CN114685257A - Method for synthesizing methyl isoamyl ketone - Google Patents
Method for synthesizing methyl isoamyl ketone Download PDFInfo
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- CN114685257A CN114685257A CN202011635892.4A CN202011635892A CN114685257A CN 114685257 A CN114685257 A CN 114685257A CN 202011635892 A CN202011635892 A CN 202011635892A CN 114685257 A CN114685257 A CN 114685257A
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- isobutyraldehyde
- acetone
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- hydrogenation
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- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 71
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000009833 condensation Methods 0.000 claims abstract description 24
- 230000005494 condensation Effects 0.000 claims abstract description 24
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 20
- SHOJXDKTYKFBRD-UHFFFAOYSA-N 4-Methyl-3-penten-2-one, 9CI Chemical compound CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 16
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 9
- 238000006482 condensation reaction Methods 0.000 description 9
- 150000001299 aldehydes Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 125000002587 enol group Chemical group 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- -1 ketone aldehyde Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
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Abstract
The invention discloses a method for synthesizing methyl isoamyl ketone. Mixing acetone and isobutyraldehyde, and then carrying out condensation dehydration reaction in a reactor containing a phosphonic acid resin catalyst under the condition of ketone-aldehyde condensation process; directly mixing the obtained reaction effluent with hydrogen without separation, and then carrying out hydrogenation under the hydrogenation reaction condition through a reactor containing a hydrogenation catalyst; and separating the obtained hydrogenation reaction effluent to obtain the methyl isoamyl ketone. The method has higher MIAK selectivity and higher industrial feasibility.
Description
Technical Field
The invention relates to a method for synthesizing methyl isoamyl ketone.
Background
Methyl isoamyl ketone (MIAK), also known as 2-octanone, has been widely used in high solids coatings and synthetic acrylic resins. With the increasingly strict requirements on environmental protection, the demand of high-solid coatings is on the increase trend, and the dosage of MIAK is also increased greatly. At present, domestic MIAK is mainly dependent on import. Therefore, the development of a method for producing MIAK is under way.
The general method for producing MIAK is: acetone and isobutyraldehyde are used as raw materials, and are condensed and dehydrated to generate 5-methyl-3-alkene-2-hexanone, and then the MIAK is generated by hydrogenation. The disadvantage of this process is that the condensation of isobutyraldehyde with isobutyraldehyde and acetone with acetone itself is accelerated by catalysis with acid or base catalysts in the first step, which leads to an increase in the by-products of the aldol condensation and a corresponding decrease in the MIAK selectivity.
Disclosure of Invention
Theoretically, the ketone (aldehyde) condensation can be catalyzed by an acid. For example, the technology for producing methyl isobutyl ketone by condensation and hydrogenation of acetone adopts sulfonic acid resin, and has good effect. However, the ketone-aldehyde condensation is not suitable if a sulfonic acid resin is used. Since both ketone and aldehyde are easily activated by the catalysis of sulfonic acid resin, the respective ketone-ketone condensation and aldehyde condensation reaction easily occurs, and thus, the ketone-aldehyde condensation product has low selectivity.
The technical problem to be solved by the invention is to provide a novel method for synthesizing methyl isoamyl ketone from acetone and isobutyraldehyde.
The method for synthesizing methyl isoamyl ketone by acetone and isobutyraldehyde comprises the following steps:
(1) mixing acetone and isobutyraldehyde, and then carrying out condensation dehydration reaction in a reactor containing a phosphonic acid resin catalyst under the condition of ketone-aldehyde condensation process;
(2) directly mixing the reaction effluent obtained in the step (1) without separation (optional separation) with hydrogen, and then, passing the mixture through a reactor containing a hydrogenation catalyst to carry out hydrogenation under the hydrogenation reaction condition;
(3) and (3) separating the hydrogenation reaction effluent obtained in the step (2) to obtain methyl isoamyl ketone.
Further, the water content (ratio) of the phosphonic acid resin catalyst is generally 35-65 wt%. The total acid of the catalyst was (90 ℃, NH)3TPD determination) 1.0-4.0 mmol/g; acid distribution (NH)3TPD assay): 2 to 20 percent at the temperature of 90 to 110 ℃; 3 to 30 percent at the temperature of 110 to 120 ℃; 5 to 50 percent of the temperature of 120 to 140 ℃;>40 to 90 percent at 140 ℃.
