CN117924059A - Method for preparing IPA (isopropyl alcohol) by acetone hydrogenation - Google Patents
Method for preparing IPA (isopropyl alcohol) by acetone hydrogenation Download PDFInfo
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- CN117924059A CN117924059A CN202211318855.XA CN202211318855A CN117924059A CN 117924059 A CN117924059 A CN 117924059A CN 202211318855 A CN202211318855 A CN 202211318855A CN 117924059 A CN117924059 A CN 117924059A
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- acetone
- ipa
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- hydrogenation
- reaction
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 title claims abstract description 373
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 44
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 title description 161
- 239000000463 material Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 230000018044 dehydration Effects 0.000 claims abstract description 14
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 14
- 238000004821 distillation Methods 0.000 claims abstract description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 9
- 238000007670 refining Methods 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 56
- 239000003054 catalyst Substances 0.000 claims description 38
- 238000001179 sorption measurement Methods 0.000 claims description 27
- 239000007800 oxidant agent Substances 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- 239000003446 ligand Substances 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012024 dehydrating agents Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002808 molecular sieve Substances 0.000 claims description 8
- 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 8
- 150000004696 coordination complex Chemical class 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000005909 Kieselgur Substances 0.000 claims description 3
- 150000004677 hydrates Chemical class 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 150000001768 cations Chemical class 0.000 abstract description 4
- 239000013064 chemical raw material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 33
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 239000012535 impurity Substances 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 10
- 239000002904 solvent Substances 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 4
- -1 4A molecular sieves Chemical compound 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/79—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/85—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of chemical raw material preparation, and discloses a method for preparing IPA by acetone hydrogenation, which comprises the following steps: s1: mixing and contacting an acetone raw material with an oxidizing reagent to obtain a mixed material, and refining the mixed material to obtain purified acetone; s2: in hydrogen atmosphere, purifying acetone to carry out hydrogenation reaction to obtain IPA product; wherein the water content in the purified acetone is not higher than 1500ppm. The IPA product provided by the invention only needs simple dehydration and distillation, and can be obtained, and the cation content, the water content and the like of the IPA product can meet the requirements of high-end wafer manufacturing (the line width is less than or equal to 90 nm).
Description
Technical Field
The invention relates to the technical field of chemical raw material preparation, in particular to a method for preparing IPA by acetone hydrogenation.
Background
The ultra-clean high-purity isopropyl alcohol (IPA) is mainly used for cleaning chips, is a key basic functional chemical in the IC manufacturing process, and plays a very key role in etching, cleanliness, yield and reliability of the chips. With the further development of integrated circuits, particularly the popularization and application of very large scale integrated circuits, the quality requirements on isopropanol are higher and higher, and strict requirements on organic impurities, metal content, particles, moisture and the like are put forward. Currently, domestic production of inorganic wet electronic chemicals has been able to reach the G5 grade (SEMI), but G5 grade organic wet electronic chemicals still rely on import.
The technology is relatively late at home, the productivity of Isopropanol (IPA) prepared by acetone hydrogenation is more than 70% of the total productivity of China in China, but the domestic products and the technical level are mainly concentrated below G3 level, the content of organic impurities in the obtained isopropanol products is higher, the requirements are difficult to meet, a certain gap exists between the technology and the international level, and the further development of the domestic chip industry is hindered.
Disclosure of Invention
The invention aims to solve the problems of low IPA selectivity and high organic impurity content in the process of preparing isopropyl alcohol (IPA) by acetone hydrogenation in the prior art. A process for preparing IPA by hydrogenating acetone is disclosed. The method is beneficial to high-efficiency and stable operation in the acetone hydrogenation process, can better improve the conversion rate of acetone and the selectivity of IPA, and can also reduce the content of organic impurities in an IPA product.
In the process of preparing IPA by acetone hydrogenation, the problems of low acetone conversion rate, low IPA selectivity and high organic impurity content in an IPA product exist, the inventor researches and discovers that the problems are caused by the fact that the water content in the acetone is too high, the main sources of the water in the acetone are water in the acetone raw material, water generated in the acetone refining process and absorbed from the environment, and the like, and the inventor experiments discover that water molecules and substrate molecules can produce competitive adsorption on a catalyst active site to reduce the activity of an acetone hydrogenation catalyst, so that the problems of high organic impurity content in the IPA product, unstable operation of the catalyst and the like are caused.
