A kind of catalyst for synthesizing 2-alkyl-anthraquinone and its preparation method and application
Technical field
The present invention relates to a kind of catalyst for synthesizing 2-alkyl-anthraquinone and preparation method thereof, particularly with 2-(4-alkane
Base benzoyl) benzoic acid is catalyst of using during Material synthesis 2-alkyl-anthraquinone and preparation method thereof, and this is urged
Agent application in synthesis 2-alkyl-anthraquinone.
Background technology
Alkyl-anthraquinone is important fine chemical material, with C1~C5Alkyl derivative the most important, wherein 2-alkyl anthracene
Quinone most has practicality, is mainly used in hydrogen peroxide synthetic catalyst, additionally also serve as dyestuff intermediate, degradative resin photosensitive
Agent, medicine and pesticide intermediate etc..Along with the fast development of the whole world industry such as hydrogen peroxide and synthetic resin, to 2-alkyl-anthraquinone
The most high-quality 2-alkyl-anthraquinone demand increases sharply, and makes 2-alkyl-anthraquinone become the most potential series and becomes more meticulous
Learn.
2-alkyl-anthraquinone is series 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.Along with the whole world hydrogen peroxide and synthetic resin etc. industry quick
Development, the yield of 2-alkyl-anthraquinone and anthraquinone can not meet growing needs.
The method of traditional production 2-alkyl-anthraquinone mainly uses phthalic anhydride and alkylbenzene to be that raw material passes through acyl
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 a kind of with 2-(4-alkylbenzoyl) benzoic acid mixture is that raw material utilizes concentrated sulphuric acid 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,
As the cracking of hydro carbons and isomery, toluene disproportionation, the transalkylation of multi-methyl benzene, macromole naphthalene disproportionation etc. in terms of carried out extensively
Research.E. Santacesaria etc. are at CATALYSIS TODAY 66(2001) report with 2-(benzoyl in 167 ~ 174
Base) benzoic acid is raw material, the Beta zeolite through a step acid exchange is catalyst, makes the work of reactant dehydration closed-loop synthesis anthraquinone
Skill, has obtained preferable effect, but reaction temperature is higher.During synthesis 2-alkyl-anthraquinone, owing to course of reaction existing
Alkyl comes off and the problem such as isomerization, therefore to obtain highly purified 2-alkyl-anthraquinone the most difficult.
CN200410155473.5 is that the acid Beta zeolite utilizing ammonium nitrate or acid solution exchange system to obtain synthesizes 2-alkane for catalyst
Base anthraquinone, the response time required when using this catalyst is longer, and reaction temperature is higher.
In synthesis anthraquinone process, US4304724 utilizes 2-(benzoyl) benzoic acid crosses fluorinated sulfonic tree at catalyst
Anthraquinone is synthesized under the effect 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 the highest.CN1879965A discloses a kind of raw for 2-alkyl-anthraquinone and anthraquinone
The catalyst produced, is to be modified by twice pair of Beta zeolite, and wherein modification for the first time is with non-metal cations solution such as
The acid solution such as citric acid, acetic acid or ammonium salt solution swap with Beta molecular sieve, and second time is 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, the modified Beta molecular sieve of employing is as catalyst, mainly by Beta molecular sieve
Tiny catalyst granules provides enough reactivities, and therefore, existing synthesis anthraquinone process is still employing batch (-type) behaviour
Make, the most just can give full play to the performance of Beta molecular sieve, improve conversion ratio and the selectivity of target product of reactant.Mesh
Before, this synthesis anthraquinone process, owing 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 causes reaction effect undesirable.
Summary of the invention
For overcoming weak point of the prior art, the invention provides a kind of catalyst for synthesizing 2-alkyl-anthraquinone
And preparation method thereof, and the application that this catalyst is in synthesis 2-alkyl-anthraquinone.Catalyst of the present invention is used for synthesizing 2-alkyl
During anthraquinone, having environmental friendliness, activity is high, and selectivity is high, the feature that efficiency is high.
