CN109647507A - Alkylaromatic hydrocarbon selectively carbonylation uses catalyst - Google Patents
Alkylaromatic hydrocarbon selectively carbonylation uses catalyst Download PDFInfo
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- CN109647507A CN109647507A CN201710933997.XA CN201710933997A CN109647507A CN 109647507 A CN109647507 A CN 109647507A CN 201710933997 A CN201710933997 A CN 201710933997A CN 109647507 A CN109647507 A CN 109647507A
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- Prior art keywords
- alkyl
- catalyst
- imidazole salts
- toluene
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 21
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 21
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 21
- 230000006315 carbonylation Effects 0.000 title claims abstract description 15
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 15
- -1 alkyl aromatic aldehyde Chemical class 0.000 claims abstract description 35
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 16
- 150000002460 imidazoles Chemical class 0.000 claims description 31
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 claims description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 150000002910 rare earth metals Chemical class 0.000 claims description 9
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 2
- BMQZYMYBQZGEEY-UHFFFAOYSA-M 1-ethyl-3-methylimidazolium chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1 BMQZYMYBQZGEEY-UHFFFAOYSA-M 0.000 claims description 2
- JOLFMOZUQSZTML-UHFFFAOYSA-M 1-methyl-3-propylimidazol-1-ium;chloride Chemical compound [Cl-].CCCN1C=C[N+](C)=C1 JOLFMOZUQSZTML-UHFFFAOYSA-M 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- GMJRWBPYCXTSEF-UHFFFAOYSA-N CNC.Cl.N1C=NC=C1 Chemical class CNC.Cl.N1C=NC=C1 GMJRWBPYCXTSEF-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- RJFSDTDWWBECIL-UHFFFAOYSA-N trifluoro(methyl)-$l^{4}-sulfane Chemical compound CS(F)(F)F RJFSDTDWWBECIL-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 40
- 238000009776 industrial production Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 147
- 238000006073 displacement reaction Methods 0.000 description 63
- 239000007789 gas Substances 0.000 description 49
- 239000000203 mixture Substances 0.000 description 46
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 44
- 238000003756 stirring Methods 0.000 description 43
- 239000000047 product Substances 0.000 description 23
- 238000010792 warming Methods 0.000 description 22
- 238000009472 formulation Methods 0.000 description 21
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- QUJLPICXDXFRSN-UHFFFAOYSA-N scandium;trifluoromethanesulfonic acid Chemical compound [Sc].OS(=O)(=O)C(F)(F)F QUJLPICXDXFRSN-UHFFFAOYSA-N 0.000 description 9
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 8
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 8
- SPLWDHARILMLDE-UHFFFAOYSA-N cerium;trifluoromethanesulfonic acid Chemical compound [Ce].OS(=O)(=O)C(F)(F)F SPLWDHARILMLDE-UHFFFAOYSA-N 0.000 description 6
- 229910052706 scandium Inorganic materials 0.000 description 6
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 6
- MRVDPBDPQPBGMS-UHFFFAOYSA-N trifluoromethanesulfonic acid;yttrium Chemical compound [Y].OS(=O)(=O)C(F)(F)F MRVDPBDPQPBGMS-UHFFFAOYSA-N 0.000 description 6
- 229910052727 yttrium Inorganic materials 0.000 description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 6
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 5
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- WTWBUQJHJGUZCY-UHFFFAOYSA-N cuminaldehyde Chemical compound CC(C)C1=CC=C(C=O)C=C1 WTWBUQJHJGUZCY-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 150000001555 benzenes Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OTXINXDGSUFPNU-UHFFFAOYSA-N 4-tert-butylbenzaldehyde Chemical compound CC(C)(C)C1=CC=C(C=O)C=C1 OTXINXDGSUFPNU-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000007336 electrophilic substitution reaction Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- BMVOVWCXVZHIQO-UHFFFAOYSA-M 1-butyl-3-ethylimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[N+]=1C=CN(CC)C=1 BMVOVWCXVZHIQO-UHFFFAOYSA-M 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 1
- 235000011437 Amygdalus communis Nutrition 0.000 description 1
- 241000220304 Prunus dulcis Species 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 235000020224 almond Nutrition 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- GWTMFFWXIDXZAB-UHFFFAOYSA-N cerium;methanesulfonic acid Chemical compound [Ce].CS(O)(=O)=O GWTMFFWXIDXZAB-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- BTRLPMRQFXBNLS-UHFFFAOYSA-N methanesulfonic acid;scandium Chemical compound [Sc].CS(O)(=O)=O BTRLPMRQFXBNLS-UHFFFAOYSA-N 0.000 description 1
- NQSZSZQNOWPBJP-UHFFFAOYSA-N methanesulfonic acid;yttrium Chemical compound [Y].CS(O)(=O)=O NQSZSZQNOWPBJP-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
- B01J31/0227—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
-
- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- B01J35/19—
-
- 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
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
Abstract
The present invention relates to alkylaromatic hydrocarbon selectivity carbonylation catalyst.Mainly solve the problems, such as that alkylaromatic hydrocarbon conversion ratio existing in the prior art and contraposition alkyl aromatic aldehyde are selectively low, the present invention is by using alkylaromatic hydrocarbon selectivity carbonylation catalyst, technical solution including halogenated alkyl imidazole salts and rare-earth salts, the technical problem is preferably resolved, can be used in the industrial production of alkyl aromatic aldehyde.