Based on the above findings, the first aspect of the present invention provides a method for preparing IPA by hydrogenating acetone, the method comprising:
S1: mixing and contacting an acetone raw material with an oxidizing reagent to obtain a mixed material, and refining the mixed material to obtain purified acetone;
s2: in hydrogen atmosphere, purifying acetone to carry out hydrogenation reaction to obtain IPA product;
wherein the water content in the purified acetone is not higher than 1500ppm.
Preferably, the water content in the purified acetone is not higher than 1000ppm.
Preferably, the water content in the purified acetone is not higher than 500ppm.
Preferably, the refining method in step S1 includes: and (5) dehydrating and distilling the mixed material in sequence to obtain the purified acetone.
Preferably, the method of dehydration comprises one or more of an adsorption material or analogue adsorption method, a chemical reaction drying method and a membrane separation method, preferably an adsorption material or analogue adsorption method, and the method of dehydration of the mixed material using the adsorption material or analogue adsorption method comprises: the mixture is passed through 1 or at least 2 adsorption columns packed with dehydrating agent in series for dehydration.
Preferably, the dehydrating agent comprises one or more of activated carbon, molecular sieves, diatomaceous earth, silica gel, resins, salts that can form crystalline hydrates.
Preferably, during distillation, the fraction at 54-58 ℃ is collected as the purified acetone.
Preferably, the distillation is an atmospheric distillation; and/or the temperature of the column bottom is 60-100 ℃, preferably 70-80 ℃ in the distillation process.
Preferably, the mixed contact conditions in step S1 include: normal temperature and normal pressure; the contact time is 0.5 to 10 hours, preferably 3 to 8 hours.
Preferably, the amount of the oxidizing agent is 0.01-0.1% by mass of the acetone raw material, preferably 0.02-0.08%.
Preferably, the oxidizing agent comprises a bidentate ligand metal complex after oxidation.
Preferably, the acetone raw material comprises one or more of industrial-grade acetone, analytical-grade acetone and electronic-grade acetone.
Preferably, in step S2, the hydrogenation catalyst used in the hydrogenation reaction process comprises one or more of a copper-based catalyst, a nickel-based catalyst and a ruthenium-based catalyst, preferably a copper-based catalyst.
Preferably, in step S2, the hydrogenation conditions include:
the inlet temperature is 70-140 ℃ and the reaction pressure is 2-8MPa; and/or
The molar ratio of the hydrogen to the acetone is (1-30): 1; the space velocity of the acetone is 0.1-3h -1.
According to the technical scheme, the acetone raw material and the oxidizing agent are mixed and contacted to obtain the mixed material, the mixed material is refined to obtain purified acetone, the water content in the purified acetone is controlled to be 1500ppm or less, the efficient and stable operation of the acetone hydrogenation reaction is facilitated, and the inventor finds that if the water content is out of the water content range, water molecules and substrate molecules produce competitive adsorption on the active site of the catalyst, the activity of the acetone hydrogenation catalyst is reduced, so that the problems of high organic impurity content in an IPA product, unstable operation of the catalyst and the like are caused, and the IPA product only needs simple dehydration and distillation to obtain the IPA product with the cation content, the water content and the like which can meet the requirements of high-end wafer manufacturing (the line width is less than or equal to 90 nm).
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the invention, if no special description exists, the normal temperature refers to 20-30 ℃; "purity" refers to mass content.
The invention provides a method for preparing IPA by acetone hydrogenation, which comprises the following steps:
S1: mixing and contacting an acetone raw material with an oxidizing reagent to obtain a mixed material, and refining the mixed material to obtain purified acetone;
s2: in hydrogen atmosphere, purifying acetone to carry out hydrogenation reaction to obtain IPA product;
wherein the water content in the purified acetone is not higher than 1500ppm.
In the present invention, the water content is measured by the karl fischer method.
According to the invention, the acetone raw material and the oxidizing agent are mixed and contacted to obtain a mixed material, then the mixed material is refined to obtain purified acetone, and meanwhile, the water content in the purified acetone is controlled to be 1500ppm or less, so that the efficient and stable operation of acetone hydrogenation reaction is facilitated, the acetone conversion rate and the IPA selectivity are increased, and the organic impurity content in an IPA product can be reduced better.
According to a preferred embodiment of the invention, the water content in the purified acetone is not higher than 1000ppm. By adopting the scheme, the conversion rate of the acetone and the yield of the purified acetone can be better increased.
