CN114192159B - Catalyst for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide, preparation method and application thereof - Google Patents
Catalyst for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide, preparation method and application thereof Download PDFInfo
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- CN114192159B CN114192159B CN202111676165.7A CN202111676165A CN114192159B CN 114192159 B CN114192159 B CN 114192159B CN 202111676165 A CN202111676165 A CN 202111676165A CN 114192159 B CN114192159 B CN 114192159B
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- catechol
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- hydrogen peroxide
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- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000003054 catalyst Substances 0.000 title claims abstract description 115
- TXXHDPDFNKHHGW-UHFFFAOYSA-N muconic acid Chemical compound OC(=O)C=CC=CC(O)=O TXXHDPDFNKHHGW-UHFFFAOYSA-N 0.000 title claims abstract description 105
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 97
- TXXHDPDFNKHHGW-CCAGOZQPSA-N Muconic acid Natural products OC(=O)\C=C/C=C\C(O)=O TXXHDPDFNKHHGW-CCAGOZQPSA-N 0.000 title claims abstract description 57
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 37
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 52
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 229910052742 iron Inorganic materials 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 22
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 17
- 239000011572 manganese Substances 0.000 claims abstract description 17
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004332 silver Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 40
- 239000002243 precursor Substances 0.000 claims description 28
- 238000009495 sugar coating Methods 0.000 claims description 28
- 239000012018 catalyst precursor Substances 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 238000000889 atomisation Methods 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 238000007792 addition Methods 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 13
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 150000002506 iron compounds Chemical class 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 150000004965 peroxy acids Chemical class 0.000 abstract description 6
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 229960002163 hydrogen peroxide Drugs 0.000 description 43
- 238000000034 method Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 description 11
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 9
- 239000000203 mixture Substances 0.000 description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 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 description 5
- 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 description 5
- 239000000126 substance Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 230000002210 biocatalytic effect Effects 0.000 description 2
- 150000001805 chlorine compounds Chemical group 0.000 description 2
- TXXHDPDFNKHHGW-HSFFGMMNSA-N cis,trans-muconic acid Chemical compound OC(=O)\C=C\C=C/C(O)=O TXXHDPDFNKHHGW-HSFFGMMNSA-N 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide, which comprises a carrier and a metal component loaded on the carrier; the metal component comprises 0.5-15% of iron and 0.5-5% of auxiliary agent; the auxiliary agent is one or more of ruthenium, silver, palladium and manganese. In addition, the invention also discloses a preparation method and application of the catalyst. The catalyst of the invention catalyzes hydrogen peroxide to oxidize catechol to synthesize muconic acid, replaces high-risk peracid as an oxidant for reaction, greatly reduces the risk coefficient, avoids the use of acid solvents, and has lower cost.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide, a preparation method and application thereof.
Background
Cis, cis-muconic acid is an important platform chemical. Cis, cis-muconic acid (cis, cis-muconic acid, MA) has two carboxyl groups and paired conjugated double bonds, has good ultraviolet absorption property at 260nm, can be used as an ultraviolet protective agent and a coating of military special products such as invisible aircrafts, is also a potential raw material for preparing functional resins, medicines and agrochemicals, and can be used for producing monomer adipic acid, dimethyl terephthalate, trimellitic acid and the like of nylon 66 of a large number of chemical products. For the production of adipic acid from renewable precursors, cis-muconic acid has therefore been utilized as a key intermediate to establish a combined biocatalytic and chemocatalytic pathway. Muconic acid and its various derivatives are also popular chemical intermediates for the production of fibers and plastics. In the reported conversion of glucose to muconic acid using a multi-step fermentation process, the biocatalytic production of muconic acid requires the aid of several different kinds of enzymes and the product yield and efficiency are very low. At present, cis-muconic acid is biosynthesized and lacks high-performance strains, and reported main engineering strains not only need to induce expression and have unstable heredity, but also have complex components of fermentation culture medium, thus being unfavorable for large-scale industrial production.
