CN112939747B - 一种愈创木酚的制备方法 - Google Patents
一种愈创木酚的制备方法 Download PDFInfo
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- CN112939747B CN112939747B CN202110229333.1A CN202110229333A CN112939747B CN 112939747 B CN112939747 B CN 112939747B CN 202110229333 A CN202110229333 A CN 202110229333A CN 112939747 B CN112939747 B CN 112939747B
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- catalyst
- guaiacol
- catechol
- phosphate
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- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229960001867 guaiacol Drugs 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000003054 catalyst Substances 0.000 claims abstract description 66
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000003607 modifier Substances 0.000 claims abstract description 19
- 239000003381 stabilizer Substances 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 230000008021 deposition Effects 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 5
- 238000006266 etherification reaction Methods 0.000 claims abstract description 5
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 239000002245 particle Substances 0.000 claims description 17
- KMPWYEUPVWOPIM-KODHJQJWSA-N cinchonidine Chemical group C1=CC=C2C([C@H]([C@H]3[N@]4CC[C@H]([C@H](C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-KODHJQJWSA-N 0.000 claims description 15
- KMPWYEUPVWOPIM-UHFFFAOYSA-N cinchonidine Natural products C1=CC=C2C(C(C3N4CCC(C(C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-UHFFFAOYSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- TYAVIWGEVOBWDZ-UHFFFAOYSA-K cerium(3+);phosphate Chemical compound [Ce+3].[O-]P([O-])([O-])=O TYAVIWGEVOBWDZ-UHFFFAOYSA-K 0.000 claims description 6
- DZNFWGVDYGAMJB-UHFFFAOYSA-K neodymium(3+);phosphate Chemical compound [Nd+3].[O-]P([O-])([O-])=O DZNFWGVDYGAMJB-UHFFFAOYSA-K 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- LQFNMFDUAPEJRY-UHFFFAOYSA-K lanthanum(3+);phosphate Chemical compound [La+3].[O-]P([O-])([O-])=O LQFNMFDUAPEJRY-UHFFFAOYSA-K 0.000 claims description 5
- GWEDODYYNURODY-UHFFFAOYSA-N 1-[ethoxy(methylsulfanyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(SC)OCC GWEDODYYNURODY-UHFFFAOYSA-N 0.000 claims description 4