According to a preferred embodiment of the invention, the water content in the purified acetone is not higher than 500ppm. By adopting the scheme, the conversion rate of the acetone and the yield of the purified acetone can be better increased.
According to a particularly preferred embodiment of the present invention, the refining method in step S1 comprises: and (5) dehydrating and distilling the mixed material in sequence to obtain the purified acetone. By adopting the scheme, the conversion rate of acetone and the selectivity of IPA can be further increased, and the content of organic impurities in IPA can be reduced.
In the present invention, a method of dehydration is not particularly limited as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the method of dehydration includes one or more of an adsorption material or the like adsorption method, a chemical reaction drying method, and a membrane separation method.
According to a particularly preferred embodiment of the present invention, the method of dehydration is an adsorption method of an adsorbent material or the like, and the method of dehydration of the mixture using the adsorption method of the adsorbent material or the like comprises: the mixture is passed through 1 or at least 2 adsorption columns packed with dehydrating agent in series for dehydration.
In the present invention, the number of adsorption columns in which the mixture flows through the adsorption column filled with the dehydrating agent is not particularly limited as long as the water content in the acetone can be reduced to a desired water content.
In the present invention, the dehydrating agent is an adsorbent material or the like, and the specific choice of the dehydrating agent is not particularly limited as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the dehydrating agent includes one or more of activated carbon, molecular sieves (e.g., 4A molecular sieves, 3A molecular sieves), diatomaceous earth, silica gel, resins (e.g., polyacrylic acid-based super absorbent resins), salts (e.g., copper sulfate, calcium sulfate, sodium sulfate) that can form crystalline hydrates.
According to a preferred embodiment of the invention, during distillation, a fraction of 54-58 ℃ is collected as the purified acetone. By adopting the scheme, the conversion rate of acetone and the yield of IPA can be better improved, and the content of organic impurities in an IPA product can be reduced.
According to a particularly preferred embodiment of the invention, the distillation is an atmospheric distillation, during which the temperature of the column bottoms is 60-100 ℃, preferably 70-80 ℃. By adopting the scheme, the water content in the purified acetone can be further reduced, so that the conversion rate of the acetone and the selectivity of IPA are increased, and the content of organic impurities in an IPA product is reduced.
In the present invention, the mixing contact condition in step S1 is not particularly limited as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the mixing contact condition in step S1 includes: normal temperature and normal pressure; the contact time is 0.5 to 10 hours, preferably 3 to 8 hours. By adopting the scheme, the content of organic impurities in the IPA product can be reduced better.
In the present invention, the amount of the oxidizing agent used is not particularly limited as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the amount of the oxidizing agent used is 0.01 to 0.1%, preferably 0.02 to 0.08% by mass of the acetone raw material. By adopting the scheme, the content of organic impurities in the IPA product can be reduced better, the yield of purified acetone is increased, and the selectivity of IPA is increased.
According to the present invention, the kind of the oxidizing agent is not particularly limited as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the oxidizing agent includes a bidentate ligand metal complex after undergoing an oxidation reaction. By adopting the scheme, the conversion rate of acetone and the selectivity of IPA can be better increased, and the content of organic impurities in an IPA product can be reduced.
According to a particularly preferred embodiment of the present invention, in the bidentate ligand metal complex, the ligand-providing compound is represented by formula (1), and the ligand-providing compound is a metal salt;
In the formula (1), X is-C (R 3)-,R11、R12、R21、R22、R3 is independently selected from H, C-C5 alkyl, benzyl, naphthyl and C1-C3 alkyl substituted phenyl, and n is an integer of 0-6).
In the present invention, it is understood that-C (R 3) -represents the number of carbon atoms participating in the formation of the ring in the formula (1), R 3 represents a substituent attached to the carbon atoms, the compound in the formula (1) is a five-membered ring structure when n is 0, and the compound in the formula (1) is a six-membered ring structure when n is 1, and according to a particularly preferred embodiment of the present invention, n is an integer of 0 to 3 in the formula (1). By adopting the scheme, the conversion rate of acetone and the yield of IPA can be better increased, and the content of organic impurities in an IPA product can be reduced.
In the present invention, the term "C1-C5 alkyl" may be a branched alkyl group or a straight-chain alkyl group, and examples of the C1-C5 alkyl group include methyl, ethyl, isopropyl, n-propyl, butyl, pentyl and the like; according to a particularly preferred embodiment of the invention, R 11、R12、R21、R22 is independently selected from H, C-C3 alkyl, benzyl, methyl-substituted phenyl. By adopting the scheme, the conversion rate of acetone and the selectivity of IPA can be further increased.
