CN114345366B - Preparation method of 3-methoxy-4-hydroxymandelic acid oxidation catalyst - Google Patents
Preparation method of 3-methoxy-4-hydroxymandelic acid oxidation catalyst Download PDFInfo
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- CN114345366B CN114345366B CN202210041636.5A CN202210041636A CN114345366B CN 114345366 B CN114345366 B CN 114345366B CN 202210041636 A CN202210041636 A CN 202210041636A CN 114345366 B CN114345366 B CN 114345366B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- CGQCWMIAEPEHNQ-UHFFFAOYSA-N Vanillylmandelic acid Chemical compound COC1=CC(C(O)C(O)=O)=CC=C1O CGQCWMIAEPEHNQ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 13
- 230000003647 oxidation Effects 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 10
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 3
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 53
- 239000007787 solid Substances 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 30
- KWGRBVOPPLSCSI-WPRPVWTQSA-N (-)-ephedrine Chemical compound CN[C@@H](C)[C@H](O)C1=CC=CC=C1 KWGRBVOPPLSCSI-WPRPVWTQSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 18
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 16
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 16
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 14
- 239000012018 catalyst precursor Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- KWGRBVOPPLSCSI-UHFFFAOYSA-N d-ephedrine Natural products CNC(C)C(O)C1=CC=CC=C1 KWGRBVOPPLSCSI-UHFFFAOYSA-N 0.000 claims description 12
- 229960002179 ephedrine Drugs 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 8
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 229940099596 manganese sulfate Drugs 0.000 claims description 5
- 235000007079 manganese sulphate Nutrition 0.000 claims description 5
- 239000011702 manganese sulphate Substances 0.000 claims description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 5
- METCDLVKDOFVTJ-UHFFFAOYSA-N O.O.O(Cl)Cl.[Zr] Chemical compound O.O.O(Cl)Cl.[Zr] METCDLVKDOFVTJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 150000002603 lanthanum Chemical class 0.000 claims description 4
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 150000003754 zirconium Chemical class 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- -1 manganese copper lanthanum zirconium Chemical compound 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000012752 auxiliary agent Substances 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 description 9
- 239000011572 manganese Substances 0.000 description 9
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 8
- 238000011049 filling Methods 0.000 description 8
- 229960002510 mandelic acid Drugs 0.000 description 8
- 239000011435 rock Substances 0.000 description 8
- CAROYFSHUHTKPM-UHFFFAOYSA-N [Cu].[Mn].[La] Chemical compound [Cu].[Mn].[La] CAROYFSHUHTKPM-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 5
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 5
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 235000012141 vanillin Nutrition 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052747 lanthanoid Inorganic materials 0.000 description 3
- 150000002602 lanthanoids Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 229960001867 guaiacol Drugs 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WJUFSDZVCOTFON-UHFFFAOYSA-N veratraldehyde Chemical compound COC1=CC=C(C=O)C=C1OC WJUFSDZVCOTFON-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 235000009499 Vanilla fragrans Nutrition 0.000 description 1
- 244000263375 Vanilla tahitensis Species 0.000 description 1
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000001085 differential centrifugation Methods 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013212 standard curve analysis Methods 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
Classifications
-
- 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 discloses a preparation method of a 3-methoxy-4-hydroxymandelic acid oxidation catalyst MCLZ. By ZrO 2 And the composite metal oxide loaded with manganese, copper, lanthanum and an auxiliary agent is used as a catalyst to catalyze the oxidation of 3-methoxy-4-hydroxy mandelic acid with high activity and high selectivity to prepare 3-methoxy-4-hydroxy phenylketoacid. The process solves the problem that the supported catalyst is easy to pulverize and low in activity when used in the strong alkaline high-temperature liquid phase reaction, and the obtained catalyst is long in service life and can stably run for 1000 hours.
Description
Technical Field
The invention relates to a preparation method of a 3-methoxy-4-hydroxymandelic acid oxidation catalyst MCLZ, which is used for preparing 3-methoxy-4-hydroxyphenylketo acid by oxidizing 3-methoxy-4-hydroxymandelic acid.
