CN104588088B - For preparing catalyst of 2 alkyl-anthraquinones and its preparation method and application - Google Patents
For preparing catalyst of 2 alkyl-anthraquinones and its preparation method and application Download PDFInfo
- Publication number
- CN104588088B CN104588088B CN201310532045.9A CN201310532045A CN104588088B CN 104588088 B CN104588088 B CN 104588088B CN 201310532045 A CN201310532045 A CN 201310532045A CN 104588088 B CN104588088 B CN 104588088B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- zirconium
- oxide
- anthraquinone
- rare earth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A kind of the invention discloses complex acid catalyst of synthesis 2 alkyl-anthraquinones and preparation method thereof, and the application in preparation 2 alkyl-anthraquinones.The composition of this catalyst includes rare earth metal, Beta zeolite, SO4 2‑, zirconium, refractory inorganic oxides, on the basis of the weight of catalyst, Beta zeolite content be 5% ~ 40%, rare earth metal counts content for 0.1% ~ 20% with oxide, zirconium counts content for 5% ~ 40% with zirconium oxide, and sulfate radical content is 0.5% ~ 20%, balance of refractory inorganic oxides.Catalyst of the present invention is used for by 2（4 alkylbenzoyl）When benzoic acid synthesizes 2 alkyl-anthraquinone, there is environmental friendliness, activity is high, and selectivity is high, and the feature of efficiency high is particularly suitable for adopting fixed-bed process.
Description
Technical field
The present invention relates to a kind of complex acid catalyst of synthesis 2- alkyl-anthraquinone and preparation method thereof, particularly with 2-（4´-
Alkylbenzoyl）Benzoic acid catalyst and preparation method thereof used in raw material preparation 2- alkyl-anthraquinone process, and should
Application in preparing 2- alkyl-anthraquinone for the catalyst.
Background technology
Alkyl-anthraquinone is important fine chemical material, with C1~C5Alkyl derivative more important, wherein 2- alkyl anthracene
Quinone most practicality, is mainly used in hydrogen peroxide synthetic catalyst, in addition also serve as dyestuff intermediate, degradative resin photosensitive
Agent, medicine and pesticide intermediate etc..With the fast development of the industry such as global hydrogen peroxide and synthetic resin, to 2- alkyl-anthraquinone
Especially high-quality 2- alkyl-anthraquinone demand increases sharply, and makes 2- alkyl-anthraquinone become quite potential series and becomes more meticulous
Learn.
2- alkyl-anthraquinone is serial fine chemical product, principal item 2-methylanthraquinone, 2-ethyl-anthraquinone, 2- amyl group anthracene
Quinone, 2- tertiary pentyl anthraquinone and 2- tert-butyl group anthraquinone etc..Generally 2- alkyl-anthraquinone is flaxen solid, and fusing point is less than anthraquinone, molten
In benzene, can be by ethanol or acetic acid recrystallization.2- alkyl-anthraquinone is mainly used in the anthraquinone carrier preparing hydrogen peroxide it is also possible to use
Make the intermediate of degradative resin, photopolymer materials or fuel.Quick with the industry such as global hydrogen peroxide and synthetic resin
Development, the yield 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 pass through acyl for raw material
Base method generates intermediate product 2-（4-alkylbenzoyl）Benzoic acid, intermediate product 2-（4-alkylbenzoyl）Benzoic acid
Again through hydrolysis, closed loop, distillating recovering solvent, oxidoreduction purifies and ethanol distillation abstraction technique finally gives purpose product 2-
Alkyl-anthraquinone.Needed for the method, chemical technology is long, and needs substantial amounts of aluminum chloride and concentrated sulphuric acid to be catalyzed in course of reaction
Agent, WO96/286140 devises one kind with 2-（4-alkylbenzoyl）Benzoic acid mixture utilizes concentrated sulphuric acid for raw material or sends out
Cigarette sulphuric acid is the method for Catalyst Production 2-ethyl-anthraquinone.The shortcoming of this method is concentrated sulphuric acid and oleum has stronger corrosion
Property and environmental hazard, and post processing work cumbersome.Therefore people try hard to prepare 2- second with a kind of eco-friendly catalyst
Base anthraquinone.