According to a particularly preferred embodiment of the invention, R 3 is H or C1-C3 alkyl. By adopting the scheme, the conversion rate of acetone and the selectivity of IPA can be further increased.
In the present invention, the term "metal salt" refers to a salt of a cation which is a metal cation, such as nitrate, chloride, and the like. The metal element in the metal salt is not particularly limited as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the metal element in the metal salt is selected from one or more of transition metal elements in the fourth period and the fifth period, preferably one or more of Mn, co, and Mo. By adopting the scheme, the content of organic impurities in IPA can be reduced better.
In the present invention, it is understood that the bidentate ligand metal complex is obtained by a coordination reaction between a compound (ligand) represented by formula (1) providing a ligand and a metal salt providing a coordination atom, and the bidentate ligand metal complex after the oxidation reaction is obtained by an oxidation reaction of the bidentate ligand metal complex, and those skilled in the art can select the conditions of the coordination reaction and the conditions of the oxidation reaction and the amounts of the ligand, the metal salt, and the oxidizing agent as needed, for example, the molar ratio of the ligand to the metal salt is (1 to 1.5): 1, the molar ratio of the oxidant to the metal salt is (1-1.5): 1.
According to a preferred embodiment of the present invention, the method for preparing an oxidizing agent comprises: in the presence of a solvent, the compound shown in the formula (1) and the metal salt are subjected to coordination reaction, then an oxidant is added for oxidation reaction, and finally the solvent is removed, and optionally the oxidant is obtained after separation. The purification step may be selected as desired after the oxidation reaction contact, for example, by extraction, drying, etc., as is conventional in the art.
In the present invention, the kind of the solvent may be selected according to necessity, in a specific reaction process, the compound represented by the formula (1) may be formulated into a solution containing the compound represented by the formula (1) using one solvent, the metal salt may be formulated into a solution containing the metal salt using one solvent, and then the solution containing the compound represented by the formula (1) and the solution containing the metal salt may be subjected to a coordination reaction, wherein the kind and amount of the solvent may be selected according to necessity by a person skilled in the art to ensure smooth progress of the coordination reaction, and the specific kind and amount of the solvent have no influence on achieving the object of the present invention, which will not be described in detail herein.
In the present invention, in order to ensure stable progress of the coordination reaction, a person skilled in the art may select the conditions of the coordination reaction as needed, for example, stirring the reaction at room temperature for 1 to 10 hours in an inert atmosphere; to ensure the successful progress of the oxidation reaction, the person skilled in the art can choose the conditions of the oxidation reaction as desired, for example, 1 to 5 hours at room temperature.
In the present invention, in order to ensure the smooth progress of the oxidation reaction, the type of the oxidizing agent may be selected by those skilled in the art as required, and according to one embodiment of the present invention, the oxidizing agent includes one or more of oxygen, hydrogen peroxide, cumene peroxide, peracetic acid, t-butyl hydroperoxide, peroxypropionic acid, perchlorate, permanganate, and dichromate.
In the present invention, the source of the acetone raw material is not particularly limited as long as the object of the present invention can be achieved, and the acetone raw material includes one or more of industrial-grade acetone (purity 99 to 99.5%), analytical-grade acetone (purity 99.5 to 99.9%) and electronic-grade acetone (purity 99.9 to 99.97%), based on the acetone raw materials existing on the market.
In the invention, the purity is the mass content unless otherwise specified.
According to a preferred embodiment of the present invention, in step S2, the hydrogenation catalyst used in the hydrogenation reaction process comprises one or more of a copper-based catalyst, a nickel-based catalyst and a ruthenium-based catalyst, preferably a copper-based catalyst. The copper-based catalyst is very sensitive to impurities such as water, industrial grade acetone is often used for preparing IPA in the prior art, but the method for preparing IPA by hydrogenation by adopting the method can better increase the conversion rate of purified acetone and the selectivity of IPA.
In the present invention, the "copper-based catalyst" refers to a catalyst using copper as an active ingredient, which may be a supported catalyst (the carrier may be alumina, silica, or the like), or may be a composite catalyst containing copper, and the nickel-based catalyst and the ruthenium-based catalyst may be supported or composite catalysts similar to the copper-based catalyst, and the specific types of hydrogenation catalysts are not limited in the present invention and are not repeated herein.
