CN108073143A - A kind of reaction control phase transfer catalyst precipitation process catalyst particle size regulates and controls method - Google Patents
A kind of reaction control phase transfer catalyst precipitation process catalyst particle size regulates and controls method Download PDFInfo
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- CN108073143A CN108073143A CN201611014832.4A CN201611014832A CN108073143A CN 108073143 A CN108073143 A CN 108073143A CN 201611014832 A CN201611014832 A CN 201611014832A CN 108073143 A CN108073143 A CN 108073143A
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Abstract
The present invention provides a kind of reaction control phase transfer catalyst precipitation process catalyst particle sizes to regulate and control method, it is to carry out the catalyst particle size in epoxidation reaction of olefines catalyst precipitation process to reaction control phase transfer catalyst, hydrogen peroxide for oxidant to regulate and control, it is controlled by conditioning agent and reaction condition, so that be precipitated catalyst particle size increase, improve catalyst recovery yield and eliminate small catalyst particles be carried or filter to subsequent technique in influence.
Description
Technical field
The invention belongs to petrochemical industries, and in particular to a kind of reaction control phase transfer catalyst precipitation process catalyst
Granularity regulates and controls method.
Background technology
Epoxidation reaction of olefines is one of most important reaction, the epoxide that epoxidation reaction generates in chemical industry
It is a kind of important intermediate, is widely used in the various fields such as petrochemical industry, organic synthesis, fine chemistry industry, is passed through in its people
It is occupied an important position in Ji.Document Xi Z W, Zhou N, Sun Y, Li K L.Reaction-Controlled Phase-
Transfer Catalysis for Propylene Epoxidation to Propylene Oxide.Science,2001,
292:1139. are put forward for the first time reaction control phase transfer catalyst concept.The characteristics of reaction control phase transfer catalyst is to react
Catalyst is insoluble in reaction system when initial, in H in reaction process2O2Under the action of, catalyst is completely dissolved, and formation is homogeneously urged
Change reaction, work as H2O2When exhausting, catalyst is precipitated in solid form from system again, can be recycled after separation.
In recent years, reaction control phase transfer catalyst achieves more progress during epoxidation reaction of olefines, this is urged
Agent is widely used in the alkene epoxidations such as propylene, butylene, isobutene, styrene, 1- octenes, cyclohexene, cyclo-octene, 1- laurylenes
In reaction.[Li Jun, invigorating, why ancestral's prestige reaction control phase transfer catalyst progress of research catalysis journal, 2010,31 (8):
895~911.]
In reaction control phase transfer catalyst catalyzing expoxidation of olefines industrialization process, the catalyst recovery yield after reaction is extremely
Close important, in catalyst recovery process, the granularity of catalyst has decisive influence, reaction controlling to catalyst recovery yield
Catalyzed By Phase-transfer Catalyst epoxidation reaction of olefines terminates rear catalyst precipitation process catalyst particle size and is distributed in 0.5~120
Between micron, the fine particle catalyst between 0.5~10 micron accounts for 10wt% of catalyst total amount or so, fine particle catalysis
Partial catalyst is easily carried in agent or filter is into subsequent technique, is caused catalyst loss and is influenced follow-up separation process,
Therefore corresponding control Catalyzed By Phase-transfer Catalyst epoxidation reaction of olefines is needed to terminate the catalyst particles of rear catalyst precipitation process
Granularity is regulated and controled so that catalyst particle size increase eliminates fine particle catalyst to subsequently dividing to reduce catalyst loss
Separating process influences.
