CN111377796A - Process method and system for producing isopropanol by acetone hydrogenation - Google Patents
Process method and system for producing isopropanol by acetone hydrogenation Download PDFInfo
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- CN111377796A CN111377796A CN202010397932.XA CN202010397932A CN111377796A CN 111377796 A CN111377796 A CN 111377796A CN 202010397932 A CN202010397932 A CN 202010397932A CN 111377796 A CN111377796 A CN 111377796A
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 title claims abstract description 222
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 title claims abstract description 196
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000008569 process Effects 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000000926 separation method Methods 0.000 claims abstract description 45
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 230000018044 dehydration Effects 0.000 claims abstract description 5
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 5
- 150000002576 ketones Chemical class 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 59
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- 239000002994 raw material Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 25
- 239000012071 phase Substances 0.000 claims description 23
- 238000005191 phase separation Methods 0.000 claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- 229910052802 copper Inorganic materials 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 20
- 239000007791 liquid phase Substances 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 17
- 150000002431 hydrogen Chemical class 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 238000004064 recycling Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 27
- 239000000047 product Substances 0.000 description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000004149 tartrazine Substances 0.000 description 5
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229910000564 Raney nickel Inorganic materials 0.000 description 4
- -1 copper-zinc-aluminum Chemical group 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000004229 Alkannin Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000002151 riboflavin Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 229910017709 Ni Co Inorganic materials 0.000 description 2
- 229910003267 Ni-Co Inorganic materials 0.000 description 2
- 229910003262 Ni‐Co Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000004283 Sodium sorbate Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004411 aluminium 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
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a process method and a system for producing isopropanol by acetone hydrogenation, wherein a solvent which is inert to ketone hydrogenation reaction is introduced in the hydrogenation process, the solvent is immiscible with water and can form a lowest azeotrope with water, the solvent enters a lightness-removing tower along with hydrogenated materials, the solvent and water are extracted from the top of the tower in the lightness-removing tower, materials at the bottom of the tower directly enter a product tower without dehydration, and the isopropanol is obtained from the top of the product tower. The isopropanol production system disclosed by the invention does not need a dehydration tower and subsequent recovery equipment of the hydrous isopropanol, so that the device investment is reduced, the separation process is simplified, the azeotropic separation process of the isopropanol and water is avoided, the hydrous isopropanol is not generated, and the total yield of the product isopropanol is improved.
Description
Technical Field
The invention relates to the technical field of isopropanol preparation, in particular to a process method and a system for producing isopropanol by acetone hydrogenation.
Background
The production of isopropanol can be carried out by hydration of propylene, such as indirect esterification using sulfuric acid, direct hydration using solid acidic catalyst or cation exchange resin catalyst, etc.
Since industrially most of acetone is obtained from cumene peroxidation and is co-produced with phenol. Due to the increase of the needed amount of phenol, a large amount of acetone is produced, imbalance of the demand occurs, and the situation that the acetone is excessive is often caused. This makes the hydrogenation of acetone to produce isopropanol an economically viable route.
The hydrogenation of acetone can be catalyzed by nickel-based or copper-based catalysts, or by noble metals such as palladium, platinum, rhodium, ruthenium, etc. The nickel catalyst is preferably Raney nickel (Raney Nickel), and may be supported on a carrier or in the form of a composite oxide. Copper is often combined with other metal oxides as a catalyst or supported on a carrier.
Acetone is hydrogenated on the above type of catalyst, a fixed bed reactor is mostly adopted, acetone and hydrogen gas enter a reactor filled with the catalyst continuously in a liquid phase or a gas phase according to a certain proportion, and the isopropanol is hydrogenated under proper temperature and hydrogen pressure.
Japanese Kokai publication Hei-3-141235 describes a process using a Raney nickel catalyst, which describes that the conversion of acetone hydrogenation and the selectivity of isopropanol hydrogenation both reach 99.9%. Hei 2-279643 describes a hydrogenation process using Ru/gamma-A12O 3 catalyst, and describes that acetone is diluted with isopropanol and then hydrogenated, the highest conversion rate can reach 99.9 percent under the pressure of 9.0MPa, and the highest selectivity of isopropanol can also reach 99.9 percent. Although the two catalysts have good activity and selectivity, the Raney nickel catalyst has higher relative price and is more complex in catalyst filling and operation; noble metal catalysts such as platinum, palladium, rhodium and the like are more expensive, and moreover, the catalyst is used for acetone hydrogenation under severe conditions and too high reaction pressure.
