CN104588088A - Catalyst used for preparing 2-alkylanthraquinone, and preparation method and application thereof - Google Patents
Catalyst used for preparing 2-alkylanthraquinone, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a composite acid catalyst used for synthesizing 2-alkylanthraquinone, a preparation method thereof, and an application thereof in preparing 2-alkylanthraquinone. The catalyst comprises the components of rare earth metal, Beta zeolite, SO4<2->, zirconium and a refractory inorganic oxide. According to the weight of the catalyst, the catalyst comprises 5-40% of Beta zeolite, 0.1-20% of rare earth metal (calculated according to oxide), 5-40% of zirconium (calculated according to zirconium oxide), 0.5-20% of sulfate, and balance of the refractory inorganic oxide. When the catalyst provided by the invention is used for synthesizing 2-alkylanthraquinone from 2-(4'-alkylbenzoyl)benzoic acid, The catalyst has the characteristics such as environment friendliness, high activity, high selectivity, and high efficiency. The catalyst is especially suitable for fixed bed processes.
Description
Technical field
The present invention relates to and a kind ofly synthesize complex acid catalyst of 2-alkyl-anthraquinone and preparation method thereof; particularly with 2-(4 '-alkylbenzoyl) benzoic acid is that the Catalysts and its preparation method used in 2-alkyl-anthraquinone process prepared by raw material, and the application of this catalyst in preparation 2-alkyl-anthraquinone.
Background technology
Alkyl-anthraquinone is important fine chemical material, with C
1~ C
5alkyl derivative outbalance, wherein 2-alkyl-anthraquinone has practicality most, is mainly used in hydrogen peroxide synthetic catalyst, in addition also as sensitising agent, the medicine and pesticide intermediate etc. of dyestuff intermediate, degradative resin.Along with the fast development of the industry such as global hydrogen peroxide and synthetic resin, 2-alkyl-anthraquinone especially high-quality 2-alkyl-anthraquinone demand is increased sharply, makes 2-alkyl-anthraquinone become quite potential serial fine chemistry.
2-alkyl-anthraquinone is serial fine chemical product, principal item 2-methylanthraquinone, 2-EAQ, 2-amyl anthraquinone, 2-tertiary pentyl anthraquinone and 2-tert-butyl group anthraquinone etc.Usual 2-alkyl-anthraquinone is flaxen solid, and fusing point, lower than anthraquinone, is dissolved in benzene, can be recrystallized by ethanol or acetic acid.2-alkyl-anthraquinone is mainly used in the anthraquinone carrier preparing hydrogen peroxide, also can be used as the intermediate of degradative resin, photopolymer materials or fuel.Along with the fast development of the industry such as global hydrogen peroxide and synthetic resin, the output of 2-alkyl-anthraquinone and anthraquinone can not meet growing needs.
The method of traditional production 2-alkyl-anthraquinone mainly adopts phthalic anhydride and alkylbenzene to be that raw material generates intermediate product 2-(4 '-alkylbenzoyl by acyl group method) benzoic acid; intermediate product 2-(4 '-alkylbenzoyl) benzoic acid process hydrolysis again; closed loop; distillating recovering solvent, redox purification and ethanol distillation abstraction technique finally obtain object product 2-alkyl-anthraquinone.Needed for the method, chemical technology is long; and need a large amount of alchlors and the concentrated sulfuric acid to make catalyst in course of reaction, WO96/286140 devises a kind of with 2-(4 '-alkylbenzoyl) benzoic acid mixture is the method that raw material utilizes that the concentrated sulfuric acid or oleum are Catalyst Production 2-EAQ.The shortcoming of this method is that the concentrated sulfuric acid and oleum have stronger corrosivity and environmental hazard, and post processing work is more loaded down with trivial details.Therefore people try hard to prepare 2-EAQ with a kind of eco-friendly catalyst.