Background
Vanillin is the first essence synthesized by human beings, also called methyl vanillin, and has a chemical name of 3-methoxy-4-hydroxybenzaldehyde, is white or yellowish crystal, has vanilla fragrance and rich milk fragrance, and is the largest variety in the perfume industry. The product has wide application, is an indispensable important raw material in the food additive industry, is widely applied to various flavoring foods needing to increase the smell of milk, and can also be applied to soaps, toothpastes, perfumes, rubber, plastics and medicines.
According to statistics, most (about 90%) of vanillin products in the market today are produced by chemical synthesis methods, and the supply is greater than the demand, wherein the technology of the glyoxylate method has the advantages of easily controlled conditions, high yield, less pollution, easily regenerated extractant, easily regenerated oxidant and the like. There have been a great deal of literature and patent reports on the synthesis of vanillin by the glyoxylate process.
The glyoxylate process is divided into two steps, the first: the guaiacol and the glyoxylic acid are subjected to condensation reaction under the action of alkali to generate 3-methoxy-4-hydroxy mandelic acid, and the unreacted guaiacol can be recovered by adjusting the pH value and extracting with toluene; and a second step of: under the action of alkali, copper oxide or air is used for oxidizing mandelic acid to generate 3-methoxy-4-hydroxy-phenylketoacid, then the pH value is regulated to be acidic, and vanillin is generated by heating and decarboxylation.
In summary, although a great deal of research results have been carried out on the preparation of 3-methoxy-4-hydroxy-phenylketoacid by oxidizing 3-methoxy-4-hydroxy-mandelic acid, the catalyst is a homogeneous catalyst or a catalyst with small particle size which is not easy to separate, because the oxidation reaction is in a strongly alkaline environment (pH > 12), the catalyst is easy to pulverize, and the adhesive is easy to decompose.
Therefore, aiming at the characteristics of easy pulverization, difficult separation and strong alkaline environment of the catalyst, a new process needs to be developed.
Disclosure of Invention
The invention aims to provide a preparation method of a 3-methoxy-4-hydroxymandelic acid oxidation catalyst MCLZ. Involving MnO 2 CuO and La 2 O 3 Co-precipitation reaction liquid of (2) and modified ZrO 2 And (3) preparation of a carrier. The catalyst is applied to the oxidation of 3-methoxy-4-hydroxy mandelic acid, the conversion rate and the selectivity can reach 95%, and the catalyst and the reaction liquid are very easy to separate and have no pulverization phenomenon.
The invention firstly provides a preparation method of a supported manganese copper lanthanum zirconium composite metal oxide catalyst MCLZ, which comprises the following steps:
1) Adding zirconium salt, manganese salt, copper salt, lanthanum salt and an auxiliary agent into deionized water, stirring and dissolving to obtain a corresponding solution, and centrifugally filtering out supernatant to obtain a corresponding solid;
2) Adding deionized water and alkali liquor into the solid in the step 1), stirring and dissolving to obtain corresponding solution, centrifuging and filtering supernatant to obtain Mn, cu and La loaded modified ZrO 2 A catalyst precursor;
3) Soaking the solid precursor in alkali liquor, and drying in an oven to obtain a solid 1;
4) Calcining the solid 1 in a muffle furnace to obtain a solid 2, namely modified ZrO 2 Supported catalyst MCLZ.
In the catalyst preparation method, in the step 1), zirconium salt is selected from one or more of zirconium oxychloride dihydrate and zirconium nitrate;
the copper salt is selected from one or more of copper nitrate, copper sulfate and copper chloride;
the manganese salt is selected from one or more of manganese nitrate and manganese sulfate;
the lanthanum salt is selected from one or more of lanthanum nitrate and lanthanum sulfate;
the auxiliary agent is one or more of sodium dodecyl benzene sulfonate or dodecyl benzene sulfonate;
preferably, the mol ratio of zirconium, manganese, copper, lanthanum and auxiliary agent is 13-28:8-17:7-16:0.2-0.3:0.1-0.3;
the amount of deionized water is not particularly limited, and the raw materials can be dissolved;
the dissolution temperature is normal temperature, and the stirring time is 2-4h;
the centrifugal speed is 500rpm-2000rpm, and the centrifugal time is 10-20 minutes.