The chemical method takes catechol as a raw material, hydrogen peroxide is taken as an oxidant and ferric salt is taken as a catalyst in a formic acid or acetic acid system to realize in-situ generation of peracid so as to promote reaction conversion, the reaction is not obvious, the peracid is unstable, great potential safety hazards exist, and the ferric salt cannot be recycled, so that great waste of resources is caused. Therefore, the design of a high-activity reusable catalyst and the avoidance of the use of peracids are an important direction for future development.
Disclosure of Invention
The invention aims to solve the technical problem of providing a catalyst for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide, and a preparation method and application thereof, aiming at the defects in the prior art. The catalyst catalyzes hydrogen peroxide to oxidize catechol to synthesize muconic acid, replaces high-risk peracid as an oxidant for reaction, greatly reduces the risk coefficient, avoids the use of acid solvents, and has lower cost.
In order to solve the technical problems, the invention adopts the following technical scheme: the catalyst for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide is characterized by comprising a carrier and a metal component loaded on the carrier; the metal component comprises 0.5-15% of iron and 0.5-5% of auxiliary agent; the auxiliary agent is one or more of ruthenium, silver, palladium and manganese;
The preparation method of the carrier comprises the following steps: adding alumina into alkaline aqueous solution, soaking for 0.5-1 h, filtering, drying and roasting to obtain the carrier.
The catalyst for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide is characterized in that the mass percentage of iron in the catalyst is 4-10%, and the mass percentage of auxiliary agent is 1-3.5%.
The catalyst for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide is characterized in that the mass percentage of iron in the catalyst is 5%, and the mass percentage of auxiliary agent is 2%.
The catalyst for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide is characterized in that the particle size of the alumina is 1.0-2.0 mm, and the specific surface area is 400m 2/g～800m2/g; the alkaline aqueous solution is an ammonia aqueous solution; the drying temperature is 80-120 ℃, and the drying time is 2-8 hours; the roasting temperature is 300-500 ℃, and the roasting time is 2-8 h.
In addition, the invention also provides a method for preparing the catalyst, which is characterized by comprising the following steps:
dissolving a soluble iron compound in water, then adding soluble salt of an auxiliary agent, and stirring to obtain a precursor solution;
step two, carrying out ultrasonic atomization on the precursor solution in the step one to obtain atomized liquid drops;
Step three, adding a carrier into a sugar coating machine, then adding the atomized liquid drops in the step two into the sugar coating machine in batches, uniformly stirring after each addition, and coating, and drying after each coating to obtain a catalyst precursor;
and step four, roasting the catalyst precursor in an air atmosphere to obtain the catalyst for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide.
The method is characterized in that in the step one, the soluble iron compound is ferric nitrate nonahydrate, and the soluble salt of the auxiliary agent is chloride of the auxiliary agent or nitrate of the auxiliary agent.
The method is characterized in that the atomized liquid drops in the third step are added into a sugar coating machine for 3 to 5 times; the temperature of the drying in the third step is 80-120 ℃, and the drying time is 2-8 hours; the roasting temperature is 300-500 ℃, and the roasting time is 2-8 h.
Further, the invention provides application of the catalyst in synthesizing muconic acid by catalyzing oxydol to oxidize catechol.
The application is characterized in that the catalysis method comprises the following steps: adding a catalyst and a solvent into a reaction kettle, dropwise adding H 2O2 at room temperature, and continuously stirring for 0.5-2H after the dropwise adding is finished; dissolving catechol in solvent, adding the dissolved catechol into a reaction system, reacting for 5 to 30 hours at the temperature of between 23 and 40 ℃, and after the reaction is finished, filtering the solution in a cold way, washing and drying the solution to obtain muconic acid.
The application is characterized in that the mass ratio of the catalyst to catechol is (5-20): 100; the solvents are all low-carbon alcohols, and the H 2O2 is industrial hydrogen peroxide.
Compared with the prior art, the invention has the following advantages:
1. The method carries out pretreatment on the carrier, and the precursor solution of the metal component is uniformly dispersed on the carrier through ultrasonic atomization, so that the dispersibility and the activity of the catalyst are improved.
2. The catalyst disclosed by the invention is simple to prepare, strong in operability, suitable for industrial production, convenient to recover, reusable and capable of greatly reducing the production cost of the catalyst.