The height that Beta zeolite is tetragonal crystal system and monoclinic system collectively constitutes piles up the zeolite molecular sieve of defect, has three
The twelve-ring duct of dimension, and there is good hydrothermal stability and anti-coking performance.At present to Beta zeolite catalysis performance,
Carry out in terms of the cracking of hydro carbons and isomery, toluene disproportionation, the transalkylation of multi-methyl benzene, disproportionation of macromole naphthalene etc. extensively
Research.E. Santacesaria etc. is in CATALYSIS TODAY 66（2001）Report with 2- in 167 ~ 174（Benzoyl
Base）Benzoic acid is raw material, and the Beta zeolite exchanging through a step acid is catalyst, makes reactant dehydration closed-loop synthesize the work of anthraquinone
Skill, has obtained preferable effect, but reaction temperature is higher.During synthesis 2- alkyl-anthraquinone, due to existing in course of reaction
Alkyl comes off and the problems such as isomerization, therefore will obtain highly purified 2- alkyl-anthraquinone relatively difficult.
CN200410155473.5 is to synthesize 2- alkane using the acid Beta zeolite that ammonium nitrate or acid solution exchange system obtain for catalyst
Base anthraquinone, longer using required response time during this catalyst, reaction temperature is higher.
In synthesis anthraquinone process, US4304724 utilizes 2-（Benzoyl）Benzoic acid crosses fluorinated sulfonic tree in catalyst
Anthraquinone is synthesized in the presence of fat.This catalyst system and catalyzing environmentally safe, operating condition is gentle.But shortcoming is 2-（Benzoyl）Benzene
Formic acid conversion ratio is relatively low, and the selectivity of anthraquinone is not high.CN1879965A discloses one kind for 2- alkyl-anthraquinone and anthraquinone life
The catalyst producing, is by being modified to Beta zeolite twice, wherein first time modification is with non-metal cations solution such as
The acid solutions such as citric acid, acetic acid or ammonium salt solution and Beta molecular sieve swap, and second modified, and the modifying agent of employing is
Acid solution or metal-oxide.When this catalyst is used for intermittent reaction, 2-（4-ethylamino benzonitrile acyl group）Benzoic conversion
The selectivity of rate and 2-ethyl-anthraquinone is higher.
In above-mentioned synthesis anthraquinone process, using modified Beta molecular sieve as catalyst, mainly use Beta molecular sieve
Providing enough reactivities, therefore, existing synthesis anthraquinone process is still using batch (-type) behaviour to tiny catalyst granules
Make, so just can give full play to the performance of Beta molecular sieve, improve the conversion ratio of reactant and the selectivity of target product.Mesh
Before, this synthesis anthraquinone process, due to being limited by catalyst performance, still cannot realize fixed bed continuous operation, because fixed bed
Shaping of catalyst need to be made the granule of greater particle size by continuous operation, and the tiny granule of Beta molecular sieve is after molding, outside it
Surface drastically reduces, and the performance of molecular sieve can not be not fully exerted, thus leading to reaction effect undesirable.
Content of the invention
For overcoming weak point of the prior art, the invention provides a kind of catalyst for preparing 2- alkyl-anthraquinone
And preparation method thereof, and application in preparing 2- alkyl-anthraquinone for this catalyst.Catalyst of the present invention is used for preparing 2- alkyl
During anthraquinone, there is environmental friendliness, activity is high, and selectivity is high, the feature of efficiency high.
The present invention is used for preparing the catalyst of 2- alkyl-anthraquinone, and its composition includes rare earth metal, Beta zeolite, SO4 2-, zirconium
And refractory inorganic oxides, on the basis of the weight of catalyst, Beta zeolite content is 5% ~ 40%, and preferred scope is 10% ~ 30%；
Rare earth metal counts content for 0.1% ~ 20% with oxide, and preferably 0.2% ~ 10%；Zirconium counts content for 5% ~ 40% with zirconium oxide, preferably
For 10% ~ 30%；Sulfate radical content is 0.5% ~ 20%, preferably 1% ~ 15%, surplus refractory inorganic oxides.