Furthermore, the water content (rate) of the phosphonic acid resin catalyst is 40-60 wt%; total acid (90 ℃, NH)3TPD measurement) 1.5 to 3.0mmol/g, acid distribution (NH)3TPD assay) was: 4 to 9 percent at the temperature of 90 to 110 ℃; 4 to 15 percent at the temperature of 110 to 120 ℃; 6 to 30 percent at the temperature of 120 to 140 ℃;>50 to 90 percent at 140 ℃.
Furthermore, the specific surface area of the phosphonic acid resin catalyst is generally 8-15 m2The specific pore volume is 0.01-0.04 mL/g, and the average pore diameter is 60-140 ANG; preferably: the specific surface area is 10-13 m2And/g, the average pore diameter is 80-110A, and the pore volume is 0.02-0.03 mL/g.
The phosphonic acid resin catalyst can be prepared by a conventional method in the field. A typical preparation method is as follows: polystyrene resin is selected as a supporter, phosphorus trichloride reacts with a Friedel-crafts catalyst, and anhydrous aluminum trichloride is selected as the Friedel-crafts catalyst. After the reaction, alkali is used for hydrolysis, and nitric acid and the like are used for oxidation to obtain the phosphonic acid resin.
Further, the ketone-aldehyde condensation process conditions in the step (1) are as follows: the reaction pressure is 2.0MPa to 6.0MPa, preferably 2.5MPa to 4.0 MPa; the inlet temperature is 80-150 ℃, preferably 80-140 ℃, and the total volume space velocity of acetone and isobutyraldehyde is 0.1h-1～5.0h-1Preferably 0.5h-1～4.0h-1(ii) a The molar ratio of acetone to isobutyraldehyde is 0.5:1 to 4:1, preferably 1:1 to 3: 1.
Go toThe hydrogenation catalyst is selected from conventional hydrogenation catalysts and can be divided into noble metal catalysts and non-noble metal catalysts. The support is generally selected from Al2O3Containing SiO2Al of (2)2O3、TiO2Molecular sieve-containing Al2O3And activated carbon. The non-noble metal catalyst is one or more of W, Mo, Ni and Co, and the non-noble metal is preferably Ni catalyst. The noble metal typically comprises one or more of Pt, Pd and Re, with Pd catalysts being preferred. The content of the noble metal is generally 0.1 to 1.0 percent by weight calculated by metal; the content of the non-noble metal component is generally 5.0 wt% -42.0 wt%.
Further, the hydrogenation process conditions in the step (2) are as follows: the reaction pressure is 1.0MPa to 8.0MPa, preferably 2.0MPa to 6.0 MPa; the reaction temperature is 40-180 ℃, preferably 50-140 ℃; volume space velocity of 0.5h-1～4.0 h-1Preferably 0.5h-1～2.0 h-1(ii) a The volume ratio of the hydrogen liquid is 100 to 500, preferably 200 to 400.
Further, the separation in step (3) generally includes gas-liquid separation and fractionation. And (3) carrying out gas-liquid separation on the hydrogenation reaction effluent, separating hydrogen from the reaction liquid, and fractionating the obtained reaction liquid to obtain an MIAK product. The fractionation process may employ a rectification operation well known in the art. The hydrogen can be recycled. And (3) separating the excessively hydrogenated alkane from the reaction liquid by a light component tower, sequentially separating water, acetone, isobutyraldehyde and methyl isobutyl ketone, and finally obtaining MIAK at the top of the product tower and heavy components at the bottom of the tower.
Further, the reactor may be in any reactor form, such as a fluidized bed, an ebullating bed, a moving bed, or a fixed bed reactor, preferably a fixed bed reactor.