3. The catalyst provided by the invention catalyzes hydrogen peroxide to oxidize catechol to synthesize muconic acid, replaces high-risk peracid as an oxidant for reaction, greatly reduces the risk coefficient, avoids the use of acid solvents, and is lower in cost.
The technical scheme of the invention is further described in detail through examples.
Detailed Description
Example 1
The catalyst for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide in the embodiment comprises a carrier and a metal component loaded on the carrier; the metal component comprises iron and an auxiliary agent, wherein the mass percentage of the iron in the catalyst is 5%, and the mass percentage of the auxiliary agent is 1%; the auxiliary agent is ruthenium;
The preparation method of the carrier comprises the following steps: adding alumina with the particle size of 1.0 mm-2.0 mm and the specific surface area of 400m 2/g～800m2/g into ammonia water solution, soaking for 0.5h, filtering, drying for 3h at 90 ℃, and roasting for 5h at 500 ℃ to obtain the carrier.
The preparation method of the catalyst of the embodiment comprises the following steps:
step one, ferric nitrate nonahydrate is dissolved in water, ruthenium chloride is added, and the mixture is stirred uniformly to obtain a precursor solution;
step two, carrying out ultrasonic atomization on the precursor solution in the step one to obtain atomized liquid drops;
thirdly, adding a carrier into a sugar coating machine, then adding the atomized liquid drops in the second step into the sugar coating machine for 3 times, uniformly stirring after each addition, and drying at 100 ℃ for 6 hours after each coating to obtain a catalyst precursor;
And step four, roasting the catalyst precursor for 5 hours at the temperature of 400 ℃ in an air atmosphere to obtain the catalyst (5% Fe-1% Ru)/Al 2O3 for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide.
Comparative example 1
The catalyst was prepared according to the procedure of example 1, using untreated alumina as a support.
Example 2
The catalyst for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide in the embodiment comprises a carrier and a metal component loaded on the carrier; the metal component comprises iron and an auxiliary agent, wherein the mass percentage of the iron in the catalyst is 5%, and the mass percentage of the auxiliary agent is 2%; the auxiliary agent is ruthenium and silver, and the mass percentage of the ruthenium and silver in the catalyst is 1%;
The preparation method of the carrier comprises the following steps: adding alumina with the particle size of 1.0 mm-2.0 mm and the specific surface area of 400m 2/g～800m2/g into ammonia water solution, soaking for 0.5h, filtering, drying for 3h at 90 ℃, and roasting for 5h at 500 ℃ to obtain the carrier.
The preparation method of the catalyst of the embodiment comprises the following steps:
step one, ferric nitrate nonahydrate is dissolved in water, ruthenium chloride and silver nitrate are added, and the mixture is stirred uniformly to obtain a precursor solution;
step two, carrying out ultrasonic atomization on the precursor solution in the step one to obtain atomized liquid drops;
thirdly, adding a carrier into a sugar coating machine, then adding the atomized liquid drops in the second step into the sugar coating machine for 3 times, uniformly stirring after each addition, and drying at 100 ℃ for 2 hours after each coating to obtain a catalyst precursor;
And step four, roasting the catalyst precursor for 5 hours at the temperature of 400 ℃ in an air atmosphere to obtain the catalyst (5% Fe-1% Ru-1% Ag)/Al 2O3 for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide.
Comparative example 2
The catalyst was prepared according to the procedure of example 2, using untreated alumina as support.
Example 3
The catalyst for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide in the embodiment comprises a carrier and a metal component loaded on the carrier; the metal component comprises iron and an auxiliary agent, wherein the mass percentage of the iron in the catalyst is 5%, and the mass percentage of the auxiliary agent is 2%; the auxiliary agent is ruthenium and palladium, and the mass percentage of the ruthenium and palladium in the catalyst is 1 percent;
The preparation method of the carrier comprises the following steps: adding alumina with the particle size of 1.0 mm-2.0 mm and the specific surface area of 400m 2/g～800m2/g into ammonia water solution, soaking for 0.5h, filtering, drying at 80 ℃ for 8h, and roasting at 500 ℃ for 5h to obtain the carrier.