The present invention for synthesizing the catalyst of 2-alkyl-anthraquinone, its composition include Beta zeolite, phosphomolybdic acid, chlorine and refractory without
Machine oxide, on the basis of the weight of catalyst, Beta zeolite content is 20.0% ~ 70.0%, preferably 30.0% ~ 60.0%, phosphorus
Molybdic acid content is 0.1% ~ 30.0%, preferably 1.0% ~ 20.0%, and chlorinity is 0.1% ~ 15.0%, preferably 0.5% ~ 10%, surplus
For refractory inorganic oxides.
The present invention is for synthesizing the catalyst of 2-alkyl-anthraquinone, and its composition is preferably the modified Beta zeolite of phosphomolybdic acid and contains
The refractory inorganic oxides of chlorine, wherein phosphomolybdic acid is 0.005 ~ 0.5:1, preferably 0.1 ~ 0.4:1 with the weight ratio of Beta zeolite,
Chlorine is 0.01 ~ 0.5:1, preferably 0.02 ~ 0.4:1 with the weight ratio of refractory inorganic oxides.
Catalyst of the present invention, Beta zeolite used is Hydrogen Beta zeolite.
Described refractory inorganic oxides is selected from aluminium oxide, titanium oxide, silicon oxide, boron oxide, magnesium oxide, Kaolin and glues
One or more in soil, preferably Kaolin are or/and clay, more preferably Kaolin.
The present invention, for synthesizing the preparation method of the catalyst of 2-alkyl-anthraquinone, can use the kneading method of routine to prepare,
Including: phosphomolybdic acid, Beta zeolite, chlorine-containing compound and refractory inorganic oxides are mixed, then molding, will be dried, and obtain this
Invention catalyst.
The preferred preparation method of catalyst of the present invention, specifically includes:
(1) being loaded to by phosphomolybdic acid on Beta zeolite, drying obtains the Beta zeolite that phosphomolybdic acid is modified;
(2) loading in refractory inorganic oxides by chlorine-containing compound, drying obtains chloride refractory inorganic oxides;
(3) the chloride refractory inorganic oxide that phosphomolybdic acid modification Beta zeolite step (1) obtained and step (2) obtain
Thing is sufficiently mixed, then molding, drying, obtains catalyst of the present invention.
Phosphomolybdic acid is loaded on Beta zeolite by step (1), kneading method or infusion process can be used to prepare, the most permissible
Appropriate water, phosphomolybdic acid and Beta zeolite are sufficiently mixed, then drying, i.e. obtain the Beta zeolite that phosphomolybdic acid is modified.
Chlorine-containing compound is loaded in refractory inorganic oxides in (2) by step, can use kneading method or dipping legal system
Standby, such as appropriate water, chlorine-containing compound and refractory inorganic oxides can be sufficiently mixed, then drying, i.e. be contained
The refractory inorganic oxides of chlorine.
Described chlorine-containing compound can be butter, such as hydrochloric acid, ammonium chloride, sodium chloride, potassium chloride, chloric acid
One or more in potassium, hypochlorous acid, magnesium chloride, calcium chloride etc., it is also possible to be organic chlorine-containing compound, such as chloroform,
One or more in dichloroethanes, carbon tetrachloride etc..It is preferably butter, the most water-soluble inorganic chlorinating
Thing, more preferably hydrochloric acid.
Described inorganic refractory oxide is selected from aluminium oxide, titanium oxide, silicon oxide, boron oxide, magnesium oxide, Kaolin and glues
One or more in soil, preferably Kaolin are or/and clay, more preferably Kaolin.
Drying condition described in step (1) and (2) is: room temperature ~ 300 DEG C, 0.1 hour ~ 100 hours, preferably 100 DEG C
~ 200 DEG C, 2 hours ~ 48 hours, drying condition can be identical, it is also possible to different.Drying condition described in step (3) is: room
Temperature ~ 200 DEG C, 0.1 hour ~ 100 hours, preferably 50 DEG C ~ 150 DEG C, 2 hours ~ 48 hours.
In the inventive method, described molding can use 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
Such as one or more in binding agent, peptizer, extrusion aid.
