesh sieve;
8. to ZMS-5 molecular sieves and Ce x Nb 2-x O 3 Adding PVA into the mixed powder for granulating;
9. calcining the particles at 500 ℃ to obtain catalyst particles;
(2) The preparation method of the anion-cation exchange membrane comprises the following steps:
1. polyether ether ketone (PEEK), PVDF/SiO is taken 2 -6 cation exchange membranes, 100g each of quaternized polyetheretherketone (qppek-OH) anion exchange membranes;
2. heating PEEK to 160 ℃ and converting the PEEK to a glassy state;
3. PVDF/SiO at 3cm thickness 2 -6, paving 1mm glass state PEEK on the surface of a cation exchange membrane;
4. heating QPPEEK-OH to 160 ℃ to partially convert the QPPEEK-OH into a glassy state;
5. paving 3cm vitrified QPPEEK-OH on the surface of the PEEK cooled and separated from the vitrified PEEK;
6. after cooling, an ion exchange membrane is obtained.
(3) 5mol of ammonia and 11mol of methanol are used for preparing under the catalysis of Ni-Pt to obtain mixed methyl amine;
(4) 2mol of gamma-butyrolactone (GBL for short), 2.6mol of mixed methyl amine (amino) and 6mol of water are added into a reactor, and 0.25w% of mixed methyl amine catalyst is added;
(5) The air pressure is kept at 1atm, the temperature of the reactor is raised to 125 ℃, and the temperature is kept for 25min;
(6) Continuously heating to 180 ℃ and preserving heat for 100min, continuously heating to 220 ℃ and preserving heat for 75min;
(7) Fractionating the obtained product after natural cooling, wherein the fraction at 20-50 ℃, 70-100 ℃ and 202-203 ℃ is separately recovered, the highest temperature cannot exceed 204 ℃, and the residual solution is crude N-methylpyrrolidone (NMP for short);
(8) Mixing 1000g of deionized water and 0.03g of CaO, and heating to 50 ℃;
(9) The aqueous solution temperature was maintained at 50℃and 10w% Co was added to the crude NMP 3 O 4 Slowly dripping the aqueous solution and continuously stirring;
(10) Stopping dripping the aqueous solution until no sediment is generated within 3min, and removing the sediment in the mixture by suction filtration to obtain NMP;
(11) Heating NMP to 110 ℃, continuing until no weight change exists, and filtering to obtain liquid;
(12) And (3) removing ionic impurities in the NMP by passing the liquid through an anion-cation exchange membrane to obtain refined NMP.
Example 2
(1) Preparation of ZMS-5/Ce x Nb 2-x O 3 The composite catalyst comprises the following steps:
1. with Ce 2 O 3 With Nb 2 O 3 Mixing the raw materials in a molar ratio of 1:38 by utilizing a wet grinding process, wherein the mass ratio of the used materials to balls to ethanol is 1:1.5:1.2, the rotating speed of a ball mill is 200r/min, and the ball milling time is 12h;
2. sieving the mixture after ball milling with a 40-mesh sieve, and drying in a dryer;
3. performing secondary ball milling, wherein the rotating speed of the ball mill is 200r/min, and the ball milling time is 12h;
4. sieving the mixture after secondary ball milling with a 60-mesh sieve, and drying;
5. calcining in a high temperature furnace at a maximum temperature of 1860 ℃, heating up at a rate of 30 ℃/min, and preserving heat at the maximum temperature for 3 hours;
6. after the calcination is finished, slowly cooling to room temperature at 20 ℃/min;
7. mixing the ZMS-5 molecular sieve with the obtained product according to the mass ratio of 20:1, crushing, and sieving with a 60-mesh sieve;
8. to ZMS-5 molecular sieve and Ce x Nb 2-x O 3 Adding PVA into the mixed powder for granulating;
9. calcining the particles at 500 ℃ to obtain catalyst particles;
(2) The preparation method of the anion-cation exchange membrane comprises the following steps:
1. polyether ether ketone (PEEK), PVDF/SiO is taken 2 -6 cation exchange membranes, 100g each of quaternized polyetheretherketone (qppek-OH) anion exchange membranes;
2. heating PEEK to 160 ℃ and converting the PEEK to a glassy state;
3. in 1cm PVDF/SiO 2 -6, paving 1mm glass state PEEK on the surface of a cation exchange membrane;
4. heating QPPEEK-OH to 160 ℃ to partially convert the QPPEEK-OH into a glassy state;
5. paving 5cm vitrified QPPEEK-OH on the surface of the PEEK cooled and separated from the vitrified PEEK;
6. after cooling, an ion exchange membrane is obtained.