In the catalyst preparation method of the present invention, in the step 2), the addition amount of deionized water is not particularly limited;
the alkali liquor is one or more of 20-40% sodium hydroxide solution or ammonia water; the addition amount is 5-30% of the solid mass;
the dissolution temperature is normal temperature, and the stirring time is 2-4h;
the centrifugal speed is 1000-2000rpm, and the centrifugal time is 10-20 minutes.
In the preparation method of the catalyst, in the step 3), the alkali liquor is ephedrine solution;
the concentration of the ephedrine solution is 10-20wt%;
the soaking time in the ephedrine solution is 10-12h;
the drying condition in the oven is 110-120 ℃ for 10-12h.
In the preparation method of the catalyst, in the step 4), the calcination procedure in the muffle furnace is 400-600 ℃ for 4-6h, and the supported catalyst MCLZ is obtained.
The catalyst prepared by the invention is used in the reaction process for preparing 3-methoxy-4-hydroxy-phenylketoacid by the oxidation reaction of 3-methoxy-4-hydroxy-mandelic acid:
the preferred steps are: filling the catalyst into a reaction kettle (rock YZSR-500 (M)), wherein the reaction raw material is 3-methoxy-4-hydroxy mandelic acid alkaline aqueous solution, introducing oxygen into the reaction, continuously stirring in the reaction, and reacting for a period of time to obtain a product 3-methoxy-4-hydroxy phenylketoacid;
in the invention, the addition amount of the catalyst is 0.5-1% of the mass of the condensation reaction liquid;
in the present invention, the concentration of 3-methoxy-4-hydroxymandelic acid is 7 to 8%, preferably 7.8 to 8%. Adding alkali liquor to adjust the pH to 10-12, wherein the alkali can be one of ammonia water or sodium hydroxide;
in the present invention, the reaction temperature is 90 to 100℃and preferably 98 to 100 ℃.
In the present invention, the pressure in the reactor is 1 to 3Bar, preferably 1 to 1.5Bar.
In the present invention, the stirring speed is 800 to 1200rpm, preferably 1100 to 1200rpm.
In the present invention, the oxidation reaction is a batch reaction.
The invention has the beneficial effects that:
the catalyst precursor is prepared by using a differential centrifugation method, so that the combination of all the components is tighter, and the mechanical strength of the catalyst is higher; and the substances after centrifugal separation are easier to dry, so that the energy consumption is effectively reduced. (2) The lanthanide metal is doped, the lanthanide metal is easy to oxidize in the air, and oxygen is introduced in the reaction, so that the catalytic effect of the catalyst can be improved; the addition of lanthanide metal can reduce Mn and Cu oxidation energy barrier, make active component be more easily oxidized by oxygen and increase oxidation capacity of catalyst. (3) The addition of sodium dodecyl benzene sulfonate in the preparation process of the catalyst precursor can increase the alkalinity of the carrier and increase the ZrO of the carrier 2 The internal pore canal increases the stability and catalytic activity of the catalyst. (4) The ephedrine solution is added before the calcination of the catalyst precursor, so that the alkalinity of the carrier can be increased, the binding force with the coprecipitation reaction liquid can be increased, and the stability and the catalytic activity of the catalyst can be increased.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The conversion was determined using a liquid chromatography external standard curve analysis, the chromatographic conditions were as follows:
instrument model: island body fluid phase chromatography SPD-20A; column incubator: CTO-10ASvp; column temperature: 40 ℃, time program: 0.01-5min 90% phase B (0.1% phosphoric acid/water); 5-17min 90% -10% phase b (0.1% phosphoric acid/water solution); 17-21min 10% phase b (0.1% phosphoric acid/water solution); 21-22min 10% -90% phase b (0.1% phosphoric acid/water solution); the solvent feed was stopped for 33 min. The total flow rate of pump A was 0.5ml/min. The detector wavelength was 254nm.