The copper-based catalyst has the advantages of simple preparation, low price and easy operation and use. The copper-based catalyst is generally carried on a carrier or is tableted and molded together with other metal oxides as promoters. The improvement of the copper-based catalyst lies in that the activity and the selectivity of the catalyst are improved by selecting a proper cocatalyst component, and the same good catalytic effect as that of the nickel catalyst can be achieved. When a catalyst supported on a carrier such as alumina or silica is used, the presence of the carrier is likely to cause other side reactions, and the selectivity of isopropyl alcohol is not high. When other metal oxides are used as promoters, the metal oxides are required to have functions of not only serving as active components for hydrogenation, but also serving for loading copper simple substances and dispersing copper microcrystals. The metal oxide used as a promoter is usually formed by tablet compression together with copper oxide, and such a promoter is required to be active only in the reaction of hydrogenating acetone to produce isopropanol, so as not to reduce the selectivity of isopropanol.
For example, Su patent SU1051055A, SU1118632A and Japanese patent application No. Hei 3-41038 describe a hydrogenation method using Cu-Cr catalyst, while Russian patent RU2047590 uses a catalyst containing NiO (25-65%), CuO (10-35%) and Cr2O3 (15-40%) for catalytic hydrogenation. The hydrogenation by adopting the catalyst has the defects that the conversion rate of acetone and the selectivity of isopropanol are not high, and are generally lower than 99.5 percent, namely the yield of the isopropanol is not high. And, use Cr2O3The toxicity of chromium compounds as a co-catalyst component makes the preparation and post-treatment of the catalyst cumbersome and causes environmental problems.
Chinese patent CN1255482A reports a method for preparing isopropanol by acetone hydrogenation using a platelet-type CuO-ZnO mixed oxide catalyst, and the acetone conversion rate and the isopropanol selectivity can both reach 99.9% at a certain temperature and pressure. However, the copper-based catalyst is easy to melt due to high reaction temperature, so that the catalyst is gradually deactivated and is operated at a lower acetone conversion rate.
Chinese patent CN1962588A reports that acetone is used as raw material and Ni-Co/AC is used as catalyst, wherein the composition of the Ni-Co/AC catalyst is: 10-70% of Ni, 1.1-30% of Co and the balance of active carbon components, and continuously reacting in a gas phase to prepare the isopropanol. The specific operating conditions are: pressure: normal pressure-2.0 MPa, temperature: 70-200 ℃, acetone liquid phase space velocity: 1.0 to 10.0 hours-1Hydrogen-ketone molar ratio: 3.0 to 15.0. By adopting the method, high-purity isopropanol for the pharmaceutical and cosmetic industries can be obtained through subsequent processing. However, in the method, the preferable Ni content is 50-65% and the Co content is 2.0-20% in the supported nickel catalyst, the preparation cost of the catalyst is high, and the economical efficiency of producing isopropanol by acetone hydrogenation is reduced.
In the prior art documents, the existing process for producing isopropanol by hydrogenating acetone has the problems of harsh reaction conditions and/or undesirable use of catalyst, and related patent reports are only limited to the catalyst, but the process is rarely involved. The reason is that the acetone hydrogenation process is not very complicated, the acetone generates isopropanol with high conversion rate and selectivity under certain temperature and pressure, and byproducts are only small amounts of 4-methyl-2-pentanol and propane, sometimes small amounts of diisopropyl ether and C9, etc., which are very small in amount and easy to separate. However, water is generated in the processes, and meanwhile, a small amount of water with the concentration of about 0.2-0.3% is brought into the raw material acetone, although the total amount of water is not large, the isopropanol and the water form an azeotrope, the azeotropic temperature is 80.2 ℃, the boiling point of the isopropanol is 82.0 ℃, and the separation is difficult; meanwhile, the purity of the isopropanol serving as a product is required to be more than 99.7 percent, and the water content is less than 0.2 percent, so that the loss of the isopropanol product cannot be avoided in the post-treatment process. In the prior art, unreacted acetone is removed from the material flow after the hydrogenation reaction, and then the material flow enters a dehydration tower, and because isopropanol azeotropes with water, the water content of a tower bottom material is controlled within a certain range by taking out a certain amount of isopropanol, so that the tower bottom material enters a product tower, and a qualified isopropanol product can be obtained at the tower top. This portion of aqueous isopropanol is generally sold as a very inexpensive waste material, resulting in loss of isopropanol product, affecting the operating costs of the plant; however, even if the part of the aqueous isopropyl alcohol is subjected to azeotropic distillation or membrane evaporation treatment, the investment and operation costs are increased, and the process operation is complicated.