(3) 5mol of ammonia and 11mol of methanol are used for preparing under the catalysis of Ni-Pt to obtain mixed methyl amine;
(4) 2mol of gamma-butyrolactone (GBL for short), 2.2mol of mixed methyl amine (amino) and 8mol of water are added into a reactor, and 0.1w% of mixed methyl amine catalyst is added;
(5) The air pressure is kept at 1atm, the temperature of the reactor is raised to 125 ℃, and the temperature is kept for 25min;
(6) Continuously heating to 180 ℃ and preserving heat for 100min, continuously heating to 220 ℃ and preserving heat for 75min;
(7) Fractionating the obtained product after natural cooling, wherein the fraction at 20-50 ℃, 70-100 ℃ and 202-203 ℃ is separately recovered, the highest temperature cannot exceed 204 ℃, and the residual solution is crude N-methylpyrrolidone (NMP for short);
(8) Mixing 1000g of deionized water and 0.01g of CaO, and heating to 50 ℃;
(9) The aqueous solution temperature was maintained at 50℃and 5w% Co was added to the crude NMP 3 O 4 Slowly dripping the aqueous solution and continuously stirring;
(10) Stopping dripping the aqueous solution until no sediment is generated within 3min, and removing the sediment in the mixture by suction filtration to obtain NMP;
(11) Heating NMP to 110 ℃, continuing until no weight change exists, and filtering to obtain liquid;
(12) And (3) removing ionic impurities in the NMP by passing the liquid through an anion-cation exchange membrane to obtain refined NMP.
Example 3
(1) Preparation of ZMS-5/Ce x Nb 2-x O 3 The composite catalyst comprises the following steps:
1. with Ce 2 O 3 With Nb 2 O 3 Mixing the raw materials in a molar ratio of 1:38 by using a wet grinding process, wherein the used materials, balls and ethanol are mixedThe mass ratio is 1:1.5:1.2, the rotating speed of the ball mill is 200r/min, and the ball milling time is 12h;
2. sieving the mixture after ball milling with a 40-mesh sieve, and drying in a dryer;
3. performing secondary ball milling, wherein the rotating speed of the ball mill is 200r/min, and the ball milling time is 12h;
4. sieving the mixture after secondary ball milling with a 60-mesh sieve, and drying;
5. calcining in a high temperature furnace at a maximum temperature of 1860 ℃, heating up at a rate of 30 ℃/min, and preserving heat at the maximum temperature for 3 hours;
6. after the calcination is finished, slowly cooling to room temperature at 20 ℃/min;
7. mixing the ZMS-5 molecular sieve with the obtained product according to the mass ratio of 20:1, crushing, and sieving with a 60-mesh sieve;
8. to ZMS-5 molecular sieve and Ce x Nb 2-x O 3 Adding PVA into the mixed powder for granulating;
9. calcining the particles at 500 ℃ to obtain catalyst particles;
(2) The preparation method of the anion-cation exchange membrane comprises the following steps:
1. polyether ether ketone (PEEK), PVDF/SiO is taken 2 -6 cation exchange membranes, 100g each of quaternized polyetheretherketone (qppek-OH) anion exchange membranes;
2. heating PEEK to 160 ℃ and converting the PEEK to a glassy state;
3. at 5cm PVDF/SiO 2 -6, paving 1mm glass state PEEK on the surface of a cation exchange membrane;
4. heating QPPEEK-OH to 160 ℃ to partially convert the QPPEEK-OH into a glassy state;
5. paving 1cm vitrified QPPEEK-OH on the surface of the PEEK cooled and separated from the vitrified PEEK;
6. after cooling, an ion exchange membrane is obtained.