Beta zeolite is the zeolite molecular sieve of the height accumulation defect that tetragonal crystal system and monoclinic system form jointly, has three-dimensional twelve-ring duct, and has good hydrothermal stability and anti-coking performance.At present to Beta zeolite catalysis performance, as the aspects such as the cracking of hydro carbons and isomery, toluene disproportionation, the transalkylation of multi-methyl benzene, the disproportionation of large molecule naphthalene conduct extensive research.E. Santacesaria etc. are at CATALYSIS TODAY 66(2001) report with 2-(benzoyl in 167 ~ 174) benzoic acid is raw material; the Beta zeolite exchanged through a step acid is catalyst; reactant dehydration closed-loop is made to synthesize the technique of anthraquinone; obtain good effect, but reaction temperature is higher.In synthesis 2-alkyl-anthraquinone process, come off and the problem such as isomerization owing to there is alkyl in course of reaction, therefore will obtain highly purified 2-alkyl-anthraquinone relatively difficult.CN200410155473.5 is the acid Beta zeolite utilizing ammonium nitrate or acid solution exchange system to obtain is catalyst synthesis 2-alkyl-anthraquinone, and the reaction time required when adopting this catalyst is longer, and reaction temperature is higher.
In synthesis anthraquinone process, US4304724 utilizes 2-(benzoyl) benzoic acid synthesizes anthraquinone under the effect of fluorinated sulfonic resin crossed by catalyst.This catalyst system and catalyzing environmentally safe, operating condition is gentle.But shortcoming is 2-(benzoyl) conversion of benzoic acid is lower, and anthraquinone is selective not high.CN1879965A discloses a kind of catalyst produced for 2-alkyl-anthraquinone and anthraquinone, carry out modification by twice pair of Beta zeolite, wherein first time modification is as the acid solution such as citric acid, acetic acid or ammonium salt solution and Beta molecular sieve exchange with non-metal cations solution, second time modification, the modifier of employing is acid solution or metal oxide.When this catalyst is used for intermittent reaction, 2-(4 '-ethylamino benzonitrile acyl group) benzoic conversion ratio and 2-EAQ selective higher.
In above-mentioned synthesis anthraquinone process, adopt modification Beta molecular sieve as catalyst, mainly utilize the tiny catalyst granules of Beta molecular sieve to provide enough reactivities, therefore, existing synthesis anthraquinone process is still employing intermittent operation, so just can give full play to the performance of Beta molecular sieve, improve the conversion ratio of reactant and the selective of target product.At present, this synthesis anthraquinone process is owing to being subject to the restriction of catalyst performance, still cannot realize fixed bed continued operation, because shaping of catalyst need be made the particle of greater particle size by fixed bed continued operation, and the tiny particle of Beta molecular sieve is after shaping, its outer surface sharply reduces, and the performance of molecular sieve can not be not fully exerted, thus causes reaction effect undesirable.
Summary of the invention
For overcoming weak point of the prior art, the invention provides a kind of Catalysts and its preparation method for the preparation of 2-alkyl-anthraquinone, and the application of this catalyst in preparation 2-alkyl-anthraquinone.When catalyst of the present invention is for the preparation of 2-alkyl-anthraquinone, there is environmental friendliness, active high, selective height, the feature that efficiency is high.
The present invention is for the preparation of the catalyst of 2-alkyl-anthraquinone, and its composition comprises rare earth metal, Beta zeolite, SO
4 2-, zirconium and refractory inorganic oxides, with the weight of catalyst for benchmark, Beta zeolite content is 5% ~ 40%, and preferable range is 10% ~ 30%; Rare earth metal for 0.1% ~ 20%, is preferably 0.2% ~ 10% with oxide basis content; Zirconium for 5% ~ 40%, is preferably 10% ~ 30% in zirconia content; Sulfate radical content is 0.5% ~ 20%, is preferably 1% ~ 15%, surplus refractory inorganic oxides.
The present invention is for the preparation of the catalyst of 2-alkyl-anthraquinone, and its composition preferably includes containing the Beta zeolite of rare earth metal, containing SO
4 2-with the refractory inorganic oxides of zirconium, wherein rare earth metal is with the weight ratio of oxide basis and Beta zeolite for 0.02 ~ 0.5:1, is preferably 0.02 ~ 0.4:1, SO
4 2-be 0.05 ~ 1:1 with the weight ratio of refractory inorganic oxides, be preferably 0.1 ~ 0.5:1, zirconium with the weight ratio of oxide basis and refractory inorganic oxides for 0.5 ~ 2.0:1, preferably 0.6 ~ 1.0:1.