Disclosure of Invention
The invention aims to solve the technical problems and provide a process method and a system for producing isopropanol by acetone hydrogenation, wherein a solvent which is inert to ketone hydrogenation reaction is introduced in the hydrogenation process, the solvent enters a separation section along with material flow after hydrogenation, a minimum azeotrope is formed by the solvent and water, part of water is taken out in a lightness-removing tower, an organic phase containing acetone is recycled, and an aqueous phase is extracted, so that qualified isopropanol meeting market requirements can be directly obtained without water separation in a product tower, the separation process is simplified, and the device investment and the production cost are greatly reduced.
In order to solve the technical problems, the invention adopts the technical scheme that: a process for preparing isopropanol by hydrogenating acetone features that a solvent which is inert to the hydrogenation reaction of ketone is introduced in the hydrogenation process and is not dissolved in water to form the lowest azeotrope, the solvent and water are extracted from the top of tower in a lightness-removing tower, the material at bottom of tower is directly introduced into product tower without dewatering, and the isopropanol is obtained from the top of tower.
The process method for producing the isopropanol by hydrogenating the acetone is further optimized as follows: mixing acetone and a solvent, then mixing the mixture with hydrogen, heating the mixed material, then adding the heated material into a hydrogenation reactor for hydrogenation reaction, cooling the hydrogenated material containing isopropanol, the solvent, unreacted acetone, a small amount of water and a recombinant, separating the material from an excess hydrogen in a lightness-removing column, extracting unreacted acetone, an organic solvent and part of water from the top of the lightness-removing column for phase separation treatment, discharging a water phase obtained by phase separation, recycling the organic phase containing the solvent and the acetone to the inlet of the hydrogenation reactor for recycling, feeding the bottom material of the lightness-removing column into a product column, and extracting an isopropanol product with the purity of more than 99.9% and the water content of not more than 0.1% from the top of the product column.
The process method for producing the isopropanol by hydrogenating the acetone is further optimized as follows: the solvent is benzene, cyclohexane or n-hexane.
The process method for producing the isopropanol by hydrogenating the acetone is further optimized as follows: the hydrogenation reaction specifically comprises the following steps: under the condition of hydrogen, acetone in the raw material contacts with a catalyst filled in a fixed bed to generate hydrogenation reaction to generate isopropanol.
The process method for producing the isopropanol by hydrogenating the acetone is further optimized as follows: the catalyst used in the hydrogenation reaction is a copper-based hydrogenation catalyst.
The process method for producing the isopropanol by hydrogenating the acetone is further optimized as follows: the conditions of the hydrogenation reaction are as follows: reaction temperature: reaction pressure at 100-250 ℃: normal pressure to 6.0MPa, molecular ratio of hydrogen to acetone: 1.0 to 100.0, CKetone liquid phase feed volume space velocity: 0.2 to 5.0 hours-1。
The process method for producing the isopropanol by hydrogenating the acetone is further optimized as follows: the conditions of the hydrogenation reaction are as follows: reaction temperature: the reaction pressure is 1.0-5.0 MPa at 150-200 ℃, the molecular ratio of hydrogen to acetone is 5.0-10.0, and the liquid phase volume space velocity of acetone is 1.0-3.0 h-1。
A process system for producing isopropanol by acetone hydrogenation comprises a raw material mixing unit, a hydrogenation reactor, a high-pressure separation tank, a low-pressure separation tank, a light component removal tower, a phase separation tank and a product tower;
the materials mixed by the raw material mixing unit are heated by a heat exchanger and a heater, the heated materials are in a gas phase state and enter a hydrogenation reactor from the upper part of the reactor, the materials after hydrogenation reaction are cooled by the heat exchanger and a cooler and then enter a high-pressure separation tank for gas-liquid separation, the gas phase separated by the high-pressure separation tank flows back to the raw material mixing unit through a pipeline, the separated liquid phase enters a low-pressure separation tank through a pipeline, the liquid phase separated by the low-pressure separation tank enters the middle lower part of a lightness-removing tower through a pipeline, the gas phase extracted from the top of the lightness-removing tower enters a phase separation tank after being cooled by a condenser, one part of the upper-layer materials of the phase separation tank flows back to the top of the lightness-removing tower, the other part of the upper-layer materials flows back to the raw material mixing unit, the materials at the bottom of the lightness-removing tower are conveyed to, an isopropanol product having a water content of no more than 0.1%.