(3) 5mol of ammonia and 11mol of methanol are used for preparing under the catalysis of Ni-Pt to obtain mixed methyl amine;
(4) 2mol of gamma-butyrolactone (GBL for short), 3mol of mixed methyl amine (amino) and 4mol of water are added into a reactor, and 0.4w% of mixed methyl amine catalyst is added;
(5) The air pressure is kept at 1atm, the temperature of the reactor is raised to 125 ℃, and the temperature is kept for 25min;
(6) Continuously heating to 180 ℃ and preserving heat for 100min, continuously heating to 220 ℃ and preserving heat for 75min;
(7) Fractionating the obtained product after natural cooling, wherein the fraction at 20-50 ℃, 70-100 ℃ and 202-203 ℃ is separately recovered, the highest temperature cannot exceed 204 ℃, and the residual solution is crude N-methylpyrrolidone (NMP for short);
(8) Mixing 1000g of deionized water and 0.05g of CaO, and heating to 50 ℃;
(9) The aqueous solution temperature was maintained at 50℃and 15w% Co was added to the crude NMP 3 O 4 Slowly dripping the aqueous solution and continuously stirring;
(10) Stopping dripping the aqueous solution until no sediment is generated within 3min, and removing the sediment in the mixture by suction filtration to obtain NMP;
(11) Heating NMP to 110 ℃, continuing until no weight change exists, and filtering to obtain liquid;
(12) And (3) removing ionic impurities in the NMP by passing the liquid through an anion-cation exchange membrane to obtain refined NMP.
Comparative example 1
The present comparative example differs from example 1 in that step (1) is:
preparation of ZMS-5/Ce 2 O 3 The composite catalyst comprises the following steps:
1. ZMS-5 molecular sieve and Ce 2 O 3 Mixing, crushing and sieving with a 60-mesh sieve according to the mass ratio of 20:1;
2. to ZMS-5 molecular sieve and Ce 2 O 3 Adding PVA into the mixed powder for granulating;
3. calcining the particles at 500 ℃ to obtain catalyst particles;
comparative example 2
The present comparative example differs from example 1 in that step (1) is:
preparation of ZMS-5/Nb 2 O 3 The composite catalyst comprises the following steps:
1. ZMS-5 molecular sieve and Nb 2 O 3 Mixing, crushing and sieving with a 60-mesh sieve according to the mass ratio of 20:1;
2. to ZMS-5 molecular sieve and Nb 2 O 3 Adding PVA into the mixed powder for granulating;
3. calcining the particles at 500 ℃ to obtain catalyst particles;
comparative example 3
The present comparative example differs from example 1 in that step (1) is:
preparation of ZMS-5/Ce x Nb 2-x O 3 The composite catalyst comprises the following steps:
1. with Ce 2 O 3 With Nb 2 O 3 Mixing the raw materials in a molar ratio of 1:25 by utilizing a wet grinding process, wherein the mass ratio of the used materials to balls to ethanol is 1:1.5:1.2, the rotating speed of a ball mill is 200r/min, and the ball milling time is 12h;
2. sieving the mixture after ball milling with a 40-mesh sieve, and drying in a dryer;
3. performing secondary ball milling, wherein the rotating speed of the ball mill is 200r/min, and the ball milling time is 12h;
4. sieving the mixture after secondary ball milling with a 60-mesh sieve, and drying;
5. calcining in a high temperature furnace at a maximum temperature of 1860 ℃, heating up at a rate of 30 ℃/min, and preserving heat at the maximum temperature for 3 hours;
6. after the calcination is finished, slowly cooling to room temperature at 20 ℃/min;
7. mixing the ZMS-5 molecular sieve with the obtained product according to the mass ratio of 20:1, crushing, and sieving with a 60-mesh sieve;
8. to ZMS-5 molecular sieve and Ce x Nb 2-x O 3 Adding PVA into the mixed powder for granulating;
9. calcining the particles at 500 ℃ to obtain catalyst particles;
comparative example 4
The present comparative example differs from example 1 in that step (1) is:
preparation of ZMS-5/Ce x Nb 2-x O 3 The composite catalyst comprises the following steps:
1. with Ce 2 O 3 With Nb 2 O 3 Mixing the materials with a mole ratio of 1:38 by wet grinding process, wherein the materials and balls are usedEthanol and the mass ratio of 1:1.5:1.2, the rotating speed of the ball mill is 200r/min, and the ball milling time is 12h;
2. sieving the mixture after ball milling with a 40-mesh sieve, and drying in a dryer;
3. performing secondary ball milling, wherein the rotating speed of the ball mill is 200r/min, and the ball milling time is 12h;
4. sieving the mixture after secondary ball milling with a 60-mesh sieve, and drying;
5. calcining in a high temperature furnace at a maximum temperature of 1860 ℃, heating up at a rate of 30 ℃/min, and preserving heat at the maximum temperature for 3 hours;
6. after the calcination is finished, slowly cooling to room temperature at 20 ℃/min;
7. mixing the ZMS-5 molecular sieve with the obtained product according to the mass ratio of 10:1, crushing, and sieving with a 60-mesh sieve;
8. to ZMS-5 molecular sieve and Ce x Nb 2-x O 3 Adding PVA into the mixed powder for granulating;
9. calcining the particles at 500 ℃ to obtain catalyst particles;
comparative example 5
This comparative example differs from example 1 in that the catalyst used in step (4) is a ZMS-5 molecular sieve.