Description
Technical field
The present invention relates to alkylaromatic hydrocarbon selectivity carbonylation catalyst and its applications.
Background technique
P-tolyl aldehyde is one of alkyl aromatic aldehyde, i.e. 4- tolyl aldehyde (p-Tolualdehyde, abbreviation
PTAL), it is colourless or light yellow transparent liquid, has the gentle fragrance of a flower and almond fragrance, there is certain stimulation to eyes and skin
Property.P-tolyl aldehyde can oxidative synthesis terephthalic acid (TPA) with high selectivity, while being also in a kind of important organic synthesis
Mesosome is widely used in fine chemistry industry and field of medicaments.
The synthetic method of alkyl aromatic aldehyde mainly has direct high-temperature oxidation, indirect electrosynthesis method and carbonylation method.With
For the synthesis of PTAL:
Direct high-temperature oxidation is to mix using paraxylene as raw material through light bromination, basic hydrolysis, hydrogen peroxide/hydrobromic acid
PTAL is made in liquid oxidation.Although the technique raw material is easy to get, is easy to operate, aromatic hydrocarbons utilization rate is low, technique is cumbersome, total conversion
Lower (26.7%) (Xiong Zhengchang, Jin Ningren, Hu Weixiao wait study on the synthesis [J] the Zhejiang Polytechnical University of p-tolyl aldehyde to learn
Report, 1999,27 (4);334-337.).
Indirect electrosynthesis method is that catalysis oxidation paraxylene prepares PTAL in electrolytic cell, this method is simple, yield is higher,
Side reaction is few, blowdown is few, environmentally friendly and economize on resources, but since its used catalyst is expensive, the device is complicated, constrains it
Industrialization development (the work of the outer formula of Tang Duo, Wang Caihong, Li Yanwei slot ultrasonic indirect electrosynthesis benzaldehyde/p-tolyl aldehyde online
Skill improves [J] Institutes Of Technology Of Taiyuan journal, 2015,46 (1): 6-10.).
Carbonylation method is that toluene and CO catalysis of carbonyl are combined to PTAL.For the technique using CO as carbonylation agent, B-L is compound
One of liquid acid catalyst, solid super strong acids catalyst and ionic liquid class catalyst are catalyst, and reaction is real
Matter is that for CO to the electrophilic substitution reaction of toluene, referred to as Jia Teman-kock (Gattermann-Koch) synthesis is anti-under acid catalysis
It answers.This method atom utilization height, simple process, raw material CO are at low cost, have good market prospects.DuPont Corporation,
Mitsubishi gas company, Exxon Mobil company etc. have successively carried out research to the technique.With B-L composite fluid acid
Class, solid super strong acids catalyst are compared, the catalytic activity of the selective carbonylation of ionic liquid-catalyzed toluene and CO
It is obviously improved.Saleh is with [emim] Cl/AlCl3(xAlCl3It=0.75) is catalyst, the mass ratio of IL/ toluene is 8.5/
1.8, at room temperature, CO is kept to divide 8.2Mpa, reacts 1h, realize 66% toluene conversion and 89.1% PTAL selection rate
(Saleh RY,Rouge B.Process for making aromatic aldehydes using ionic liquids
[P].US:6320083,2001-11-20.).Its further application is the PTAL that will be isolated to through oxidative synthesis pair
Phthalic acid uses in the production of industrial polyester as monomer, and demand is larger.But in above-mentioned patent, there are catalyst
The problem that dosage is big, toluene conversion is low and p-tolyl aldehyde is selectively low.