Example 1:
(1) Differential speedCentrifugal precipitation method for preparing ZrO loaded by lanthanum-manganese-copper 2 Catalyst:
1) Adding zirconium nitrate, manganese sulfate, copper nitrate, lanthanum nitrate and sodium dodecyl benzene sulfonate into deionized water, stirring for 3 hours to dissolve to obtain a corresponding solution, centrifuging at 1000rpm for 10min, and filtering out supernatant to obtain a corresponding solid; wherein, the mol ratio of zirconium, manganese, copper, lanthanum and sodium dodecyl benzene sulfonate is 17:17:16:0.2:0.2;
2) Adding deionized water and 40% sodium hydroxide solution into the solid obtained in the step 1), stirring for 3h to obtain corresponding solution, centrifuging at 1000rpm for 10min, and filtering to obtain Mn, cu and La loaded modified ZrO 2 A catalyst precursor; wherein, the addition amount of the sodium hydroxide solution is 20% of the solid mass;
3) Soaking the solid precursor in ephedrine solution (20wt%) for 10 hr, drying at 120deg.C for 10 hr to obtain solid 1;
4) Calcining the solid 1 at 500 ℃ for 4 hours to obtain modified ZrO 2 Supported catalyst MCZ-50-5.
Catalyst performance evaluation:
the catalyst is filled into a reaction kettle (rock YZSR-500 (M)), the filling amount of the catalyst is 2g, the reaction temperature is 100 ℃, the reaction raw material is 300g of 3-methoxy-4-hydroxy mandelic acid alkaline aqueous solution (mandelic acid content is 8%, pH is 12), oxygen is introduced into the reaction to keep the pressure in the kettle to be 1Bar, and the reaction is carried out at 1200rpm for continuous stirring, and the 3-methoxy-4-hydroxy-phenylketoacid is obtained after the reaction is carried out for 5 hours. Conversion 100% and selectivity 96%.
Example 2:
(1) Differential centrifugal precipitation method for preparing ZrO loaded by lanthanum-manganese-copper 2 Catalyst:
1) Adding zirconium oxychloride dihydrate, manganese nitrate, copper nitrate, lanthanum nitrate and sodium dodecyl benzene sulfonate into deionized water, stirring for 3 hours to dissolve to obtain a corresponding solution, centrifuging at 1000rpm for 10 minutes, and filtering out supernatant to obtain a corresponding solid; wherein, the mol ratio of zirconium, manganese, copper, lanthanum and sodium dodecyl benzene sulfonate is 25:10:16:0.2:0.2;
2) Adding deionized water and 40% sodium hydroxide solution into the solid obtained in the step 1)Stirring the solution for 2h to dissolve to obtain corresponding solution, centrifuging at 1000rpm for 20min, and filtering to obtain supernatant to obtain Mn, cu and La loaded modified ZrO 2 A catalyst precursor; wherein the addition amount of the sodium hydroxide solution is 15% of the solid mass;
3) Soaking the solid precursor in ephedrine solution (20wt%) for 10 hr, drying at 120deg.C for 10 hr to obtain solid 1;
4) Calcining the solid 1 at 500 ℃ for 4 hours to obtain modified ZrO 2 Supported catalyst MCZ-80-5.
Catalyst performance evaluation:
the catalyst is filled into a reaction kettle (rock YZSR-500 (M)), the filling amount of the catalyst is 2g, the reaction temperature is 100 ℃, the reaction raw material is 300g of 3-methoxy-4-hydroxy mandelic acid alkaline aqueous solution (mandelic acid content is 8%, pH is 12), oxygen is introduced into the reaction to keep the pressure in the kettle to be 1Bar, and the reaction is carried out at 1200rpm for continuous stirring, and the 3-methoxy-4-hydroxy-phenylketoacid is obtained after the reaction is carried out for 5 hours. The conversion rate is 100% and the selectivity is 95.5%.
