CN117384038A - Preparation method of cyclohexane-1, 2-dicarboxylic acid dibasic ester - Google Patents
Preparation method of cyclohexane-1, 2-dicarboxylic acid dibasic ester Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 58
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000004805 Cyclohexane-1,2-dicarboxylic acid Substances 0.000 title claims abstract description 19
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 156
- 238000000034 method Methods 0.000 claims abstract description 47
- 238000005984 hydrogenation reaction Methods 0.000 claims description 127
- 239000011248 coating agent Substances 0.000 claims description 32
- 238000000576 coating method Methods 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims description 31
- 238000011068 loading method Methods 0.000 claims description 31
- 239000001257 hydrogen Substances 0.000 claims description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 29
- -1 phthalic acid diester Chemical class 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 19
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 18
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- 238000004821 distillation Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 239000004005 microsphere Substances 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- QALZILIGOXJDCX-UHFFFAOYSA-N carbonyl dichloride;ruthenium Chemical compound [Ru].ClC(Cl)=O QALZILIGOXJDCX-UHFFFAOYSA-N 0.000 claims description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical group CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims 2
- 238000012805 post-processing Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 64
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000004014 plasticizer Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 22
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 21
- 102100035474 DNA polymerase kappa Human genes 0.000 description 9
- 101710108091 DNA polymerase kappa Proteins 0.000 description 9
- 238000009495 sugar coating Methods 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- OVHKECRARPYFQS-UHFFFAOYSA-N cyclohex-2-ene-1,1-dicarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC=C1 OVHKECRARPYFQS-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 5
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 5
- HORIEOQXBKUKGQ-UHFFFAOYSA-N bis(7-methyloctyl) cyclohexane-1,2-dicarboxylate Chemical compound CC(C)CCCCCCOC(=O)C1CCCCC1C(=O)OCCCCCCC(C)C HORIEOQXBKUKGQ-UHFFFAOYSA-N 0.000 description 5
- 239000004806 diisononylester Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000004439 Isononyl alcohol Substances 0.000 description 2
- 229910002787 Ru-Ni Inorganic materials 0.000 description 2
- 229910002793 Ru–Ni Inorganic materials 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000011344 liquid material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000386 microscopy Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- VWVRASTUFJRTHW-UHFFFAOYSA-N 2-[3-(azetidin-3-yloxy)-4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound O=C(CN1C=C(C(OC2CNC2)=N1)C1=CN=C(NC2CC3=C(C2)C=CC=C3)N=C1)N1CCC2=C(C1)N=NN2 VWVRASTUFJRTHW-UHFFFAOYSA-N 0.000 description 1
- SIXWIUJQBBANGK-UHFFFAOYSA-N 4-(4-fluorophenyl)-1h-pyrazol-5-amine Chemical compound N1N=CC(C=2C=CC(F)=CC=2)=C1N SIXWIUJQBBANGK-UHFFFAOYSA-N 0.000 description 1
- YMQOOTWYZHVYES-UHFFFAOYSA-N 7-methyloctyl cyclohexanecarboxylate Chemical compound CC(C)CCCCCCOC(=O)C1CCCCC1 YMQOOTWYZHVYES-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- KLLLNQNWDPIVSC-UHFFFAOYSA-N bis(6-methylheptyl) cyclohexane-1,1-dicarboxylate Chemical compound CC(C)CCCCCOC(=O)C1(C(=O)OCCCCCC(C)C)CCCCC1 KLLLNQNWDPIVSC-UHFFFAOYSA-N 0.000 description 1
- TUOSWEIWIXJUAU-UHFFFAOYSA-N bis(7-methyloctyl) cyclohexane-1,1-dicarboxylate Chemical compound CC(C)CCCCCCOC(=O)C1(C(=O)OCCCCCCC(C)C)CCCCC1 TUOSWEIWIXJUAU-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- IZRBAWXNLPBYKE-UHFFFAOYSA-N cyclohexane dioctyl benzene-1,2-dicarboxylate Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1CCCCC1 IZRBAWXNLPBYKE-UHFFFAOYSA-N 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical class OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- KFIKNZBXPKXFTA-UHFFFAOYSA-N dipotassium;dioxido(dioxo)ruthenium Chemical compound [K+].[K+].[O-][Ru]([O-])(=O)=O KFIKNZBXPKXFTA-UHFFFAOYSA-N 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to the field of synthesis of environment-friendly plasticizers, and discloses a preparation method of cyclohexane-1, 2-dicarboxylic acid dibasic ester. The method has higher conversion rate and selectivity, the purity of the obtained product is higher, the catalysis of the metal component on the catalyst can be fully exerted, and the utilization rate of the metal component is higher.
Description
Technical Field
The invention relates to the field of synthesis of environment-friendly plasticizers, in particular to a preparation method of cyclohexane-1, 2-dicarboxylic acid dibasic ester.
Background
With the deep concept of environmental protection, green and no toxicity, phthalate plasticizers are not suitable for the current development requirements, so new generation of novel environment-friendly plasticizers are urgently needed to be developed, and direct catalysis of phthalate to form cyclohexane dicarboxylic acid ester is a hot spot of current research.
The cyclohexane dicarboxylic acid ester synthesis method comprises a direct hydrogenation method: namely, the catalyst is prepared by directly catalyzing and hydrogenating phthalate; or synthesizing o-cyclohexanedicarboxylic acid by hydrogenating the phthalic anhydride, and preparing the o-cyclohexanedicarboxylic acid by esterification. The phthalate molecule not only contains benzene rings but also contains ester functional groups, and the ester groups of the phthalate can also undergo hydrogenation reaction in the hydrogenation process to generate acid, alcohol and other byproducts, so that the product yield is reduced, and the product purification flow is increased. The following known techniques all suffer from a number of disadvantages:
document shandong chemical industry, 2012, 41 (7): 31-33 report that the Ni-based catalyst is prepared by a complexation method, the influence of temperature, pressure, airspeed and reaction of generating cyclohexane-dioctyl phthalate by hydrogenating dioctyl phthalate is examined, and under the conditions of 8MPa,180 ℃ and 0.5h < -1 >, the hydrogenation selectivity of dioctyl phthalate can reach 99%, but the method has low treatment capacity, low substrate concentration and difficult industrial amplification.