Summary of the invention
The first technical problem to be solved by the present invention is alkylaromatic hydrocarbon conversion ratio and contraposition alkyl aromatic aldehyde selectivity
Low problem, provides a kind of catalyst of new synthesis of alkyl aromatic aldehyde, which has alkylaromatic hydrocarbon high conversion rate and right
The selectively high feature of position alkyl aromatic aldehyde.
The second technical problem to be solved by the present invention is the application using catalyst described in one of above-mentioned technical problem.
One of to solve the above-mentioned problems, The technical solution adopted by the invention is as follows:
Alkylaromatic hydrocarbon selectively carbonylation catalyst, including halogenated alkyl imidazole salts and rare-earth salts.
In above-mentioned technical proposal, the preferred rare earth fluorinated alkyl sulfonate of rare-earth salts.
In above-mentioned technical proposal, the halogenated alkyl imidazole salts preferably be selected from the imidazole salts A for having the following structure formula A and/or
Have the following structure the imidazole salts B: of formula B:
Wherein, R1And R2It is independently selected from C1~C4 alkyl, R3Alkylene selected from C1~C6, R4And R5It is independently selected from C1~C4
Alkyl, X and Y are independently selected from least one of chlorine or bromine.
In above-mentioned technical proposal, R3It is preferred that the alkylidene of C1~C6 or the arlydene of C6~C10.Such as, but not limited to R3
For-(CH2)k(k=1~6) or-C6H4(two of them substituent group can be located at ortho position, meta or para position in phenyl ring).
In above-mentioned technical proposal, R1And R2Preferably identical alkyl is more preferably methyl simultaneously.
In above-mentioned technical proposal, the halogenated alkyl imidazole salts preferably include two kinds in imidazole salts A and imidazole salts B, should
Two kinds of halogenated alkyl imidazole salts have synergistic effect in terms of improving alkylaromatic hydrocarbon conversion ratio.At this time to imidazole salts A and imidazole salts B
Between ratio be not particularly limited, the weight ratio of such as, but not limited to imidazole salts A and imidazole salts B are 0.1~10, in this range
It is interior more specifically infinite ratio be 0.2,0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.1,1.2,1.3,1.4,1.5,
2.0,2.5,3.0,3.5,4.0,4.5,5.0,5.5,6.0,7.0,8.0,9.0 etc..
In above-mentioned technical proposal, the imidazole salts A is such as, but not limited to such as at least one in flowering structure compound represented
Kind:
The more preferable halogen imidazole salts A is imidazole salts (a).
In above-mentioned technical proposal, the imidazole salts B can be selected from 1- butyl -3- ethylimidazolium chloride, 1- butyl -3- methyl
Imidazolitm chloride, 1- n-propyl -3- methylimidazolium chloride, 1- ethyl -3- methylimidazolium chloride, N, N- dimethylammonium chloride imidazoles, 1-
Butyl -3- methy limidazolium, 1- n-propyl -3- methy limidazolium, 1- ethyl -3- methy limidazolium and N, N- dimethyl
One of limidazolium, more preferably 1- ethyl -3- methy limidazolium.
In above-mentioned technical proposal, the rare earth fluorinated alkyl sulfonate is preferably rare earth fluoroform sulphonate.
In above-mentioned technical proposal, the rare earth is preferably included selected from least one of scandium, cerium and yttrium.
In above-mentioned technical proposal, the rare earth more preferably includes at least two in scandium, cerium and yttrium, two kinds of rare earths simultaneously
There is synergistic effect in terms of improving contraposition alkyl aromatic aldehyde selectivity between the fluorinated alkyl sulfonate of element.At this point, to two
Between the fluorinated alkyl sulfonate of kind rare earth element (such as perfluoro alkyl sulfonic acid scandium and perfluoro alkyl sulfonic acid cerium, perfluoroalkyl sulphur
Between sour scandium and perfluoro alkyl sulfonic acid yttrium, perfluoro alkyl sulfonic acid cerium and perfluoro alkyl sulfonic acid yttrium) ratio is not particularly limited, such as
But be not limited to weight ratio meter be 0.1~10, within this range more specifically infinite ratio be 0.2,0.4,0.5,0.6,
0.7、0.8、0.9、1.0、1.1、1.2、1.3、1.4、1.5、2.0、2.5、3.0、3.5、4.0、4.5、5.0、5.5、6.0、7.0、
8.0,9.0 etc..