The present invention is used for preparing the catalyst of 2- alkyl-anthraquinone, its composition preferably include Beta zeolite containing rare earth metal,
Containing SO4 2-With the refractory inorganic oxides of zirconium, wherein rare earth metal with oxide count with the weight of Beta zeolite than for 0.02 ~
0.5:1, preferably 0.02 ~ 0.4:1, SO4 2-With the weight of refractory inorganic oxides than for 0.05 ~ 1:1, preferably 0.1 ~ 0.5:
1, zirconium is counted with the weight of refractory inorganic oxides than for 0.5 ~ 2.0 with oxide: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 of lanthanum, cerium or two kinds.
Described inorganic refractory oxide be selected from aluminium oxide, titanium oxide, silicon oxide, boron oxide, magnesium oxide, Kaolin and
One or more of clay, preferably aluminium oxide.
The present invention is used for preparing the preparation method of the catalyst of 2- alkyl-anthraquinone, can be prepared using conventional kneading method,
Including：By the compound containing rare earth metal, Beta zeolite, containing sulfate radicals compound, zirconium-containing compound and refractory inorganic oxides
Mixing, then molding, drying obtains catalyst of the present invention.
The preferred preparation method of catalyst of the present invention, specifically includes：
（1）By on the compound loaded zeolite to Beta containing rare earth metal, drying, obtain the Beta boiling containing rare earth metal
Stone；
（2）Containing sulfate radicals compound and zirconium-containing compound are loaded in refractory inorganic oxides, drying, obtain containing zirconium
Refractory inorganic oxides with sulfate radical；
（3）By step（1）The Beta zeolite containing rare earth metal obtaining and step（2）Obtain is resistance to containing zirconium and sulfate radical
Molten inorganic oxide is sufficiently mixed, and through molding, is dried, obtains catalyst of the present invention.
Step（1）Middle by the compound loaded zeolite to Beta containing rare earth metal, can using conventional kneading method or
Infusion process loads, for example, can be sufficiently mixed the compound containing rare earth metal, appropriate water and Beta zeolite, then through dry
Dry, that is, obtain the Beta zeolite containing rare earth metal.Described rare earth metal is one of lanthanum, cerium or two kinds, containing rare earth metal
Compound can be oxide or salt, preferably solubility salt, such as Lanthanum (III) nitrate, cerous nitrate, lanthanum chloride, cerium chloride etc.
One or more of, preferably Lanthanum (III) nitrate and/or cerous nitrate.
Step（2）Middle containing sulfate radicals compound and zirconium-containing compound are loaded to refractory inorganic oxides, can be using often
The kneading method of rule or infusion process load, for example can will be inorganic to containing sulfate radicals compound, zirconium-containing compound, appropriate water and refractory
Oxide is sufficiently mixed, then drying, that is, obtain the refractory inorganic oxides containing zirconium and sulfate radical.Described containing sulfate radicals
Compound can be mineral sulfatess or sulphuric acid, preferably ammonium sulfate or sulphuric acid, more preferably ammonium sulfate.Described chemical combination containing zirconium
Thing can be all of compound containing zirconium, preferably one or more of zirconyl chloride, zirconium nitrate, zirconium oxysulfate etc., more
It is preferably zirconium oxysulfate.
Described inorganic refractory oxide be selected from aluminium oxide, titanium oxide, silicon oxide, boron oxide, magnesium oxide, Kaolin and
One or more of clay, preferably aluminium oxide.
Described drying condition is：Room temperature ~ 300 DEG C, 0.1 hour ~ 100 hours, preferably 100 DEG C ~ 200 DEG C, 2 hours ~
48 hours.Step（1）、（2）With（3）Above-mentioned drying condition all can be adopted, in each step, the concrete drying condition adopting is permissible
Identical it is also possible to different.
In the inventive method, described molding can adopt conventional method molding, such as extruded moulding method, can be according to need
Bar shaped to be made, Herba Trifolii Pratentis, Herba Galii Bungei, cylinder, spherical etc..The shaping assistant of routine can be added in forming process, than
As one or more of binding agent, peptizer, extrusion aid.