The preparation method of the catalyst of the embodiment comprises the following steps:
step one, ferric nitrate nonahydrate is dissolved in water, ruthenium chloride and palladium chloride are added, and the mixture is stirred uniformly to obtain a precursor solution;
step two, carrying out ultrasonic atomization on the precursor solution in the step one to obtain atomized liquid drops;
Thirdly, adding a carrier into a sugar coating machine, then adding the atomized liquid drops in the second step into the sugar coating machine for 3 times, uniformly stirring after each addition, and drying at 80 ℃ for 8 hours after each coating to obtain a catalyst precursor;
And step four, roasting the catalyst precursor for 5 hours at the temperature of 400 ℃ in an air atmosphere to obtain the catalyst (5% Fe-1% Ru-1% Pd)/Al 2O3 for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide.
Comparative example 3
The catalyst was prepared according to the procedure of example 3, using untreated alumina as a support.
Example 4
The catalyst for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide in the embodiment comprises a carrier and a metal component loaded on the carrier; the metal component comprises iron and an auxiliary agent, wherein the mass percentage of the iron in the catalyst is 5%, and the mass percentage of the auxiliary agent is 2%; the auxiliary agent is ruthenium and manganese, and the mass percentage of the ruthenium and manganese in the catalyst is 1 percent;
the preparation method of the carrier comprises the following steps: adding alumina with the particle size of 1.0 mm-2.0 mm and the specific surface area of 400m 2/g～800m2/g into ammonia water solution, soaking for 0.5h, filtering, drying at 90 ℃ for 3h, and roasting at 500 ℃ for 5h to obtain the carrier.
The preparation method of the catalyst of the embodiment comprises the following steps:
Step one, ferric nitrate nonahydrate is dissolved in water, then ruthenium chloride and manganese nitrate tetrahydrate are added, and the mixture is stirred uniformly to obtain a precursor solution;
step two, carrying out ultrasonic atomization on the precursor solution in the step one to obtain atomized liquid drops;
Thirdly, adding a carrier into a sugar coating machine, then adding the atomized liquid drops in the second step into the sugar coating machine for 3 times, uniformly stirring after each addition, and drying at 100 ℃ for 5 hours after each coating to obtain a catalyst precursor;
And step four, roasting the catalyst precursor for 5 hours at the temperature of 400 ℃ in an air atmosphere to obtain the catalyst (5% Fe-1% Ru-1% Mn)/Al 2O3 for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide.
Comparative example 4
The catalyst was prepared according to the procedure of example 4, using untreated alumina as support.
Example 5
The catalyst for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide in the embodiment comprises a carrier and a metal component loaded on the carrier; the metal component comprises iron and an auxiliary agent, wherein the mass percentage of the iron in the catalyst is 5%, and the mass percentage of the auxiliary agent is 1.5%; the auxiliary agent is ruthenium and palladium, the mass percentage of ruthenium in the catalyst is 1%, and the mass percentage of palladium in the catalyst is 0.5%;
the preparation method of the carrier comprises the following steps: adding alumina with the particle size of 1.0 mm-2.0 mm and the specific surface area of 400m 2/g～800m2/g into ammonia water solution, soaking for 0.5h, filtering, drying at 90 ℃ for 3h, and roasting at 500 ℃ for 5h to obtain the carrier.
The preparation method of the catalyst of the embodiment comprises the following steps:
step one, ferric nitrate nonahydrate is dissolved in water, ruthenium chloride and palladium chloride are added, and the mixture is stirred uniformly to obtain a precursor solution;
step two, carrying out ultrasonic atomization on the precursor solution in the step one to obtain atomized liquid drops;
thirdly, adding a carrier into a sugar coating machine, then adding the atomized liquid drops in the second step into the sugar coating machine for 3 times, uniformly stirring after each addition, and drying at 80 ℃ for 6 hours after each coating to obtain a catalyst precursor;
And step four, roasting the catalyst precursor for 5 hours at the temperature of 400 ℃ in an air atmosphere to obtain the catalyst (5% Fe-1% Ru-0.5% Pd)/Al 2O3 for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide.
Comparative example 5
The catalyst was prepared according to the procedure of example 5, using untreated alumina as support.