In above-mentioned technical proposal, the halogenated alkyl imidazole salts and the weight ratio of the rare earth fluorinated alkyl sulfonate are preferred
For 100:(50~300).
In above-mentioned technical proposal, the preparation method of catalyst is not particularly limited, and can be mixed both according to required component
It can;Reaction system can also separately or concurrently be added according to required component in the reaction for synthesis of alkyl aromatic aldehyde, such as
If fruit is separately added into, the addition sequence of each component is also not particularly limited.
As non-restrictive, in the preparation of catalyst, when according to required component mixing, those skilled in the art
Member, which knows, preferably to carry out in CO atmosphere, to improve the solubility of CO;Rate is mixed in the catalyst components
100~800rpm;The catalyst components incorporation time is preferably 0.5h~2h.
To solve the above-mentioned problems two, The technical solution adopted by the invention is as follows:
Catalyst described in any one of technical solution of one of technical problem is in alkylaromatic hydrocarbon selectivity carbonyl compound at alkane
Application in base aromatic aldehyde.
In above-mentioned technical proposal, the alkylaromatic hydrocarbon preferably is selected from monoalkyl substituted benzene.
In above-mentioned technical proposal, the alkyl in the monoalkyl substituted benzene is preferably the alkyl of C1~C6, such as but unlimited
In the monoalkyl substituted benzene be toluene, ethylbenzene, isopropylbenzene, n-butyl benzene, 2-methyl-2-phenylpropane, just own benzene etc. single compound or it
Mixture.
One skilled in the art will appreciate that carbonylation is electrophilic substitution reaction, according to the positioning of the monosubstituted aromatic hydrocarbons of alkyl
Rule, the monosubstituted aromatic hydrocarbons of alkyl and CO carbonylation, resulting superiority orientation product are contraposition alkyl aromatic aldehyde, are this
The target product of invention.
In above-mentioned technical proposal, the key of the application is the selection of catalyst, and for the process conditions of concrete application
Those skilled in the art can reasonably select and not have to make the creative labor, such as, but not limited to:
The synthetic method of alkyl aromatic aldehyde is urged including catalyst described in any one of technical solution in one of technical problem
Change lower alkylaromatic hydrocarbon and CO carries out carbonylation synthesis of alkyl aromatic aldehyde.
The weight ratio of the catalyst and the alkylaromatic hydrocarbon is not particularly limited, such as can be (1~12): 1;
The reaction temperature is preferably 20~150 DEG C;
The reaction pressure is preferably 1~8MPa;
The reaction time is preferably 1~12h.
The specific steps of synthesis of alkyl aromatic aldehyde may is that
(1) catalyst components are added in autoclave;
(2) air first uses N in kettle2Displacement 3 times, then with CO gas displacement 3 times, be stirred;
(3) alkylaromatic hydrocarbon is added, then with CO gas displacement 3 times;
(4) reaction pressure for being warming up to reaction temperature, keeping constant, stirring, is reacted, obtains alkyl aromatic containing product
The mixture of aldehyde.
In the present invention, if not specializing, pressure refers both to gauge pressure.
Sample treatment and analysis method are as follows:
With the ice water washed product mixture of 2 times of above-mentioned product mixtures volumes, water phase is discarded, by organic phase ether
Three times, the ether that extraction uses every time is equal with organic phase volume for extraction.Ether extraction liquid it will merge three times, revolving, residue
As alkyl aromatic aldehyde crude product, carries out gas chromatographic analysis for this crude product, calculates turning for alkylaromatic hydrocarbon based on the analysis results
The selectivity of rate and contraposition alkyl aromatic aldehyde, calculation formula are as follows:
After technical solution of the present invention, the conversion ratio of toluene is up to 87.8%, the choosing of corresponding p-tolyl aldehyde
Selecting property achieves beneficial technical effect up to 94.2%, can be used for alkylaromatic hydrocarbon and CO carbonylation prepares alkyl aromatic aldehyde
In production.
Specific embodiment
The preparation of imidazole salts (a): preparation method reference literature (the Yanhong Wang, Tianyong of imidazole salts (a)
Zhang,Bin Li,et al.Synthesis,characterization,electrochemical properties and
catalytic reactivity of the N-heterocyclic carbene-containing diironcomplexes
[J] .RSC Advances, 2015,5 (37): 29022-29031.) described in preparation method, be embodied it is as follows:
Under nitrogen atmosphere, CH is sequentially added in 1000mL three-necked flask3CN (400mL), 1- methylimidazole (49.8g,
0.6mol) with 1,2- Bromofume (56.4g, 0.3mol), 72h is stirred to react at 80 DEG C.It is cooled to room temperature, filters, solid is used
THF washs (3 times × 200mL/ times), is dried in vacuo at 30 DEG C, obtains above-mentioned imidazole salts (a) (100.6g, 95.3%).
