CN115536507B - Process for producing butanone from butadiene - Google Patents
Process for producing butanone from butadiene Download PDFInfo
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- CN115536507B CN115536507B CN202110729195.3A CN202110729195A CN115536507B CN 115536507 B CN115536507 B CN 115536507B CN 202110729195 A CN202110729195 A CN 202110729195A CN 115536507 B CN115536507 B CN 115536507B
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- butanone
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 186
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000008569 process Effects 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000003377 acid catalyst Substances 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 230000009471 action Effects 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 30
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- IVKNZCBNXPYYKL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical group CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 IVKNZCBNXPYYKL-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 208000012839 conversion disease Diseases 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- -1 ketone compounds Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- LPRSRULGRPUBTD-UHFFFAOYSA-N butan-2-one;hydrate Chemical compound O.CCC(C)=O LPRSRULGRPUBTD-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- KXUHSQYYJYAXGZ-UHFFFAOYSA-N isobutylbenzene Chemical compound CC(C)CC1=CC=CC=C1 KXUHSQYYJYAXGZ-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000002966 varnish Substances 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
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a process method for producing butanone from butadiene, and belongs to the technical field of butanone production. The invention comprises the following steps: (1) Heating butadiene and desalted water in a heat exchanger, then entering a main reactor, and reacting the butadiene with water under the action of an acid catalyst to generate butanone; (2) Butadiene, water and butanone enter a first rectifying tower, separation is realized through rectification, butadiene at the top of the tower and water are mixed and then enter a heat exchanger for heating, and then enter a secondary reactor for reaction under the action of an acid catalyst to generate butanone; (3) Butadiene, water and butanone enter a second rectifying tower, unreacted butadiene is obtained at the top of the second rectifying tower, a butanone and water mixture obtained at the bottoms of the first rectifying tower and the second rectifying tower enter a third rectifying tower, butanone is obtained at the top of the third rectifying tower, and water is obtained at the bottom of the third rectifying tower. The method has simple flow, directly converts butadiene into butanone, has lower energy consumption and higher economic benefit.
Description
Technical Field
The invention relates to a process method for producing butanone from butadiene, and belongs to the technical field of butanone production.
Background
Butanone is also known as 2-butanone, and is commonly known as MEK in factories and is a colorless liquid. Melting point-85.9 ℃, boiling point 79.6 ℃, relative density 0.8054 (20 ℃/4 ℃ water=1), gas phase relative density 2.42 (air=1). Is soluble in about 4 times of water and can be dissolved in organic solvents such as ethanol, diethyl ether and the like. A constant boiling mixture (88.7% butanone) with water was formed, boiling at 73.4 ℃. Can be used as paint and varnish, adhesive, dewaxing agent, and solution of ethylene copolymer or other resin for coating paper or fabric, extractant, etc.
In cracking carbon four, the butadiene ratio exceeds 50%, and the yield of the cracking device is greatly increased along with the rapid increase of the number of the cracking devices. Butadiene is mainly used as Styrene Butadiene Rubber (SBR), polybutadiene rubber (PBR), styrene thermoplastic elastomer (SBS) and ABS resin and other raw materials. At present, the domestic butadiene production capacity is about 450 ten thousand tons, the actual butadiene production capacity is about 300 ten thousand tons, the device operating rate is about 67%, and the butadiene device operating rate is further reduced along with the dispute of newly-built steam cracking devices.
The butanone production method includes sec-butanol dehydrogenation, direct butene oxidation, liquid butane oxidation, isobutylbenzene, isobutylaldehyde isomerization, biological fermentation, etc. The current mainstream of production is still the dehydrogenation of sec-butanol. The macroporous strong acid ion exchange resin is used as a catalyst, the n-butene is hydrated to generate sec-butyl alcohol, and then the sec-butyl alcohol is dehydrogenated to generate butanone.
The patent CN105967989A provides a process for preparing butanone from sec-butanol, which adopts a fixed bed reactor, the reaction temperature is 200-250 ℃, the reaction pressure is 0.01-0.2 MPa, and the airspeed is 0.1-10 h -1 The sec-butyl alcohol is contacted with the copper-based catalyst to perform dehydrogenation reaction, and the conversion rate of the sec-butyl alcohol is improved and the occurrence of side reaction is obviously inhibited by adding a trace amount of hydrogen and water. However, the raw material sec-butyl alcohol of the invention is mainly obtained by hydration of 2-butene, and then oxidative dehydrogenation is carried out to generate butanone, so that the process flow is complex and the total conversion rate is low.