Catalyst of the present invention, Beta zeolite used is Hydrogen Beta zeolite.
Described rare earth metal is one or both in lanthanum, cerium.
Described inorganic refractory oxide is be selected from one or more in aluminium oxide, titanium oxide, silica, boron oxide, magnesia, kaolin and clay, is preferably aluminium oxide.
The present invention is for the preparation of the preparation method of the catalyst of 2-alkyl-anthraquinone, conventional kneading method preparation can be adopted, comprise: by containing the mixing of the compound of rare earth metal, Beta zeolite, containing sulfate radicals compound, zirconium-containing compound and refractory inorganic oxides, then shaping, by drying, obtain catalyst of the present invention.
The preferred preparation method of catalyst of the present invention, specifically comprises:
(1) will the compound loaded on Beta zeolite of rare earth metal be contained, drying, obtain the Beta zeolite containing rare earth metal;
(2) containing sulfate radicals compound and zirconium-containing compound are loaded in refractory inorganic oxides, drying, obtain the refractory inorganic oxides containing zirconium and sulfate radical;
(3) refractory inorganic oxides containing zirconium and sulfate radical that the Beta zeolite containing rare earth metal step (1) obtained and step (2) obtain fully mixes, through shaping, dry, obtains catalyst of the present invention.
The compound loaded on Beta zeolite of rare earth metal will be contained in step (1), conventional kneading method or infusion process load can be adopted, such as fully can mix containing the compound of rare earth metal, appropriate water and Beta zeolite, then drying, namely obtain the Beta zeolite containing rare earth metal.Described rare earth metal is one or both in lanthanum, cerium, can be oxide or salt containing rare earth compound, be preferably solubility salt, such as, in lanthanum nitrate, cerous nitrate, lanthanum chloride, cerium chloride etc. one or more, preferred lanthanum nitrate and/or cerous nitrate.
Containing sulfate radicals compound and zirconium-containing compound are loaded to refractory inorganic oxides in (2) by step, conventional kneading method or infusion process load can be adopted, such as containing sulfate radicals compound, zirconium-containing compound, appropriate water and refractory inorganic oxides fully can be mixed, then drying, namely obtains the refractory inorganic oxides containing zirconium and sulfate radical.Described containing sulfate radicals compound can be mineral sulfates or sulfuric acid, is preferably ammonium sulfate or sulfuric acid, is more preferably ammonium sulfate.Described zirconium-containing compound can be all compounds containing zirconium, is preferably one or more in zirconyl chloride, zirconium nitrate, zirconium oxysulfate etc., is more preferably zirconium oxysulfate.
Described inorganic refractory oxide is be selected from one or more in aluminium oxide, titanium oxide, silica, boron oxide, magnesia, kaolin and clay, is preferably aluminium oxide.
Described drying condition is: room temperature ~ 300 DEG C, 0.1 hour ~ 100 hours, is preferably 100 DEG C ~ 200 DEG C, 2 hours ~ 48 hours.Step (1), (2) and (3) all can adopt above-mentioned drying condition, and in each step, the concrete drying condition adopted can be identical, also can be different.
In the inventive method, the described shaping conventional method that can adopt is shaping, such as extruded moulding method, can make bar shaped, clover, bunge bedstraw herb, cylindrical, spherical etc. as required.Conventional shaping assistant can be added, one or more in such as adhesive, peptizing agent, extrusion aid in forming process.
When catalyst of the present invention is for the preparation of 2-alkyl-anthraquinone, reaction condition is: reaction temperature 150 DEG C ~ 350 DEG C, pressure 0.1MPa ~ 10MPa, volume space velocity 0.1h
-1~ 10h
-1, gas agent volume ratio 50 ~ 1000.Optimum condition is: reaction temperature 200 DEG C ~ 300 DEG C, pressure 0.2MPa ~ 2.0MPa, volume space velocity 0.5h
-1~ 3.0h
-1, gas agent volume ratio 100 ~ 500.The gas medium of reaction system is inert gas, such as, in argon gas, neon, nitrogen etc. one or more, is preferably nitrogen.Reacting the raw material that uses is 2-(4 '-alkylbenzoyl) benzoic acid, such as 2-(4 '-methyl benzoyl) benzoic acid, 2-(4 '-ethylamino benzonitrile acyl group) benzoic acid, 2-(4 '-third class benzoyl) benzoic acid, 2-(4 '-butylbenzoyl) benzoic acid or 2-(4 '-amyl-benzoyl) benzoic acid etc.Product is 2-alkyl-anthraquinone, such as 2-methylanthraquinone, 2-EAQ, 2-third class anthraquinone, 2-butyl anthraquinone or 2-amyl anthraquinone.
