CN107098802A - The 2 alkyl-anthraquinone preparation methods based on Beta zeolites - Google Patents
The 2 alkyl-anthraquinone preparation methods based on Beta zeolites Download PDFInfo
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- CN107098802A CN107098802A CN201710238897.5A CN201710238897A CN107098802A CN 107098802 A CN107098802 A CN 107098802A CN 201710238897 A CN201710238897 A CN 201710238897A CN 107098802 A CN107098802 A CN 107098802A
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Abstract
The invention discloses a kind of 2 alkyl-anthraquinone preparation methods based on Beta zeolites, comprise the following steps that：Solvent is used as using biphenyl, isopropyl biphenyl, diisopropyl biphenyl, phthalic acid dimethyl ester, diethyl phthalate, dipropyl phthalate; with 2 (4 ' alkylbenzoyl) benzoic acid, HBeta catalyst hybrid reactions, 2 alkyl-anthraquinones are obtained；Reacted catalyst is collected, repeats to prepare 2 alkyl-anthraquinones；After catalyst activity reduction, collect and repeat reacted catalyst, washing, dry after, continue to repeat to react.The specific pore passage structure of catalyst of the present invention is conducive to the generation of purpose product, and selected solvent promotes the diffusion of raw material and product in catalyst duct, and the two promotes mutually, obtains more preferable reaction result；Selected solvent, while also functioning to increase catalyst and reactant compatibility, diluting reaction thing, the effect for improving catalyst stability.
Description
Technical field
The invention belongs to synthesize technical field of chemical engineering, prepared by the 2- alkyl-anthraquinones of more particularly to a kind of Beta zeolites
Method.
Background technology
2- alkyl-anthraquinones be hydrogen dioxide solution production by anthraquinone process, Photoactive compounds, dyestuff and degradative resin primary raw material and in
Mesosome.With the continuous growth of dioxygen water demand, the demand to 2- alkyl-anthraquinones increases sharply.
The industrialized preparing process of current 2- alkyl-anthraquinones mainly includes two steps, is alkylbenzene and phthalic anhydride first in tri-chlorination
Intermediate product 2- (4 '-alkylbenzoyl) benzoic acid is obtained in the presence of aluminium, then is dehydrated through oleum or sulphuric acid catalysis
Closed loop obtains 2- alkyl-anthraquinones (referring to world patent WO96/28410).A large amount of spent acid that the technique is produced, not only etching apparatus,
And pollution environment, it can not meet the demand of sustainable development.Therefore people try hard to a kind of environment-friendly catalyst come
Prepare 2- alkyl-anthraquinones.
HBeta zeolites have caused extensive attention as a kind of environment-friendly catalyst in catalytic field.It has
Suitable pore passage structure, abundant surface area, can modulation acid feature and recyclability, shown in catalytic reaction good
Performance.
Reported in Chinese patent (patent No. ZL 200410155473.5) HBeta zeolites for catalyst by 2- (4 '-
Alkylbenzoyl) benzoic acid dehydration synthesis 2- alkyl-anthraquinones method.But HBeta is used for molecular weight than larger reactant
Conversion reaction, due to pore size, its reusability is poor, it is necessary to frequently roasting regeneration.
Alkali desiliconization is reported in Chinese patent (patent No. ZL 201410114035.8) and prepares HBeta catalyst for 2-
The method of (4 '-alkylbenzoyl) benzoic acid dehydration synthesis 2- alkyl-anthraquinones, this method can improve conversion ratio and yield.
The content of the invention
It is an object of the invention to provide a kind of preparation method of 2- alkyl-anthraquinones, ensure its reaction efficiency, yield and
While selective, making the stability of catalyst is improved, and improves the repeat performance of catalyst, reduces production cost.
To reach above-mentioned purpose, the invention provides a kind of 2- alkyl-anthraquinone preparation methods based on Beta zeolites, specifically
Step is as follows：
After S1, Na-Beta zeolite are handled with ammonium nitrate solution, dry, roasting obtains HBeta catalyst standby；
S2, preparation 2- alkyl-anthraquinones：With biphenyl, isopropyl biphenyl, diisopropyl biphenyl, phthalic acid dimethyl ester, neighbour
One or more of mixing in diethyl phthalate, dipropyl phthalate are as solvent, by solvent volume:2- (4 '-alkane
Base benzoyl) benzoic acid Mass：HBeta catalyst quality=10.0~50.0 made from step S1:1.0~30.0:1(ml/
G/g ratio), the solvent, 2- (4 '-alkylbenzoyl) benzoic acid and HBeta catalyst are added in reactor, heating
200~350 DEG C are warming up to, stirring reaction 0.4~1.0 hour obtains 2- alkyl-anthraquinones；
S3, repetition prepare 2- alkyl-anthraquinones：Collection step S2 prepares the HBeta catalyst after 2- alkyl-anthraquinones, using with
Step S2 identical reaction conditions, repeat to prepare 2- alkyl-anthraquinones；Said process is repeated 1~11 time；
S4, catalyst regeneration：After the HBata catalyst activities reduction, collection step S3 repeats reacted
HBata catalyst, by one or more of mixing, washings in methanol, ethanol, acetone, dioxane, after vacuum drying, continues
Repeat step S2, step S3 processes.