US6284917 reports that after 4 hours of reaction at 80 ℃ and 20MPa using a kettle reactor, ru catalyst, the conversion of diisooctyl phthalate was 99.9% and the selectivity to diisooctyl cyclohexanedicarboxylate was 99.7%. However, the catalytic reaction is kettle type reaction, the service life of the catalyst is low, and the large-scale production is not easy.
US6888021 reports that after 4 hours of reaction at 80 ℃ and 20MPa using a kettle reactor with Ru catalyst, the conversion of diisononyl phthalate was 99.9% and the selectivity to diisononyl phthalate was 99.5%. However, the catalyst has low service life and large dosage, the catalyst and the product are not easy to separate, and the process is not easy to scale up.
CN101417950a discloses a catalyst for the preparation of 1, 2-cyclohexanedicarboxylic acid ester, the conversion of terephthalic acid by the catalyst is greater than 96%, and the selectivity to 1, 2-cyclohexanedicarboxylic acid ester is greater than 94%. However, the concentration of the raw materials is low, a noble metal catalyst is adopted as a main catalyst, transition metal is adopted as a cocatalyst, the catalyst is expensive, the preparation is complex, and the large-scale production is not suitable.
CN101927166a discloses a supported nickel catalyst, its preparation method and use, and the catalyst used is a supported nickel-based catalyst. The reaction temperature is 100-200 ℃, preferably 130-160 ℃, and H is added 2 The pressure is increased to 3.0-6.0MPa, the reaction is carried out for 20-60min under stirring, and the volume airspeed of the dioctyl phthalate is 1.2h -1 . The conversion of dioctyl phthalate was 94.3% and the selectivity of dioctyl phthalate was 98.4%. However, the catalyst activity is low.
CN110437067a discloses a process for preparing cyclohexanedicarboxylic acid esters, the crude esterified product of which is the hydrogenation feedstock. Ru catalyst is used as main catalyst, the metal loading capacity is high, ru falling in micropores of the carrier cannot contact with reactants, so that hydrogenation is not performed, and the utilization rate of Ru is low.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a preparation method of cyclohexane-1, 2-dicarboxylic acid dibasic ester, which has higher conversion rate and selectivity, and the obtained product has higher purity, can fully play the catalysis of metal components on the catalyst, and has higher utilization rate of the metal components.
In order to achieve the above object, the present invention provides a method for preparing cyclohexane-1, 2-dicarboxylic acid dibasic ester, comprising: and (3) carrying out hydrogenation reaction on the phthalic acid diester and hydrogen in the presence of a catalyst, wherein the catalyst has a structure taking a carrier as a core and taking an active component Ru and an optional auxiliary agent M as a shell.
The technical scheme of the invention has higher conversion rate and selectivity, fewer side reactions, higher purity of the obtained product, full play of the catalysis of the metal component on the catalyst, higher utilization rate of the metal component and higher stability of the catalyst. In addition, the technical scheme of the invention has simple process flow, easy amplification and good economic benefit and industrial application prospect.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In a first aspect, the present invention provides a process for the preparation of cyclohexane-1, 2-dicarboxylic acid dibasic esters, comprising: and (3) carrying out hydrogenation reaction on the phthalic acid diester and hydrogen in the presence of a catalyst, wherein the catalyst has a structure taking a carrier as a core and taking an active component Ru and an optional auxiliary agent M as a shell.
The inventor of the present invention found in the research that when the catalyst with the core-shell structure is adopted to carry out hydrogenation reaction, active components on the catalyst can fully play a role, side reactions can be effectively reduced, and the product purity is higher.
According to the present invention, in order to further improve the conversion rate and selectivity of the reaction, it is preferable that the loading amount of Ru element is 0.01 to 2wt% with respect to the total weight of the catalyst, and the molar ratio of Ru element to M element is 3 to 10:1.
according to the invention, the active components Ru and/or auxiliary M are preferably present in the form of nanoparticles having a particle diameter of 1 to 5 nm.
According to the present invention, preferably, the auxiliary agent M is selected from at least one of Pd, rh and Ni.
According to the invention, the shell preferably has a thickness of 40-150 μm and the core has a diameter of 1-10mm.
When the above range is satisfied, the utilization ratio of the active component can be further increased during the hydrogenation reaction, and the conversion rate and selectivity of the reaction can be further increased.
According to the present invention, preferably, the hydrogenation reaction comprises: (1) a first hydrogenation step: carrying out first hydrogenation on phthalic acid dibasic ester and hydrogen in the presence of a first catalyst and a hydrogenation solvent;
(2) A second hydrogenation step: subjecting the product after the first hydrogenation to a second hydrogenation in the presence of a second catalyst;
(3) Optionally, post-treating the product after the second hydrogenation to obtain cyclohexane-1, 2-dicarboxylic acid dibasic ester.
The inventors of the present invention have found in the study that the reaction can be made more complete and the conversion and selectivity higher when hydrogenated according to the stepwise method described above. It will be appreciated that in the first hydrogenation step, the phthalate diol can react with hydrogen to form cyclohexane-1, 2-dicarboxylic acid diol, and that there may be some intermediate cyclohexanedicarboxylic acid diol and cyclohexene dicarboxylic acid diol, and that the phthalate diol may not be completely converted. In the second hydrogenation step, the intermediate products of the cyclohexyl dicarboxylic acid diester and the cyclohexene dicarboxylic acid diester can be sufficiently hydrogenated to obtain the cyclohexane-1, 2-dicarboxylic acid diester, and the phthalic acid diester can be sufficiently converted into a product. After the hydrogenation is completed, some carboxylic acid by-products are also present.
According to the present invention, it is preferable that the first catalyst has a structure in which nano Ru is used as a shell and a carrier is used as a core, the thickness of the shell is 60 to 80 μm, and the diameter of the core is 2 to 6mm.