Example 6
The catalyst for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide in the embodiment comprises a carrier and a metal component loaded on the carrier; the metal component comprises iron and an auxiliary agent, wherein the mass percentage of the iron in the catalyst is 5%, and the mass percentage of the auxiliary agent is 3.5%; the auxiliary agent comprises ruthenium, palladium and manganese, wherein the mass percentage of ruthenium in the catalyst is 1%, the mass percentage of palladium is 0.5%, and the mass percentage of manganese is 2%;
the preparation method of the carrier comprises the following steps: adding alumina with the particle size of 1.0 mm-2.0 mm and the specific surface area of 400m 2/g～800m2/g into ammonia water solution, soaking for 0.5h, filtering, drying at 90 ℃ for 3h, and roasting at 500 ℃ for 5h to obtain the carrier.
The preparation method of the catalyst of the embodiment comprises the following steps:
step one, ferric nitrate nonahydrate is dissolved in water, then soluble salt of an auxiliary agent is added, and stirring is carried out to obtain a precursor solution; the soluble salt of the auxiliary agent is chloride of the auxiliary agent or nitrate of the auxiliary agent;
step two, carrying out ultrasonic atomization on the precursor solution in the step one to obtain atomized liquid drops;
Thirdly, adding a carrier into a sugar coating machine, then adding the atomized liquid drops in the second step into the sugar coating machine for 3 times, uniformly stirring after each addition, and drying at 100 ℃ for 8 hours after each coating to obtain a catalyst precursor;
And step four, roasting the catalyst precursor for 5 hours at the temperature of 500 ℃ in an air atmosphere to obtain the catalyst (5% Fe-1% Ru-0.5% Pd-2% Mn)/Al 2O3 for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide.
Comparative example 6
The catalyst was prepared according to the procedure of example 6, using untreated alumina as support.
Example 7
The catalyst for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide in the embodiment comprises a carrier and a metal component loaded on the carrier; the metal component comprises iron and an auxiliary agent, wherein the mass percentage of the iron in the catalyst is 4%, and the mass percentage of the auxiliary agent is 3.5%; the auxiliary agent comprises ruthenium, palladium and manganese, wherein the mass percentage of ruthenium in the catalyst is 1%, the mass percentage of palladium is 0.5%, and the mass percentage of manganese is 2%;
The preparation method of the carrier comprises the following steps: adding alumina with the particle size of 1.0 mm-2.0 mm and the specific surface area of 400m 2/g～800m2/g into ammonia water solution, soaking for 1h, filtering, drying at 120 ℃ for 2h, and roasting at 300 ℃ for 8h to obtain the carrier.
The preparation method of the catalyst of the embodiment comprises the following steps:
Step one, ferric nitrate nonahydrate is dissolved in water, ruthenium chloride, palladium chloride and manganese nitrate are added, and the precursor solution is obtained through stirring;
step two, carrying out ultrasonic atomization on the precursor solution in the step one to obtain atomized liquid drops;
step three, adding a carrier into a sugar coating machine, then adding the atomized liquid drops in the step two into the sugar coating machine for 5 times, uniformly stirring after each addition, and drying at 120 ℃ for 2 hours after each coating to obtain a catalyst precursor;
And step four, roasting the catalyst precursor for 8 hours at the temperature of 300 ℃ in an air atmosphere to obtain the catalyst (4% Fe-1% Ru-0.5% Pd-2% Mn)/Al 2O3 for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide.
Comparative example 7
The catalyst was prepared according to the procedure of example 7, using untreated alumina as support.
Example 8
The catalyst for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide in the embodiment comprises a carrier and a metal component loaded on the carrier; the metal component comprises iron and an auxiliary agent, wherein the mass percentage of the iron in the catalyst is 15%, and the mass percentage of the auxiliary agent is 3.5%; the auxiliary agent comprises ruthenium, palladium and manganese, wherein the mass percentage of ruthenium in the catalyst is 1%, the mass percentage of palladium is 0.5%, and the mass percentage of manganese is 2%;
The preparation method of the carrier comprises the following steps: adding alumina with the particle size of 1.0 mm-2.0 mm and the specific surface area of 400m 2/g～800m2/g into ammonia water solution, soaking for 0.8h, filtering, drying at 120 ℃ for 2h, and roasting at 400 ℃ for 6h to obtain the carrier.
