CN114345366A - 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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- CN114345366A CN114345366A CN202210041636.5A CN202210041636A CN114345366A CN 114345366 A CN114345366 A CN 114345366A CN 202210041636 A CN202210041636 A CN 202210041636A CN 114345366 A CN114345366 A CN 114345366A
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- lanthanum
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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 48
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 13
- 238000002360 preparation method 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 65
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 10
- 229910052746 lanthanum Inorganic materials 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
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 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
- 239000000243 solution Substances 0.000 claims description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 239000007787 solid Substances 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- KWGRBVOPPLSCSI-WPRPVWTQSA-N (-)-ephedrine Chemical compound CN[C@@H](C)[C@H](O)C1=CC=CC=C1 KWGRBVOPPLSCSI-WPRPVWTQSA-N 0.000 claims description 22
- 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
- 239000006228 supernatant Substances 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 15
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 15
- 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
- 239000003513 alkali Substances 0.000 claims description 13
- 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
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- KWGRBVOPPLSCSI-UHFFFAOYSA-N d-ephedrine Natural products CNC(C)C(O)C1=CC=CC=C1 KWGRBVOPPLSCSI-UHFFFAOYSA-N 0.000 claims description 11
- 229960002179 ephedrine Drugs 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000001035 drying Methods 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
- 238000005119 centrifugation Methods 0.000 claims description 8
- 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
- 229940099596 manganese sulfate Drugs 0.000 claims description 5
- 239000011702 manganese sulphate Substances 0.000 claims description 5
- 235000007079 manganese sulphate Nutrition 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
- 239000012295 chemical reaction liquid Substances 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
- 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
- -1 manganese-copper-lanthanum-zirconium Chemical compound 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
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 17
- 239000007791 liquid phase Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- 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
- 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
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 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
- 239000003205 fragrance Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229960001867 guaiacol Drugs 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 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
- 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
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 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
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 238000004458 analytical method Methods 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
- 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
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005265 energy consumption 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
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 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
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- WKOLLVMJNQIZCI-UHFFFAOYSA-N vanillic acid Chemical compound COC1=CC(C(O)=O)=CC=C1O WKOLLVMJNQIZCI-UHFFFAOYSA-N 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
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a 3-methoxy-4-hydroxymandelic acid oxidation catalyst MCLZ. Using ZrO2The 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-hydroxymandelic acid with high activity and high selectivity to prepare the 3-methoxy-4-hydroxyphenylketo acid. The process solves the problem that the supported catalyst is easy to pulverize and has low activity when used in strong-basicity high-temperature liquid phase reaction, and the obtained catalyst has long 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-hydroxybenzene keto acid by oxidizing 3-methoxy-4-hydroxymandelic acid.
Background
Vanillin is the first essence synthesized by human, also called methyl vanillin, with the chemical name of 3-methoxy-4-hydroxybenzaldehyde, is white or yellowish crystal, has vanilla fragrance and strong 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 milk fragrance, and can also be used for perfumed soaps, toothpastes, perfumes, rubbers, plastics and pharmaceuticals.
According to statistics, most (about 90%) vanillin products in the market are produced by a chemical synthesis method, which is more than demanded, wherein the process of the glyoxylic acid method has the advantages of easily controlled conditions, high yield, less pollution, easily regenerated extractant, easily regenerated oxidant and the like. There are a lot of literature and patent reports on the research on the synthesis of vanillin by the glyoxylic acid method.
The glyoxylate process is divided into two steps, the first step: carrying out condensation reaction on guaiacol and glyoxylic acid under the action of alkali to generate 3-methoxy-4-hydroxymandelic acid, and extracting and recovering unreacted guaiacol by toluene by adjusting pH; the second step is that: under the action of alkali, copper oxide or air is used for oxidizing mandelic acid to generate 3-methoxy-4-hydroxybenzene keto-acid, then the pH is adjusted to acidity, and vanillin is generated by heating and decarboxylation.
In summary, although a great deal of research results have been shown in the preparation of 3-methoxy-4-hydroxybenzenecarboxylic acid by oxidizing 3-methoxy-4-hydroxymandelic acid, the catalyst is a homogeneous catalyst or a catalyst with a small particle size which is not easy to separate, because the oxidation reaction is in a strong alkaline environment (pH > 12), the catalyst is easy to pulverize, and the adhesive is easy to decompose.