- CZGGKXNYNPJFAX-UHFFFAOYSA-N Dimethyldithiophosphate Chemical compound COP(S)(=S)OC CZGGKXNYNPJFAX-UHFFFAOYSA-N 0.000 claims description 4
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 4
- 239000006200 vaporizer Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- IRDLUHRVLVEUHA-UHFFFAOYSA-N diethyl dithiophosphate Chemical compound CCOP(S)(=S)OCC IRDLUHRVLVEUHA-UHFFFAOYSA-N 0.000 claims description 3
- CKSHRDPCFLDKPV-UHFFFAOYSA-N diphenoxy-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1OP(=S)(S)OC1=CC=CC=C1 CKSHRDPCFLDKPV-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- KDCUNMWWJBHRSC-UHFFFAOYSA-K praseodymium(3+);phosphate Chemical compound [Pr+3].[O-]P([O-])([O-])=O KDCUNMWWJBHRSC-UHFFFAOYSA-K 0.000 claims description 2
- 229910000164 yttrium(III) phosphate Inorganic materials 0.000 claims description 2
- UXBZSSBXGPYSIL-UHFFFAOYSA-K yttrium(iii) phosphate Chemical compound [Y+3].[O-]P([O-])([O-])=O UXBZSSBXGPYSIL-UHFFFAOYSA-K 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 230000011987 methylation Effects 0.000 abstract description 10
- 238000007069 methylation reaction Methods 0.000 abstract description 10
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- 229930013930 alkaloid Natural products 0.000 abstract description 2
- 150000003797 alkaloid derivatives Chemical class 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 16
- 238000004939 coking Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- ZSSIYIZVIFNDRJ-UHFFFAOYSA-N hydroxy-phenoxy-phenylsulfanyl-sulfanylidene-lambda5-phosphane Chemical compound C=1C=CC=CC=1SP(=S)(O)OC1=CC=CC=C1 ZSSIYIZVIFNDRJ-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Chemical group C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930002341 quinoline alkaloid Natural products 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JHGWQSGWUPCKNT-UHFFFAOYSA-N 2-tert-butyl-4-methyl-1,3,5-trinitrobenzene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C(C(C)(C)C)=C1[N+]([O-])=O JHGWQSGWUPCKNT-UHFFFAOYSA-N 0.000 description 1
- -1 205 °C Chemical compound 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 1
- 239000005770 Eugenol Substances 0.000 description 1