The preparation method of the catalyst of the embodiment comprises the following steps:
Step one, ferric nitrate nonahydrate is dissolved in water, ruthenium chloride, palladium chloride and manganese nitrate are added, and the precursor solution is obtained through stirring;
step two, carrying out ultrasonic atomization on the precursor solution in the step one to obtain atomized liquid drops;
Step three, adding a carrier into a sugar coating machine, then adding the atomized liquid drops in the step two into the sugar coating machine for 4 times, uniformly stirring after each addition, and drying at 100 ℃ for 4 hours after each coating to obtain a catalyst precursor;
And step four, roasting the catalyst precursor for 2 hours at the temperature of 500 ℃ in an air atmosphere to obtain the catalyst (15% Fe-1% Ru-0.5% Pd-2% Mn)/Al 2O3 for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide.
Comparative example 8
The catalyst was prepared according to the procedure of example 8, using untreated alumina as support.
Example 9
The catalyst for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide in the embodiment comprises a carrier and a metal component loaded on the carrier; the metal component comprises iron and an auxiliary agent, wherein the mass percentage of the iron in the catalyst is 10%, and the mass percentage of the auxiliary agent is 5%; the auxiliary agent comprises 0.5% of ruthenium, 1% of silver, 0.5% of palladium and 3% of manganese in the catalyst;
the preparation method of the carrier comprises the following steps: adding alumina with the particle size of 1.0 mm-2.0 mm and the specific surface area of 400m 2/g～800m2/g into ammonia water solution, soaking for 0.5h, filtering, drying at 90 ℃ for 3h, and roasting at 500 ℃ for 5h to obtain the carrier.
The preparation method of the catalyst of the embodiment comprises the following steps:
Step one, ferric nitrate nonahydrate is dissolved in water, ruthenium chloride, silver chloride, palladium chloride and manganese nitrate are added, and the precursor solution is obtained through stirring;
step two, carrying out ultrasonic atomization on the precursor solution in the step one to obtain atomized liquid drops;
thirdly, adding a carrier into a sugar coating machine, then adding the atomized liquid drops in the second step into the sugar coating machine for 3 times, uniformly stirring after each addition, and drying at 100 ℃ for 2 hours after each coating to obtain a catalyst precursor;
And step four, roasting the catalyst precursor for 5 hours at the temperature of 500 ℃ in an air atmosphere to obtain the catalyst (10% Fe-0.5% Ru-1% Ag-0.5% Pd-3% Mn)/Al 2O3 for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide.
Comparative example 9
The catalyst was prepared according to the procedure of example 9, using untreated alumina as the support.
Example 10
The catalyst for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide in the embodiment comprises a carrier and a metal component loaded on the carrier; the metal component comprises iron and an auxiliary agent, wherein the mass percentage of the iron in the catalyst is 10%, and the mass percentage of the auxiliary agent is 3.5%; the auxiliary agent comprises ruthenium, palladium and manganese, wherein the mass percentage of ruthenium in the catalyst is 1%, the mass percentage of palladium is 0.5%, and the mass percentage of manganese is 2%;
The preparation method of the carrier comprises the following steps: adding alumina with the particle size of 1.0 mm-2.0 mm and the specific surface area of 400m 2/g～800m2/g into ammonia water solution, soaking for 0.5h, filtering, drying at 80 ℃ for 8h, and roasting at 400 ℃ for 2h to obtain the carrier.
The preparation method of the catalyst of the embodiment comprises the following steps:
Step one, ferric nitrate nonahydrate is dissolved in water, ruthenium chloride, palladium chloride and manganese nitrate are added, and the precursor solution is obtained through stirring;
step two, carrying out ultrasonic atomization on the precursor solution in the step one to obtain atomized liquid drops;
thirdly, adding a carrier into a sugar coating machine, then adding the atomized liquid drops in the second step into the sugar coating machine for 3 times, uniformly stirring after each addition, and drying at 100 ℃ for 2 hours after each coating to obtain a catalyst precursor;
And step four, roasting the catalyst precursor for 3 hours at the temperature of 500 ℃ in an air atmosphere to obtain the catalyst (10% Fe-1% Ru-0.5% Pd-2% Mn)/Al 2O3 for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide.