The process system for producing the isopropanol by acetone hydrogenation is further optimized as follows: the raw materials mixing unit includes first blender and second blender, and first blender is used for the mixture of acetone raw materials and the material that phase separating tank circulates back, and the second blender is used for the mixture of the material that first blender mixes back, high pressure knockout drum circulate back material and hydrogen.
The process system for producing the isopropanol by acetone hydrogenation is further optimized as follows: a pressure reducing valve is arranged on a pipeline between the high-pressure separating tank and the low-pressure separating tank.
The method and the system for producing the isopropanol by hydrogenating the acetone have the following beneficial effects:
1. the isopropanol production system does not need a dehydration tower and subsequent recovery equipment of the hydrous isopropanol, thereby reducing the investment of the device and simplifying the separation process;
2. the isopropanol production method avoids the azeotropic separation process of isopropanol and water, does not generate hydrous isopropanol, and improves the total yield of the product isopropanol;
3. the isopropanol production method of the invention ensures the recovery of the unreacted acetone, avoids the circulation accumulation of water and reduces the unit consumption of the raw material acetone.
Drawings
FIG. 1 is a schematic flow diagram of a process system for the hydrogenation of acetone to produce isopropanol in example 4;
FIG. 2 is a schematic flow diagram of a process system for producing isopropanol by hydrogenating acetone in comparative example 1;
the labels in the figure are: r101, a hydrogenation reactor, T201, a light component removal tower, T202, a product tower, E101, a heater, E102, a heat exchanger, E103, a cooler, E201, a condenser, V103, a high-pressure separation tank, V104, a low-pressure separation tank, V201, a phase separation tank, H101, a first mixer, H102 and a second mixer.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
The technical solution of the present invention is further described below with reference to specific embodiments.
Example 1
A process for preparing isopropanol by hydrogenating acetone includes such steps as mixing acetone with n-hexane, mixing with hydrogen, heating, and hydrogenating in hydrogenation reactor. The hydrogenation reaction comprises the following specific steps: under the condition of hydrogen gas, acetone in the raw material contacts with catalyst filled in fixed bed to produce hydrogenation reaction to produce isopropanol, the catalyst is copper-based hydrogenation catalyst, and other metal components can be zinc, aluminium, chromium, manganese, magnesium, iron, potassium, sodium and calcium, etc., but it is not limited thereto, the copper-based hydrogenation catalyst makes the acetone contact with catalyst filled in fixed bed to produce isopropanolBefore use, reduction activation is carried out. The conditions of the hydrogenation reaction are as follows: reaction temperature: the reaction pressure is 5.0MPa at 200 ℃, the molecular ratio of hydrogen to acetone is 5.0, and the liquid phase volume space velocity of acetone is 3.0h-1。
After the material containing isopropanol, normal hexane, unreacted acetone, a small amount of water and a recombinant product is subjected to cooling and excessive hydrogen separation, the material enters a light component removal tower for separation, the unreacted acetone, the normal hexane and the water are extracted from the top of the light component removal tower for phase separation treatment, the water phase obtained by phase separation is discharged, the organic phase containing the solvent and the acetone obtained by phase separation is recycled to the inlet of the hydrogenation reactor for recycling, the bottom material of the light component removal tower enters a product tower, and the isopropanol product with the purity of more than 99.9 percent and the water content of not more than 0.1 percent is extracted from the top of the product tower.