When catalyst of the present invention is used for preparing 2- alkyl-anthraquinone, reaction condition is：150 DEG C ~ 350 DEG C of reaction temperature, pressure
0.1MPa ~ 10MPa, volume space velocity 0.1h-1~10h-1, gas agent volume ratio 50 ~ 1000.Optimum condition is：200 DEG C of reaction temperature ~
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 of reaction system
Medium is noble gases, such as one or more of argon, neon, nitrogen etc., preferably nitrogen.React used raw material
For 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 group benzoyl
Base）Benzoic acid etc..Product is 2- alkyl-anthraquinone, such as 2-methylanthraquinone, 2-ethyl-anthraquinone, 2- third class anthraquinone, 2- butyl anthraquinone
Or 2- amyl anthraquinone.
When being used for preparing 2- alkyl-anthraquinone using preferred catalyst of the present invention, 2- can be adopted（4-ethylamino benzonitrile acyl group）
The selection performance that benzoic conversion ratio can reach more than 95%, 2- alkyl-anthraquinone reaches more than 97%.
Specific embodiment
To further illustrate catalyst of the present invention below by embodiment, but to invention should not be deemed limited to following
In embodiment.
Catalyst of the present invention is to be evaluated using 10ml fixed bed reactors, and loaded catalyst is 10ml, raw material 2-
（4- alkylbenzoyl）It is to be in granular form solid under benzoic acid room temperature, need to carry out heating fusing before charging, and entirely
The pipeline of system needs to be incubated (heating), the reaction condition of system is adjusted to the appreciation condition designing, starts into raw material,
Appreciation condition is shown in Table 2.After stable reaction 4 hours, take a certain amount of product to be dissolved in Isosorbide-5-Nitrae-dioxane solvent, use Agilent
1100 type high pressure liquid chromatography are analyzed to product composition, and chromatographic column is ZORBAX SB-C18, and multi-wavelength UV-detector is entered
Row detection.
Beta zeolite used by the present invention is commercially available silica alumina ratio（SiO2/Al2O3）Hydrogen beta zeolite for 47；
2-（4-alkylbenzoyl）Benzoic acid adopts commercially available 2-（4-alkylbenzoyl）Benzoic acid solid particle.
Embodiment 1
A kind of preparation method preparation process of catalyst of the present invention is as follows：
（1）Weigh 30 grams of Beta zeolites, 40 gram of six water La (NO3)3·6H2O is sufficiently mixed and 150 milliliters of water, fully mixed
Close, 120 DEG C of dryings 6 hours, obtain the Beta zeolite containing rare earth metal.
（2）By 105 grams of Zr (NO3)4·5H2O, 14 grams of ammonium sulfate, 150 grams of water are sufficiently mixed with 35 grams of aluminium hydroxide, and 100
DEG C drying 12 hours, obtains the aluminium oxide containing zirconium and sulfate radical.
（3）Toward step（1）The Beta zeolite containing rare earth metal obtaining and step（2）The oxygen containing zirconium and sulfate radical obtaining
Change after aluminum is sufficiently mixed and add appropriate water, abundant kneading becomes plastic paste, be extruded into the bar that section is Herba Galii Bungei,
180 DEG C of dryings 8 hours, obtain catalyst of the present invention, numbering is E-1.
Laboratory is evaluated to E-1 catalyst, and appreciation condition is shown in Table 2, and evaluation result is shown in Table 3.
Embodiment 2 ~ 7
With embodiment 1, difference is composition, appreciation condition and evaluation result to the preparation method of each embodiment catalyst
Difference, specific catalyst composition is shown in Table 1, and appreciation condition is shown in Table 2, and evaluation result is shown in Table 3.
Embodiment 8
With embodiment 3, difference is catalyst preparation step to a kind of preparation method of catalyst of the present invention（1）And step
Suddenly（2）It is combined into together, will La (NO3)3·6H2O, Beta zeolite, ammonium sulfate, Zr (NO3)4·5H2O, aluminium oxide, nitric acid and water
Fully kneading becomes plastic paste, is extruded into the bar that section is Herba Galii Bungei, 180 DEG C of dryings 8 hours, obtains present invention catalysis
Agent, numbering E-8, catalyst composition is shown in Table 1, and appreciation condition is shown in Table 2, and evaluation result is shown in Table 3.
Comparative example 1 ~ 4
With embodiment 3, difference is composition, appreciation condition and comments comparative example 1 ~ 3 catalyst C-1 ~ C-3 preparation method
Valency result is different, and specific catalyst composition is shown in Table 1, and appreciation condition is shown in Table 2, and evaluation result is shown in Table 3.