The content of the invention
The purpose of the present invention is be directed to that Catalyzed By Phase-transfer Catalyst epoxidation reaction of olefines should be controlled to terminate rear catalyst analysis
Going out process has a fine particle, and a part of catalyst in fine particle catalyst is easily carried or filter is into subsequent technique,
It causes catalyst loss and influences the deficiency of follow-up separation process, regulation and control increase is carried out to catalyst precipitation process after reaction
Catalyst particle size is precipitated, improves catalyst recovery yield and elimination small catalyst particles are carried or filter is into subsequent technique
Influence.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：
A kind of reaction control phase transfer catalyst precipitation process catalyst particle size regulates and controls method, is that reaction controlling phase is turned
The catalyst particle size that shifting catalyst, hydrogen peroxide are carried out for oxidant in epoxidation reaction of olefines catalyst precipitation process carries out
Regulation and control are controlled by conditioning agent and reaction condition so that catalyst particle size increase is precipitated.
Reaction control phase transfer catalyst in above-mentioned technical proposal is quaternary ammonium salt phosphor-tungstic heteropoly acid, and chemical formula is
QmPWpO4+3p, wherein, Q is cationic moiety, uses R1R2R3N or with [R1R2R3R4N+] represent, wherein R1R2R3N is quaternized pyridinium
Salt, R1R2R3N or [R1R2R3R4N+] in R1、R2、R3、R4It is C respectively5~C20Linear chain or branch chain alkyl, C4~C18Cycloalkanes
One kind in base, benzyl, R1、R2、R3、R4It can be identical or differs；2≤m≤7, p=2,3 or 4.
Hydrogen peroxide mass concentration scope in above-mentioned technical proposal is 3%~75%
Alkene in above-mentioned technical proposal is：Wherein R1, R2Respectively：C1~C12 straight chain alkane
Base, C3~C15 bands branched alkyl, the mono- halogen substituted straight chain alkyl of C1~C8, the double halogen substituted straight chain alkyl of C1~C8, C5~C8
The monosubstituted phenol of cyclic alkyl, phenol, C1~C5, the disubstituted phenol of C1~C4.
Conditioning agent in above-mentioned technical proposal is inorganic salts, catalyst QmPWpO4+3pIn cationic moiety and inorganic salts group
Close object, catalyst QmPWpO4+3pIn anionicsite and inorganic salts cationic compositions in any one, inorganic salts the moon from
Subdivision in salt acid group, sulfate radical, acetate, carbonate, phosphate radical, hydrogen phosphate, bisulfate ion, bicarbonate radical one
Kind, cationic moiety H+、K+、Na+、NH4 +In one kind.
Progressively to regulate and control condensation temperature in catalyst precipitation process, rate of temperature fall is tune empty condition in above-mentioned technical proposal
5~25 DEG C/5min, condensation temperature is most down to 0 DEG C；System pressure where catalyst is stepped up, rate of pressure rise for 0.005~
0.5MP/5min, system maximum pressure where catalyst are 2.0MPa.
Conditioning agent dosage in above-mentioned technical proposal is 0.01~the 10 ‰ of input catalyst amount.
The technical solution adopted by the present invention is catalyzed after corresponding to control Catalyzed By Phase-transfer Catalyst epoxidation reaction of olefines
After agent precipitation process catalyst particle size is regulated and controled, catalyst particle size is precipitated and is distributed between 10~150 microns, wherein having
The precipitation catalyst particle size 0.5 that there are about 85wt% catalyst particle sizes between 80~120 microns, not to be regulated and controled relatively~
120 microns are precipitated catalyst particle size and greatly increase, and improve catalyst recovery yield and eliminate because fine particle carries or saturating
Filter is to the influence in subsequent technique, suitable for that should control Catalyzed By Phase-transfer Catalyst epoxidation reaction of olefines industrialization process.
Below by embodiment, the present invention will be further described.
Specific embodiment
Embodiment 1
In 1000ml reaction kettles, solvent acetonitrile addition is added in as 200g, 10g catalyst [(CH)3C16H33N](PO4)
(W03)4], propylene 100g is added in, 50% hydrogen peroxide 28g, reaction temperature is 75 DEG C, reaction pressure 1.0MPa, when reaction 1.5 is small
The direct 7 DEG C of water cooling 25min of reaction mass afterwards, then reaction mass is urged by centrifuging and being dried in vacuo to dry to recycle to be precipitated
Agent, catalyst recovery yield 98.9%, between 0.5~120 micron of catalyst particle size.