According to the present invention, it is preferable that the second catalyst has a structure in which nano Ru and nano M are used as shells and a carrier is used as a core, the thickness of the shell is 60-120 μm, and the diameter of the core is 2-6mm.
According to the present invention, it is preferable that the loading amount of the Ru element in the first catalyst is 0.1 to 1.5wt%, more preferably 0.3 to 1wt%, relative to the total weight of the first catalyst.
According to the present invention, it is preferable that the particle diameter of the nano Ru in the first catalyst is 1 to 2nm.
According to the present invention, preferably, in the first catalyst, the carrier is Al 2 O 3 、SiO 2 、ZrO 2 、TiO 2 And at least one of carbon microspheres, more preferably Al 2 O 3 . The carrier is generally spherical.
When the above range is satisfied, higher conversion rate and selectivity in hydrogenation reaction can be further ensured.
According to the present invention, preferably, the preparation method of the first catalyst comprises: and coating the nano Ru coating liquid on the surface of a carrier, and drying, roasting and reducing to obtain the first catalyst.
The inventor of the present invention further found in the research that the catalyst prepared by the above method has active components located in the shell layer and substantially not penetrating into the carrier, so that the active components can be fully contacted with the reactant during the reaction, and the catalyst can perform better. Compared with the catalyst prepared by the traditional impregnation method, the catalyst prepared by the method has a better effect.
According to the present invention, preferably, the method for preparing the nano Ru coating liquid includes: mixing Ru source, stabilizer and solvent to obtain precursor solution, and heating at 130-150deg.C for 90-150min to obtain Ru sol; and mixing Ru sol and water to obtain nano Ru precipitate particles, and dispersing the nano Ru precipitate particles in the water to obtain the nano Ru coating liquid with Ru concentration of 0.01-0.04 g/mL.
According to the present invention, preferably, the Ru source is selected from at least one of Ru trichloride, ruthenium carbonyl chloride, ammonium chlororuthenate, sodium chlororuthenate, and potassium chlororuthenate, and more preferably, ruthenium trichloride.
According to the present invention, preferably, the stabilizer is selected from at least one of alkali metal formate, alkali metal acetate and alkali metal citrate, more preferably sodium acetate.
According to the present invention, the solvent is preferably selected from at least one of C2-C5 polyols, more preferably at least one of ethylene glycol, propylene glycol and glycerol.
According to the present invention, it is preferable that the concentration of Ru element in the precursor solution is 0.01-0.05mol/L.
According to the present invention, preferably, the stabilizer/ru=8-12 by mass: 1. when the above range is satisfied, the sol can be sufficiently stabilized without affecting the hydrogenation activity.
It can be understood that the particle size of the nano Ru precipitate particles, i.e., the particle size of the nano Ru supported on the catalyst.
If the carrier is a carrier corresponding to the metal oxide, the impurity can be removed by baking before use, and the baking temperature can be 450-550 ℃. And the size of the carrier selected, i.e., the size of the core of the catalyst obtained.
The specific operation of the coating is not particularly limited, and for example, spraying may be performed, a coating machine may be used, the carrier is rotated with a drum of the coating machine to perform rotary spraying, and the thickness of the shell of the obtained catalyst may be adjusted by controlling the temperature and flow rate of hot air in the coating machine by controlling the amount of the coating liquid. And the sugar coating machine is easy to operate, can process more amount in unit time, has higher production efficiency and is easier to industrialize.
According to the present invention, preferably, the hydrogenation solvent is selected from at least one of isononanol, dioxane, tetrahydrofuran, cyclohexane, methanol and decalin, more preferably at least one of isononanol, dioxane and tetrahydrofuran. This further ensures the selectivity and conversion of the reaction.
According to the invention, the hydrogenation solvent is preferably used in such an amount that the phthalate dibasic ester is 20-80% by weight of the sum of the mass amounts of hydrogenation solvent and phthalate dibasic ester.
The phthalate dibasic ester and the hydrogenation solvent can be mixed in a dissolution tank, and then the mixed material and hydrogen are subjected to gas-liquid dispersion, and the mixed material and hydrogen are sent into a first hydrogenation reaction tower filled with a catalyst from the bottom of the tower.
According to the present invention, preferably, the conditions for the first hydrogenation include: the temperature is 165-180 ℃, the hydrogen partial pressure is 7-10MPa, and the hydrogen-oil volume ratio is 200-600:1, the volume space velocity of the mixture of the phthalic acid dibasic ester and the hydrogenation solvent is 0.3 to 1h -1 。
The amount of the catalyst is not particularly limited, and may be a conventional amount in the art. For example, in a fixed bed reactor, the loading height of the catalyst is greater than 10 times the diameter of the reaction tubes.
When the above range is satisfied, the conversion rate and selectivity of the reaction can be further ensured.
According to the present invention, preferably, in the second catalyst, the loading amount of the Ru element is 0.5 to 1wt% with respect to the total weight of the second catalyst, and the molar ratio of the Ru element to the M element is 5 to 10:1, a step of;
preferably, in the second catalyst, the carrier is Al 2 O 3 、SiO 2 、ZrO 2 、TiO 2 And at least one of carbon microspheres, more preferably Al 2 O 3 ；
Preferably, the auxiliary M is selected from at least one of Pd, rh and Ni.
When the above range is satisfied, higher conversion rate and selectivity in hydrogenation reaction can be further ensured.
According to the present invention, preferably, the preparation method of the second catalyst comprises: and (3) coating a bimetallic solution containing Ru and M on the surface of a carrier, and drying, roasting and reducing to obtain the second catalyst.
According to the present invention, preferably, the method for preparing a bimetallic solution containing Ru and M comprises: preparing an aqueous solution of Ru source, and then adding an M source to obtain the Ru element with the concentration of 0.01-0.05mol/L, wherein the mol ratio of Ru element to M element is 5-10:1 containing Ru and M.