Comparative example 6
The present comparative example differs from example 1 in that step (2) is:
the preparation method of the anion-cation exchange membrane comprises the following steps:
1. polyether ether ketone (PEEK), PVDF/SiO is taken 2 -6 cation exchange membranes, polynorbornene type anion exchange membranes 100g each;
2. heating PEEK to 160 ℃ and converting the PEEK to a glassy state;
3. PVDF/SiO at 3mm 2 -6, paving 1mm glass state PEEK on the surface of a cation exchange membrane;
4. paving a 3mm polynorbornene anion exchange membrane on the surface of the PEEK cooled and separated from the glass state;
6. after cooling, an ion exchange membrane is obtained.
Comparative example 7
The present comparative example differs from example 1 in that step (2) is:
the preparation method of the anion-cation exchange membrane comprises the following steps:
1. taking 100g of polyether-ether-ketone (PEEK), SPVDF cation exchange membranes and quaternary phosphorized polyether-ether-ketone (QPPEEK-OH) anion exchange membranes respectively;
2. heating PEEK to 160 ℃ and converting the PEEK to a glassy state;
3. 1mm glassy PEEK was spread on the surface of a 1mm SPVDF cation exchange membrane;
4. heating QPPEEK-OH to 160 ℃ to partially convert the QPPEEK-OH into a glassy state;
5. paving 5mm vitrified QPPEEK-OH on the surface of the PEEK cooled and separated from the vitrified PEEK;
6. after cooling, an ion exchange membrane is obtained.
Comparative example 8
This comparative example differs from example 1 in that CaO in step (8) is Ba (OH) 2 。
Comparative example 9
This comparative example differs from example 1 in that Co in step (9) 3 O 4 Is NiO.
Product determination:
n-methylpyrrolidone was purified according to examples 1 to 3 and comparative examples 1 to 6,
1) Conversion and selectivity tests were performed: the resulting samples were measured in an uv-vis spectrometer to obtain the concentration of GBL and the concentration of NMP, the GBL conversion was the ratio of GBL consumed to original addition (i.e., GBL conversion=1-GBL residual amount/GBL initial amount), the NMP selectivity was the product of NMP purity (i.e., NMP mass ratio in the resulting mixture) and GBL conversion (i.e., NMP selectivity=nmp purity×gbl conversion), and the data obtained are shown in table 1.
2) And (3) measuring impurity removal effect: 10g of the product after fractionation, precipitation and filtration is taken for measuring GBL and other impurity contents by an infrared spectrometer, and the contents are shown in table 1.
3) Ion residue measurement was performed: 10g of the sample was measured by ion chromatography, the sample was separated on an ion exchange column, and the concentration of each ion was detected by a detector and the anion and cation concentrations were classified and counted as shown in Table 1.