Under equal conditions, when reaction 1.5 is small after add in conditioning agent (NH4)2HPO40.05g, system pressure where catalyst by
1.0MPa boosts to 1.5MPa with 0.1MP/min rates, and simultaneous reactions temperature is cooled to 15 by 75 DEG C with 1 DEG C/min rate of temperature fall
DEG C, then catalyst is precipitated by centrifuging and being dried in vacuo to dry to recycle in reaction mass, catalyst recovery yield 99.9%,
Catalyst particle size is distributed as between 15~120 microns.
Embodiment 2
In 1000ml reaction kettles, addition chloropropene 300g, 50% hydrogen peroxide 90g, addition 20g catalyst [π-
C5H5NC16H33]3(PO4)(W03)4], reaction temperature be 45 DEG C, reaction pressure 0.5MPa, reaction 2.5 it is small when after reaction mass
Direct 7 DEG C of water cooling 25min, then catalyst, catalysis is precipitated by centrifuging and being dried in vacuo drying recycling in reaction mass
The agent rate of recovery is 97.8%, between 0.5~120 micron of catalyst particle size.
Under equal conditions, when reaction 2.5 is small after add in conditioning agent 0.5g Na3PW12O40, system pressure where catalyst by
0.5MPa boosts to 1.0MPa with 0.05MP/min rates, and simultaneous reactions temperature is cooled down by 45 DEG C with 0.5 DEG C/min rate of temperature fall
Catalyst is precipitated by centrifuging and being dried in vacuo drying recycling to 10 DEG C, then by reaction mass, catalyst recovery yield is
99.9%, catalyst particle size is distributed as between 12~115 microns.
Embodiment 3
In 1000ml reaction kettles, 1- laurylenes 300g, 30% hydrogen peroxide 120g are added in, adds in 15g catalyst
[(C5H5NC4H9]3(PO4)(W03)4], reaction temperature be 65 DEG C, reaction pressure 0.5MPa, reaction 3 it is small when after reaction mass it is straight
7 DEG C of water cooling 25min are met, then catalyst, catalyst is precipitated by centrifuging and being dried in vacuo drying recycling in reaction mass
The rate of recovery is 87.8%, between 0.5~120 micron of catalyst particle size.
Under equal conditions, when reaction 3 is small after add in conditioning agent 0.5g Na3PW12O40, system pressure where catalyst by
0.5MPa boosts to 1.0MPa with 0.05MP/min rates, and simultaneous reactions temperature is cooled down by 45 DEG C with 0.5 DEG C/min rate of temperature fall
Catalyst is precipitated by centrifuging and being dried in vacuo drying recycling to 10 DEG C, then by reaction mass, catalyst recovery yield is
99.9%.Catalyst particle size is distributed as between 10~100 microns.
Embodiment 4
In 1000ml reaction kettles, cyclohexene 300g, 30% hydrogen peroxide 120g are added in, adds in 15g catalyst
[(C5H5NC4H9]3(PO4)(W03)4], reaction temperature be 65 DEG C, reaction pressure 0.5MPa, reaction 3 it is small when after reaction mass it is straight
7 DEG C of water cooling 25min are met, then catalyst, catalyst is precipitated by centrifuging and being dried in vacuo drying recycling in reaction mass
The rate of recovery is 87.8%, between 0.5~120 micron of catalyst particle size.
Under equal conditions, when reaction 3 is small after add in conditioning agent 0.05g [π-C5H5NC16H33]+With 0.05g CH3COOH is mixed
Object, system pressure where catalyst boost to 1.0MPa by 0.5MPa with 0.05MP/min rates, and simultaneous reactions temperature is by 65 DEG C
10 DEG C are cooled to 0.5 DEG C/min rate of temperature fall, then reaction mass is precipitated by centrifuging and being dried in vacuo drying recycling
Catalyst, catalyst recovery yield 97.9%, catalyst particle size are distributed as between 12~110 microns.