Comparative example 10
The catalyst was prepared according to the procedure of example 10, using untreated alumina as the support.
Example 11
The catalyst for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide in the embodiment comprises a carrier and a metal component loaded on the carrier; the metal component comprises iron and an auxiliary agent, wherein the mass percentage of the iron in the catalyst is 0.5%, and the mass percentage of the auxiliary agent is 0.5%; the auxiliary agent is manganese;
The preparation method of the carrier comprises the following steps: adding alumina with the particle size of 1.0 mm-2.0 mm and the specific surface area of 400m 2/g～800m2/g into ammonia water solution, soaking for 0.5h, filtering, drying at 80 ℃ for 8h, and roasting at 400 ℃ for 2h to obtain the carrier.
The preparation method of the catalyst of the embodiment comprises the following steps:
Step one, ferric nitrate nonahydrate is dissolved in water, then manganese nitrate is added, and the mixture is stirred to obtain a precursor solution;
step two, carrying out ultrasonic atomization on the precursor solution in the step one to obtain atomized liquid drops;
Thirdly, adding a carrier into a sugar coating machine, then adding the atomized liquid drops in the second step into the sugar coating machine for 3 times, uniformly stirring after each addition, and drying at 100 ℃ for 5 hours after each coating to obtain a catalyst precursor;
And step four, roasting the catalyst precursor for 4 hours at the temperature of 500 ℃ in an air atmosphere to obtain the catalyst (0.5% Fe-0.5% Mn)/Al 2O3 for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide.
Comparative example 11
No auxiliary agent was contained, and the procedure of example 1 was repeated.
Comparative example 12
The calcination temperature of the support was 800℃and the same as in example 1 was repeated.
Comparative example 13
The calcination temperature of the support was 800℃and the calcination temperature of the catalyst precursor was 600℃in the same manner as in example 1.
Example 12
The catalyst of the invention is used for catalyzing hydrogen peroxide to oxidize catechol to synthesize muconic acid, and the catalysis method comprises the following steps: adding the catalyst and the solvent into a reaction kettle, dropwise adding H 2O2 at room temperature, and continuously stirring for 1H after the dropwise adding is finished; dissolving catechol with a solvent, adding the dissolved catechol into a reaction system, reacting for 20 hours at 30 ℃, cooling and filtering after the reaction is finished, and washing and drying to obtain muconic acid; the mass ratio of the catalyst to the catechol is 5:100; the solvents are all low-carbon alcohols, and the H 2O2 is industrial hydrogen peroxide.
Example 13
The catalyst of the invention is used for catalyzing hydrogen peroxide to oxidize catechol to synthesize muconic acid, and the catalysis method comprises the following steps: adding the catalyst and the solvent into a reaction kettle, dropwise adding H 2O2 at room temperature, and continuously stirring for 2 hours after the dropwise adding is finished; dissolving catechol with a solvent, adding the dissolved catechol into a reaction system, reacting for 30 hours at the temperature of 23 ℃, cooling and filtering after the reaction is finished, and washing and drying to obtain muconic acid; the mass ratio of the catalyst to the catechol is 20:100; the solvents are all low-carbon alcohols, and the H 2O2 is industrial hydrogen peroxide.
Example 14
The catalyst of the invention is used for catalyzing hydrogen peroxide to oxidize catechol to synthesize muconic acid, and the catalysis method comprises the following steps: adding the catalyst and the solvent into a reaction kettle, dropwise adding H 2O2 at room temperature, and continuously stirring for 0.5H after the dropwise adding is finished; dissolving catechol with a solvent, adding the dissolved catechol into a reaction system, reacting for 5 hours at 40 ℃, cooling and filtering after the reaction is finished, and washing and drying to obtain muconic acid; the mass ratio of the catalyst to the catechol is 10:100; the solvents are all low-carbon alcohols, and the H 2O2 is industrial hydrogen peroxide.