[embodiment 1]
Above-mentioned imidazole salts (a) 40g and trifluoromethanesulfonic acid cerium 80g are added in 250mL autoclave, air first uses N in kettle2
Displacement 3 times, then with CO gas displacement 3 times;500rpm stirs 1h;Toluene 50g is added, then with CO gas displacement 3 times;It is warming up to 50
DEG C, CO pressure 2.0MPa is kept, 500rpm stirring reacts 5h, obtains the product mixtures containing p-tolyl aldehyde.
For the ease of comparing and illustrating, the selectivity of catalyst formulation, the conversion ratio of toluene and p-tolyl aldehyde is arranged
In table 1.
[embodiment 2]
1- ethyl -3- methy limidazolium 40g and trifluoromethanesulfonic acid cerium 80g, sky in kettle are added in 250mL autoclave
Gas first uses N2Displacement 3 times, then with CO gas displacement 3 times;500rpm stirs 1h;Toluene 50g is added, then with CO gas displacement 3 times;
50 DEG C are warming up to, CO pressure 2.0MPa is kept, 500rpm stirring reacts 5h, obtains the product mixtures containing p-tolyl aldehyde.
For the ease of comparing and illustrating, the selectivity of catalyst formulation, the conversion ratio of toluene and p-tolyl aldehyde is arranged
In table 1.
[embodiment 3]
Above-mentioned imidazole salts (a) 40g and trifluoromethanesulfonic acid yttrium 80g are added in 250mL autoclave, air first uses N in kettle2
Displacement 3 times, then with CO gas displacement 3 times;500rpm stirs 1h;Toluene 50g is added, then with CO gas displacement 3 times;It is warming up to 50
DEG C, CO pressure 2.0MPa is kept, 500rpm stirring reacts 5h, obtains the product mixtures containing p-tolyl aldehyde.
For the ease of comparing and illustrating, the selectivity of catalyst formulation, the conversion ratio of toluene and p-tolyl aldehyde is arranged
In table 1.
[embodiment 4]
1- ethyl -3- methy limidazolium 40g and trifluoromethanesulfonic acid yttrium 80g, sky in kettle are added in 250mL autoclave
Gas first uses N2Displacement 3 times, then with CO gas displacement 3 times;500rpm stirs 1h;Toluene 50g is added, then with CO gas displacement 3 times;
50 DEG C are warming up to, CO pressure 2.0MPa is kept, 500rpm stirring reacts 5h, obtains the product mixtures containing p-tolyl aldehyde.
For the ease of comparing and illustrating, the selectivity of catalyst formulation, the conversion ratio of toluene and p-tolyl aldehyde is arranged
In table 1.
[embodiment 5]
Above-mentioned imidazole salts (a) 40g and trifluoromethanesulfonic acid scandium 80g are added in 250mL autoclave, air first uses N in kettle2
Displacement 3 times, then with CO gas displacement 3 times;500rpm stirs 1h;Toluene 50g is added, then with CO gas displacement 3 times;It is warming up to 50
DEG C, CO pressure 2.0MPa is kept, 500rpm stirring reacts 5h, obtains the product mixtures containing p-tolyl aldehyde.
For the ease of comparing and illustrating, the selectivity of catalyst formulation, the conversion ratio of toluene and p-tolyl aldehyde is arranged
In table 1.
[embodiment 6]
1- ethyl -3- methy limidazolium 40g and trifluoromethanesulfonic acid scandium 80g, sky in kettle are added in 250mL autoclave
Gas first uses N2Displacement 3 times, then with CO gas displacement 3 times;500rpm stirs 1h;Toluene 50g is added, then with CO gas displacement 3 times;
50 DEG C are warming up to, CO pressure 2.0MPa is kept, 500rpm stirring reacts 5h, obtains the product mixtures containing p-tolyl aldehyde.
For the ease of comparing and illustrating, the selectivity of catalyst formulation, the conversion ratio of toluene and p-tolyl aldehyde is arranged
In table 1.