The Ru source water solution is prepared first, and then the M source is added to facilitate the complete dissolution of the M source.
According to the present invention, preferably, the Ru source is selected from at least one of Ru trichloride, ruthenium carbonyl chloride, ammonium ruthenate, sodium ruthenate and potassium ruthenate, more preferably ruthenium trichloride.
The specific mode of coating can be spraying, for example, in a coating machine, the carrier is rotated and sprayed along with the rotation of a rotary drum, and the thickness of the shell layer on the prepared catalyst is controlled by controlling the temperature and flow of hot air in the coating machine and the coating amount.
In the preparation of the first catalyst and the second catalyst, the drying can be vacuum drying, the temperature can be 100-120 ℃, and the time can be 8-16h. The roasting temperature can be 400-500 ℃ and the roasting time can be 2-4h. The conditions of the reduction may include: the temperature is 280-350 ℃, and the reduction is carried out for 2-4h in the atmosphere with the hydrogen concentration of 20-50 vol%.
According to the present invention, preferably, the conditions for the second hydrogenation include: the temperature is 130-160 ℃, the hydrogen partial pressure is 3-6MPa, and the hydrogen-oil volume ratio is 200-600:1, the volume space velocity of the liquid phase material obtained by the first hydrogenation is 0.5-2h -1 . It can be understood that hydrogen in the hydrogen-to-oil ratio refers to newly added hydrogen at the time of the second hydrogenation.
Within the above range, the reaction selectivity and conversion can be further ensured.
And (3) carrying out gas-liquid dispersion on the material after the first hydrogenation and hydrogen, and then sending the material into a second hydrogenation reaction tower filled with a catalyst from the bottom of the tower.
According to the present invention, preferably, the post-treatment includes: and sequentially carrying out gas-liquid separation, reduced pressure distillation, alkali washing and reduced pressure steam stripping on the product after the second hydrogenation.
According to the present invention, preferably, the reduced pressure distillation is performed in a reduced pressure distillation column operated under the following conditions: the pressure is 40-50kPa (absolute pressure), the temperature of the top of the tower is 90-100 ℃, and the temperature of the bottom of the tower is 120-140 ℃.
During gas-liquid separation, the materials are decompressed, and the separated hydrogen can be reused in hydrogenation reaction; the separated liquid enters a reduced pressure distillation tower, and the gas at the top of the distillation tower is cooled and dried to be used as a hydrogenation solvent for recycling. And (3) the tower bottom product of the distillation tower enters an alkaline washing tank for alkaline washing, the monoisononyl o-cyclohexylformate is removed, and the distillation tower is kept stand for water separation after alkaline washing. The upper oil phase enters a decompression stripping tower (the pressure can be 50kPa-90kPa, the temperature can be 90-120 ℃), trace water is removed, and cyclohexane-1, 2-dicarboxylic acid dibasic ester is obtained at the bottom of the stripping tower. It will be appreciated that the material obtained at the bottom of the stripper column contains cyclohexane-1, 2-dicarboxylic acid diester and other unreacted reactants, which have been difficult to separate further, and therefore a higher selectivity of the reaction is also required in order to obtain cyclohexane-1, 2-dicarboxylic acid diester of high purity.
According to the invention, preferably, the phthalic acid diester is phthalic anhydride or the esterification product of phthalic acid with an alcohol selected from the group consisting of C1-C10 alcohols.
According to a particularly preferred embodiment of the invention, the phthalate dibasic ester is diisononyl phthalate.
The present invention will be described in detail by way of preparation examples and examples.
The method comprises the steps of (1) measuring the load of Ru element or auxiliary agent element on a catalyst by adopting an inductively coupled plasma atomic emission spectrum (ICP), wherein the load refers to the weight ratio of certain element relative to the total weight of the catalyst; the shell and core thicknesses of the catalyst were determined by Electron Probe Microscopy (EPMA) and the particle size of the nano Ru was determined by Transmission Electron Microscopy (TEM).
The method for calculating the conversion rate of the dibasic phthalate (DINP) comprises the following steps: calculating to obtain the ratio of the mass of the converted phthalate dibasic ester to the mass of the phthalate dibasic ester initially input according to the mass of all products obtained by the reaction;
the cyclohexane-1, 2-dicarboxylic acid Diester (DINCH) selectivity was calculated by: based on the mass of the DINCH obtained by the reaction, the ratio of the mass of the phthalate dibasic ester converted to DINCH to the mass of the phthalate dibasic ester converted was calculated. The selectivity calculation method of other products is similar.
In the second hydrogenation, the diisononyl cyclohexene dicarboxylate is hydrogenated to obtain cyclohexane-1, 2-dicarboxylic acid dibasic ester, so the conversion rate of the diisononyl cyclohexene dicarboxylate is calculated by the following method: subtracting the amount of the diisononyl cyclohexene dicarboxylate in the material after the first-stage hydrogenation from the amount of the diisononyl cyclohexene dicarboxylate in the material after the second-stage hydrogenation, and obtaining a ratio of the difference value to the amount of the diisononyl cyclohexene dicarboxylate in the product after the first-stage hydrogenation. The method for measuring the content of the diisononyl cyclohexene dicarboxylate in the material is a liquid chromatography method, and the conditions of the liquid chromatography include: c18 chromatographic column, mobile phase HPLC methanol, flow rate of 1.2mL/min, column temperature of 30deg.C, and ultraviolet detection of 207nm.
Preparation example 1
For explaining the preparation of a catalyst having a structure in which nano Ru is used as a shell and a carrier is used as a core
RuCl is taken 3 Stabilizer CH 3 COONa and glycol as solvent to prepare RuCl 3 The concentration is 0.03mol/L, CH 3 COONa/ru=10:1 (mass ratio) precursor solution. In an air atmosphere, controlling the temperature of the precursor solution at 140 ℃ and maintaining for 120min to obtain Ru sol. Then, water was added to the Ru sol in an amount 3 times the volume of the Ru sol to precipitate nano Ru particles (measurement revealed that the nano Ru particles had a particle size of 1-2 nm). Then the nanometer Ru particles are dispersed in water again by ultrasonic, the dosage of the water is controlled to ensure that the Ru concentration is 0.03g/mL, and the nanometer Ru coating liquid is prepared.