The current method for synthesizing MIAK is a kettle type batch method, which is completed by two steps: the first step of synthesizing 5-methyl-3-alkene-2-hexanone uses acid or alkali as catalyst. The second step is to carry out olefin hydrogenation saturation on the ketene generated in the first step, and a conventional hydrogenation catalyst is adopted. Theoretically, the ketone (aldehyde) condensation can be catalyzed by an acid. For example, the technique for producing methyl isobutyl ketone by condensation and hydrogenation of acetone adopts sulfonic acid resin, and has good effect. However, the ketone-aldehyde condensation is not suitable if a sulfonic acid resin is used, and industrialization is difficult to realize due to low selectivity of the ketone-aldehyde condensation product. In the first step, sulfonic acid type resin catalyst is usually selected for acid catalysis, and both ketone and aldehyde are easy to be activated, so that when the catalyst is used for ketone aldehyde condensation, a large amount of self-condensation reaction of acetone and self-condensation reaction of isobutyraldehyde and isobutyraldehyde can easily occur. The amount of by-products generated in the condensation reaction of ketone and aldehyde is large, and the selectivity of the target product is not high. The method is difficult to industrialize due to poor economy. Aiming at the problems, the invention is based on the research on the principle of ketone-aldehyde condensation reaction, selects a special resin, namely phosphonic acid resin, carries out ketone-aldehyde condensation reaction on a phosphonic acid resin catalyst, then carries out hydrogenation, and synthesizes MIAK through two-step reaction.
Wherein, a phosphonic acid type resin catalyst is selected in the first step of condensation dehydration reaction, and the reaction formula is shown as formula (1):
in the second hydrogenation step, a conventional Pd-based or Ni-based hydrogenation catalyst is selected, and the reaction formula is shown as formula (2):
the research of the inventor of the application finds that the selectivity of the ketone-aldehyde condensation product is unexpectedly and greatly improved by adopting the phosphonic acid type resin catalyst, the generation of byproducts of the ketone-ketone condensation and aldehyde condensation reaction is greatly reduced, and the economic efficiency is higher.
Compared with the prior art, the method for synthesizing methyl isoamyl ketone by the two-step method has the following beneficial effects:
1. in the process of synthesizing MIAK, the first step of condensation dehydration reaction adopts a phosphonic acid type resin catalyst, the resin catalyst reduces the byproducts of the ketone condensation reaction and the aldehyde condensation reaction, and the selectivity of 5-methyl-3-alkene-2-hexanone is obviously improved. This is because, when a sulfonic resin is used as a catalyst: acetone is protonated by carbonyl first and then forms an enol-type structure as shown in a formula (3); at the same time, isobutyraldehyde is protonated by carbonyl group and then forms enol structure, as shown in formula (4). In this case, a condensation product of acetone itself with isobutyraldehyde itself is produced in a large amount, which in turn leads to a decrease in the selectivity for MIAK. The MIAK is generated by the addition reaction of an enol structure of acetone and isobutyraldehyde, as shown in formula (5). After the phosphonic acid type resin catalyst is adopted, the effect of activating acetone by the phosphonic acid resin is obviously lower than that of activating acetone by the sulfonic acid resin catalyst, and isobutyraldehyde is easily activated by the phosphonic acid resin into a carbonyl protonation form, so that the selectivity of 5-methyl-3-alkene-2-hexanone can be greatly improved, and more MIAK products can be obtained by hydrogenation.
2. The inventor of the present application found through research that phosphonic acid resin is easy to form hydrogen bond with isobutyraldehyde with a larger structure. After hydrogen bonds are formed, due to steric effect and repulsion, the other isobutyraldehyde is difficult to approach the acid center or the adjacent acid center, acetone is easier to be activated on the adjacent acid center, the probability of alternately activating the acetone and the isobutyraldehyde is increased, so that the selectivity of the 5-methyl-3-alkene-2-hexanone is greatly improved, and more MIAK products can be obtained through hydrogenation.
Drawings
FIG. 1 is a schematic flow diagram of the process of the present invention.
In FIG. 1: 1-propanone; 2-butyraldehyde; 3-a condensation dehydration reactor; 4-fresh hydrogen; 5-a hydrogenation reactor; 6-a gas-liquid separator; 7-recycling hydrogen; 8-reaction solution.
Detailed Description
The method of the invention is described in more detail below with reference to the figures and specific examples.