Therefore, a new process needs to be developed for the characteristics that the catalyst is easily pulverized and not easily separated, and the reaction liquid is in a strong alkaline environment.
Disclosure of Invention
The invention aims to provide a preparation method of a 3-methoxy-4-hydroxymandelic acid oxidation catalyst MCLZ. To MnO2CuO and La2O3Coprecipitation reaction solution of (1), and modified ZrO2And (3) preparing a carrier. The catalyst is applied to the oxidation of 3-methoxy-4-hydroxymandelic acid, the conversion rate and the selectivity can reach 95 percent, and the catalyst and a reaction solution are 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 auxiliary agent into deionized water, stirring and dissolving to obtain corresponding solution, and centrifugally filtering to remove supernatant to obtain corresponding solid;
2) adding deionized water and alkali liquor into the solid in the step 1), stirring and dissolving to obtain corresponding solution, and centrifugally filtering to remove supernatant to obtain modified ZrO loaded with Mn, Cu and La2A 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 the modified ZrO2Supported catalyst MCLZ.
In the preparation method of the catalyst, in the 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;
the auxiliary agent is one or more of sodium dodecyl benzene sulfonate or dodecyl benzene sulfonic acid;
preferably, the molar 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 dissolving temperature is normal temperature, and the stirring time is 2-4 h;
the centrifugation speed is 500rpm-2000rpm, and the centrifugation time is 10-20 minutes.
In the preparation method of the catalyst, in the step 2), the adding amount of the deionized water is not particularly limited;
the alkali liquor is one or more of 20-40% sodium hydroxide solution or ammonia water; the adding amount is 5-30% of the solid mass;
the dissolving temperature is normal temperature, and the stirring time is 2-4 h;
the centrifugation speed is 1000-2000rpm, and the centrifugation 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 10-20 wt%;
soaking in the ephedrine solution for 10-12 h;
the drying condition in the oven is 110-120 ℃ for 10-12 h.
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-hydroxybenzeneacid by oxidation reaction of 3-methoxy-4-hydroxymandelic acid:
the preferred steps are: filling the catalyst into a reaction kettle (YangyzSR-500 (M)), wherein the reaction raw material is 3-methoxy-4-hydroxymandelic acid alkaline aqueous solution, introducing oxygen in the reaction, continuously stirring in the reaction, and reacting for a period of time to obtain a product, namely 3-methoxy-4-hydroxyphenylketo acid;
in the invention, the adding 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 solution to adjust 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 tank is 1 to 3Bar, preferably 1 to 1.5 Bar.
In the present invention, the stirring speed is 800-.
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 centrifugal method, so that the components can be combined more tightly, and the mechanical strength of the catalyst is higher; and the substance after centrifugal separation is easier to dry, thereby effectively reducing energy consumption. Doping lanthanide metal, which is easily oxidized in air, and introducing oxygen in the reaction to increase the catalytic effect of the catalyst; the addition of lanthanide series metal can lower the oxidation energy barrier of Mn and Cu, make the active component be easily oxidized by oxygen, and increase the oxidation capacity of the catalyst. ③ the sodium dodecyl benzene sulfonate is added in the preparation process of the catalyst precursor, so as to increase the alkalinity of the carrier and the ZrO of the carrier2The internal pore channels increase the stability and catalytic activity of the catalyst. Adding ephedrine solution before calcining the catalyst precursor, and can increase the alkalinity of the carrier, increase the binding force with the co-precipitation reaction liquid, and increase the stability and catalytic activity of the catalyst.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The conversion rate is determined by using the analysis of a liquid chromatography external standard curve method, and the chromatographic analysis conditions are as follows:
the instrument model is as follows: shimadzu liquid chromatography SPD-20A; column oven: CTO-10 ASvp; column temperature: 40 ℃, time program: 0.01-5min 90% phase B (0.1% phosphoric acid/water solution); 5-17min 90% -10% of phase B (0.1% phosphoric acid/water solution); 17-21min 10% phase B (0.1% phosphoric acid/water solution); 10% -90% of phase B (0.1% phosphoric acid/water solution) for 21-22 min; the solvent was stopped at 33 min. Pump A has a total flow rate of 0.5 ml/min. The detector wavelength is 254 nm.