[embodiment 7]
Above-mentioned imidazole salts (a) 20g, 1- ethyl -3- methy limidazolium 20g and trifluoro are added in 250mL autoclave
Methanesulfonic acid cerium 80g, air first uses N in kettle2Displacement 3 times, then with CO gas displacement 3 times;500rpm stirs 1h;Toluene 50g is added,
It uses CO gas displacement 3 times again;50 DEG C are warming up to, CO pressure 2.0MPa is kept, 500rpm stirring is reacted 5h, obtained containing to methylbenzene
The product mixtures of formaldehyde.
For the ease of comparing and illustrating, the selectivity of catalyst formulation, the conversion ratio of toluene and p-tolyl aldehyde is arranged
In table 1.
[embodiment 8]
Above-mentioned imidazole salts (a) 20g, 1- ethyl -3- methy limidazolium 20g and trifluoro are added in 250mL autoclave
Methanesulfonic acid yttrium 80g, air first uses N in kettle2Displacement 3 times, then with CO gas displacement 3 times;500rpm stirs 1h;Toluene 50g is added,
It uses CO gas displacement 3 times again;50 DEG C are warming up to, CO pressure 2.0MPa is kept, 500rpm stirring is reacted 5h, obtained containing to methylbenzene
The product mixtures of formaldehyde.
For the ease of comparing and illustrating, the selectivity of catalyst formulation, the conversion ratio of toluene and p-tolyl aldehyde is arranged
In table 1.
[embodiment 9]
Above-mentioned imidazole salts (a) 20g, 1- ethyl -3- methy limidazolium 20g and trifluoro are added in 250mL autoclave
Methanesulfonic acid scandium 80g, air first uses N in kettle2Displacement 3 times, then with CO gas displacement 3 times;500rpm stirs 1h;Toluene 50g is added,
It uses CO gas displacement 3 times again;50 DEG C are warming up to, CO pressure 2.0MPa is kept, 500rpm stirring is reacted 5h, obtained containing to methylbenzene
The product mixtures of formaldehyde.
For the ease of comparing and illustrating, the selectivity of catalyst formulation, the conversion ratio of toluene and p-tolyl aldehyde is arranged
In table 1.
[embodiment 10]
Above-mentioned imidazole salts (a) 40g, trifluoromethanesulfonic acid cerium 40g and trifluoromethanesulfonic acid scandium are added in 250mL autoclave
40g, air first uses N in kettle2Displacement 3 times, then with CO gas displacement 3 times;500rpm stirs 1h;Toluene 50g is added, then with CO gas
Body is replaced 3 times;50 DEG C are warming up to, CO pressure 2.0MPa is kept, 500rpm stirring reacts 5h, obtains the production containing p-tolyl aldehyde
Object mixture.
For the ease of comparing and illustrating, the selectivity of catalyst formulation, the conversion ratio of toluene and p-tolyl aldehyde is arranged
In table 1.
[embodiment 11]
1- ethyl -3- methy limidazolium 40g, trifluoromethanesulfonic acid cerium 40g and fluoroform are added in 250mL autoclave
Sulfonic acid scandium 40g, air first uses N in kettle2Displacement 3 times, then with CO gas displacement 3 times;500rpm stirs 1h;Toluene 50g is added, then
With CO gas displacement 3 times;50 DEG C are warming up to, CO pressure 2.0MPa is kept, 500rpm stirring is reacted 5h, obtained containing to methylbenzene first
The product mixtures of aldehyde.
For the ease of comparing and illustrating, the selectivity of catalyst formulation, the conversion ratio of toluene and p-tolyl aldehyde is arranged
In table 1.
[embodiment 12]
Above-mentioned imidazole salts (a) 40g, trifluoromethanesulfonic acid cerium 40g and trifluoromethanesulfonic acid yttrium are added in 250mL autoclave
40g, air first uses N in kettle2Displacement 3 times, then with CO gas displacement 3 times;500rpm stirs 1h;Toluene 50g is added, then with CO gas
Body is replaced 3 times;50 DEG C are warming up to, CO pressure 2.0MPa is kept, 500rpm stirring reacts 5h, obtains the production containing p-tolyl aldehyde
Object mixture.
For the ease of comparing and illustrating, the selectivity of catalyst formulation, the conversion ratio of toluene and p-tolyl aldehyde is arranged
In table 1.
[embodiment 13]
1- ethyl -3- methy limidazolium 40g, trifluoromethanesulfonic acid cerium 40g and fluoroform are added in 250mL autoclave
Sulfonic acid yttrium 40g, air first uses N in kettle2Displacement 3 times, then with CO gas displacement 3 times;500rpm stirs 1h;Toluene 50g is added, then
With CO gas displacement 3 times;50 DEG C are warming up to, CO pressure 2.0MPa is kept, 500rpm stirring is reacted 5h, obtained containing to methylbenzene first
The product mixtures of aldehyde.