As shown in fig. 1, the method for synthesizing methyl isoamyl ketone of the present invention comprises: respectively pumping raw materials of acetone 1 and butyraldehyde 2 into a condensation dehydration reactor 3, feeding reaction liquid into a hydrogenation reactor 5 after condensation dehydration, simultaneously feeding fresh hydrogen 4 and circulating hydrogen 7 into the hydrogenation reactor 5 by a hydrogen compressor, feeding the reaction liquid into a gas-liquid separator 6 after full reaction, obtaining the circulating hydrogen 7 at the upper part of the gas-liquid separator after gas-liquid separation, and obtaining reaction liquid 8 after hydrogenation at the lower part of the gas-liquid separator.
Examples 1 to 5
The physical properties of the phosphonic acid resin catalyst used in the first step are shown in Table 1, the physical properties of the hydrogenation catalyst used in the second step are shown in Table 2, and the reaction conditions and the reaction results are shown in tables 3 to 4.
Table 1 phosphonic acid resin catalyst properties.
Table 2 hydrogenation catalyst physicochemical properties.
The conversion rate and selectivity in the examples and comparative examples were calculated as follows:
acetone molar conversion = (moles of acetone in starting material-moles of acetone in product)/moles of acetone in starting material;
isobutyraldehyde molar conversion = (number of moles of isobutyraldehyde in raw material-number of moles of isobutyraldehyde in product)/number of moles of isobutyraldehyde in raw material;
4-methyl-3-penten-2-one molar selectivity = (moles of 4-methyl-3-penten-2-one in product x 2)/(moles of acetone in feed-moles of acetone in product + moles of isobutyraldehyde in feed-moles of isobutyraldehyde in product);
5-methyl-3-en-2-hexanone molar selectivity = (moles of 5-methyl-3-en-2-hexanone in product x 2)/(moles of acetone in starting material-moles of acetone in product + moles of isobutyraldehyde in starting material-moles of isobutyraldehyde in product/h);
4-methyl-3-penten-2-one molar conversion = (moles of 4-methyl-3-penten-2-one in feed-moles of 4-methyl-3-penten-2-one remaining in product)/moles of 4-methyl-3-penten-2-one in feed;
5-methyl-3-en-2-hexanone molar conversion = (moles of 5-methyl-3-en-2-hexanone in feed-moles of 5-methyl-3-en-2-hexanone remaining in product)/moles of 5-methyl-3-en-2-hexanone in feed;
MIBK molar selectivity = (moles of MIBK in product x 2)/(moles of 4-methyl-3-penten-2-one in starting material-moles of 4-methyl-3-penten-2-one remaining in product);
MIAK molar selectivity = (moles of MIAK in product x 2)/(moles of 5-methyl-3-en-2-hexanone in starting material-moles of 5-methyl-3-en-2-hexanone remaining in product).
Table 3 reaction conditions and reaction results.
Table 4 reaction conditions and results.
Comparative examples 1 to 5
The resin catalyst used in the comparative examples was a sulfonic acid resin, and the physical and chemical properties thereof are shown in Table 5. The hydrogenation catalyst used was the same as in the examples, and the physicochemical properties are shown in Table 2. The reaction conditions of the comparative examples were the same as those of the examples, and the specific reaction conditions and results are shown in tables 6 to 7.
Table 5 sulfonic acid resin catalyst properties.
Table 6 comparative example reaction conditions and reaction results.
Table 7 comparative example reaction conditions and reaction results.
Under the same process conditions, the results of the examples and the comparative examples show that the MIAK is synthesized by adopting the two-step method, and the method can reduce the selectivity of the MIBK and greatly improve the selectivity of the target product MIAK.
Claims (10)
1. A method for synthesizing methyl isoamyl ketone by acetone and isobutyraldehyde comprises the following steps:
(1) mixing acetone and isobutyraldehyde, and then carrying out condensation dehydration reaction in a reactor containing a phosphonic acid resin catalyst under the condition of ketone-aldehyde condensation process;
(2) mixing the reaction effluent obtained in the step (1) with hydrogen, and then, passing through a reactor containing a hydrogenation catalyst to carry out hydrogenation under the hydrogenation reaction condition;
(3) and (3) separating the hydrogenation reaction effluent obtained in the step (2) to obtain methyl isoamyl ketone.