Claims (7)
1. a kind of reaction control phase transfer catalyst precipitation process catalyst particle size regulates and controls method, it is characterized in that：Reaction is controlled
Phase transfer catalyst processed, hydrogen peroxide carry out the catalyst granules in epoxidation reaction of olefines catalyst precipitation process for oxidant
Degree is regulated and controled, and is controlled by conditioning agent and reaction condition so that catalyst particle size increase is precipitated.
2. according to the method described in claim 1, it is characterized in that：The reaction control phase transfer catalyst is miscellaneous more for phosphorus tungsten
Sour quaternary ammonium salt, chemical formula QmPWpO4+3p, wherein, Q is cationic moiety, uses R1R2R3N or with [R1R2R3R4N+] represent, wherein
R1R2R3N is pyridine quaternary ammonium salt, R1R2R3N or [R1R2R3R4N+] in R1、R2、R3、R4It is C respectively5~C20Linear chain or branch chain alkane
Base, C4~C18Cycloalkyl, one kind in benzyl, R1、R2、R3、R4It can be identical or differs；2≤m≤7, p=2,3 or 4.
3. according to the method described in claim 1, it is characterized in that：The hydrogen peroxide mass concentration scope for 3%~
75%.
4. according to the method described in claim 1, it is characterized in that：The alkene is：Wherein R1,
R2Respectively：C1~C12 straight chained alkyls, C3~C15 bands branched alkyl, the mono- halogen substituted straight chain alkyl of C1~C8, C1~C8 are double
Halogen substituted straight chain alkyl, the monosubstituted phenol of C5~C8 cyclic alkyls, phenol, C1~C5, the disubstituted phenol of C1~C4.
5. according to the method described in claim 1, it is characterized in that：The conditioning agent is inorganic salts, catalyst QmPWpO4+3p
In cationic moiety and mineral salt compositions, catalyst QmPWpO4+3pIn anionicsite and inorganic salts cationic compositions
In any one, inorganic salts anionicsite be selected from salt acid group, sulfate radical, acetate, carbonate, phosphate radical, hydrogen phosphate,
One kind in bisulfate ion, bicarbonate radical, inorganic salts zwitterion part are selected from H+、K+、Na+、NH4 +In one kind.
6. according to the method described in claim 1, it is characterized in that：The tune empty condition be catalyst precipitation process in progressively
Regulate and control condensation temperature, rate of temperature fall is 5~25 DEG C/5min, and condensation temperature is most down to 0 DEG C；System pressure where catalyst is progressively
Rise, rate of pressure rise are 0.005~0.5MP/5min, and system maximum pressure where catalyst is 2.0MPa.
7. according to the method described in claim 1, it is characterized in that：The conditioning agent dosage is input catalyst amount
0.01~10 ‰.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110090666A (en) * | 2019-06-03 | 2019-08-06 | 江苏扬农化工集团有限公司 | A method of improving the heteropolyacid catalyst rate of recovery |
| CN110833866A (en) * | 2019-11-14 | 2020-02-25 | 江苏扬农化工集团有限公司 | Method for improving recovery rate of epoxidation catalyst |
| CN113717130A (en) * | 2021-10-08 | 2021-11-30 | 中化学科学技术研究有限公司 | Continuous production device and method of epoxy cyclohexane |
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| CN110090666A (en) * | 2019-06-03 | 2019-08-06 | 江苏扬农化工集团有限公司 | A method of improving the heteropolyacid catalyst rate of recovery |
| CN110833866A (en) * | 2019-11-14 | 2020-02-25 | 江苏扬农化工集团有限公司 | Method for improving recovery rate of epoxidation catalyst |
| CN113717130A (en) * | 2021-10-08 | 2021-11-30 | 中化学科学技术研究有限公司 | Continuous production device and method of epoxy cyclohexane |
| CN113717130B (en) * | 2021-10-08 | 2024-04-05 | 中化学科学技术研究有限公司 | Continuous production method of epoxycyclohexane |
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