Under preferred embodiment, solvent described in step S2 is in biphenyl or repefral.
Under preferred embodiment, solvent volume described in step S2:2- (4 '-alkylbenzoyl) benzoic acid Mass：Step S1 systems
The HBeta catalyst qualities obtained are 20.0~35.0:2.0~10.0:1(ml/g/g).
Under preferred embodiment, experimentation described in step S3 is repeated 6~11 times.
The present invention is compared to the advantage with prior art：
1st, the present invention is using Beta zeolites as catalyst, with biphenyl, isopropyl biphenyl, diisopropyl biphenyl, phthalic acid
Two formicesters, diethyl phthalate, dipropyl phthalate are conducive to mesh as solvent, the specific pore passage structure of catalyst
Product generation, and selected solvent promotes the diffusion of raw material and product in catalyst duct, and the two promotes mutually, obtains
To more preferable reaction result.
2nd, the selected solvent of the present invention, while also functioning to increase catalyst and reactant compatibility, diluting reaction thing, raising
The effect of catalyst stability.
3rd, raw material 2- (4 '-alkylbenzoyl) conversion of benzoic acid of the present invention is up to 97%, and product 2- alkyl-anthraquinones are received
Rate is up to 94%.
4th, during the inventive method prepares 2- alkyl-anthraquinones, catalyst repeats reaction 6-11 times, recovers initial after regeneration
Activity；Regenerated catalyst feed stock conversion is up to 97%, and product 2- alkyl-anthraquinone yields are up to 94%.
Brief description of the drawings
Fig. 1 is the catalyst XRD that embodiment 1 is handled by ammonium nitrate；
Fig. 2 is catalyst XRD of the embodiment 1 by 11 secondary responses；
Fig. 3 is catalyst XRD of the embodiment 1 by regeneration.
Embodiment
The inventive method is described further with reference to specific embodiment.
Embodiment 1
S1, Na-Beta zeolites are swapped into processing with ammonium nitrate solution.50 grams of Na-Beta zeolite powders are weighed, are poured into
In beaker, 500mL1mol/L ammonium nitrate solutions are added, are exchanged 1.5 hours at 80 DEG C, are dried after exchanging three times, Ran Houfang
Enter Muffle kiln roasting, obtain HBeta catalyst standby；
S2, using 2- (4 '-ethylamino benzonitrile acyl group) benzoic acid as raw material, material quality 3.5g, with biphenyl solvent, by solvent body
Product:Quality：HBeta catalyst quality=20 made from step S1:3.5:1 (ml/g/g) ratio, by the solvent, 2- (4 '-
Ethylamino benzonitrile acyl group) benzoic acid and HBeta catalyst added in reactor, is heated to 260 DEG C, stirring reaction 0.4 hour,
Obtain 2- EAQs；
S3, repetition prepare 2- EAQs：Collection step S2 prepares the HBeta catalyst after 2- EAQs, using with
Step S2 identical reaction conditions, repeat to prepare 2- EAQs；Said process is repeated 11 times；
Above steps reaction result is as shown in table 1, wherein, S2 represents the result of step S2 reactions, and S3-1 represents step
S3 repeats the reaction result of first time, by that analogy.
The reaction result of table 1
As can be seen from Table 1, the present embodiment initial feed conversion ratio is up to 99.4%, and product yield is reachable
92.5%；During catalyst repeats reaction 11 times, feed stock conversion is down to 96.0% by 99.4%, product yield by
92.5% is down to 88.1%, and catalyst catalytic performance is varied less, and illustrates under above-mentioned reaction condition, catalyst performance stabilised.
S4, catalyst regeneration：After the HBata catalyst activities reduction, collection step S3 repeats reacted
HBata catalyst, is washed by methanol, after vacuum drying, repeat step S2 processes, step S3 processes；
Reaction result is as shown in table 2, wherein, 2S2 is represented by the step S4 catalyst repeat step S2 reactions handled
As a result, 2S3-1 represents to continue the reaction result of repeat step S3 first times, by that analogy.
The reaction result of table 2
As can be seen from Table 2, regenerated catalyst recovers initial activity；Keep reaction condition constant, regeneration catalyzing
Agent still has fabulous reaction stability.