According to a preferred embodiment of the present invention, in step S2, the hydrogenation conditions include: the inlet temperature is 70-140 ℃ and the reaction pressure is 2-8MPa.
According to a preferred embodiment of the present invention, in step S2, the hydrogenation conditions include: the molar ratio of the hydrogen to the acetone is (1-30): 1; the space velocity of the acetone is 0.1-3h -1.
The present invention will be described in detail by examples. In the following examples and comparative examples:
Purified acetone conversion= (1-acetone content in raw material purified acetone chromatogram/acetone content in raw material IPA product GC chromatogram after reaction) ×100%;
IPA selectivity = peak area ratio of IPA in non-acetone species in GC chromatogram of reacted feed IPA product;
Purity of purified acetone = peak area ratio of acetone in purified acetone as measured by gas chromatography area normalization.
Example 1
Preparation of an oxidizing reagent:
Mixing a ligand solution containing a ligand shown in the formula (1-1) and a molybdenum chloride-containing solution containing Mo atoms according to the mol ratio of molybdenum chloride to the ligand of 1:1.1 in an inert atmosphere, magnetically stirring and carrying out coordination reaction at room temperature for 5 hours, continuously adding an oxidant (potassium permanganate, the mol ratio of which to metal salt is 1.25:1), carrying out oxidation reaction for 2 hours, then carrying out desolventizing, extracting and drying to obtain the molybdenum chloride-containing compound;
preparation of IPA product:
Mixing industrial-grade acetone with the purity of 98% with an oxidizing reagent (the dosage of 0.03wt% of industrial-grade acetone) for 5 hours under normal temperature and normal pressure to obtain a mixed material, and then dehydrating the mixed material in 1 adsorption column filled with 3A molecular sieve to obtain dehydrated acetone; then, the dehydrated acetone is distilled under normal pressure at the temperature of 74 ℃ in the tower kettle, and the fraction at 54-58 ℃ is collected as purified acetone;
Purified acetone enters an acetone hydrogenation reactor filled with a Cu/SiO 2 catalyst with the weight percent for hydrogenation reaction (the reaction inlet temperature is 100 ℃, the reaction pressure is 4MPa, the molar ratio of hydrogen to acetone is 8:1, and the acetone airspeed is 1.0h -1) to obtain an IPA product.
The water content in the purified acetone, the acetone conversion and the IPA selectivity are shown in table 1.
Example 2
Preparation of IPA product:
Mixing industrial-grade acetone with the purity of 98% with an oxidizing reagent (the same amount is 0.03wt% of industrial-grade acetone in example 1) for 5 hours at normal temperature and normal pressure to obtain a mixed material, and then dehydrating the mixed material by passing the mixed material through 2 adsorption columns filled with 3A molecular sieves in series to obtain dehydrated acetone; then, the dehydrated acetone is distilled under normal pressure at the temperature of 74 ℃ in the tower kettle, and the fraction at 54-58 ℃ is collected as purified acetone;
purified acetone enters an acetone hydrogenation reactor filled with a Cu/SiO2 catalyst with 5 weight percent for hydrogenation reaction (the reaction inlet temperature is 100 ℃, the reaction pressure is 4MPa, the molar ratio of hydrogen to acetone is 8:1, and the acetone airspeed is 1.0h -1) to obtain an IPA product.
The water content in the purified acetone, the acetone conversion and the IPA selectivity are shown in table 1.
Example 3
Preparation of an oxidizing reagent:
Mixing a ligand solution containing a ligand shown in the formula (1-3) and a molybdenum chloride-containing solution containing Mo atoms according to the mol ratio of molybdenum chloride to the ligand of 1:1.1 in an inert atmosphere, magnetically stirring and carrying out coordination reaction at room temperature for 5 hours, continuously adding an oxidant (isopropylbenzene peroxide, the mol ratio of which to metal salt is 1.25:1), carrying out oxidation reaction for 2 hours, then carrying out desolventizing, extracting and drying to obtain the molybdenum chloride-containing material;
preparation of IPA product:
Mixing industrial-grade acetone with the purity of 98% with an oxidizing reagent (the dosage of 0.03wt% of industrial-grade acetone) for 5 hours under normal temperature and normal pressure to obtain a mixed material, and then dehydrating the mixed material in 1 adsorption column filled with 3A molecular sieve to obtain dehydrated acetone; then, the dehydrated acetone is distilled under normal pressure at the temperature of 80 ℃ in the tower kettle, and the fraction at 54-58 ℃ is collected as purified acetone;
Purified acetone enters an acetone hydrogenation reactor filled with a Cu/SiO 2 catalyst with the weight percent for hydrogenation reaction (the reaction inlet temperature is 100 ℃, the reaction pressure is 4MPa, the molar ratio of hydrogen to acetone is 8:1, and the acetone airspeed is 1.5h -1) to obtain an IPA product.