Example 3:
(1) Differential centrifugal precipitation method for preparing ZrO loaded by lanthanum-manganese-copper 2 Catalyst:
1) Adding zirconium oxychloride dihydrate, manganese nitrate, copper sulfate, lanthanum nitrate and sodium dodecyl benzene sulfonate into deionized water, stirring for 2 hours to dissolve to obtain a corresponding solution, centrifuging at 1500rpm for 10 minutes, and filtering out supernatant to obtain a corresponding solid; wherein, the mol ratio of zirconium, manganese, copper, lanthanum and sodium dodecyl benzene sulfonate is 15:16:16:0.2:0.2;
2) Adding deionized water and 40% sodium hydroxide solution into the solid obtained in the step 1), stirring for 3h to obtain corresponding solution, centrifuging at 1000rpm for 10min, and filtering to obtain Mn, cu and La loaded modified ZrO 2 A catalyst precursor; wherein, the addition amount of the sodium hydroxide solution is 20% of the solid mass;
3) Soaking the solid precursor in ephedrine solution (15 wt%) for 10 hr, drying at 110 deg.C for 10 hr to obtain solid 1;
4) Calcining the solid 1 at 550 ℃ for 4 hours to obtain modified ZrO 2 Supported catalyst MCZ-30-5.
Catalyst performance evaluation:
the catalyst is filled into a reaction kettle (rock YZSR-500 (M)), the filling amount of the catalyst is 2g, the reaction temperature is 100 ℃, the reaction raw material is 300g of 3-methoxy-4-hydroxy mandelic acid alkaline aqueous solution (mandelic acid content is 7%, pH is 12), oxygen is introduced during the reaction to keep the pressure in the kettle to be 2Bar, and the reaction is continuously stirred at 1200rpm, and the 3-methoxy-4-hydroxy-phenylketoacid is obtained after the reaction is carried out for 5 hours. Conversion 100% and selectivity 96%.
Example 4:
(1) Differential centrifugal precipitation method for preparing ZrO loaded by lanthanum-manganese-copper 2 Catalyst:
1) Adding zirconium nitrate, manganese nitrate, copper chloride, lanthanum sulfate and sodium dodecyl benzene sulfonate into deionized water, stirring for 3 hours to dissolve to obtain a corresponding solution, centrifuging at 1000rpm for 10min, and filtering out supernatant to obtain a corresponding solid; wherein, the mol ratio of zirconium, manganese, copper, lanthanum and sodium dodecyl benzene sulfonate is 20:17:10:0.2:0.3;
2) Adding deionized water and 30% sodium hydroxide solution into the solid obtained in the step 1), stirring for 3h to obtain corresponding solution, centrifuging at 1000rpm for 10min, and filtering to obtain Mn, cu and La loaded modified ZrO 2 A catalyst precursor; wherein, the addition amount of the sodium hydroxide solution is 20% of the solid mass;
3) Soaking the solid precursor in ephedrine solution (20wt%) for 12 hr, drying at 120deg.C for 10 hr to obtain solid 1;
4) Calcining the solid 1 at 500 ℃ for 5 hours to obtain modified ZrO 2 Supported catalyst MCZ-50-3.
Catalyst performance evaluation:
the catalyst is filled into a reaction kettle (rock YZSR-500 (M)), the filling amount of the catalyst is 2g, the reaction temperature is 100 ℃, the reaction raw material is 300g of 3-methoxy-4-hydroxy mandelic acid alkaline aqueous solution (mandelic acid content is 8%, pH is 11), oxygen is introduced into the reaction kettle to keep the pressure in the kettle to be 2Bar, and the reaction is carried out at 1200rpm for continuous stirring, and the 3-methoxy-4-hydroxy-phenylketoacid is obtained after the reaction is carried out for 5 hours. The conversion rate is 100% and the selectivity is 95%.