When adopting preferred catalyst of the present invention for the preparation of 2-alkyl-anthraquinone, 2-(4 '-ethylamino benzonitrile acyl group can be adopted) the benzoic conversion ratio selectivity that can reach more than 95%, 2-alkyl-anthraquinone reaches more than 97%.
Detailed description of the invention
Further illustrate catalyst of the present invention below by embodiment, but invention should not be deemed limited in following embodiment.
Catalyst of the present invention adopts 10ml fixed bed reactors to evaluate; loaded catalyst is 10ml; raw material 2-(4-alkylbenzoyl) be in granular solids under benzoic acid normal temperature; need to carry out heat fused before charging; and the pipeline of whole system needs to carry out being incubated (heating); the reaction condition of system is adjusted to the appreciation condition of design, start into raw material, appreciation condition is in table 2.Stable reaction, after 4 hours, is got a certain amount of product and is dissolved in Isosorbide-5-Nitrae-dioxane solvent, and analyze product composition by Agilent 1100 type high pressure liquid chromatography, chromatographic column is ZORBAX SB-C18, and multi-wavelength UV-detector detects.
The present invention's Beta zeolite used is commercially available silica alumina ratio (SiO
2/ Al
2o
3) be 47 Hydrogen beta zeolite; 2-(4 '-alkylbenzoyl) benzoic acid adopts commercially available 2-(4 '-alkylbenzoyl) benzoic acid solid particle.
embodiment 1
A kind of preparation method's preparation process of catalyst of the present invention is as follows:
(1) 30 grams of Beta zeolites, 40 gram of six water La (NO is taken
3)
36H
2o fully mixes and 150 ml waters, fully mixes, 120 DEG C of dryings 6 hours, obtains the Beta zeolite containing rare earth metal.
(2) by 105 grams of Zr (NO
3)
45H
2o, 14 grams of ammonium sulfate, 150 grams of water fully mix with 35 grams of aluminium hydroxides, 100 DEG C of dryings 12 hours, obtain the aluminium oxide containing zirconium and sulfate radical.
(3) appropriate water is added after the aluminium oxide containing zirconium and sulfate radical obtained containing the Beta zeolite of rare earth metal and step (2) obtained toward step (1) fully mixes, abundant kneading becomes plastic paste, be extruded into the bar that cross section is bunge bedstraw herb, 180 DEG C of dryings 8 hours, obtain catalyst of the present invention, be numbered E-1.
Laboratory is evaluated E-1 catalyst, and appreciation condition is in table 2, and evaluation result is in table 3.
embodiment 2 ~ 7
The preparation method of each embodiment catalyst is with embodiment 1, and difference is that composition, appreciation condition are different with evaluation result, and concrete catalyst composition is in table 1, and appreciation condition is in table 2, and evaluation result is in table 3.
embodiment 8
A kind of preparation method of catalyst of the present invention is with embodiment 3, and difference is that catalyst preparation step (1) and step (2) are combined into together, by La (NO
3)
36H
2o, Beta zeolite, ammonium sulfate, Zr (NO
3)
45H
2o, aluminium oxide, nitric acid become plastic paste with the abundant kneading of water, are extruded into the bar that cross section is bunge bedstraw herb, and 180 DEG C of dryings 8 hours, obtain catalyst of the present invention, numbering E-8, and catalyst composition is in table 1, and appreciation condition is in table 2, and evaluation result is in table 3.
comparative example 1 ~ 4
Comparative example 1 ~ 3 catalyst C-1 ~ C-3 preparation method is with embodiment 3, and difference is that composition, appreciation condition are different with evaluation result, and concrete catalyst composition is in table 1, and appreciation condition is in table 2, and evaluation result is in table 3.
the composition of each embodiment of table 1 (comparative example) catalyst(unreceipted content is weight percent content)
the appreciation condition of each catalyst of table 2
the evaluation result of each catalyst of table 3
Conversion ratio in table 3 and selectivity of product are molar percentage.