2. A process according to claim 1, wherein the phosphonic acid resin catalyst has a water content of 35 to 65 wt.%, preferably 40 to 60 wt.%.
3. A process according to claim 1 or 2, characterized in that the total acid of the phosphonic resin catalyst is 1.0 to 4.0 mmol/g, preferably 1.5 to 3.0 mmol/g.
4. The process of claim 3, wherein the phosphonic resin catalyst has an acid distribution as follows: 2 to 20 percent at the temperature of 90 to 110 ℃; 3 to 30 percent at the temperature of 110 to 120 ℃; 5 to 50 percent of the temperature of 120 to 140 ℃; 40-90% at 140 ℃.
5. The process of claim 4, wherein the phosphonic resin catalyst has an acid distribution of: 4 to 9 percent at the temperature of 90 to 110 ℃; 4 to 15 percent at the temperature of 110 to 120 ℃; 6 to 30 percent at the temperature of 120 to 140 ℃; 50-90% at 140 ℃.
6. The method of claim 1, wherein the phosphonic acid resin catalyst has a specific surface area of 8 to 15 m2And/g, the average pore diameter is 60-140A, and the pore volume is 0.01-0.04 mL/g.
7. The method of claim 6, wherein the phosphonic acid resin catalyst has a specific surface area of 10 to 13 m2The average pore diameter is 80-110A, and the pore volume is 0.02-0.03 mL/g.
8. The process of claim 1, wherein the ketoaldehyde condensation process conditions are: the reaction pressure is 2.0MPa to 6.0MPa, the inlet temperature is 80 ℃ to 150 ℃, and the total volume space velocity of the acetone and the isobutyraldehyde is 0.1h-1～5.0h-1The molar ratio of acetone to isobutyraldehyde is 0.5: 1-4: 1.
9. The process of claim 8, wherein said ketoaldehyde condensation process conditions are: the reaction pressure is 2.5MPa to 4.0MPa, the inlet temperature is 80 ℃ to 140 ℃, and the total volume space velocity of the acetone and the isobutyraldehyde is 0.5h-1～4.0h-1The molar ratio of acetone to isobutyraldehyde is 1: 1-3:1。
10. the process of claim 1, wherein the hydrogenation process conditions are: the reaction pressure is 1.0MPa to 8.0MPa, preferably 2.0MPa to 6.0 MPa; the reaction temperature is 40-180 ℃, preferably 50-140 ℃; volume space velocity of 0.5h-1～4.0 h-1Preferably 0.5h-1～2.0 h-1(ii) a The volume ratio of the hydrogen liquid is 100 to 500, preferably 200 to 400.
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|---|---|---|---|---|
| CN87102882A (en) * | 1986-04-16 | 1987-10-28 | 催化剂公司 | Acid catalyzed process |
| CN1511818A (en) * | 2002-12-26 | 2004-07-14 | ������������ʽ���� | Process for preparing 2-(alkyl) cyclic ketone |
| CN101925569A (en) * | 2007-12-14 | 2010-12-22 | 罗狄亚聚酰胺特殊品有限公司 | Method for obtaining alcohol from aldehyde |
| WO2012080809A1 (en) * | 2010-12-16 | 2012-06-21 | Rhodia Poliamida E Especialidades Ltda | Process for producing dibk |
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| CN87102882A (en) * | 1986-04-16 | 1987-10-28 | 催化剂公司 | Acid catalyzed process |
| CN1511818A (en) * | 2002-12-26 | 2004-07-14 | ������������ʽ���� | Process for preparing 2-(alkyl) cyclic ketone |
| CN101925569A (en) * | 2007-12-14 | 2010-12-22 | 罗狄亚聚酰胺特殊品有限公司 | Method for obtaining alcohol from aldehyde |
| WO2012080809A1 (en) * | 2010-12-16 | 2012-06-21 | Rhodia Poliamida E Especialidades Ltda | Process for producing dibk |
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