For the ease of comparing and illustrating, the selectivity of catalyst formulation, the conversion ratio of toluene and p-tolyl aldehyde is arranged
In table 1.
[embodiment 14]
Above-mentioned imidazole salts (a) 40g, trifluoromethanesulfonic acid scandium 40g and trifluoromethanesulfonic acid yttrium are added in 250mL autoclave
40g, air first uses N in kettle2Displacement 3 times, then with CO gas displacement 3 times;500rpm stirs 1h;Toluene 50g is added, then with CO gas
Body is replaced 3 times;50 DEG C are warming up to, CO pressure 2.0MPa is kept, 500rpm stirring reacts 5h, obtains the production containing p-tolyl aldehyde
Object mixture.
For the ease of comparing and illustrating, the selectivity of catalyst formulation, the conversion ratio of toluene and p-tolyl aldehyde is arranged
In table 1.
[embodiment 15]
1- ethyl -3- methy limidazolium 40g, trifluoromethanesulfonic acid scandium 40g and fluoroform are added in 250mL autoclave
Sulfonic acid yttrium 40g, air first uses N in kettle2Displacement 3 times, then with CO gas displacement 3 times;500rpm stirs 1h;Toluene 50g is added, then
With CO gas displacement 3 times;50 DEG C are warming up to, CO pressure 2.0MPa is kept, 500rpm stirring is reacted 5h, obtained containing to methylbenzene first
The product mixtures of aldehyde.
For the ease of comparing and illustrating, the selectivity of catalyst formulation, the conversion ratio of toluene and p-tolyl aldehyde is arranged
In table 1.
[embodiment 16]
Above-mentioned imidazole salts (a) 20g, 1- ethyl -3- methy limidazolium 20g fluoroform is added in 250mL autoclave
Cerous iodate 40g and trifluoromethanesulfonic acid scandium 40g, air first uses N in kettle2Displacement 3 times, then with CO gas displacement 3 times;500rpm stirring
1h;Toluene 50g is added, then with CO gas displacement 3 times;50 DEG C are warming up to, CO pressure 2.0MPa, 500rpm stirring, reaction are kept
5h obtains the product mixtures containing p-tolyl aldehyde.
For the ease of comparing and illustrating, the selectivity of catalyst formulation, the conversion ratio of toluene and p-tolyl aldehyde is arranged
In table 1.
[embodiment 17]
Above-mentioned imidazole salts (a) 20g, 1- ethyl -3- methy limidazolium 20g fluoroform is added in 250mL autoclave
Cerous iodate 40g and trifluoromethanesulfonic acid yttrium 40g, air first uses N in kettle2Displacement 3 times, then with CO gas displacement 3 times;500rpm stirring
1h;Toluene 50g is added, then with CO gas displacement 3 times;50 DEG C are warming up to, CO pressure 2.0MPa, 500rpm stirring, reaction are kept
5h obtains the product mixtures containing p-tolyl aldehyde.
For the ease of comparing and illustrating, the selectivity of catalyst formulation, the conversion ratio of toluene and p-tolyl aldehyde is arranged
In table 1.
[embodiment 18]
Above-mentioned imidazole salts (a) 20g, 1- ethyl -3- methy limidazolium 20g fluoroform is added in 250mL autoclave
Sulfonic acid scandium 40g and trifluoromethanesulfonic acid yttrium 40g, air first uses N in kettle2Displacement 3 times, then with CO gas displacement 3 times;500rpm stirring
1h;Toluene 50g is added, then with CO gas displacement 3 times;50 DEG C are warming up to, CO pressure 2.0MPa, 500rpm stirring, reaction are kept
5h obtains the product mixtures containing p-tolyl aldehyde.
For the ease of comparing and illustrating, the selectivity of catalyst formulation, the conversion ratio of toluene and p-tolyl aldehyde is arranged
In table 1.
[embodiment 19]
Above-mentioned imidazole salts (a) 20g, 1- ethyl -3- methy limidazolium 20g fluoroform is added in 250mL autoclave
Cerous iodate 40g and trifluoromethanesulfonic acid scandium 40g, air first uses N in kettle2Displacement 3 times, then with CO gas displacement 3 times;500rpm stirring
1h;Ethylbenzene 50g is added, then with CO gas displacement 3 times;50 DEG C are warming up to, CO pressure 2.0MPa, 500rpm stirring, reaction are kept
5h obtains the product mixtures containing p-ethylbenzaldehyde.