From the results shown in Table 3; catalyst of the present invention is with 2-(4 '-alkylbenzoyl) benzoic acid is the technical process that 2-alkyl-anthraquinone produced by raw material; no matter at 2-(4 '-alkylbenzoyl) benzoic conversion ratio; or the selective aspect of 2-alkyl-anthraquinone, is all obviously better than the reaction result of catalyst in comparative example.And the reaction effect of the catalyst (E-1 ~ E-7) adopting the preferred process of the present invention to prepare is significantly better than the catalyst (E-8) adopting conventional kneading method to prepare.
Claims (24)
1., for the preparation of a catalyst for 2-alkyl-anthraquinone, its composition comprises rare earth metal, Beta zeolite, SO
4 2-, zirconium and refractory inorganic oxides, with the weight of catalyst for benchmark, Beta zeolite content is 5% ~ 40%, and rare earth metal is with oxide basis content for 0.1% ~ 20%, and zirconium is in zirconia content for 5% ~ 40%, and sulfate radical content is 0.5% ~ 20%, refractory oxide surplus.
2. according to catalyst according to claim 1, it is characterized in that described catalyst, with the weight of catalyst for benchmark, Beta zeolite content is 10% ~ 30%, rare earth metal with oxide basis content for 0.2% ~ 10%, zirconium is in zirconia content for 10% ~ 30%, and sulfate radical content is 1% ~ 15%, and surplus is refractory inorganic oxides.
3., according to catalyst according to claim 1, it is characterized in that the refractory inorganic oxides consisting of Beta zeolite containing rare earth metal and containing sulfate radicals and zirconium of described catalyst.
4. according to the catalyst described in claim 1 or 3, it is characterized in that in described catalyst, rare earth metal with the weight ratio of oxide basis and Beta zeolite for 0.02 ~ 0.5:1, the weight ratio of sulfate radical and refractory inorganic oxides is 0.05 ~ 1:1, zirconium with the weight ratio of oxide basis and refractory inorganic oxides for 0.5 ~ 2.0:1.
5. according to the catalyst described in claim 1 or 3, it is characterized in that in described catalyst, rare earth metal with the weight ratio of oxide basis and Beta zeolite for 0.02 ~ 0.4:1, the weight ratio of sulfate radical and refractory inorganic oxides is 0.1 ~ 0.5:1, zirconium with the weight ratio of oxide basis and refractory inorganic oxides for 0.6 ~ 1.0:1.
6., according to the catalyst described in claim 1 or 3, it is characterized in that Beta zeolite used is Hydrogen Beta zeolite.
7., according to the catalyst described in claim 1 or 3, it is characterized in that described rare earth metal is one or both in lanthanum, cerium.
8., according to the catalyst described in claim 1 or 3, it is characterized in that described refractory inorganic oxides is be selected from one or more in aluminium oxide, titanium oxide, silica, boron oxide, magnesia, kaolin and clay.
9., according to the catalyst described in claim 1 or 3, it is characterized in that described refractory inorganic oxides is aluminium oxide.
10. the preparation method of catalyst according to claim 1, comprise: by containing the mixing of the compound of rare earth metal, Beta zeolite, containing sulfate radicals compound, zirconium-containing compound and refractory inorganic oxides, then shaping, drying process, obtains the catalyst for the preparation of 2-alkyl-anthraquinone.
11. in accordance with the method for claim 10, it is characterized in that, the preparation method of described catalyst comprises:
(1) will the compound loaded on Beta zeolite of rare earth metal be contained, drying, obtain the Beta zeolite containing rare earth metal;
(2) containing sulfate radicals compound and zirconium-containing compound are loaded in refractory inorganic oxides, drying, obtain the refractory inorganic oxides containing zirconium and sulfate radical;
(3) refractory inorganic oxides containing zirconium and sulfate radical that the Beta zeolite containing rare earth metal step (1) obtained and step (2) obtain fully mixes, through shaping, dry, obtains the catalyst for the preparation of 2-alkyl-anthraquinone.