Fig. 1-3 is respectively that the present embodiment is handled by ammonium nitrate, by 11 secondary responses and by the catalyst XRD of regeneration
Figure；It can be seen that reacting middle catalyst structure of the present invention is all the time without significant change, Stability Analysis of Structures, stable in catalytic performance.
Embodiment 2
S1 and the step S1 same treatments of embodiment 1, obtain HBeta catalyst standby；
S2, using 2- (4 '-ethylamino benzonitrile acyl group) benzoic acid as raw material, material quality 3.5g, with phthalic acid dimethyl ester
As solvent, by solvent volume:2- (4 '-ethylamino benzonitrile acyl group) benzoic acid Mass：HBeta catalyst qualities made from step S1
=10.0:7:1 (ml/g/g) ratio, the solvent, 2- (4 '-ethylamino benzonitrile acyl group) benzoic acid and HBeta catalyst are added
Enter in reactor, be heated to 280 DEG C, stirring reaction 1.0 hours obtains 2- EAQs；
S3, repetition prepare 2- EAQs：Collection step S2 prepares the HBeta catalyst after 2- EAQs, using with
Step S2 identical reaction conditions, repeat to prepare 2- EAQs；Said process is repeatedly；
S4, catalyst regeneration：After the HBeta catalyst activities reduction, collection step S3 repeats reacted
HBata catalyst, is washed by acetone, after vacuum drying, continues repeat step S2, step S3 processes.
As shown in table 3, S2 represents the result of step S2 reactions to reaction result, and S3 represents the result of step S3 reactions, 2S2 tables
Show the catalyst result that first time repeat step S2 reacts after step S4 processing for the first time, 2S3 represents to repeat to walk for the first time
Rapid S3 reaction result, 3S2 represents the result of second of first time repeat step S2 reaction after step S4 processing of catalyst,
By that analogy.
The reaction result of table 3
Embodiment 3
The catalyst prepared using embodiment 1, using isopropyl biphenyl as solvent, by solvent volume:2-(4’-
Amyl-benzoyl) benzoic acid Mass：Catalyst quality=30.0:10:1 (ml/g/g) ratio, by the solvent, 2- (4 '-
Amyl-benzoyl) benzoic acid and HBeta catalyst added in reactor, is heated to 290 DEG C, stirring reaction 0.6 hour,
Obtain 2- amyl anthraquinones；Process catalyst regeneration step be the same as Example 2, repeats to prepare 2- amyl anthraquinones, reaction result is as shown in table 4.
The reaction result of table 4
Embodiment 4
The catalyst prepared using embodiment 1, solvent, solvent volume are used as using diethyl phthalate:2-
(4 '-tert-butyl-benzoyl) benzoic acid Mass：Catalyst quality=30.0:15:1 (ml/g/g), 270 DEG C of reaction temperature, its
Its condition be the same as Example 2, repeats to prepare 2- tert-butyl group anthraquinones, after catalyst catalytic performance is reduced, by ethanol regenerated from washing,
Reaction result is as shown in table 5.
The reaction result of table 5
Embodiment 5
The catalyst prepared using embodiment 1, solvent, solvent volume are used as using dipropyl phthalate:2-
(4 '-ethylamino benzonitrile acyl group) benzoic acid Mass：Catalyst quality=20.0:3.5:1 (ml/g/g), 258 DEG C of reaction temperature is other
Condition be the same as Example 2, repeats to prepare 2- EAQs, after catalyst catalytic performance is reduced, and passes through ethanol regenerated from washing, reaction
As a result it is as shown in table 6.
The reaction result of table 6
Comparative example 1
S1 and the step S1 same treatments of embodiment 1, obtain HBeta catalyst standby；
S2, using 2- (4 '-ethylamino benzonitrile acyl group) benzoic acid as raw material, not solubilizer, other reaction condition be the same as Examples 1,
Prepare 2- EAQs；
S3, repetition prepare 2- EAQs：Collection step S2 prepares the HBeta catalyst after 2- EAQs, using with
Step S2 identical reaction conditions, repeat to prepare 2- EAQs；Said process is repeated 11 times；
Above steps reaction result is as shown in table 7, wherein, S2 represents the result of step S2 reactions, and S3-1 represents step
S3 repeats the reaction result of first time, by that analogy.
The reaction result of table 7
As can be seen from Table 7, the present embodiment initial feed conversion ratio is 97.5%, and product yield is up to 77.6%；
Catalyst is repeated during reacting 9 times, and feed stock conversion is down to 84.0% by 97.5%, and product yield is down to by 77.6%
23.5%, catalyst catalytic performance is changed greatly, and catalyst repeats reactivity worth when contrast adds solvent, illustrates in not solubilizer
Reaction condition under, catalyst performance is decreased obviously.