When catalyst of the present invention is used for synthesizing 2-alkyl-anthraquinone, having environmental friendliness, activity and selectivity is high, and especially
It is adapted for use in fixed bed continuous flow procedure, is greatly improved production efficiency.
When catalyst of the present invention is used for synthesizing 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 of reaction system
Medium is noble gas, such as one or more in argon, neon, nitrogen etc., preferably nitrogen.The raw material that reaction is used
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-amylbenzene formyl
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 using currently preferred catalyst for synthesizing 2-alkyl-anthraquinone, 2-(4-ethylamino benzonitrile acyl group) benzoic acid
Conversion ratio can reach more than 96%, the selection performance of 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 to following
In embodiment.
Catalyst of the present invention is to use 10ml fixed bed reactors to be evaluated, and loaded catalyst is 10ml, raw material 2-
It is to be in granular form solid under (4-alkylbenzoyl) benzoic acid room temperature, needs to melt before charging, and whole system
Pipeline need to carry out being incubated (heating), the reaction condition of system is adjusted to the appreciation condition of design, starts into raw material, evaluation
Condition is shown in Table 2.After stable reaction 4 hours, take a certain amount of product and be dissolved in Isosorbide-5-Nitrae-dioxane solvent, by Agilent 1100
Product composition is analyzed by type high pressure liquid chromatography, and chromatographic column is ZORBAX SB-C18, and multi-wavelength UV-detector is examined
Survey.
Beta zeolite used by the present invention is commercially available silica alumina ratio (SiO2/Al2O3) be 47 Hydrogen Beta zeolite;
2-(4-alkylbenzoyl) benzoic acid uses 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 70 grams of Beta zeolites, 10 grams of phosphomolybdic acid are sufficiently mixed and 150 milliliters of water, are sufficiently mixed, and 120 DEG C are dried 6
Hour, obtain loading the Beta zeolite of phosphomolybdic acid.
(2) hydrochloric acid that 20 gram mass marks are 20%, 50 grams of water and 15 grams of Kaolin being sufficiently mixed, 100 DEG C are dried 12 little
Time, obtain chloride Kaolin.
(3) the Beta zeolite of the load phosphomolybdic acid obtained toward step (1) adds the chloride height that 20 grams of steps (2) obtain
Ridge soil, adds appropriate water after being sufficiently mixed, abundant kneading becomes plastic paste, is extruded into the bar that cross section is Herba Galii Bungei,
180 DEG C are dried 8 hours, obtain catalyst of the present invention, numbered E-1.
E-1 catalyst is evaluated by laboratory, and appreciation condition is shown in Table 2, and evaluation result is shown in Table 3.
Embodiment 2 ~ 7
The preparation method of each embodiment catalyst is with embodiment 1, and difference is composition, appreciation condition and evaluation result
Difference, concrete 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
A kind of preparation method of catalyst of the present invention is with embodiment 3, and difference is catalyst preparation step (1) and step
Suddenly (2) are combined into together, phosphomolybdic acid, Beta zeolite, hydrochloric acid, aluminium oxide, nitric acid kneading abundant with water will become plastic paste,
Being extruded into the bar that cross section is Herba Galii Bungei, 180 DEG C are dried 8 hours, obtain catalyst of the present invention, numbering E-8, and catalyst composition is shown in
Table 1, appreciation condition is shown in Table 2, and evaluation result is shown in Table 3.
Comparative example 1 ~ 3
The preparation method of comparative example 1 ~ 3 catalyst C-1 ~ C-3 with embodiment 3, difference be composition, appreciation condition and
Evaluation result is different, and concrete catalyst composition is shown in Table 1, and appreciation condition is shown in Table 2, and evaluation result is shown in Table 3.