By mixing the carrier Al 2 O 3 (diameter: 2 mm) was baked at 500℃to remove impurities. Then spraying the nano Ru coating liquid on the carrier Al after impurity removal by a sugar coating machine 2 O 3 The surface is opened with hot air, vacuum drying (the temperature is 110 ℃ for 12 h), roasting (the temperature is 400 ℃ for 2 h), and reducing (the temperature is 300 ℃ and the reduction is carried out for 2h in the atmosphere with the hydrogen concentration of 20 volume percent) are carried out after coating, thus obtaining the catalyst, and the catalyst with the structure taking nano Ru as a shell and taking a carrier as a core is prepared and is marked as Ru@Al 2 O 3 . The loading capacity of Ru element on the catalyst is 0.5wt%, and the thickness of the nano Ru shell layer is 70 mu m; the grain diameter of the nanometer Ru is 1-2nm.
Preparation example 2
For explaining the preparation of a catalyst having Ru and Pd as shells and a carrier as a core
RuCl with Ru concentration of 0.05mol/L is prepared 3 Is an aqueous solution of (a)PdCl is then added 2 And adding the mixture into the solution to dissolve the mixture, and enabling the mol ratio of Ru to Pd to be 5:1, thus obtaining the bimetallic solution containing Ru and Pd.
By mixing the carrier Al 2 O 3 (diameter: 6 mm) was baked at 500℃to remove impurities. Coating the bimetal solution on the Al after impurity removal in a sugar coating machine 2 O 3 The surface, the temperature of hot air in the sugar coating machine is 60 ℃, the flow rate of hot air is 500mL/min, the speed of a revolving drum of the sugar coating machine is 100rpm, vacuum drying (the temperature is 110 ℃, the time is 12 h), roasting (the temperature is 400 ℃, the time is 2 h), and reducing (the temperature is 300 ℃ and reducing is 2h in the atmosphere with the hydrogen concentration of 20 volume percent) are carried out after coating, and the catalyst is obtained and is recorded as Ru-Pd@Al 2 O 3 . The loading of Ru element on the catalyst is 0.5wt%, the loading of Pd is 0.1wt%, and the thickness of the shell layer is 80 mu m.
Preparation example 3
A catalyst was prepared according to the method of preparation example 1, except that the amount of coating and the temperature and flow rate of hot air in the sugar coating machine were adjusted so that the loading amount of Ru element on the catalyst was 0.3wt% and the thickness of the nano Ru shell layer was 60. Mu.m.
Preparation example 4
A catalyst was prepared according to the method of preparation example 1, except that the amount of coating and the temperature and flow rate of hot air in the sugar coating machine were adjusted so that the loading amount of Ru element on the catalyst was 1wt% and the thickness of the nano Ru shell layer was 80. Mu.m.
Preparation example 5
A catalyst was prepared according to the method of preparation example 2, except that in the bimetallic solution, the Ru/Pd molar ratio was 7:1; and the coating amount, the temperature and the flow rate of hot air in the sugar coating machine are adjusted so that the loading amount of Ru element on the catalyst is 0.7wt%, the loading amount of Pd is 0.1wt% and the thickness of a shell layer is 80 mu m.
Preparation example 6
A catalyst was prepared according to the method of preparation example 2, except that in the bimetallic solution, the Ru/Pd molar ratio was 10:1; and the coating amount, the temperature and the flow rate of hot air in the sugar coating machine are adjusted so that the loading amount of Ru element on the catalyst is 1wt%, the loading amount of Pd is 0.1wt% and the thickness of a shell layer is 120 mu m.
Preparation example 7
A catalyst was prepared according to the method of preparation example 1, except that the carrier Al after impurity removal 2 O 3 Immersed in a nano Ru coating solution, wherein the volume of the nano Ru coating solution is 4 times that of the carrier (so that the loading of Ru element on the catalyst is about 0.5% by volume), filtered after immersion for 12 hours, then vacuum dried (temperature 110 ℃ C., time 12 hours), calcined (temperature 400 ℃ C., time 2 hours), and reduced (temperature 300 ℃ C., reduction 2 hours in an atmosphere with a hydrogen concentration of 30% by volume). The prepared catalyst is recorded as Ru/Al 2 O 3 。
Preparation example 8
A catalyst was prepared according to the method of preparation example 2, except that the carrier Al after impurity removal 2 O 3 Immersed in a bimetal solution having a volume 4 times the volume of the support (thus enabling the loading of Ru element on the catalyst to be about 0.5% by weight and the loading of Pd to be about 0.1% by weight), filtered after immersion for 12 hours, then vacuum dried (temperature 110 ℃ C., time 12 hours), calcined (temperature 400 ℃ C., time 2 hours), and reduced (temperature 300 ℃ C., reduction 2 hours in an atmosphere having a hydrogen concentration of 30% by volume). The prepared catalyst is recorded as Ru-Pd/Al 2 O 3 。
Preparation example 9
A catalyst was prepared according to the method of preparation example 2, except that the support was replaced with SiO respectively 2 、ZrO 2 、TiO 2 And carbon microspheres (except for the carbon microspheres, other carriers are baked at 500 ℃ to remove impurities before being coated), the diameter of the carriers is 4mm, and the prepared catalysts are respectively recorded as Ru-Pd@SiO 2 、Ru-Pd@ZrO 2 、Ru-Pd@TiO 2 And Ru-Pd@C (catalyst using carbon microspheres as a carrier).
Preparation example 10
A catalyst was prepared according to the method of preparation example 2, except that the promoter metals were replaced with Rh and Ni, respectively, and the prepared catalysts were denoted Ru-Rh@Al, respectively 2 O 3 And Ru-Ni@Al 2 O 3 。
PREPARATION EXAMPLE 11
A catalyst was prepared according to the method of preparation example 1, except that the amount of coating was controlled so that the loading of Ru element on the catalyst was 0.25wt% and the thickness of the nano Ru shell layer was 40. Mu.m.