Example 2
A process for preparing isopropanol by hydrogenating acetone includes such steps as mixing acetone with n-hexane, mixing with hydrogen, heating, and hydrogenating in hydrogenation reactor. The hydrogenation reaction comprises the following specific steps: under the condition of hydrogen, acetone in the raw material contacts with a catalyst filled in a fixed bed to generate a hydrogenation reaction to generate isopropanol, the catalyst is a copper-based hydrogenation catalyst, and other metal components can be zinc, aluminum, chromium, manganese, magnesium, iron, potassium, sodium, calcium and the like, but the copper-based hydrogenation catalyst is not limited to the copper-based hydrogenation catalyst, and reduction activation is carried out before the copper-based hydrogenation catalyst is used. The conditions of the hydrogenation reaction are as follows: reaction temperature: 250 ℃, reaction pressure: normal pressure, hydrogen to acetone molecular ratio: 1.0, acetone liquid phase feed volume space velocity: 0.2h-1。
After the material containing isopropanol, normal hexane, unreacted acetone, a small amount of water and a recombinant product is subjected to cooling and excessive hydrogen separation, the material enters a light component removal tower for separation, the unreacted acetone, the normal hexane and the water are extracted from the top of the light component removal tower for phase separation treatment, the water phase obtained by phase separation is discharged, the organic phase containing the solvent and the acetone obtained by phase separation is recycled to the inlet of the hydrogenation reactor for recycling, the bottom material of the light component removal tower enters a product tower, and the isopropanol product with the purity of more than 99.9 percent and the water content of not more than 0.1 percent is extracted from the top of the product tower.
Example 3
A process for preparing isopropanol by hydrogenating acetone includes such steps as mixing acetone with n-hexane, mixing with hydrogen, heating, and hydrogenating in hydrogenation reactor. The hydrogenation reaction comprises the following specific steps: under the condition of hydrogen, acetone in the raw material contacts with a catalyst filled in a fixed bed to generate a hydrogenation reaction to generate isopropanol, the catalyst is a copper-based hydrogenation catalyst, and other metal components can be zinc, aluminum, chromium, manganese, magnesium, iron, potassium, sodium, calcium and the like, but the copper-based hydrogenation catalyst is not limited to the copper-based hydrogenation catalyst, and reduction activation is carried out before the copper-based hydrogenation catalyst is used. The conditions of the hydrogenation reaction are as follows: reaction temperature: 150 ℃, reaction pressure: 2.0MPa, hydrogen to acetone molecular ratio: 100, acetone liquid phase feed volume space velocity: 2.0h-1。
After the material containing isopropanol, normal hexane, unreacted acetone, a small amount of water and a recombinant product is subjected to cooling and excessive hydrogen separation, the material enters a light component removal tower for separation, the unreacted acetone, the normal hexane and the water are extracted from the top of the light component removal tower for phase separation treatment, the water phase obtained by phase separation is discharged, the organic phase containing the solvent and the acetone obtained by phase separation is recycled to the inlet of the hydrogenation reactor for recycling, the bottom material of the light component removal tower enters a product tower, and the isopropanol product with the purity of more than 99.9 percent and the water content of not more than 0.1 percent is extracted from the top of the product tower.