The composition (unreceipted content is weight percent content) of table 1 each embodiment (comparative example) catalyst
Numbering |
Beta, % |
Phosphomolybdic acid, % |
Chlorine, % |
Refractory inorganic oxides, % |
Remarks * |
E-1 |
70 |
10 |
5 |
Surplus |
Kaolin |
E-2 |
60 |
25 |
0.2 |
Surplus |
Clay |
E-3 |
60 |
15 |
5 |
Surplus |
Aluminium oxide |
E-4 |
50 |
7 |
1 |
Surplus |
Kaolin |
E-5 |
60 |
20 |
0.5 |
Surplus |
Kaolin |
E-6 |
40 |
12 |
10 |
Surplus |
Kaolin |
E-7 |
20 |
2 |
13 |
Surplus |
Kaolin |
E-8 |
60 |
15 |
5 |
Surplus |
Aluminium oxide |
C-1 |
60 |
15 |
0 |
Surplus |
Aluminium oxide |
C-2 |
0 |
15 |
5 |
Surplus |
Aluminium oxide |
C-3 |
60 |
0 |
5 |
Surplus |
Aluminium oxide |
* refractory inorganic oxides used by each embodiment and comparative example in remarks.
The appreciation condition of each catalyst of table 2
Numbering |
Reaction temperature, DEG C |
Reaction pressure, MPa |
Volume space velocity, h-1 |
Gas agent volume ratio |
E-1 |
228 |
0.2 |
0.5 |
200 |
E-2 |
235 |
0.5 |
0.8 |
300 |
E-3 |
240 |
1.0 |
1.0 |
400 |
E-4 |
243 |
2.0 |
1.0 |
400 |
E-5 |
248 |
3.0 |
1.0 |
400 |
E-6 |
224 |
4.0 |
1.0 |
400 |
E-7 |
231 |
5.0 |
1.0 |
400 |
E-8 |
240 |
1.0 |
1.0 |
400 |
C-1 |
240 |
1.0 |
1.0 |
400 |
C-2 |
240 |
1.0 |
1.0 |
400 |
C-3 |
240 |
1.0 |
1.0 |
400 |
The evaluation result of each catalyst of table 3
Numbering |
Raw material |
Conversion ratio, % |
Product |
Selectivity of product, % |
E-1 |
2-(4-methyl benzoyl) benzoic acid |
99.1 |
2-methylanthraquinone |
98.4 |
E-2 |
2-(4-ethylamino benzonitrile acyl group) benzoic acid |
98.5 |
2-ethyl-anthraquinone |
97.3 |
E-3 |
2-(4-ethylamino benzonitrile acyl group) benzoic acid |
99.3 |
2-ethyl-anthraquinone |
99.2 |
E-4 |
2-(4-ethylamino benzonitrile acyl group) benzoic acid |
98.8 |
2-ethyl-anthraquinone |
99.1 |
E-5 |
2-(4-propylbenzoyl) benzoic acid |
96.2 |
2-propyl group anthraquinone |
98.4 |
E-6 |
2-(4-butylbenzoyl) benzoic acid |
98.7 |
2-butyl anthraquinone |
99.1 |
E-7 |
2-(4-amyl-benzoyl) benzoic acid |
96.6 |
2-amyl anthraquinone |
97.6 |
E-8 |
2-(4-methyl benzoyl) benzoic acid |
84.3 |
2-methylanthraquinone |
96.4 |
C-1 |
2-(4-ethylamino benzonitrile acyl group) benzoic acid |
75.5 |
2-ethyl-anthraquinone |
91.2 |
C-2 |
2-(4-ethylamino benzonitrile acyl group) benzoic acid |
13.0 |
2-ethyl-anthraquinone |
68.1 |
C-3 |
2-(4-ethylamino benzonitrile acyl group) benzoic acid |
80.8 |
2-ethyl-anthraquinone |
93.7 |
Conversion ratio and selectivity of product in table 3 are molar percentage.
From the results shown in Table 3, catalyst of the present invention is with 2-(4-alkylbenzoyl) benzoic acid is that raw material is raw
Produce the technical process of 2-alkyl-anthraquinone, no matter at 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, use the preferred process of the present invention to prepare
The reaction effect of catalyst (E-1 ~ E-7) is significantly better than the catalyst (E-8) using conventional kneading method to prepare.