Preparation example 12
A catalyst was prepared in the same manner as in preparation example 2 except that in the bimetallic solution, the concentration of Ru element was 0.015mol/L and the molar ratio of Ru/Pd was 1:1; and the shell thickness and the amount of Ru and Pd supported are controlled by controlling the temperature, flow and coating amount of hot air, so that the loading amount of Ru element on the catalyst is 0.25wt%, the loading amount of Pd is 0.25wt%, and the shell thickness is 70 mu m.
The catalysts obtained in the above preparation examples were analyzed by Electron Probe Microscopy (EPMA), and it was found that the metal of the shell layer did not substantially penetrate into the inside of the support in the catalysts obtained in the other preparation examples except for preparation examples 7 to 8.
In the examples below, all catalysts were activated at 200 ℃ to remove surface oxide layers prior to hydrogenation. The catalyst is filled in the fixed bed reactor, the catalyst filling amount is 30ml, the inner diameter of the reaction tube is 20mm, and the filling height is more than 10 times of the diameter of the reaction tube, (the channeling phenomenon of the reaction liquid passing through the bed layer is prevented).
In the examples below, the volume space velocity of the first hydrogenation refers to the volume space velocity of the mixture of the phthalate dibasic ester and the hydrogenation solvent; the volume space velocity of the second hydrogenation refers to the volume space velocity of the liquid phase material obtained by the first hydrogenation.
In the following examples, after the first hydrogenation and the second hydrogenation, the product after the second hydrogenation is subjected to gas-liquid separation, reduced pressure distillation, alkali washing and reduced pressure steam stripping in sequence to obtain the target product cyclohexane-1, 2-dicarboxylic acid diester. Wherein the reduced pressure distillation is performed in a reduced pressure distillation column, and the operating conditions of the reduced pressure distillation column are as follows: the pressure was 45kPa, the temperature at the top of the column was 95℃and the temperature at the bottom of the column was 130 ℃. The tower top gas of the vacuum distillation tower is cooled and dried, and then the hydrogenation solvent is recovered for recycling. Directly feeding the tower bottom product of the distillation tower into an alkaline washing tank for alkaline washing to remove the byproduct of the adjacent cyclohexaneMonoisononyl benzoate. The volume ratio of alkali liquor to tower bottom product used for alkali washing is 1:10, and the alkali liquor concentration is Na with mass concentration of 1wt% 2 CO 3 The temperature of the solution, alkaline washing, was 60 ℃. Standing for water separation after alkali washing, and enabling an upper oil phase to enter a stripping tower for decompressing and removing trace water, wherein the decompressing and stripping conditions comprise: the pressure was 70kPa and the temperature was 100 ℃. The stripper bottoms are cyclohexane-1, 2-dicarboxylic acid dibasic ester and incompletely reacted reactants (both of which are difficult to separate further).
Example 1
Taking the catalyst prepared in preparation example 1 as a first catalyst, taking isononyl alcohol as a hydrogenation solvent, wherein the amount of the hydrogenation solvent is 20wt% of the sum of the mass dosages of the hydrogenation solvent and the diisononyl phthalate, the catalyst loading is 30mL, and the volume space velocity of the first hydrogenation is 0.5h -1 . Under the above conditions, the first hydrogenation reaction was carried out once by changing the conditions of the temperature of the first hydrogenation, the hydrogen partial pressure and the hydrogen oil volume ratio, and the reaction results are shown in Table 1.
TABLE 1
Therefore, when the method provided by the invention is adopted for carrying out the first hydrogenation step, higher conversion rate and selectivity can be obtained, and side reactions are fewer. The other products in table 1 are mainly by-products of carboxylic acids.
Example 2
Taking the catalyst prepared in preparation example 1 as a first catalyst, taking isononanol as a hydrogenation solvent, and taking 30mL of catalyst loading, wherein the first hydrogenation conditions comprise: the temperature is 170 ℃, the hydrogen partial pressure is 8MPa, and the hydrogen-oil volume ratio is 600:1.
under the above conditions, the amount of the hydrogenation solvent was changed so that the ratio of diisononyl phthalate to the sum of the mass amounts of the hydrogenation solvent and diisononyl phthalate was changed, and the volume space velocity was changed, and the first hydrogenation was carried out once, respectively, with the reaction results shown in Table 2. In Table 2, the DINP concentration is the ratio of diisononyl phthalate to the sum of the amounts of hydrogenation solvent and diisononyl phthalate by mass.
TABLE 2
Therefore, by adopting the method provided by the invention, higher selectivity and conversion rate can be obtained under different DINP concentration and volume space velocity conditions.
Example 3
The catalyst prepared in preparation example 1 was taken as a first catalyst, and the amount of the hydrogenation solvent was such that diisononyl phthalate was 20% by weight based on the sum of the mass amounts of the hydrogenation solvent and diisononyl phthalate, and the catalyst loading was 30ml. The conditions for the first hydrogenation include: the temperature is 170 ℃, the hydrogen partial pressure is 8MPa, and the hydrogen-oil volume ratio is 600:1, volume space velocity of 0.5h -1 。
Under the above conditions, the hydrogenation solvents were changed, and the first hydrogenation was carried out once, respectively, and the reaction results are shown in Table 3.
TABLE 3 Table 3
Therefore, by adopting the method provided by the invention, higher conversion rate and selectivity can be obtained when different hydrogenation solvents are used.
Example 4
The catalyst prepared in preparation example 1 was taken as a first catalyst, isononyl alcohol was taken as a hydrogenation solvent in an amount such that diisononyl phthalate accounted for 20wt% of the sum of the mass amounts of the hydrogenation solvent and the diisononyl phthalate, and the catalyst loading was 30mL. The conditions for the first hydrogenation include: the temperature is 170 ℃, the hydrogen partial pressure is 8MPa, and the hydrogen-oil volume ratio is 600:1, volume space velocity of 0.5h -1 . Under the above conditions, the hydrogenation reaction was carried out a plurality of times so that the service time of the catalyst amounted to 500 hours, and the conversion and selectivity data of the reaction were recorded at intervals, and the results are shown in Table 4.