The water content in the purified acetone, the acetone conversion and the IPA selectivity are shown in table 1.
Example 4
Preparation of IPA product:
Mixing industrial-grade acetone with the purity of 98% with an oxidizing agent (the same amount is 0.03wt% of industrial-grade acetone in example 1) for 5 hours under normal temperature and normal pressure to obtain a mixed material, and then dehydrating the mixed material in 1 adsorption column filled with polyacrylic acid super absorbent resin to obtain dehydrated acetone; then, the dehydrated acetone is distilled under normal pressure at the temperature of74 ℃ in the tower kettle, and the fraction at 54-58 ℃ is collected as purified acetone;
Purified acetone enters an acetone hydrogenation reactor filled with a Cu/SiO 2 catalyst with the weight percent for hydrogenation reaction (the reaction inlet temperature is 100 ℃, the reaction pressure is 4MPa, the molar ratio of hydrogen to acetone is 8:1, and the acetone airspeed is 1.0h -1) to obtain an IPA product.
The water content in the purified acetone, the acetone conversion and the IPA selectivity are shown in table 1.
Example 5
Preparation of IPA product:
Mixing industrial-grade acetone with the purity of 98% with chromium trioxide (the dosage of which is 0.03wt% of that of the industrial-grade acetone) for 5 hours under the condition of normal temperature and normal pressure to obtain a mixed material, and then dehydrating the mixed material in 1 adsorption columns filled with 3A molecular sieves to obtain dehydrated acetone; then, the dehydrated acetone is distilled under normal pressure at the temperature of 74 ℃ in the tower kettle, and the fraction at 54-58 ℃ is collected as purified acetone;
Purified acetone enters an acetone hydrogenation reactor filled with a Cu/SiO 2 catalyst with the weight percent for hydrogenation reaction (the reaction inlet temperature is 100 ℃, the reaction pressure is 4MPa, the molar ratio of hydrogen to acetone is 8:1, and the acetone airspeed is 1.0h -1) to obtain an IPA product.
The water content in the purified acetone, the acetone conversion and the IPA selectivity are shown in table 1.
Example 6
Preparation of IPA product:
Mixing industrial-grade acetone with the purity of 98% with an oxidizing agent (the same amount is 0.03wt% of industrial-grade acetone in example 1) for 15 hours at normal temperature and normal pressure to obtain a mixed material, and then dehydrating the mixed material in 1 adsorption column filled with 3A molecular sieve to obtain dehydrated acetone; then, the dehydrated acetone is distilled under normal pressure at the temperature of 74 ℃ in the tower kettle, and the fraction at 54-58 ℃ is collected as purified acetone;
Purified acetone enters an acetone hydrogenation reactor filled with a Cu/SiO 2 catalyst with the weight percent for hydrogenation reaction (the reaction inlet temperature is 100 ℃, the reaction pressure is 4MPa, the molar ratio of hydrogen to acetone is 8:1, and the acetone airspeed is 1.0h -1) to obtain an IPA product.
The water content in the purified acetone, the acetone conversion and the IPA selectivity are shown in table 1.
Example 7
Preparation of IPA product:
Mixing industrial-grade acetone with the purity of 98% with an oxidizing agent (the same amount is 0.1wt% of industrial-grade acetone in example 1) for 5 hours under normal temperature and normal pressure to obtain a mixed material, and then dehydrating the mixed material in 1 adsorption column filled with 3A molecular sieve to obtain dehydrated acetone; then, the dehydrated acetone is distilled under normal pressure at the temperature of 74 ℃ in the tower kettle, and the fraction at 54-58 ℃ is collected as purified acetone;
Purified acetone enters an acetone hydrogenation reactor filled with a Cu/SiO 2 catalyst with the weight percent for hydrogenation reaction (the reaction inlet temperature is 100 ℃, the reaction pressure is 4MPa, the molar ratio of hydrogen to acetone is 8:1, and the acetone airspeed is 1.0h -1) to obtain an IPA product.