The each embodiment of table 1（Comparative example）The composition of 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 given birth to for raw material
Produce the technical process of 2- alkyl-anthraquinone, no matter in 2-（4-alkylbenzoyl）Benzoic conversion ratio, or 2- alkyl-anthraquinone
Selectivity aspect, be all substantially better than the reaction result of catalyst in comparative example.And, using preferred process of the present invention preparation
Catalyst（E-1~E-7）Reaction effect be significantly better than the catalyst using conventional kneading method preparation（E-8）.
Claims (23)
1. a kind of catalyst for preparing 2- alkyl-anthraquinone, its composition includes rare earth metal, Beta zeolite, SO4 2-, zirconium and resistance to
Molten inorganic oxide, on the basis of the weight of catalyst, Beta zeolite content is 5% ~ 40%, rare earth metal content in terms of oxide
For 0.1% ~ 20%, zirconium counts content for 5% ~ 40% with zirconium oxide, and sulfate radical content is 0.5% ~ 20%, refractory inorganic oxides surplus,
Wherein, the Beta zeolite consisting of containing rare earth metal of described catalyst and the refractory inorganic oxides of containing sulfate radicals and zirconium.
2. according to the catalyst described in claim 1 it is characterised in that described catalyst, on the basis of the weight of catalyst,
Beta zeolite content is 10% ~ 30%, and rare earth metal counts content for 0.2% ~ 10% with oxide, zirconium with zirconium oxide count content for 10% ~
30%, sulfate radical content is 1% ~ 15%, balance of refractory inorganic oxides.
3. according to the catalyst described in claim 1 it is characterised in that in described catalyst, rare earth metal in terms of oxide with
The weight of Beta zeolite is than for 0.02 ~ 0.5:1, the weight of sulfate radical and refractory inorganic oxides is than for 0.05 ~ 1:1, zirconium is with oxygen
The weight of compound meter and refractory inorganic oxides is than for 0.5 ~ 2.0:1.
4. according to the catalyst described in claim 1 it is characterised in that in described catalyst, rare earth metal in terms of oxide with
The weight of Beta zeolite is than for 0.02 ~ 0.4:1, the weight of sulfate radical and refractory inorganic oxides is than for 0.1 ~ 0.5:1, zirconium is with oxygen
The weight of compound meter and refractory inorganic oxides is than for 0.6 ~ 1.0:1.
5. according to the catalyst described in claim 1 it is characterised in that Beta zeolite used is Hydrogen Beta zeolite.
6. according to the catalyst described in claim 1 it is characterised in that described rare earth metal is one of lanthanum, cerium or two
Kind.
7. according to the catalyst described in claim 1 it is characterised in that described refractory inorganic oxides are selected from aluminium oxide, oxygen
Change one or more of titanium, silicon oxide, boron oxide, magnesium oxide and clay.
8. according to the catalyst described in claim 1 it is characterised in that described refractory inorganic oxides are aluminium oxide.
9. the preparation method of the catalyst described in claim 1, including：By the compound containing rare earth metal, Beta zeolite, sulfur-bearing
Acid group compound, zirconium-containing compound and refractory inorganic oxides mixing, then molding, drying is processed, and obtains for preparing 2-
The catalyst of alkyl-anthraquinone.
10. in accordance with the method for claim 9 it is characterised in that the preparation method of described catalyst includes：
（1）By on the compound loaded zeolite to Beta containing rare earth metal, 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 containing zirconium and sulfur
The refractory inorganic oxides of acid group；
（3）By step（1）The Beta zeolite containing rare earth metal obtaining and step（2）The refractory containing zirconium and sulfate radical obtaining is no
Machine oxide is sufficiently mixed, and through molding, is dried, obtains the catalyst for preparing 2- alkyl-anthraquinone.
11. according to the preparation method described in claim 10 it is characterised in that step（1）Middle by the compound containing rare earth metal
Load on Beta zeolite, using kneading method or infusion process preparation.
12. according to the preparation method described in claim 10 it is characterised in that step（2）Middle by containing sulfate radicals compound with contain
Zirconium compoundss load in refractory inorganic oxides, using kneading method or infusion process preparation.