Example 1:
(1) differential centrifugal precipitation method for preparing manganese-copper-lanthanum-loaded ZrO2Catalyst:
1) adding zirconium nitrate, manganese sulfate, copper nitrate, lanthanum nitrate and sodium dodecyl benzene sulfonate into deionized water, stirring for 3h to dissolve to obtain corresponding solution, centrifuging at 1000rpm for 10min, and filtering to remove supernatant to obtain corresponding solid; wherein the molar 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 for dissolving to obtain corresponding solution, centrifuging at 1000rpm for 10min, and filtering to remove supernatant to obtain modified ZrO loaded with Mn, Cu and La2A catalyst precursor; wherein the addition amount of the sodium hydroxide solution is 20 percent of the solid mass;
3) soaking the solid precursor in ephedrine solution (20 wt%) for 10h, and drying at 120 deg.C for 10h to obtain solid 1;
4) calcining the solid 1 at 500 ℃ for 4h to obtain modified ZrO2Supported catalyst MCZ-50-5.
Evaluation of catalyst Performance:
the catalyst is filled into a reaction kettle (YangyzSR-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-hydroxymandelic acid alkaline aqueous solution (the content of mandelic acid is 8 percent, the pH value is 12), oxygen is introduced in the reaction to keep the pressure in the kettle at 1Bar, the reaction is continuously stirred at 1200rpm, and the product of 3-methoxy-4-hydroxyphenylketo acid is obtained after the reaction is carried out for 5 hours. The conversion rate is 100%, and the selectivity is 96%.
Example 2:
(1) differential centrifugal precipitation method for preparing manganese-copper-lanthanum-loaded ZrO2Catalyst:
1) adding zirconium oxychloride dihydrate, manganese nitrate, copper nitrate, lanthanum nitrate and sodium dodecyl benzene sulfonate into deionized water, stirring for 3h to dissolve to obtain a corresponding solution, centrifuging at 1000rpm for 10min, and filtering to remove supernatant to obtain a corresponding solid; wherein the molar 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 for 2h to dissolve to obtain corresponding solution, centrifuging at 1000rpm for 20min, and filtering to remove supernatant to obtain modified ZrO loaded with Mn, Cu and La2A catalyst precursor; wherein the addition amount of the sodium hydroxide solution is 15 percent of the solid mass;
3) soaking the solid precursor in ephedrine solution (20 wt%) for 10h, and drying at 120 deg.C for 10h to obtain solid 1;
4) calcining the solid 1 at 500 ℃ for 4h to obtain modified ZrO2Supported catalyst MCZ-80-5.
Evaluation of catalyst Performance:
the catalyst is filled into a reaction kettle (YangyzSR-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-hydroxymandelic acid alkaline aqueous solution (the content of mandelic acid is 8 percent, the pH value is 12), oxygen is introduced in the reaction to keep the pressure in the kettle at 1Bar, the reaction is continuously stirred at 1200rpm, and the product of 3-methoxy-4-hydroxyphenylketo acid is obtained after the reaction is carried out for 5 hours. The conversion rate was 100% and the selectivity was 95.5%.
Example 3:
(1) differential centrifugal precipitation method for preparing manganese-copper-lanthanum-loaded ZrO2Catalyst:
1) adding zirconium oxychloride dihydrate, manganese nitrate, copper sulfate, lanthanum nitrate and sodium dodecyl benzene sulfonate into deionized water, stirring for 2h to dissolve to obtain a corresponding solution, centrifuging at 1500rpm for 10min, and filtering to remove supernatant to obtain a corresponding solid; wherein the molar 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 for dissolving to obtain corresponding solution, centrifuging at 1000rpm for 10min, and filtering to remove supernatant to obtain modified ZrO loaded with Mn, Cu and La2A catalyst precursor; wherein the addition amount of the sodium hydroxide solution is 20 percent of the solid mass;
3) soaking the solid precursor in ephedrine solution (15 wt%) for 10h, and drying at 110 deg.C for 10h to obtain solid 1;
4) calcining the solid 1 at 550 ℃ for 4 hours to obtain modified ZrO2Supported catalyst MCZ-30-5.