The water content in the purified acetone, the acetone conversion and the IPA selectivity are shown in table 1.
Comparative example 1
The procedure of example 2 was followed, except that: mixing industrial-grade acetone with purity of 98% with an oxidizing agent (the dosage is 0.03wt% of industrial-grade acetone) for 5 hours under normal temperature and normal pressure to obtain a mixed material, then distilling the mixed material at the tower kettle temperature of 74 ℃ under normal pressure, and collecting fractions at 54-58 ℃ to obtain purified acetone;
The remainder was the same as in example 2.
The water content in the purified acetone, the acetone conversion and the IPA selectivity are shown in table 1.
Comparative example 2
The procedure of example 2 was followed, except that: industrial-grade acetone is not contacted with an oxidizing agent, namely, the industrial-grade acetone with the purity of 98 percent and the oxidizing agent flow through 2 adsorption columns which are connected in series and are filled with 3A molecular sieves for dehydration to obtain dehydrated acetone; and then the dehydrated acetone is distilled under normal pressure at the temperature of 74 ℃ in the tower kettle, and the fraction at 54-58 ℃ is collected as purified acetone.
The remainder was the same as in example 2.
The water content in the purified acetone, the acetone conversion and the IPA selectivity are shown in table 1.
TABLE 1
As can be seen from the results in Table 1, the IPA examples 1 to 7 prepared by the method of the present invention not only can increase the yield of purified acetone, but also have good economic effects, and the conversion rate of purified acetone is high, and the yield of the final product IPA is high.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A process for the hydrogenation of acetone to produce IPA, comprising:
S1: mixing and contacting an acetone raw material with an oxidizing reagent to obtain a mixed material, and refining the mixed material to obtain purified acetone;
s2: in hydrogen atmosphere, purifying acetone to carry out hydrogenation reaction to obtain IPA product;
wherein the water content in the purified acetone is not higher than 1500ppm.
2. The method of claim 1, wherein,
The water content in the purified acetone is not higher than 1000ppm;
preferably, the water content in the purified acetone is not higher than 500ppm.
3. The method according to claim 1 or 2, wherein,
The refining method in the step S1 comprises the following steps: and (5) dehydrating and distilling the mixed material in sequence to obtain the purified acetone.
4. The method of claim 3, wherein,
The method of dehydration includes one or more of adsorption of an adsorbent material or the like, chemical reaction drying, and membrane separation, preferably adsorption of an adsorbent material or the like, and the method of dehydration of a mixture using the adsorbent material or the like includes: passing the mixture through 1 or at least 2 adsorption columns filled with dehydrating agent in series for dehydration;
preferably, the dehydrating agent comprises one or more of activated carbon, molecular sieves, diatomaceous earth, silica gel, resins, salts that can form crystalline hydrates.
5. The method according to claim 3 or 4, wherein,
During the distillation process, collecting the fraction at 54-58 ℃ as the purified acetone;
preferably, the method comprises the steps of,
The distillation is atmospheric distillation; and/or
In the distillation process, the temperature of the tower kettle is 60-100 ℃, preferably 70-80 ℃.
6. The method according to any one of claims 1 to 5, wherein,
The mixing contact conditions in step S1 include: normal temperature and normal pressure; the contact time is 0.5 to 10 hours, preferably 3 to 8 hours.
7. The method according to any one of claims 1-6, wherein,
The dosage of the oxidizing agent is 0.01-0.1% of the mass of the acetone raw material, and is preferably 0.02-0.08%;
Preferably, the oxidizing agent comprises a bidentate ligand metal complex after oxidation.
8. The method according to any one of claims 1-7, wherein,
The acetone raw material comprises one or more of industrial-grade acetone, analysis-grade acetone and electronic-grade acetone.
9. The method according to any one of claims 1-8, wherein,
In step S2, the hydrogenation catalyst used in the hydrogenation reaction process includes one or more of a copper-based catalyst, a nickel-based catalyst and a ruthenium-based catalyst, preferably a copper-based catalyst.
10. The method according to any one of claims 1-9, wherein,
In step S2, the hydrogenation conditions include:
the inlet temperature is 70-140 ℃ and the reaction pressure is 2-8MPa; and/or
The molar ratio of the hydrogen to the acetone is (1-30): 1; the space velocity of the acetone is 0.1-3h -1.
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