13. according to the preparation method described in claim 9 or 10 it is characterised in that described containing sulfate radicals compound be sulphuric acid
Ammonium or sulphuric acid.
14. according to the preparation method described in claim 9 or 10 it is characterised in that described zirconium-containing compound be zirconyl chloride,
One or more of zirconium nitrate, zirconium oxysulfate.
15. according to the preparation method described in claim 9 or 10 it is characterised in that containing rare earth metal compound be Lanthanum (III) nitrate,
One or more of cerous nitrate, lanthanum chloride, cerium chloride.
16. according to the preparation method described in claim 9 or 10 it is characterised in that described refractory inorganic oxides be selected from oxygen
Change one or more of aluminum, titanium oxide, silicon oxide, boron oxide, magnesium oxide and clay.
17. according to the preparation method described in claim 10 it is characterised in that step（1）, step（2）, step（3）Described in
Drying condition be：Room temperature ~ 300 DEG C drying 0.1 hour ~ 100 hours.
18. according to the preparation method described in claim 9 it is characterised in that described drying condition is：Room temperature ~ 300 DEG C drying
0.1 hour ~ 100 hours.
19. one kind are by 2-（4-alkylbenzoyl）Benzoic acid prepares the method for 2- alkyl-anthraquinone it is characterised in that adopting right
Require 1 ~ 8 arbitrary described catalyst.
20. in accordance with the method for claim 19 it is characterised in that adopt fixed-bed process, and 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.
21. in accordance with the method for claim 20 it is characterised in that adopt fixed-bed process, and 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.
22. according to the method described in claim 20 or 21 it is characterised in that the gas medium of reaction system be noble gases.
23. in accordance with the method for claim 19 it is characterised in that react used raw material 2-（4-alkyl benzoyl
Base）Benzoic acid is 2-（4-methyl benzoyl）Benzoic acid, 2-（4-ethylamino benzonitrile acyl group）Benzoic acid, 2-（4-propylbenzene first
Acyl group）Benzoic acid, 2-（4-butylbenzoyl）Benzoic acid or 2-（4-amyl-benzoyl）Benzoic acid, its product 2- alkyl
Anthraquinone phase should be 2-methylanthraquinone, 2-ethyl-anthraquinone, 2- propyl group anthraquinone, 2- butyl anthraquinone or 2- amyl anthraquinone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310532045.9A CN104588088B (en) | 2013-11-03 | 2013-11-03 | For preparing catalyst of 2 alkyl-anthraquinones and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310532045.9A CN104588088B (en) | 2013-11-03 | 2013-11-03 | For preparing catalyst of 2 alkyl-anthraquinones and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104588088A CN104588088A (en) | 2015-05-06 |
| CN104588088B true CN104588088B (en) | 2017-03-01 |
Family
ID=53114343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310532045.9A Active CN104588088B (en) | 2013-11-03 | 2013-11-03 | For preparing catalyst of 2 alkyl-anthraquinones and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104588088B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110935486B (en) * | 2018-09-25 | 2022-07-12 | 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 |
| CN111410602B (en) * | 2020-04-21 | 2024-05-10 | 青岛科技大学 | Preparation method of anthraquinone |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4379092A (en) * | 1980-12-16 | 1983-04-05 | P C U K Produits Chimiques Ugine Kuhlmann | Process for the preparation of anthraquinone and its substituted derivatives |
| CN1152476A (en) * | 1995-12-19 | 1997-06-25 | 南开大学 | Catalyst for preparing methyl tert-butyl ether |
| CN1651386A (en) * | 2004-11-24 | 2005-08-10 | 大连理工大学 | Synthesis method of 2-alkyl anthraquinone |
| CN1743069A (en) * | 2004-08-31 | 2006-03-08 | 中国石油化工股份有限公司 | Method for preparing solid super-strong acid catalytic material |
| CN1879965A (en) * | 2005-07-12 | 2006-12-20 | 大连理工大学 | Preparation method of catalyst for 2-alkyl anthraqunone and anthraqunone production |
-