The patent CN91103052 provides a preparation method of ketone, which adopts a catalytic system composed of VIII family metal source and protonic acid to convert conjugated diene and water into corresponding ketone compounds. However, the catalytic system adopted in the reaction is complex, one metal of ruthenium, rhodium, iridium and iron in the VIII group is required, a proper ligand and protonic acid are also required to ensure the catalytic effect, the conjugated diene is converted into the ketone compound, and in the production process, a solvent is required, and the separation of the ketone compound and the solvent is required to be considered.
Disclosure of Invention
The invention aims to provide a process method for producing butanone by butadiene, which has simple flow, directly converts butadiene into butanone, has lower energy consumption and higher economic benefit.
The technological process of producing butanone with butadiene includes the following steps:
(1) Heating butadiene and desalted water in a heat exchanger, then entering a main reactor, and reacting the butadiene with water under the action of an acid catalyst to generate butanone;
(2) Butadiene, water and butanone enter a first rectifying tower, separation is realized through rectification, butadiene at the top of the tower and water are mixed and then enter a heat exchanger for heating, and then enter a secondary reactor for reaction under the action of an acid catalyst to generate butanone;
(3) Butadiene, water and butanone enter a second rectifying tower, unreacted butadiene is obtained at the top of the second rectifying tower, a butanone-water mixture obtained at the bottoms of the first rectifying tower and the second rectifying tower enters a third rectifying tower, 88.7% of butanone is obtained at the top of the third rectifying tower, and water is obtained at the bottom of the third rectifying tower.
Preferably, in the step (1), the molar ratio of desalted water to butadiene is 3 to 20.
The acid catalyst is an activated carbon supported acid catalyst, a resin catalyst, a super acidic catalyst or a solid phosphoric acid catalyst.
Preferably, the solid phosphoric acid catalyst is modified by phosphomolybdic acid, and the mass content of molybdenum in the prepared modified solid phosphoric acid catalyst is 3-6%.
Specifically, the preparation method of the modified solid phosphoric acid catalyst comprises the following steps:
mixing 50-100 meshes of silicon oxide powder with 20-30% of phosphoric acid aqueous solution according to the ratio of 0.5-1.5:1, filtering to obtain filter residue and filtrate after adsorption saturation, drying the filter residue at 150 ℃, roasting at 500-600 ℃, and grinding the roasted solid into 70-120 meshes of powder; uniformly mixing the powder, a binder and phosphomolybdic acid according to a certain proportion, extruding strips, controlling the mole ratio of phosphorus to molybdenum to be 10-15:1, drying the catalyst at 120 ℃, and roasting at 500-700 ℃; and (3) introducing air with the water mass content of 3-6% into the catalyst during roasting so as to improve the strength of the catalyst.
In step (1), a solubilizing agent is added to the main reactor. Because the polarity difference of water and butadiene is more, the solubility is poorer, in order to promote the solubility of the water and the butadiene, the reaction rate is ensured, and the solubilization is realized by adopting an organic solvent.
Preferably, the solubilizer is OP-10, butanone or sec-butanol. Butanone is more preferred.
Preferably, the mass ratio of butadiene to solubilizer is 1:1-1:6.
The process conditions of the main reactor and the auxiliary reactor are as follows: the temperature is 150-350 ℃, the pressure is 0.5-1.0 MPa, and the volume airspeed is 0.3-5 h -1 . Preferably, the temperature is 200-250 ℃, the pressure is 0.5-0.3 MPa, and the volume airspeed is 0.5-2 h -1 。
The first rectifying tower and the second rectifying tower can adopt a plate tower or a filler tower, and the process conditions are as follows: the tower plate number is 10-50, the tower top pressure is 0.02-1.5 MPa, the tower bottom pressure is 0.05-1.6 MPa, the tower top temperature is 40-90 ℃, and the tower bottom temperature is 90-180 ℃. Preferably, the tower plate number is 20-40, the tower top pressure is 0.8-1.2 MPa, the tower bottom pressure is 0.9-1.3 MPa, the tower top temperature is 55-80 ℃, and the tower bottom temperature is 105-155 ℃.