Example 4
A process system for producing isopropanol by acetone hydrogenation comprises a raw material mixing unit, a hydrogenation reactor R101, a high-pressure separation tank V103, a low-pressure separation tank V104, a light component removal tower T201, a phase separation tank V201 and a product tower T202;
the raw materials mixing unit includes first blender H101 and second blender H102, and first blender H101 is used for the mixture of acetone raw materials and the material that phase separation jar V201 circulated back, and second blender H102 is used for the mixture of the material that first blender H101 mixes back, the material that high pressure knockout drum V103 circulated back and hydrogen. The material mixed by the raw material mixing unit is heated by a heat exchanger E102 and a heater E101 to 190 ℃, the heated material becomes a gas phase state and enters a hydrogenation reactor R101 from the upper part of the reactor to contact with a catalystHydrogenation reaction is carried out, the hydrogenation catalyst is a copper-zinc-aluminum catalyst, and the bulk density of the hydrogenation catalyst is 1.36g/cm3The normal hexane is not reacted, after the temperature of a material subjected to hydrogenation reaction is reduced through a heat exchanger E102 and a cooler E103 (cooled to 40 ℃), the material enters a high-pressure separation tank V103 for gas-liquid separation, a gas phase separated by the high-pressure separation tank V103 flows back to a raw material mixing unit through a pipeline, a separated liquid phase enters a low-pressure separation tank V104 through a pipeline, dissolved hydrogen in a product is further released, a pressure reducing valve is arranged on a pipeline between the high-pressure separation tank V103 and the low-pressure separation tank V104, the separated liquid phase enters a low-pressure separation tank V104 after pressure reduction, the liquid phase separated by the low-pressure separation tank V104 enters the middle lower portion of a light-weight separation tower T201 through a pipeline, the classical liquid phase composition is 1.6% of acetone, 0.3% of water, 93.8% of the isopropyl alcohol, 0.8% of the MIBC, 3.5% of the light-weight T201 is a floating valve, the operation of the floating valve, the normal-pressure separation tower top of the light-weight recovery tower is a tower top water phase recovery tower, the light-phase recovery tower is a tower top water-recovery tower, the light-phase recovery tower, the light-recovery tower is a tower top water-phase-recovery tower, the light-recovery water-recovery tower top water-recovery tower, the light-recovery tower is a light-recovery tower, the light-phase-recovery tower top water-recovery tower, the light-recovery tower top water-recovery tower, the light-recovery tower is a light-recovery tower top water-recovery tower, the light-recovery tower is a light-recovery tower, the light-recovery tower is a light-recovery tower, the light-recovery tower.
Comparative example 1
Mixing a raw material with 99.8% of acetone and 0.2% of water with unreacted acetone circulated back, boosting the pressure to 4.0MPa by a feed pump, entering a pipeline mixer through a pipeline to mix with hydrogen, entering a reactor inlet and outlet heat exchanger E102, entering a reactor inlet heater E101 for heating the raw material after heat exchange to 190 ℃, entering a hydrogenation reactor R101 from the upper part of the reactor in a gas phase state to contact with a catalyst for hydrogenation reaction, wherein the hydrogenation catalyst adopts a copper-zinc-aluminum catalyst, the stacking density of the copper-zinc-aluminum catalyst is 1.36g/cm3, the size of the copper-zinc-aluminum catalyst is phi 4.5 × -5, converting about 98% of acetone into isopropanol and a small amount of recombinant MIBC (methyl isobutyl carbinol), cooling the reacted gas-phase product to 40 ℃ by a reactor inlet and outlet heat exchanger E102 and a hydrogenation product cooler E103, entering a high-pressure separation tank V103 for gas-liquid separation, circulating excessive hydrogen and a small amount of non-condensable gas to the feeding tower inlet in a gas-phase mode, entering a low-pressure separation tank V104, further releasing the tower top of the tower, introducing the product into a tower top of a light liquid-phase reflux tower with a theoretical water reflux ratio T20.20% of acetone, wherein the acetone is equal to 60% of acetone, the acetone is equal to 20.1.2% of the acetone, the acetone is equal to 20%, the acetone, the light liquid-35.2% of the light liquid-35% of the light liquid-isopropyl alcohol, the light liquid-35% of the light-35% of the light.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. A process method for producing isopropanol by acetone hydrogenation is characterized in that: introducing a solvent which is inert to the ketone hydrogenation reaction in the hydrogenation process, wherein the solvent is immiscible with water and can form a lowest azeotropic substance with water, the solvent enters a light component removal tower along with the hydrogenated material, the solvent and the water are extracted from the top of the light component removal tower in the light component removal tower, the material at the bottom of the tower directly enters a product tower without dehydration, and the isopropanol is obtained from the top of the product tower.
2. The process for the hydrogenation of acetone to produce isopropanol as claimed in claim 1 wherein: mixing acetone and a solvent, then mixing the mixture with hydrogen, heating the mixed material, then adding the heated material into a hydrogenation reactor for hydrogenation reaction, cooling the hydrogenated material containing isopropanol, the solvent, unreacted acetone, a small amount of water and a recombinant, separating the material from an excessive hydrogen in a lightness-removing column, extracting unreacted acetone, the solvent and part of water from the top of the lightness-removing column for phase separation treatment, discharging a water phase obtained by phase separation, recycling an organic phase containing the solvent and acetone to the inlet of the hydrogenation reactor for recycling, feeding a bottom material of the lightness-removing column into a product column, and extracting an isopropanol product with the purity of more than 99.9% and the water content of not more than 0.1% from the top of the product column.