TABLE 4 Table 4
Therefore, under the condition that the reaction time is up to 500 hours, the conversion rate of DINP is still stably maintained above 90% and the selectivity is stably maintained above 95% by adopting the catalyst provided by the invention. And, in 500h, the liquid material of partial reaction is taken at intervals for detection, no metal ions are found in the liquid material, and the metal loaded on the catalyst is basically not lost. From the above, the catalyst used in the present invention has excellent hydrogenation stability.
Example 5
Taking part of the material obtained by the reaction in the example 4 as a raw material for second hydrogenation, wherein the catalyst for the second hydrogenation is the catalyst in the preparation example 2, the catalyst loading is 30mL, the hydrogen partial pressure for the second hydrogenation is 6MPa, and the hydrogen-oil ratio is 600:1.
under the above conditions, the temperature and the volume space velocity conditions of the second hydrogenation were changed, and the second hydrogenation was performed, respectively, with the reaction results shown in Table 5.
TABLE 5
Taking part of the material obtained in the reaction of the example 4 as a raw material for second hydrogenation, wherein a catalyst for the second hydrogenation is a catalyst for preparation example 2, the catalyst loading is 30mL, the reaction temperature for the second hydrogenation is 160 ℃, and the volume space velocity is 1h -1 。
Under the above conditions, the hydrogen partial pressure and the hydrogen-oil volume ratio of the second hydrogenation were changed, and the second hydrogenation was performed, respectively, with the reaction results shown in table 6.
TABLE 6
Therefore, the method provided by the invention can obtain higher selectivity and conversion rate under different temperature and volume space velocity conditions.
Example 6
A portion of the material obtained in the reaction of example 4 was used as a starting material for the second hydrogenation reaction, and the catalyst loading was 30mL. The conditions for the second hydrogenation include: the temperature is 160 ℃, the hydrogen partial pressure is 6MPa, and the hydrogen-oil volume ratio is 600:1, volume space velocity of 1h -1 。
Under the above conditions, the second catalysts were the catalysts Ru-Pd@Al of preparation example 2, respectively 2 O 3 And Ru-Pd@SiO in preparation example 9 2 、Ru-Pd@ZrO 2 、Ru-Pd@TiO 2 And Ru-Pd@C, respectively carrying out primary hydrogenation reaction. The results are shown in Table 7.
TABLE 7
According to the results, the second catalysts obtained by adopting different carriers have higher hydrogenation activity, and the diisononyl cyclohexanedicarboxylate obtained by the first hydrogenation can be completely converted into DINCH after the second hydrogenation, so that the conversion rate is higher.
Example 7
A portion of the material obtained by the reaction in example 4 was taken as a starting material for the second hydrogenation, and the catalyst loading was 30mL. The conditions for the second hydrogenation include: the temperature is 160 ℃, the hydrogen partial pressure is 6MPa, and the hydrogen-oil volume ratio is 600:1, volume space velocity of 1h -1 。
Under the above conditions, the second catalysts were the catalysts Ru-Pd@Al of preparation example 2, respectively 2 O 3 And Ru-Rh@Al of preparation example 10 2 O 3 And Ru-Ni@Al 2 O 3 Respectively carrying out primary hydrogenation reactionShould be. The results are shown in Table 8.
TABLE 8
Therefore, under the condition of adopting different auxiliary metals, the catalyst provided by the invention has higher benzene ring hydrogenation activity and olefin hydrogenation activity.
Example 8
The catalyst Ru/Al of preparation 7 was taken 2 O 3 As the first catalyst, catalyst Ru-Pd/Al of preparation 8 2 O 3 As a second catalyst, a first hydrogenation was carried out according to the conditions in example 4, and the resulting material was subjected to a second hydrogenation according to the conditions in example 6. The reaction results are shown in Table 9. As in example 6, ru-Pd@Al was used 2 O 3 The data for the reactions are shown in Table 9.
TABLE 8
Wherein, the conversion rate of DINP corresponding to the first catalyst refers to the conversion rate of DINP after the first hydrogenation; the conversion of DINP corresponding to the second catalyst means the conversion of DINP after the second hydrogenation.
Therefore, compared with the traditional catalyst prepared by the impregnation method, the catalyst provided by the invention can obtain higher conversion rate and selectivity.
Example 9
The first hydrogenation conditions in example 4 and the second hydrogenation conditions in example 6 were followed, but the first hydrogenation reaction was carried out according to the combination of the first catalyst and the second catalyst in the following table, respectively, and the results are shown in table 10.
Table 10
Example 10
The catalyst prepared in preparation example 2 was used as a first catalyst and a second catalyst, and the first hydrogenation was carried out under the conditions in example 4, and the material after the first hydrogenation was subjected to the second hydrogenation under the conditions in example 6, and the results are shown in Table 11.
Comparative example 1
Ru/Al of preparation 7 2 O 3 As the first catalyst, ru-Pd/Al of preparation 8 was taken 2 O 3 The first hydrogenation was carried out for the second catalyst under the conditions in example 4, and the material after the first hydrogenation was subjected to the second hydrogenation under the conditions in example 6, and the results are shown in table 11.
TABLE 11
| Examples numbering | Example 10 | Comparative example 1 |
| DINP conversion/% | 100 | 85 |
| Conversion of diisononyl cyclohexene dicarboxylate/% | 100 | 100 |
| DINCH selectivity/% | 89.6 | 82.5 |
| Cyclohexyldicarboxylic acid mono-esterIsononyl ester selectivity/% | 10.2 | 12.7 |
| Other product Selectivity/% | 0.4 | 5.8 |
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A process for the preparation of cyclohexane-1, 2-dicarboxylic acid dibasic esters, comprising: and (3) carrying out hydrogenation reaction on the phthalic acid diester and hydrogen in the presence of a catalyst, wherein the catalyst has a structure taking a carrier as a core and taking an active component Ru and an optional auxiliary agent M as a shell.