Example 5:
(1) Differential centrifugal precipitation method for preparing ZrO loaded by lanthanum-manganese-copper 2 Catalyst:
1) Adding zirconium nitrate, manganese nitrate, copper chloride, lanthanum sulfate and sodium dodecyl benzene sulfonate into deionized water, stirring for 3 hours to dissolve to obtain a corresponding solution, centrifuging at 1000rpm for 10min, and filtering out supernatant to obtain a corresponding solid; wherein, the mol ratio of zirconium, manganese, copper, lanthanum and sodium dodecyl benzene sulfonate is 18:16:14:0.2:0.1;
2) Adding deionized water and 40% sodium hydroxide solution into the solid obtained in the step 1), stirring for 3h to obtain corresponding solution, centrifuging at 1000rpm for 10min, and filtering to obtain Mn, cu and La loaded modified ZrO 2 A catalyst precursor; wherein, the addition amount of the sodium hydroxide solution is 20% of the solid mass;
3) Soaking the solid precursor in ephedrine solution (20wt%) for 10 hr, drying at 110 deg.C for 10 hr to obtain solid 1;
4) Calcining the solid 1 at 500 ℃ for 6 hours to obtain modified ZrO 2 Supported catalyst MCLZ.
Catalyst performance evaluation:
the catalyst is filled into a reaction kettle (rock YZSR-500 (M)), the filling amount of the catalyst is 2g, the reaction temperature is 100 ℃, the reaction raw material is 300g of 3-methoxy-4-hydroxy mandelic acid alkaline aqueous solution (mandelic acid content is 8%, pH is 12), oxygen is introduced into the reaction to keep the pressure in the kettle to be 1Bar, and the reaction is carried out at 1200rpm for continuous stirring, and the 3-methoxy-4-hydroxy-phenylketoacid is obtained after the reaction is carried out for 5 hours. The conversion rate is 100% and the selectivity is 95%.
Comparative example 1:
(1) Differential centrifugal precipitation method for preparing ZrO loaded by lanthanum-manganese-copper 2 Catalyst:
1) Adding zirconium nitrate, manganese sulfate, copper nitrate and lanthanum nitrate into deionized water, stirring for 3 hours to dissolve to obtain a corresponding solution, centrifuging at 1000rpm for 10 minutes, and filtering out supernatant to obtain a corresponding solid; wherein, the mol ratio of zirconium, manganese, copper and lanthanum is 17:17:16:0.2;
2) Adding deionized water and 40% sodium hydroxide solution into the solid obtained in the step 1), stirring for 3h to dissolve to obtainCentrifuging the corresponding solution at 1000rpm for 10min, and filtering to obtain Mn, cu and La loaded modified ZrO 2 A catalyst precursor; wherein, the addition amount of the sodium hydroxide solution is 20% of the solid mass;
3) Soaking the solid precursor in ephedrine solution (20wt%) for 10 hr, drying at 120deg.C for 10 hr to obtain solid 1;
4) Calcining the solid 1 at 500 ℃ for 4 hours to obtain modified ZrO 2 Supported catalyst MCZ-50-5-300.
Catalyst performance evaluation:
the catalyst is filled into a reaction kettle (rock YZSR-500 (M)), the filling amount of the catalyst is 2g, the reaction temperature is 100 ℃, the reaction raw material is 300g of 3-methoxy-4-hydroxy mandelic acid alkaline aqueous solution (mandelic acid content is 8%, pH is 12), oxygen is introduced into the reaction to keep the pressure in the kettle to be 1Bar, and the reaction is carried out at 1200rpm for continuous stirring, and the 3-methoxy-4-hydroxy-phenylketoacid is obtained after the reaction is carried out for 5 hours. The conversion rate is 85% and the selectivity is 89%.
Comparative example 2:
(1) Differential centrifugal precipitation method for preparing ZrO loaded by lanthanum-manganese-copper 2 Catalyst:
1) Adding zirconium nitrate, manganese sulfate, copper nitrate, lanthanum nitrate and sodium dodecyl benzene sulfonate into deionized water, stirring for 3 hours to dissolve to obtain a corresponding solution, centrifuging at 1000rpm for 10min, and filtering out supernatant to obtain a corresponding solid; wherein, the mol ratio of zirconium, manganese, copper, lanthanum and sodium dodecyl benzene sulfonate is 17:17:16:0.2:0.2;
2) Adding deionized water and 40% sodium hydroxide solution into the solid obtained in the step 1), stirring for 3h to obtain corresponding solution, centrifuging at 1000rpm for 10min, and filtering to obtain Mn, cu and La loaded modified ZrO 2 A catalyst precursor; wherein, the addition amount of the sodium hydroxide solution is 20% of the solid mass;
4) Calcining the catalyst precursor at 500 ℃ for 4 hours to obtain modified ZrO 2 The supported catalyst MCZ-50-5-500.