S4, catalyst regeneration：After the HBata catalyst activities reduction, collection step S3 repeats reacted
HBata catalyst, is washed by methanol, after vacuum drying, repeat step S2 processes, step S3 processes；
Reaction result is as shown in table 8, wherein, 2S2 represents the result of repeat step S2 reactions, and 2S3-1 represents repeat step
The reaction result of S3 first times, by that analogy.
The reaction result of table 8
As can be seen from Table 8, using renovation process same as Example 1, the catalyst after regeneration can not be complete
Recover initial activity；Comparative example 1, regenerated catalyst activity can not be recovered completely, and increase with regeneration times, and raw material turns
Rate and product yield decline.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art in the technical scope of present disclosure, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (4)
1. a kind of 2- alkyl-anthraquinone preparation methods based on Beta zeolites, it is characterised in that comprise the following steps that：
After S1, Na-Beta zeolite are handled with ammonium nitrate solution, dry, roasting obtains HBeta catalyst standby；
S2, preparation 2- alkyl-anthraquinones：With biphenyl, isopropyl biphenyl, diisopropyl biphenyl, phthalic acid dimethyl ester, adjacent benzene two
One or more of mixing in formic acid diethylester, dipropyl phthalate are as solvent, by solvent volume:2- (4 '-alkylbenzenes
Formoxyl) benzoic acid Mass：HBeta catalyst quality=10.0~50.0 made from step S1:1.0~30.0:1(ml/g/g)
Ratio, by the solvent, 2- (4 '-alkylbenzoyl) benzoic acid and HBeta catalyst add reactor in, heat temperature raising
To 200~350 DEG C, stirring reaction 0.4~1.0 hour obtains 2- alkyl-anthraquinones；
S3, repetition prepare 2- alkyl-anthraquinones：Collection step S2 prepares the HBeta catalyst after 2- alkyl-anthraquinones, using with step
S2 identical reaction conditions, repeat to prepare 2- alkyl-anthraquinones；Said process is repeated 1~11 time；
S4, catalyst regeneration：After the HBata catalyst activities reduction, collection step S3 repeats reacted HBata
Catalyst, by one or more of mixing, washings in methanol, ethanol, acetone, dioxane, after vacuum drying, continues to repeat
Step S2, step S3 processes.
2. 2- alkyl-anthraquinone preparation methods based on Beta zeolites according to claim 1, it is characterised in that described in step S2
Solvent is one kind in biphenyl or repefral.
3. 2- alkyl-anthraquinone preparation methods based on Beta zeolites according to claim 1, it is characterised in that described in step S2
Solvent volume:2- (4 '-alkylbenzoyl) benzoic acid Mass：HBeta catalyst qualities made from step S1 be 20.0~
35.0:2.0~10.0:1(ml/g/g).
4. 2- alkyl-anthraquinone preparation methods based on Beta zeolites according to claim 1, it is characterised in that described in step S3
Experimentation is repeated 6~11 times.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020103118A1 (en) * | 2018-11-23 | 2020-05-28 | Solvay Sa | Process for producing substituted anthraquinone |
| WO2022104763A1 (en) * | 2020-11-23 | 2022-05-27 | Solvay Sa | Process for preparing 2-alkylanthraquinone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999064129A2 (en) * | 1998-06-10 | 1999-12-16 | Korea Research Institute Of Chemical Technology | Process for preparing hydroxylated aromatics by hydrogen and oxygen |
| CN1651386A (en) * | 2004-11-24 | 2005-08-10 | 大连理工大学 | Synthesis method of 2-alkyl anthraquinone |
| CN103833534A (en) * | 2014-03-25 | 2014-06-04 | 黑龙江大学 | Method for catalytically preparing 2-ethyl anthraquinone by alkali desilicicated modified Hbeta molecular sieve |
-
2017
- 2017-04-13 CN CN201710238897.5A patent/CN107098802B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999064129A2 (en) * | 1998-06-10 | 1999-12-16 | Korea Research Institute Of Chemical Technology | Process for preparing hydroxylated aromatics by hydrogen and oxygen |
| CN1651386A (en) * | 2004-11-24 | 2005-08-10 | 大连理工大学 | Synthesis method of 2-alkyl anthraquinone |
| CN103833534A (en) * | 2014-03-25 | 2014-06-04 | 黑龙江大学 | Method for catalytically preparing 2-ethyl anthraquinone by alkali desilicicated modified Hbeta molecular sieve |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020103118A1 (en) * | 2018-11-23 | 2020-05-28 | Solvay Sa | Process for producing substituted anthraquinone |
| WO2022104763A1 (en) * | 2020-11-23 | 2022-05-27 | Solvay Sa | Process for preparing 2-alkylanthraquinone |
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