2. The process according to claim 1, wherein the loading of Ru element is 0.01 to 2wt%, and the molar ratio of Ru element to M element is 3 to 10:1, a step of;
and/or the active component Ru and/or the auxiliary agent M are/is present in the form of nanoparticles with a particle size of 1-5 nm;
and/or the auxiliary agent M is at least one of Pd, rh and Ni;
and/or the shell has a thickness of 40-150 μm and the core has a diameter of 1-10mm.
3. The method of claim 1, wherein the hydrogenation reaction comprises: (1) a first hydrogenation step: carrying out first hydrogenation on phthalic acid dibasic ester and hydrogen in the presence of a first catalyst and a hydrogenation solvent;
(2) A second hydrogenation step: subjecting the product after the first hydrogenation to a second hydrogenation in the presence of a second catalyst;
(3) Optionally, carrying out post-treatment on the product after the second hydrogenation to obtain cyclohexane-1, 2-dicarboxylic acid dibasic ester;
preferably, the first catalyst has a structure with nano Ru as a shell and a carrier as a core, wherein the thickness of the shell is 60-80 mu m, and the diameter of the core is 2-6mm;
preferably, the second catalyst has a structure with nano Ru and nano M as shells and a carrier as a core, wherein the thickness of the shell is 60-120 mu M, and the diameter of the core is 2-6mm.
4. A process according to claim 3, wherein the loading of Ru element in the first catalyst is 0.1-1.5wt%, preferably 0.3-1wt%, relative to the total weight of the first catalyst;
and/or, in the first catalyst, the particle size of the nano Ru is 1-2nm;
and/or, in the first catalyst, the carrier is Al 2 O 3 、SiO 2 、ZrO 2 、TiO 2 And at least one of carbon microspheres, preferably Al 2 O 3 。
5. The method according to claim 3 or 4, wherein the first catalyst is prepared by a method comprising: coating the nano Ru coating liquid on the surface of a carrier, and drying, roasting and reducing to obtain a first catalyst;
preferably, the preparation method of the nano Ru coating liquid comprises the following steps: mixing Ru source, stabilizer and solvent to obtain precursor solution, and heating at 130-150deg.C for 90-150min to obtain Ru sol; mixing Ru sol and water to obtain nano Ru precipitation particles, and dispersing the nano Ru precipitation particles in the water to obtain nano Ru coating liquid with Ru concentration of 0.01-0.04 g/mL;
preferably, the Ru source is selected from at least one of Ru trichloride, ruthenium carbonyl chloride, ammonium chlororuthenate, sodium chlororuthenate, and potassium chlororuthenate, more preferably ruthenium trichloride;
preferably, the stabilizer is selected from at least one of alkali metal formate, alkali metal acetate and alkali metal citrate, more preferably sodium acetate;
preferably, the solvent is selected from at least one of C2-C5 polyols, more preferably at least one of ethylene glycol, propylene glycol and glycerol;
preferably, the concentration of Ru element in the precursor solution is 0.01-0.05mol/L;
preferably, stabilizer/ru=8-12 by mass: 1.
6. the process according to claim 3, wherein the hydrogenation solvent is at least one selected from isononanol, dioxane, tetrahydrofuran, cyclohexane, methanol and decalin;
and/or the amount of the hydrogenation solvent is such that the phthalate dibasic ester is 20 to 80wt% of the sum of the mass amounts of the hydrogenation solvent and the phthalate dibasic ester;
and/or, the conditions for the first hydrogenation include: the temperature is 165-180 ℃, the hydrogen partial pressure is 7-10MPa, and the hydrogen-oil volume ratio is 200-600:1, the volume space velocity of the mixture of the phthalic acid dibasic ester and the hydrogenation solvent is 0.3 to 1h -1 。
7. A process according to claim 3, wherein the loading of Ru element in the second catalyst is 0.5 to 1wt%, and the molar ratio of Ru element to M element is 5 to 10:1, a step of;
and/or, in the second catalyst, the carrier is Al 2 O 3 、SiO 2 、ZrO 2 、TiO 2 And at least one of carbon microspheres, preferably Al 2 O 3 ；
And/or the auxiliary M is at least one selected from Pd, rh and Ni.
8. The method according to claim 3 or 7, wherein the second catalyst is prepared by a method comprising: coating a bimetallic solution containing Ru and M on the surface of a carrier, and drying, roasting and reducing to obtain a second catalyst;
preferably, the preparation method of the bimetallic solution containing Ru and M comprises the following steps: preparing an aqueous solution of Ru source, and then adding an M source to obtain the Ru element with the concentration of 0.01-0.05mol/L, wherein the mol ratio of Ru element to M element is 5-10:1, a bimetallic solution containing Ru and M;
preferably, the Ru source is selected from at least one of Ru trichloride, ruthenium carbonyl chloride, ammonium chlororuthenate, sodium chlororuthenate, and potassium chlororuthenate, more preferably ruthenium trichloride.
9. The process of claim 3, wherein the second hydrogenation conditions comprise: the temperature is 130-160 ℃, the hydrogen partial pressure is 3-6MPa, and the hydrogen-oil volume ratio is 200-600:1, the volume space velocity of the liquid phase material obtained by the first hydrogenation is 0.5-2h -1 ；
And/or, the post-processing comprises: sequentially carrying out gas-liquid separation, reduced pressure distillation, alkali washing and reduced pressure steam stripping on the product after the second hydrogenation;
preferably, the reduced pressure distillation is performed in a reduced pressure distillation column operated under the following conditions: the pressure is 40-50kPa, the temperature of the top of the tower is 90-100 ℃, and the temperature of the bottom of the tower is 120-140 ℃.
10. The process according to claim 1 or 2, wherein the phthalic acid diester is phthalic anhydride or an esterification product of phthalic acid with an alcohol selected from C1-C10 alcohols.
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