Catalyst performance evaluation:
the catalyst is filled into a reaction kettle (rock YZSR-500 (M)), the filling amount of the catalyst is 2g, the reaction temperature is 100 ℃, the reaction raw material is 300g of 3-methoxy-4-hydroxy mandelic acid alkaline aqueous solution (mandelic acid content is 8%, pH is 12), oxygen is introduced during the reaction to keep the pressure in the kettle to be 1Bar, and the reaction is continuously stirred at 1200rpm, and the 3-methoxy-4-hydroxy-phenylketoacid is obtained after the reaction is carried out for 5 hours. Conversion 90% and selectivity 92%.
Claims (11)
1. The preparation method of the supported manganese copper lanthanum zirconium composite metal oxide catalyst is characterized by comprising the following steps of:
1) Adding zirconium salt, manganese salt, copper salt, lanthanum salt and sodium dodecyl benzene sulfonate into deionized water, stirring and dissolving to obtain a solution, and centrifugally filtering out supernatant to obtain a solid;
2) Adding deionized water and alkali liquor into the solid obtained in the step 1), stirring and dissolving to obtain a solution, and centrifugally filtering out supernatant to obtain a catalyst precursor;
3) Soaking the precursor in ephedrine solution, and drying to obtain solid 1;
4) Calcining the solid 1 to obtain a solid 2, namely the supported catalyst.
2. The method according to claim 1, wherein in step 1), the zirconium salt is selected from one or more of zirconium oxychloride dihydrate and zirconium nitrate;
the copper salt is selected from one or more of copper nitrate, copper sulfate and copper chloride;
the manganese salt is selected from one or more of manganese nitrate and manganese sulfate;
the lanthanum salt is selected from one or more of lanthanum nitrate and lanthanum sulfate.
3. The method according to claim 2, wherein the molar ratio of zirconium, manganese, copper, lanthanum, sodium dodecyl benzene sulfonate is 13-28:8-17:7-16:0.2-0.3:0.1-0.3.
4. A method according to any one of claims 1 to 3, wherein in step 1), the dissolution temperature is normal temperature and the stirring time is 2 to 4 hours;
the centrifugal speed is 500rpm-2000rpm, and the centrifugal time is 10-20 minutes.
5. The method according to claim 1, wherein in step 2), the lye is one or more of sodium hydroxide solution or ammonia water; the concentration of the alkali liquor is 20-40wt%, and the addition amount is 5-30% of the solid mass;
the dissolution temperature is normal temperature, and the stirring time is 2-4h;
the centrifugal speed is 1000-2000rpm, and the centrifugal time is 10-20 minutes.
6. The method of claim 1, wherein in step 3), the concentration of the ephedrine solution is 10-20wt%;
the soaking time is 10-12h; the drying condition is that the drying is carried out for 10-12 hours at the temperature of 110-120 ℃.
7. The method of claim 1, wherein in step 4), the calcination is performed in a muffle furnace at 400-600 ℃ for 4-6 hours.
8. Use of a catalyst prepared according to the method of any one of claims 1-7 for the oxidation of 3-methoxy-4-hydroxymandelic acid to prepare 3-methoxy-4-hydroxyphenylketo acid.
9. Use according to claim 8, comprising: the 3-methoxy-4-hydroxy mandelic acid alkaline aqueous solution is used as a raw material, oxygen is introduced under the catalysis of a supported catalyst, and the 3-methoxy-4-hydroxy phenylketoacid is prepared by continuous stirring reaction.
10. Use according to claim 9, characterized in that the concentration of the alkaline aqueous solution of 3-methoxy-4-hydroxymandelic acid is 8% and the pH is 10-12.
11. Use according to claim 9 or 10, characterized in that the reaction temperature is 90-100 ℃, the catalyst is added in an amount of 0.5-1% by mass of the condensation reaction liquid, and the partial pressure of oxygen in the reaction kettle is 1-3Bar.
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