Evaluation of catalyst Performance:
the catalyst is filled into a reaction kettle (YangyzSR-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-hydroxymandelic acid alkaline aqueous solution (the content of mandelic acid is 7 percent, the pH is 12), oxygen is introduced in the reaction to keep the pressure in the kettle at 2Bar, the reaction is continuously stirred at 1200rpm, and the product of 3-methoxy-4-hydroxyphenylketo acid is obtained after the reaction is carried out for 5 hours. The conversion rate is 100%, and the selectivity is 96%.
Example 4:
(1) differential centrifugal precipitation method for preparing manganese-copper-lanthanum-loaded ZrO2Catalyst:
1) adding zirconium nitrate, manganese nitrate, copper chloride, lanthanum sulfate and sodium dodecyl benzene sulfonate into deionized water, stirring for 3h to dissolve to obtain corresponding solution, centrifuging at 1000rpm for 10min, and filtering to remove supernatant to obtain corresponding solid; wherein the molar 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 dissolve to obtain corresponding solution, centrifuging at 1000rpm for 10min, and filtering to remove supernatant to obtain modified ZrO loaded with Mn, Cu and La2A catalyst precursor; wherein the addition amount of the sodium hydroxide solution is solid20% of the mass;
3) soaking the solid precursor in ephedrine solution (20 wt%) for 12h, and drying at 120 deg.C for 10h to obtain solid 1;
4) calcining the solid 1 at 500 ℃ for 5 hours to obtain modified ZrO2Supported catalyst MCZ-50-3.
Evaluation of catalyst Performance:
the catalyst is filled into a reaction kettle (YangyzSR-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-hydroxymandelic acid alkaline aqueous solution (the content of mandelic acid is 8 percent, the pH is 11), oxygen is introduced in the reaction to keep the pressure in the kettle at 2Bar, the reaction is continuously stirred at 1200rpm, and the product of 3-methoxy-4-hydroxyphenylketo acid 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 manganese-copper-lanthanum-loaded ZrO2Catalyst:
1) adding zirconium nitrate, manganese nitrate, copper chloride, lanthanum sulfate and sodium dodecyl benzene sulfonate into deionized water, stirring for 3h to dissolve to obtain corresponding solution, centrifuging at 1000rpm for 10min, and filtering to remove supernatant to obtain corresponding solid; wherein the molar 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 for dissolving to obtain corresponding solution, centrifuging at 1000rpm for 10min, and filtering to remove supernatant to obtain modified ZrO loaded with Mn, Cu and La2A catalyst precursor; wherein the addition amount of the sodium hydroxide solution is 20 percent of the solid mass;
3) soaking the solid precursor in ephedrine solution (20 wt%) for 10h, and drying at 110 deg.C for 10h to obtain solid 1;
4) calcining the solid 1 at 500 ℃ for 6 hours to obtain modified ZrO2Supported catalyst MCLZ.
Evaluation of catalyst Performance:
the catalyst is filled into a reaction kettle (YangyzSR-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-hydroxymandelic acid alkaline aqueous solution (the content of mandelic acid is 8 percent, the pH value is 12), oxygen is introduced in the reaction to keep the pressure in the kettle at 1Bar, the reaction is continuously stirred at 1200rpm, and the product of 3-methoxy-4-hydroxyphenylketo acid 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 manganese-copper-lanthanum-loaded ZrO2Catalyst:
1) adding zirconium nitrate, manganese sulfate, copper nitrate and lanthanum nitrate into deionized water, stirring for 3h to dissolve to obtain corresponding solution, centrifuging at 1000rpm for 10min, and filtering to remove supernatant to obtain corresponding solid; wherein the molar 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 for dissolving to obtain corresponding solution, centrifuging at 1000rpm for 10min, and filtering to remove supernatant to obtain modified ZrO loaded with Mn, Cu and La2A catalyst precursor; wherein the addition amount of the sodium hydroxide solution is 20 percent of the solid mass;
3) soaking the solid precursor in ephedrine solution (20 wt%) for 10h, and drying at 120 deg.C for 10h to obtain solid 1;
4) calcining the solid 1 at 500 ℃ for 4h to obtain modified ZrO2And supported catalyst MCZ-50-5-300.