Table 1NMP refining process measurement data
Claims (4)
1. A refining method of N-methyl pyrrolidone is characterized in that:
the refining method comprises the following steps:
s01, preparing under Ni-Pt catalysis by using the molar ratio of ammonia to methanol of 1:2.2 to obtain mixed methyl amine;
s02, adding gamma-butyrolactone, mixed methyl amine and water into a reactor, wherein the molar ratio of the gamma-butyrolactone to the mixed methyl amine to the water is 1:1-1.6:2-4, and adding 0.1-0.4 w% of mixed methyl amine as a catalyst;
s03, keeping the air pressure at 1atm, heating the reactor to 125 ℃, and preserving the heat for 25min;
s04, continuously heating to 180 ℃ and preserving heat for 100min, continuously heating to 220 ℃ and preserving heat for 75min;
s05, naturally cooling, then fractionating the obtained product, and separately recovering fractions at 20-50 ℃, 70-100 ℃ and 202-203 ℃, wherein the residual solution is crude N-methylpyrrolidone;
s06, separating the residual gamma-butyrolactone by using a composite precipitator;
s07, separating gamma-butyrolactone, and removing ionic impurities in the N-methylpyrrolidone through an anion-cation exchange membrane to obtain refined N-methylpyrrolidone.
2. The method for purifying N-methylpyrrolidone according to claim 1, wherein:
the catalyst in S02 is ZMS-5 molecular sieve, ce x Nb 2-x O 3 The mass ratio is 20:1, and the preparation method is as follows:
s11, using Ce 2 O 3 With Nb 2 O 3 Mixing the raw materials in a molar ratio of 1:38 by utilizing a wet grinding process, wherein the mass ratio of the used materials to balls to ethanol is 1:1.5:1.2, the rotating speed of a ball mill is 200r/min, and the ball milling time is 12h;
s12, sieving the mixture after ball milling with a 40-mesh sieve, and drying in a dryer;
s13, performing secondary ball milling, wherein the rotating speed of the ball mill is 200r/min, and the ball milling time is 12h;
s14, sieving the mixture after secondary ball milling with a 60-mesh sieve, and drying;
s15, calcining in a high-temperature furnace at the highest temperature of 1860 ℃, heating up at a rate of 30 ℃/min, and preserving heat at the highest temperature for 3 hours;
s16, after the calcination is finished, slowly cooling to room temperature at 20 ℃/min;
s17, mixing the ZMS-5 molecular sieve with the obtained product, crushing, and sieving with a 60-mesh sieve;
s18, molecular sieve ZMS-5 and Ce x Nb 2-x O 3 Granulating the mixed powder by adding PVA;
s19, calcining the particles at 500 ℃ to obtain the catalyst particles.
3. The method for purifying N-methylpyrrolidone according to claim 1, wherein:
the separation steps of the gamma-butyrolactone in the step S06 are as follows:
s21, mixing 1000 parts by mass of deionized water and 0.01-0.05 part by mass of CaO, and heating to 50 ℃;
s22, maintaining the temperature of the aqueous solution at 50 ℃, and adding 5-15 w% Co into the crude N-methylpyrrolidone 3 O 4 Slowly dripping the aqueous solution and continuously stirring;
s23, stopping dripping the aqueous solution until no sediment is generated within 3min, and removing the sediment in the mixture through suction filtration to obtain NMP;
s24, heating the N-methyl pyrrolidone to 110 ℃ to remove water, continuing until no weight change exists, and filtering to obtain liquid.
4. The method for purifying N-methylpyrrolidone according to claim 1, wherein:
the preparation steps of the anion-cation exchange membrane described in S07 are as follows:
s31, taking polyether-ether-ketone, PVDF/SiO 2 -6 cation exchange membrane, ji Linhua Poly100g of ether ketone anion exchange membranes;
s32, heating polyether-ether-ketone to 160 ℃ and converting to a glassy state;
s33, PVDF/SiO with thickness of 1-5 cm 2 -6 spreading 1mm glass state polyether-ether-ketone on the surface of the cation exchange membrane;
s34, heating the quaternary phosphatized polyether-ether-ketone to 160 ℃ and partially converting into a glassy state;
s35, paving 1-5 cm vitrified quaternary phosphorized polyether-ether-ketone on the surface of the cooled and separated glassy polyether-ether-ketone;
s36, obtaining the ion exchange membrane after cooling.
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