For the ease of comparing and illustrating, the selectivity of catalyst formulation, the conversion ratio of ethylbenzene and p-ethylbenzaldehyde is arranged
In table 1.
[embodiment 20]
Above-mentioned imidazole salts (a) 20g, 1- ethyl -3- methy limidazolium 20g fluoroform is added in 250mL autoclave
Cerous iodate 40g and trifluoromethanesulfonic acid scandium 40g, air first uses N in kettle2Displacement 3 times, then with CO gas displacement 3 times;500rpm stirring
1h;Isopropylbenzene 50g is added, then with CO gas displacement 3 times;50 DEG C are warming up to, keeps CO pressure 2.0MPa, 500rpm to stir, instead
5h is answered, the product mixtures containing cumaldehyde are obtained.
For the ease of comparing and illustrating, by the selection of catalyst formulation, the conversion ratio of isopropylbenzene and cumaldehyde
Property is listed in Table 1 below.
[embodiment 21]
Above-mentioned imidazole salts (a) 20g, 1- ethyl -3- methy limidazolium 20g fluoroform is added in 250mL autoclave
Cerous iodate 40g and trifluoromethanesulfonic acid scandium 40g, air first uses N in kettle2Displacement 3 times, then with CO gas displacement 3 times;500rpm stirring
1h;2-methyl-2-phenylpropane 50g is added, then with CO gas displacement 3 times;50 DEG C are warming up to, keeps CO pressure 2.0MPa, 500rpm to stir, instead
5h is answered, the product mixtures containing p-t-Butylbenzaldehyde are obtained.
For the ease of comparing and illustrating, by the selection of catalyst formulation, the conversion ratio of 2-methyl-2-phenylpropane and p-t-Butylbenzaldehyde
Property is listed in Table 1 below.
Table 1
Note: the alkylaromatic hydrocarbon that embodiment 1~18 uses is toluene, and embodiment 19 is ethylbenzene, and embodiment 20 is isopropylbenzene, real
Applying example 21 is 2-methyl-2-phenylpropane.
Claims (10)
1. alkylaromatic hydrocarbon selectively carbonylation catalyst, including halogenated alkyl imidazole salts and rare-earth salts.
2. catalyst according to claim 1, it is characterized in that the rare-earth salts is rare earth fluorinated alkyl sulfonate.
3. catalyst according to claim 1, it is characterized in that the halogenated alkyl imidazole salts, which are selected from, has the following structure formula A
Imidazole salts A and/or have the following structure the imidazole salts B of formula B:
Wherein, R1And R2It is independently selected from C1~C4 alkyl, R3Alkylene selected from C1~C6, R4And R5It is independently selected from C1~C4 alkane
Base, X and Y are independently selected from least one of chlorine or bromine.
4. catalyst according to claim 1, it is characterized in that R1And R2For identical alkyl.
5. catalyst according to claim 1, it is characterized in that the N- methyl alkyl imidazoles B is selected from 1- butyl -3- methyl
Imidazolitm chloride, 1- n-propyl -3- methylimidazolium chloride, 1- ethyl -3- methylimidazolium chloride, N, N- dimethylammonium chloride imidazoles, 1-
Butyl -3- methy limidazolium, 1- n-propyl -3- methy limidazolium, 1- ethyl -3- methy limidazolium and N, N- dimethyl
At least one of limidazolium.
6. catalyst according to claim 2, it is characterized in that the rare earth fluorinated alkyl sulfonate is rare earth trifluoro methylsulphur
Hydrochlorate.
7. catalyst according to claim 2, it is characterized in that the halogenated alkyl imidazole salts and the rare earth perfluoroalkyl
The weight ratio of sulfonate is 100:(50~300).
8. catalyst described in any one of claim 1~7 is in alkylaromatic hydrocarbon selectivity carbonyl compound in alkyl aromatic aldehyde
Using.
9. application according to claim 8, it is characterized in that the alkylaromatic hydrocarbon is monoalkyl substituted benzene.
10. application according to claim 9, it is characterized in that the monoalkyl in the monoalkyl substituted benzene is the alkane of C1~C6
Base.
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JPH06157391A (en) * | 1992-11-25 | 1994-06-03 | Nippon Steel Corp | Method for formylating aromatic compound |
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