2013
- 2013-11-03 CN CN201310532045.9A patent/CN104588088B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4379092A (en) * | 1980-12-16 | 1983-04-05 | P C U K Produits Chimiques Ugine Kuhlmann | Process for the preparation of anthraquinone and its substituted derivatives |
| CN1152476A (en) * | 1995-12-19 | 1997-06-25 | 南开大学 | Catalyst for preparing methyl tert-butyl ether |
| CN1743069A (en) * | 2004-08-31 | 2006-03-08 | 中国石油化工股份有限公司 | Method for preparing solid super-strong acid catalytic material |
| CN1651386A (en) * | 2004-11-24 | 2005-08-10 | 大连理工大学 | Synthesis method of 2-alkyl anthraquinone |
| CN1879965A (en) * | 2005-07-12 | 2006-12-20 | 大连理工大学 | Preparation method of catalyst for 2-alkyl anthraqunone and anthraqunone production |
Non-Patent Citations (2)
| Title |
|---|
| 改性β分子筛催化苯与苯酐合成蒽醌的研究;贾振等;《应用化工》;20090131;第38卷(第1期);文章第100页1.2.3节、1.2.4节、表2，第101页第3节 * |
| 硼酸改性Hβ沸石分子筛催化2-(4"-乙基苯甲酰基)苯甲酸脱水合成2-乙基蒽醌;孔岩等;《工业催化》;20130531;第21卷(第5期);第66-71页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104588088A (en) | 2015-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104588088B (en) | For preparing catalyst of 2 alkyl-anthraquinones and its preparation method and application | |
| CN102909064B (en) | The Catalysts and its preparation method of a kind of toluene and methanol alkylation and application | |
| CN104843731A (en) | Preparation method of nanometer stepped hole mordenite molecular sieve | |
| CN103121909B (en) | Ethanol and benzene vapor-phase alkylation produce the method for ethylbenzene | |
| WO2016078035A1 (en) | Active aluminosilicate material and preparation method therefor | |
| CN104926580A (en) | Method for preparing ethylbenzene and styrene through toluene and methanol side chain alkylation | |
| CN104588087B (en) | Catalyst for preparing 2-alkyl anthraquinone, and preparation method and application thereof | |
| CN106076404A (en) | Catalyst and preparation method thereof, application and the preparation method of durol | |
| CN107777698B (en) | B-NaY molecular sieve and preparation method and application thereof | |
| CN101722020A (en) | Eutectic zeolite catalyst containing EUO structure and preparation and application thereof | |
| CN102247884B (en) | Catalyst used in process of preparing vinyl chloride from 1,2-ethylene dichloride and preparation method of catalyst | |
| CN104588103B (en) | A kind of catalyst for synthesizing 2-alkyl-anthraquinone and its preparation method and application | |
| CN103785464A (en) | High-activity catalyst for toluene alkylation with methanol and preparation method and application thereof | |
| CN106824249A (en) | One species graphite-phase nitrogen carbide loads the preparation method of selenium catalysis material | |
| CN102380404A (en) | Catalyst used for producing promoter N-cyclohexyl benzothiazole sulfonamide and its preparation method | |
| CN101927185A (en) | Preparation of macroporous strong-acid cation-exchange resin catalyst and use thereof in catalytic synthesis of methyl 2-keto-L-gulonate | |
| CN101805244B (en) | Cyclohexene hydrating process | |
| CN104588107B (en) | Catalyst used for synthesizing 2-alkylanthraquinone, and preparation method and application thereof | |
| CN101602003B (en) | Oxide catalyst for preparing styrene by ethylbenzene dehydrogenation | |
| CN107790148B (en) | Catalyst for preparing divinylbenzene by dehydrogenating diethylbenzene and preparation method and application thereof | |
| CN102276412A (en) | Method for producing ethylbenzene from ethanol and benzene | |
| CN104548919A (en) | Air purifying agent and preparation method thereof | |
| CN104888846A (en) | CuO modified HZSM-5 molecular sieve catalysts, preparation method and applications thereof | |
| CN102247885B (en) | Method for preparing AlCl3/zeolite molecular sieve solid acid catalyst | |
| CN106517233B (en) | The method of the Beta zeolite molecular sieve of floride-free solvent-free route synthesis B bodies enrichment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230823 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |
|
| TR01 | Transfer of patent right |