The third rectifying tower can adopt a plate tower or a packed tower, and the process conditions are as follows: the tower plate number is 5-50, the tower top pressure is 0.02-1.5 MPa, the tower bottom pressure is 0.05-1.6 MPa, the tower top temperature is 60-120 ℃, and the tower bottom temperature is 120-200 ℃. Preferably, the tower plate number is 10-20, the tower top pressure is 0.1-0.5 MPa, the tower bottom pressure is 0.2-0.6 MPa, the tower top temperature is 65-100 ℃, and the tower bottom temperature is 110-150 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts a simple acid catalyst, directly converts butadiene into butanone in a two-section fixed bed reactor, and then obtains 88.7wt% of butanone through rectification;
(2) According to the invention, the solubilizer is added, so that the later separation cost is reduced;
(3) The invention has simple process flow, lower energy consumption and higher economic benefit.
Drawings
FIG. 1 is a schematic illustration of the process flow of the present invention;
wherein: 1. a heat exchanger; 2. a main reactor; 3. a first rectifying column; 4. a heat exchanger; 5. a secondary reactor; 6. a second rectifying column; 7. and a third rectifying tower.
Detailed Description
The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples.
A process method for producing butanone by butadiene comprises the following steps:
(4) Butadiene and desalted water are heated in a heat exchanger 1 and then enter a main reactor 2, and under the action of an acid catalyst, the butadiene reacts with water to generate butanone;
(5) Butadiene, water and butanone enter a first rectifying tower 3, separation is realized through rectification, the butadiene at the top of the tower and the water are mixed and then enter a heat exchanger 4 for heating, and then enter a secondary reactor 5 for reaction under the action of an acid catalyst to generate butanone;
(6) Butadiene, water and butanone enter a second rectifying tower 6, unreacted butadiene is obtained at the top of the tower, a butanone-water mixture obtained at the bottoms of the first rectifying tower 3 and the second rectifying tower 6 enters a third rectifying tower 7, butanone is obtained at the top of the tower, and water is obtained at the bottom of the tower.
Example 1
Effect of water to butadiene molar ratio on butadiene conversion and butanone selectivity:
the effect of water to butadiene molar ratio on butadiene conversion and butanone selectivity using the resin catalyst according to the process scheme is shown in table 1.
TABLE 1 influence of the molar ratio of water to butadiene on the conversion and selectivity
As can be seen from Table 1, the water to butadiene molar ratio has a large effect on butadiene conversion and butanone selectivity. According to the reaction chemical balance, the mole ratio of water to butadiene is 1, but when the mole ratio of water to butadiene is relatively low, butadiene is easy to undergo oligomerization reaction under the action of an acid catalyst, so that side reactions are more. With the increase of the water consumption, the rate of polymerization side reaction of butadiene is greatly reduced, and the butadiene conversion rate and butanone selectivity are increased. The molar ratio of water to butadiene is in a certain range, and the butadiene conversion and butanone selectivity are basically unchanged. As the water usage continues to increase, the butadiene concentration decreases resulting in poor conversion and butanone selectivity.
Example 2
Influence of catalyst type on butadiene conversion and butanone selectivity:
the effect of catalyst type on butadiene conversion and butanone selectivity according to the process of the present invention with a water to butadiene molar ratio of 5 is shown in table 2.
As can be seen from table 2, the catalyst type has a large influence on the butadiene conversion and butanone selectivity. At high temperature, the acidity of the resin catalyst is low, and the catalyst effect is poor; the activity of the activated carbon supported acid catalyst is substantially equal to that of the resin catalyst, and the butadiene conversion rate and butanone selectivity are substantially equal. The solid acid and the super acid are used as catalysts, so that the conversion rate and the selectivity of butadiene are increased. After modification, when the mass content of molybdenum is 3.5%, the butadiene conversion rate and the selectivity are both highest.
TABLE 2 influence of catalyst species on conversion and selectivity
Example 3
Influence of reaction space velocity on butadiene conversion and butanone selectivity:
according to the process flow of the present invention, the effect of the space velocity of the reaction on butadiene conversion and butanone selectivity using the modified solid phosphoric acid catalyst at a water to butadiene molar ratio of 5 is shown in Table 3.
TABLE 3 influence of catalyst species on conversion and selectivity
As can be seen from Table 3, the volume space velocity has a large effect on butadiene conversion and butanone selectivity. At lower volume space velocity, longer residence time, higher reaction conversion, but lower selectivity. As the volumetric space velocity increases, the reaction conversion decreases, but the selectivity increases; as the volumetric space velocity further increases, the reaction conversion continues to decrease, as does the selectivity.
Example 4
Effect of butadiene to butanone mass ratio on butadiene conversion and butanone selectivity:
the effect of butadiene to butanone mass ratio on butadiene conversion and butanone selectivity using a modified solid phosphoric acid catalyst according to the process of the present invention, with a water to butadiene molar ratio of 5, is shown in table 4.