Catalyst catalytic performance test:
The catalysts of examples 1-11 and comparative examples 1-12 are used for catalyzing hydrogen peroxide to oxidize catechol to synthesize muconic acid, and the specific method comprises the following steps: adding 10g of catalyst and 100 g of ethanol into a reaction kettle, dripping hydrogen peroxide of the processing industry at room temperature, and continuously stirring for 1h after dripping; 200g of catechol is dissolved by 50 g of ethanol and then added into a reaction system for reaction for 20 hours at 30 ℃, and after the reaction is finished, the muconic acid is obtained by cold filtration, washing and drying. The results are shown in Table 1.
TABLE 1 evaluation results of examples 1-11 and comparative examples 1-12
According to Table 1, the conversion rate of catechol catalyzed by each catalyst of examples 1-11 is more than or equal to 90%, the highest conversion rate is 95.5%, the highest selectivity is 93.8%, and the catalyst has high reaction performance.
Catalyst stability performance test:
The catalyst was recovered and tested for stability by performing a catalytic oxidation repeatability test, the test results are shown in table 2.
TABLE 2 parallel evaluation results of repeated catalytic oxidation reactions for different catalysts
As is apparent from Table 2, the catalyst provided by the invention has stable performance and good repeatability.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent variation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (7)
1. The application of the catalyst in catalyzing hydrogen peroxide to oxidize catechol to synthesize muconic acid is characterized in that the catalyst comprises a carrier and a metal component loaded on the carrier; the metal component comprises 4-10% of iron and 1-3.5% of auxiliary agent; the auxiliary agent is one or more of ruthenium, silver, palladium and manganese;
The preparation method of the carrier comprises the following steps: adding alumina into alkaline aqueous solution, soaking for 0.5-1 h, filtering, drying and roasting to obtain the carrier;
the preparation method of the catalyst comprises the following steps:
dissolving a soluble iron compound in water, then adding soluble salt of an auxiliary agent, and stirring to obtain a precursor solution;
step two, carrying out ultrasonic atomization on the precursor solution in the step one to obtain atomized liquid drops;
Step three, adding a carrier into a sugar coating machine, then adding the atomized liquid drops in the step two into the sugar coating machine in batches, uniformly stirring after each addition, and coating, and drying after each coating to obtain a catalyst precursor;
and step four, roasting the catalyst precursor in an air atmosphere to obtain the catalyst for synthesizing muconic acid by oxidizing catechol with hydrogen peroxide.
2. The use according to claim 1, wherein the catalyst comprises 5% by mass of iron and 2% by mass of auxiliary agent.
3. The use according to claim 1, wherein the alumina has a particle size of 1.0mm to 2.0mm and a specific surface area of 400m 2/g～800m2/g; the alkaline aqueous solution is an ammonia aqueous solution; the drying temperature is 80-120 ℃, and the drying time is 2-8 hours; in the preparation method of the carrier, the roasting temperature is 300-500 ℃, and the roasting time is 2-8 h.
4. The use according to claim 1, wherein in step one the soluble iron compound is ferric nitrate nonahydrate and the soluble salt of the promoter is the chloride of the promoter or the nitrate of the promoter.
5. The use according to claim 1, wherein in step three the atomized droplets are added 3-5 times to the sugar coating machine; the temperature of the drying in the third step is 80-120 ℃, and the drying time is 2-8 hours; and step four, the roasting temperature is 300-500 ℃, and the roasting time is 2-8 hours.
6. The use according to claim 1, characterized in that the step of applying is: adding a catalyst and a solvent into a reaction kettle, dropwise adding H 2O2 at room temperature, and continuously stirring for 0.5-2H after the dropwise adding is finished; dissolving catechol in solvent, adding the dissolved catechol into a reaction system, reacting for 5 to 30 hours at the temperature of between 23 and 40 ℃, and after the reaction is finished, filtering the solution in a cold way, washing and drying the solution to obtain muconic acid.
7. The use according to claim 6, wherein the mass ratio of catalyst to catechol is (5-20): 100; the solvents are all low-carbon alcohols, and the H 2O2 is industrial hydrogen peroxide.
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