12., according to preparation method according to claim 11, is characterized in that, will contain the compound loaded on Beta zeolite of rare earth metal in step (1), adopt kneading method or infusion process preparation.
13., according to preparation method according to claim 11, is characterized in that, containing sulfate radicals compound and zirconium-containing compound load in refractory inorganic oxides in (2) by step, adopt kneading method or infusion process preparation.
14., according to the preparation method described in claim 10 or 11, is characterized in that, described containing sulfate radicals compound is ammonium sulfate or sulfuric acid.
15., according to the preparation method described in claim 10 or 11, is characterized in that, described zirconium-containing compound is one or more in zirconyl chloride, zirconium nitrate, zirconium oxysulfate.
16., according to the preparation method described in claim 10 or 11, is characterized in that, the compound containing rare earth metal is one or more in lanthanum nitrate, cerous nitrate, lanthanum chloride, cerium chloride.
17., according to the preparation method described in claim 10 or 11, is characterized in that, described inorganic refractory oxide is selected from one or more in aluminium oxide, titanium oxide, silica, boron oxide, magnesia, kaolin and clay.
18., according to preparation method according to claim 11, is characterized in that, step (1), step (2), the drying condition described in step (3) are: room temperature ~ 300 DEG C drying 0.1 hour ~ 100 hours.
19. according to preparation method according to claim 10, it is characterized in that described drying condition is: room temperature ~ 300 DEG C drying 0.1 hour ~ 100 hours.
20. 1 kinds by 2-(4 '-alkylbenzoyl) benzoic acid prepares the method for 2-alkyl-anthraquinone, it is characterized in that adopting the arbitrary described catalyst of claim 1 ~ 9.
21. in accordance with the method for claim 21, it is characterized in that, adopt fixed-bed process, reaction condition is: reaction temperature 150 DEG C ~ 350 DEG C, pressure 0.1MPa ~ 10MPa, volume space velocity 0.1h
-1~ 10h
-1, gas agent volume ratio 50 ~ 1000.
22. in accordance with the method for claim 21, it is characterized in that, adopt fixed-bed process, reaction condition is: reaction temperature 200 DEG C ~ 300 DEG C, pressure 0.2MPa ~ 2.0MPa, volume space velocity 0.5h
-1~ 3.0h
-1, gas agent volume ratio 100 ~ 500.
23., according to the method described in claim 21 or 22, is characterized in that, the gas medium of reaction system is inert gas.
24. in accordance with the method for claim 20; it is characterized in that; react raw material 2-(4 '-alkylbenzoyl of using) benzoic acid is 2-(4 '-methyl benzoyl) benzoic acid, 2-(4 '-ethylamino benzonitrile acyl group) benzoic acid, 2-(4 '-third class benzoyl) benzoic acid, 2-(4 '-butylbenzoyl) benzoic acid or 2-(4 '-amyl-benzoyl) benzoic acid, its product 2-alkyl-anthraquinone should be 2-methylanthraquinone, 2-EAQ, 2-third class anthraquinone, 2-butyl anthraquinone or 2-amyl anthraquinone mutually.
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Cited By (3)
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| CN110935486A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Catalyst for preparing 2-alkyl anthraquinone and preparation method thereof |
| WO2020103118A1 (en) * | 2018-11-23 | 2020-05-28 | Solvay Sa | Process for producing substituted anthraquinone |
| CN111410602A (en) * | 2020-04-21 | 2020-07-14 | 青岛科技大学 | Preparation method of anthraquinone |
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Cited By (5)
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| CN110935486A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Catalyst for preparing 2-alkyl anthraquinone and preparation method thereof |
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| WO2020103118A1 (en) * | 2018-11-23 | 2020-05-28 | Solvay Sa | Process for producing substituted anthraquinone |
| CN111410602A (en) * | 2020-04-21 | 2020-07-14 | 青岛科技大学 | Preparation method of anthraquinone |
| CN111410602B (en) * | 2020-04-21 | 2024-05-10 | 青岛科技大学 | Preparation method of anthraquinone |
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| Publication number | Publication date |
|---|---|
| CN104588088B (en) | 2017-03-01 |
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