Evaluation of catalyst Performance:
the catalyst is filled into a reaction kettle (YangyzSR-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-hydroxymandelic acid alkaline aqueous solution (the content of mandelic acid is 8 percent, the pH value is 12), oxygen is introduced in the reaction to keep the pressure in the kettle at 1Bar, the reaction is continuously stirred at 1200rpm, and the product of 3-methoxy-4-hydroxyphenylketo acid is obtained after the reaction is carried out for 5 hours. The conversion rate is 85 percent, and the selectivity is 89 percent.
Comparative example 2:
(1) differential centrifugal precipitation method for preparing manganese-copper-lanthanum-loaded ZrO2Catalyst:
1) adding zirconium nitrate, manganese sulfate, copper nitrate, lanthanum nitrate and sodium dodecyl benzene sulfonate into deionized water, stirring for 3h to dissolve to obtain corresponding solution, centrifuging at 1000rpm for 10min, and filtering to remove supernatant to obtain corresponding solid; wherein the molar 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 for dissolving to obtain corresponding solution, centrifuging at 1000rpm for 10min, and filtering to remove supernatant to obtain modified ZrO loaded with Mn, Cu and La2A catalyst precursor; wherein the addition amount of the sodium hydroxide solution is 20 percent of the solid mass;
4) calcining the catalyst precursor at 500 ℃ for 4h to obtain modified ZrO2And supported catalyst MCZ-50-5-500.
Evaluation of catalyst Performance:
the catalyst is filled into a reaction kettle (YangyzSR-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-hydroxymandelic acid alkaline aqueous solution (the content of mandelic acid is 8 percent, the pH value is 12), oxygen is introduced in the reaction to keep the pressure in the kettle at 1Bar, the reaction is continuously stirred at 1200rpm, and the product of 3-methoxy-4-hydroxyphenylketo acid is obtained after the reaction is carried out for 5 hours. Conversion 90% and selectivity 92%.
Claims (10)
1. A preparation method of a supported manganese-copper-lanthanum-zirconium composite metal oxide catalyst is characterized by comprising the following steps:
1) adding zirconium salt, manganese salt, copper salt, lanthanum salt and auxiliary agent into deionized water, stirring and dissolving to obtain solution, and centrifugally filtering supernatant to obtain 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 to remove supernatant to obtain a catalyst precursor;
3) soaking the precursor in alkali liquor, and drying to obtain a 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;
the auxiliary agent is one or more of sodium dodecyl benzene sulfonate or dodecyl benzene sulfonic acid;
preferably, the molar ratio of the zirconium, the manganese, the copper, the lanthanum and the auxiliary agent is 13-28:8-17: 7-16: 0.2-0.3: 0.1-0.3.
3. The method according to claim 1 or the step 1), wherein in the step 1), the dissolving temperature is normal temperature, and the stirring time is 2-4 h;
the centrifugation speed is 500rpm-2000rpm, and the centrifugation time is 10-20 minutes.
4. The method according to claim 1, wherein in the step 2), the alkali liquor is one or more of sodium hydroxide solution or ammonia water; the concentration of the alkali liquor is 20-40 wt%, and the addition amount is 5-30% of the solid mass;
the dissolving temperature is normal temperature, and the stirring time is 2-4 h;
the centrifugation speed is 1000-2000rpm, and the centrifugation time is 10-20 minutes.
5. The method as claimed in claim 1, wherein, in step 3), the alkali solution is ephedrine solution; the concentration is 10-20 wt%;
preferably, the soaking time is 10-12 h; the drying condition is 110-120 ℃ for 10-12 h.
6. The method as claimed in claim 1, wherein in the step 4), the muffle furnace is calcined at 400-600 ℃ for 4-6 h.
7. Use of the catalyst according to any one of claims 1 to 6 for the oxidation of 3-methoxy-4-hydroxymandelic acid to 3-methoxy-4-hydroxyphenylketo acid.
8. Use according to claim 7, comprising: the 3-methoxy-4-hydroxymandelic 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-hydroxymandelic acid is prepared by continuous stirring reaction.
9. The use according to claim 8, wherein the basic aqueous solution of 3-methoxy-4-hydroxymandelic acid has a concentration of 8% and a pH of 10 to 12.
10. The use according to claim 8 or 9, characterized in that the reaction temperature is 90-100 ℃, the amount of catalyst added is 0.5-1% of the mass of the condensation reaction liquid, and the partial pressure of oxygen in the reaction kettle is 1-3 Bar.
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