- 206010062717 Increased upper airway secretion Diseases 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- PKUWKAXTAVNIJR-UHFFFAOYSA-M O,O-diethyl thiophosphate Chemical compound CCOP([O-])(=S)OCC PKUWKAXTAVNIJR-UHFFFAOYSA-M 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 201000006549 dyspepsia Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229960002217 eugenol Drugs 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003589 local anesthetic agent Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 208000026435 phlegm Diseases 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/83—Aluminophosphates [APO 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO 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
- B01J31/0255—Phosphorus containing compounds
- B01J31/0269—Phosphorus containing compounds on mineral substrates
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明提供一种愈创木酚的制备方法。该方法将邻苯二酚与甲醇在催化剂的作用下,发生醚化反应生成愈创木酚,所述催化剂含有生物碱修饰剂,并含有硫代磷酸酯稳定剂。本发明在得到高收率愈创木酚的同时,提高了催化剂的使用寿命,降低了催化剂的再生频率,降低了产品提纯难度,进而提高了邻苯二酚甲基化法制备愈创木酚的经济性,其中,邻苯二酚转化率>80%,愈创木酚选择性>95%,装置运行3000h催化剂的积碳率<5%。
Description
技术领域
本发明属于催化合成领域,具体涉及一种愈创木酚的制备方法。
背景技术
愈创木酚为白色或微黄色结晶或无色至淡黄色透明油状液体,具有芳香气味,在工业上应用广泛,常用来生产各种香料,如丁香酚、香兰素和人造麝香。愈创木酚在医药上也有大量应用,它可被用于合成苯磺酸愈创木酚,用作局部麻醉剂或防腐剂,还可以祛痰和治疗消化不良。由于愈创木酚具有还原性,常在化妆品中少量添加作为抗氧化剂。由于愈创木酚与氧反应会显深色,还被用作染料。此外,愈创木酚也可用作有机合成原料及分析测定的标准物质。
愈创木酚的制备方法有以下几种:天然物中提取、邻氨基苯甲醚法、邻苯二酚甲基化法。其中,从天然物中提取的愈创木酚数量有限,不能满足市场需求;用邻氨基苯甲醚重氮化水解生成愈创木酚的方法存在污染严重等问题;邻苯二酚甲基化法是工业中常用的方法,甲基化试剂有一氯甲烷、硫酸二甲酯、碳酸二甲酯和甲醇,碳酸二甲酯和甲醇作为甲基化试剂,存在原料毒性小、生产工艺腐蚀性小、成本低、三废少等特点,是最具前景的生产工艺,但也存在催化剂易结焦的缺点。
CN201610183357.7公开了通过控制邻苯二酚和甲醇的反应温度不超过275℃的方法来避免邻苯二酚析碳现象的发生,但是未给出工艺条件下邻苯二酚的转化率及愈创木酚的选择性。
CN201910032138.2中提供了一种碱性催化剂,在控制反应体系的温度不超过350℃时,催化剂NaTiPSiAlO催化效果最佳,邻苯二酚转化率为88.9%,愈创木酚选择性为98.2%,但未给催化剂的使用寿命及使用过程中催化剂的结焦生碳情况。
在催化剂的催化下,甲醇和邻苯二酚在催化剂酸性位上发生醚化反应,生成愈创木酚,反应式如下所示:
若愈创木酚在催化剂作用下继续与甲醇进行醚化,则生成藜芦醚,反应式如下所示:
藜芦醚的沸点206℃与愈创木酚的沸点205℃非常接近,得到纯度高的愈创木酚难度大。并且邻苯二酚在催化剂酸性位上很容易结焦生碳,使催化剂失活,降低了催化剂的使用寿命。
综上所述,需要寻找一种新的邻苯二酚甲基化法生成愈创木酚的催化剂,在得到高收率愈创木酚的同时,提高催化剂的使用寿命,降低催化剂的再生频率,降低产品提纯难度,进而提高邻苯二酚甲基化法制备愈创木酚的经济性。
发明内容
本发明的目的在于提供一种愈创木酚的制备方法,具体地说是提供一种邻苯二酚甲基化法生成愈创木酚的改性催化剂,使在这种催化剂的作用下,提高邻苯二酚转化率、愈创木酚选择性,并降低催化剂的积碳率。在改进催化剂的催化下,能够有效地抑制催化剂的结焦速率,极大地提高了邻苯二酚甲基化法生产愈创木酚工艺的稳定性和经济性。
为达到以上发明目的,本发明的技术方案如下:
一种愈创木酚的制备方法,所述方法中原料邻苯二酚与甲醇在催化剂的作用下发生醚化反应生成愈创木酚;其中,所述催化剂含有生物碱修饰剂,并含有硫代磷酸酯稳定剂。
本发明中,所述的催化剂包含:载体70wt%~80wt%,活性组分5wt%~20wt%,稳定剂5wt%~10wt%,修饰剂1wt%~5wt%,以催化剂总质量计。
本发明中,所述载体为氧化铝、氧化硅、二氧化钛、二氧化锆、磷酸铝分子筛和硅磷酸铝分子筛中的一种或多种。
本发明中,所述活性组分为磷酸钕、磷酸钇、磷酸镨、磷酸铈和磷酸镧中的一种或多种,优选磷酸钕、磷酸铈和磷酸镧中的一种或多种。
本发明中,所述稳定剂为二硫代磷酸二甲酯、甲基硫代磷酸二乙酯、二硫代磷酸二乙酯和二苯基二硫代磷酸中的一种或多种。邻苯二酚和甲醇反应生成愈创木酚的过程中,邻苯二酚在催化剂B酸位上易发生偶联聚合反应,进而结焦成碳,造成催化剂失活。本发明在催化剂中加入了稳定剂,主要原因是硫代磷酸酯在高温下能分解产生SH·自由基,产生的SH·自由基还能与邻苯二酚裂解产生的R·自由基(R·表示)反应,有效地阻止了邻苯二酚的结焦生碳,反应方程式如下:
R·+SH·=RH+S
本发明中,所述修饰剂为喹啉型生物碱,优选辛可尼定和/或辛可宁。其中辛可尼定、辛可宁的结构式分别如下:
修饰剂的加入能够降低催化剂中酸性中心的强度,也能起到抑制催化剂结焦的作用。同时喹啉型生物碱中的亲核的奎宁环与活性组分中的金属元素M键合,使得苯酚更容易吸附在催化剂的M位点上,催化剂上的M金属元素取代苯酚羟基上的H;同时甲醇吸附在催化剂载体上的L酸位点上,L酸性位使甲醇中的OH键断裂,CH3·与吸附在金属元素M上的苯酚结合,产物从催化剂的M位点上脱离出来,生成愈创木酚。其中M优选钕、钇、镨、铈、镧。以辛可尼定为例,具体催化过程的催化机理如下:
a、修饰剂对活性组分中金属元素M的影响
b、催化剂催化邻苯二酚和甲醇的反应过程
本发明中,催化剂的制备方法为浸渍法;优选地,所述方法包含如下步骤:
S1:将载体和活性组分混合、挤压成型、破碎,得到固体颗粒;稳定剂与修饰剂混合后溶解得到溶液;
S2:将S1的固体颗粒加入所述溶液,搅拌、烘干、焙烧,得到负载有稳定剂和修饰剂的催化剂。
本发明中,所述S1中固体颗粒粒径为20目~40目。
本发明中,所述S1中的溶液为乙醇溶液,优选90wt%~95wt%的乙醇溶液。
本发明中,所述S2在20℃~60℃下搅拌2h~12h,在50℃~80℃下烘干4h~8h,在150℃~200℃下焙烧4h~8h。
本发明中,所述方法采用的反应器为釜式反应器或固定床反应器,优选固定床反应器。
本发明中,通过汽化器汽化后的甲醇和汽化后的邻苯二酚的摩尔比为1:1~5:1。
本发明中,处理1Kg邻苯二酚需催化剂0.01mL~20mL,优选需催化剂0.1mL~5mL。
本发明中,原料经过预热器预热至反应温度后进入反应器,反应温度为200℃~300℃,优选230℃~280℃,反应压力为0~0.8MPag,优选0~0.3MPag,空速为0.1h-1~0.5h-1,优选0.2h-1~0.3h-1。
本发明中,所述反应的邻苯二酚转化率>80%,愈创木酚选择性>95%,装置运行3000h催化剂的积碳率<5%。
本发明的另一目的在于提供一种愈创木酚产品。
一种愈创木酚产品,采用上述的制备方法制备获得。
本发明中所述的压力均为表压。
本发明的积极效果在于:
(1)针对催化剂易结焦生碳的问题,通过添加稳定剂,有效抑制了催化剂的结焦生碳,延长了催化剂的寿命;通过添加修饰剂喹啉型生物碱,在改变催化剂酸强度和降低催化剂结焦速率的同时,使邻苯二酚和甲醇的醚化反应更容易进行,从而提高了愈创木酚的选择性。本发明中,邻苯二酚的转化率>80%,愈创木酚选择性>95%,装置运行3000h催化剂的积碳率<5%。
(2)通过解决催化剂结焦生碳的问题,提高了催化剂的使用寿命,从而提高了装置的经济性。
具体实施方式
下面结合实施例进一步阐述本发明。这些实施例仅用于说明本发明,而非限制本发明的范围。
主要原料信息如下:
设备信息如下:
设备名称 | 设备规格 | 设备厂家 |
固定床反应器 | 反应管长1.2m,直径20mm | 科立化工设备有限公司 |
压片机 | 不锈钢旋转式XYP-17D压片机 | 飞驰机械设备有限公司 |
气相色谱分析条件为:
分析仪器:安捷伦7820,毛细管柱(Rtx-5MS);
气相分析方法:面积归一化法;
气相分析条件:气化室温度为250℃,检测器温度250℃,柱温为程序升温:50℃,1min;80℃,1min;10℃/min至250℃,15min。
对比例1
将80g磷酸铝分子筛和20g磷酸铈混合,用压片机挤压成型后破碎,制得20目~40目的固体颗粒,在200℃下焙烧4h,得到催化剂-0。
实施例1
将72g磷酸铝分子筛和18g磷酸铈混合,用压片机挤压成型后破碎,制得20目~40目的固体颗粒。将8g二硫代磷酸二甲酯与2g辛可尼定混合后,溶解在90g乙醇中,配制成乙醇含量为90wt%的乙醇溶液,将制得的20目~40目的固体颗粒加入到溶有二硫代磷酸二甲酯和辛可尼定的乙醇溶液中,在20℃下搅拌12h,50℃下烘干8h,将乙醇挥发完全后在200℃下焙烧4h,得到负载有稳定剂和修饰剂的催化剂-1。
实施例2