TABLE 4 influence of catalyst species on conversion and selectivity
As can be seen from Table 4, the butadiene to butanone mass ratio has a greater impact on butadiene conversion and butanone selectivity. When the mass ratio of butadiene to butanone is low, the miscibility effect of butadiene and water in butanone is poor, so that the conversion rate and selectivity of the reaction are low; as the mass ratio of butadiene to butanone increases, the miscibility effect of butadiene and water in butanone becomes better, and the conversion rate and selectivity of the corresponding reaction are both increased; as the mass ratio of butadiene to butanone increases, the concentration of butadiene and water decreases significantly, resulting in a significant decrease in the conversion and selectivity of the reaction.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (9)
1. A process method for producing butanone by butadiene is characterized in that: the method comprises the following steps:
(1) Heating butadiene and desalted water in a heat exchanger, then entering a main reactor, and reacting the butadiene with water under the action of an acid catalyst to generate butanone;
(2) Butadiene, water and butanone enter a first rectifying tower, separation is realized through rectification, butadiene at the top of the tower and water are mixed and then enter a heat exchanger for heating, and then enter a secondary reactor for reaction under the action of an acid catalyst to generate butanone;
(3) Butadiene, water and butanone enter a second rectifying tower, unreacted butadiene is obtained at the top of the second rectifying tower, a butanone and water mixture obtained at the bottoms of the first rectifying tower and the second rectifying tower enter a third rectifying tower, butanone is obtained at the top of the third rectifying tower, and water is obtained at the bottom of the third rectifying tower;
the acidic catalyst is a solid phosphoric acid catalyst, the solid phosphoric acid catalyst is obtained by modifying the solid phosphoric acid catalyst by phosphomolybdic acid, and the mass content of molybdenum in the prepared modified solid phosphoric acid catalyst is 3-6%;
the preparation method of the modified solid phosphoric acid catalyst comprises the following steps: mixing 50-100 meshes of silicon oxide powder with 20-30% of phosphoric acid aqueous solution according to the ratio of 0.5-1.5:1, filtering to obtain filter residue and filtrate after adsorption saturation, drying the filter residue at 150 ℃, roasting at 500-600 ℃, and grinding the roasted solid into 70-120 meshes of powder; uniformly mixing the powder, a binder and phosphomolybdic acid according to a certain proportion, extruding strips, controlling the mole ratio of phosphorus to molybdenum to be 10-15:1, drying the catalyst at 120 ℃, and roasting at 500-700 ℃; and (3) introducing air with the water mass content of 3-6% into the catalyst during roasting so as to improve the strength of the catalyst.
2. The process for producing butanone from butadiene as claimed in claim 1, wherein: in the step (1), the molar ratio of desalted water to butadiene is 3-20.
3. The process for producing butanone from butadiene as claimed in claim 1, wherein: the solid phosphoric acid catalyst is modified by phosphomolybdic acid, and the mass content of molybdenum in the prepared modified solid phosphoric acid catalyst is 3-6%.
4. The process for producing butanone from butadiene as claimed in claim 1, wherein: in step (1), a solubilizing agent is added to the main reactor.
5. The process for producing butanone from butadiene as claimed in claim 4, wherein: the solubilizer is OP-10, butanone or sec-butanol.
6. The process for producing butanone from butadiene as claimed in claim 4, wherein: the mass ratio of butadiene to the solubilizer is 1:1-1:6.
7. The process for producing butanone from butadiene as claimed in claim 1, wherein: the process conditions of the main reactor and the auxiliary reactor are as follows: the temperature is 150-350 ℃, the pressure is 0.5-1.0 MPa, and the volume airspeed is 0.3-5 h < -1 >.
8. The process for producing butanone from butadiene as claimed in claim 1, wherein: the process conditions of the first rectifying tower and the second rectifying tower are as follows: the tower plate number is 10-50, the tower top pressure is 0.02-1.5 MPa, the tower bottom pressure is 0.05-1.6 MPa, the tower top temperature is 40-90 ℃, and the tower bottom temperature is 90-180 ℃.
9. The process for producing butanone from butadiene as claimed in claim 1, wherein: the process conditions of the third rectifying tower are as follows: the tower plate number is 5-50, the tower top pressure is 0.02-1.5 MPa, the tower bottom pressure is 0.05-1.6 MPa, the tower top temperature is 60-120 ℃, and the tower bottom temperature is 120-200 ℃.
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