3. The process for the hydrogenation of acetone to produce isopropanol according to claim 1 or 2, wherein: the solvent is benzene, cyclohexane or n-hexane.
4. The process for the hydrogenation of acetone to produce isopropanol according to claim 1 or 2, wherein: the hydrogenation reaction specifically comprises the following steps: under the condition of hydrogen, acetone in the raw material contacts with a catalyst filled in a fixed bed to generate hydrogenation reaction to generate isopropanol.
5. The process for the hydrogenation of acetone to produce isopropanol as claimed in claim 4 wherein: the catalyst used in the hydrogenation reaction is a copper-based hydrogenation catalyst.
6. The process for the hydrogenation of acetone to produce isopropanol as claimed in claim 5 wherein: the conditions of the hydrogenation reaction are as follows: reaction temperature: reaction pressure at 100-250 ℃: normal pressure to 6.0MPa, molecular ratio of hydrogen to acetone: 1.0-100.0, acetone liquid phase feeding volume airspeed: 0.2 to 5.0 hours-1。
7. The process for the hydrogenation of acetone to produce isopropanol as claimed in claim 6 wherein: the conditions of the hydrogenation reaction are as follows: reaction temperature: the reaction pressure is 1.0-5.0 MPa at 150-200 ℃, the molecular ratio of hydrogen to acetone is 5.0-10.0, and the liquid phase volume space velocity of acetone is 1.0-3.0 h-1。
8. A process system for producing isopropanol by acetone hydrogenation is characterized in that: comprises a raw material mixing unit, a hydrogenation reactor, a high-pressure separation tank, a low-pressure separation tank, a light component removal tower, a phase separation tank and a product tower;
the materials mixed by the raw material mixing unit are heated by a heat exchanger and a heater, the heated materials are in a gas phase state and enter a hydrogenation reactor from the upper part of the reactor, the materials after hydrogenation reaction are cooled by the heat exchanger and a cooler and then enter a high-pressure separation tank for gas-liquid separation, the gas phase separated by the high-pressure separation tank flows back to the raw material mixing unit through a pipeline, the separated liquid phase enters a low-pressure separation tank through a pipeline, the liquid phase separated by the low-pressure separation tank enters the middle lower part of a lightness-removing tower through a pipeline, the gas phase extracted from the top of the lightness-removing tower enters a phase separation tank after being cooled by a condenser, one part of the upper-layer materials of the phase separation tank flows back to the top of the lightness-removing tower, the other part of the upper-layer materials flows back to the raw material mixing unit, the materials at the bottom of the lightness-removing tower are conveyed to, an isopropanol product having a water content of no more than 0.1%.
9. The process system for producing isopropanol by hydrogenating acetone according to claim 8, wherein: the raw materials mixing unit includes first blender and second blender, and first blender is used for the mixture of acetone raw materials and the material that phase separating tank circulates back, and the second blender is used for the mixture of the material that first blender mixes back, high pressure knockout drum circulate back material and hydrogen.
10. The process system for producing isopropanol by hydrogenating acetone according to claim 8, wherein: a pressure reducing valve is arranged on a pipeline between the high-pressure separating tank and the low-pressure separating tank.
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| CN102690172A (en) * | 2011-03-25 | 2012-09-26 | 中国石油化工股份有限公司 | Method for producing isopropanol by acetone hydrogenation |
| CN106905114A (en) * | 2015-12-23 | 2017-06-30 | 中国石油天然气股份有限公司 | Method and device for separating isopropanol from aqueous acetone hydrogenation product |
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| CN102690172A (en) * | 2011-03-25 | 2012-09-26 | 中国石油化工股份有限公司 | Method for producing isopropanol by acetone hydrogenation |
| CN106905114A (en) * | 2015-12-23 | 2017-06-30 | 中国石油天然气股份有限公司 | Method and device for separating isopropanol from aqueous acetone hydrogenation product |
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| CN116041144A (en) * | 2022-11-01 | 2023-05-02 | 上海化盈通电子商务有限公司 | Method for producing isopropanol by acetone hydrogenation |
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