将20g氧化铝、60g硅磷酸铝分子筛和5g磷酸镧混合,用压片机挤压成型后破碎,制得20目~40目的固体颗粒。将5g甲基硫代磷酸二乙酯、5g二苯基二硫代磷酸和5g辛可宁混合后,溶解在135g乙醇中,配制成乙醇含量为90wt%的乙醇溶液,将制得的20目~40目的固体颗粒加入到溶有甲基硫代磷酸二乙酯、二苯基二硫代磷酸和辛可宁的乙醇溶液中,在60℃下搅拌2h,80℃下烘干4h,将乙醇挥发完全后在180℃下焙烧6h,得到负载有稳定剂和修饰剂的催化剂-2。
实施例3
将70g二氧化锆和20g磷酸钕混合,用挤条机挤压成型后破碎,制得20目~40目的固体颗粒。将5g二硫代磷酸二乙酯和5g辛可宁混合后,溶解在115g乙醇中,配制成乙醇含量为92wt%的乙醇溶液,将制得的20目~40目的固体颗粒加入到溶有硫代磷酸二乙酯和辛可宁的乙醇溶液中,在35℃下搅拌6h,60℃下烘干6h,将乙醇挥发完全后在150℃下焙烧8h,得到负载有稳定剂和修饰剂的催化剂-3。
实施例4
将75g二氧化钛和16g磷酸钕混合,用挤条机挤压成型后破碎,制得20目~40目的固体颗粒。将8g二苯基二硫代磷酸和1g辛可尼定混合后,溶解在171g乙醇中,配制成乙醇含量为95wt%的乙醇溶液,将制得的20目~40目的固体颗粒加入到溶有二苯基二硫代磷酸和辛可尼定的乙醇溶液中,在50℃下搅拌10h,7℃下烘干7h,将乙醇挥发完全后在180℃下焙烧6h,得到负载有稳定剂和修饰剂的催化剂-4。
将上面制得的不同催化剂分别装填在反应管长1.2m、内径为20mm的固定床反应管中进行反应,反应管材质为316L,原料通过固定床的汽化器汽化,经预热器预热至反应温度后,进入反应管反应,反应条件如表1所示。
表1反应条件
反应结果如表2所示,加入稳定剂和修饰剂后的催化剂均能催化邻苯二酚转化率达到80%以上,愈创木酚选择性高于95%,装置连续运转3000h后催化剂的积碳率小于5%。
表2反应结果
本领域技术人员可以理解,在本说明书的教导之下,可对本发明做出一些修改或调整。这些修改或调整也应当在本发明权利要求所限定的范围之内。
Claims (12)
1.一种愈创木酚的制备方法,其特征在于,所述方法中原料邻苯二酚与甲醇在催化剂的作用下发生醚化反应生成愈创木酚;
所述催化剂的组成为载体70wt%~80wt%,活性组分5wt%~20wt%,稳定剂5wt%~10wt%,修饰剂1wt%~5wt%,以催化剂总质量计;
其中,所述载体为氧化铝、氧化硅、二氧化钛、二氧化锆、磷酸铝分子筛和硅磷酸铝分子筛中的一种或多种;所述活性组分为磷酸钕、磷酸钇、磷酸镨、磷酸铈和磷酸镧中的一种或多种;所述稳定剂为硫代磷酸酯和/或二苯基二硫代磷酸;所述修饰剂为辛可尼定和/或辛可宁。
2.根据权利要求1所述的制备方法,其特征在于,所述稳定剂为二硫代磷酸二甲酯、甲基硫代磷酸二乙酯、二硫代磷酸二乙酯和二苯基二硫代磷酸中的一种或多种。
3.根据权利要求1所述的制备方法,其特征在于,所述活性组分为磷酸钕、磷酸铈和磷酸镧中的一种或多种。
4.根据权利要求1或2所述的制备方法,其特征在于,所述催化剂的比表面积为80m2/g ~500m2/g,孔容为0.1cm3/g~0.5cm3/g,孔径为30Å~300Å。
5.根据权利要求1或2所述的制备方法,其特征在于,所述催化剂的比表面积为120m2/g~220m2/g,孔容为0.2cm3/g~0.4cm3/g,孔径为70Å~100Å。
6.根据权利要求1或2所述的制备方法,其特征在于,催化剂的制备方法为浸渍法。
7.根据权利要求1或2所述的制备方法,其特征在于,所述催化剂的制备方法包含如下步骤:
S1:将载体和活性组分混合、挤压成型、破碎,得到固体颗粒;稳定剂与修饰剂混合后溶解得到溶液;
S2:将S1的固体颗粒加入所述溶液,搅拌、烘干、焙烧,得到负载有稳定剂和修饰剂的催化剂。
8.根据权利要求7所述的制备方法,其特征在于,所述S1中固体颗粒粒径为20目~40目;
和/或,所述S1中的溶液为乙醇溶液;
和/或,所述S2在20℃~60℃下搅拌2h~12h,在50℃~80℃下烘干4h~8h,在150℃~200℃下焙烧4h~8h。
9.根据权利要求8所述的制备方法,其特征在于,所述S1中的溶液为90wt%~95wt%的乙醇溶液。
10.根据权利要求1或2所述的制备方法,其特征在于,所述方法采用的反应器为釜式反应器或固定床反应器;
和/或,原料通过汽化器,汽化后的甲醇和汽化后的邻苯二酚的摩尔比为1:1~5:1;
和/或,处理1kg 邻苯二酚需催化剂0.01mL~20mL;
和/或,原料经过预热器预热至反应温度后,进入反应器,反应温度为200℃~300℃,反应压力为0~0.8MPag,空速为0.1h-1~0.5h-1。
11.根据权利要求10所述的制备方法,其特征在于,所述方法采用的反应器为固定床反应器;
和/或,处理1kg 邻苯二酚需催化剂0.1mL~5mL;
和/或,反应温度为230℃~280℃,反应压力为0~0.3MPag,空速为0.2h-1~0.3h-1。
12.根据权利要求1或2所述的制备方法,其特征在于,所述反应的邻苯二酚转化率>80%,愈创木酚选择性>95%,装置运行3000h催化剂的积碳率<5%。
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