CN109232197A - A kind of method of 2- positive propoxy ethyl alcohol chlorination synthesis chloromethyl positive propyl ether - Google Patents
A kind of method of 2- positive propoxy ethyl alcohol chlorination synthesis chloromethyl positive propyl ether Download PDFInfo
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- CN109232197A CN109232197A CN201811097900.7A CN201811097900A CN109232197A CN 109232197 A CN109232197 A CN 109232197A CN 201811097900 A CN201811097900 A CN 201811097900A CN 109232197 A CN109232197 A CN 109232197A
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- positive
- catalyst
- ethyl alcohol
- propyl ether
- positive propoxy
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/7276—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a kind of methods of 2- positive propoxy ethyl alcohol chlorination synthesis chloromethyl positive propyl ether, using the Cu-Zn/MCM-22 catalyst of support type, 2- positive propoxy ethyl alcohol chlorination synthesizes chloromethyl positive propyl ether high catalytic efficiency, and hydrogen chloride utilization rate is high, selectivity is high, and product yield is high；Catalyst is disposably put into when need to only drive, so that it may it is recycled, reduces the expenses such as dosage and the recycling of catalyst, do not generate harmful waste water or waste residue, it is environmentally protective.
Description
Technical field
The present invention relates to field of compound preparation, and in particular to a kind of 2- positive propoxy ethyl alcohol chlorination synthesis chloromethyl positive third
The method of ether.
Background technique
Chloroethyl positive propyl ether is to prepare one of important source material of herbicide pretilachlor, the herbicide be it is a kind of efficiently, low toxicity,
Early stage wide spectrum rice field major selection sprouting stage herbicide, is widely used in field of rice cultivation.
Currently, preparing the chloroethyl positive propyl ether mainly using 2- positive propoxy ethyl alcohol as primary raw material, using different chlorinating agents
Chlorine substitution reaction is carried out with it.Yang Jianping etc. (synthetic method of 2- positive propoxy chloroethanes, Zhejiang chemical industry, volume 1999,30,
4th phase) using 2- positive propoxy ethyl alcohol and thionyl chloride as reaction raw materials, using composite catalyst, after reaction with 10%
Lye neutralizes it, so that a large amount of organic wastewaters are generated, product content 98.1%, yield 97%.Tong Guotong is in patent
A kind of preparation method of intermediate epichlorophdrin of herbicide pretilachlor is disclosed in CN200810061878.0, and this method is with bis- (three chloromethanes
Base) carbonic ester be chlorinating agent, instead of chlorinating agents such as traditional chlorinated sulfoxide, phosphorus oxychloride, hydrogen chloride, under the conditions of organic solvent,
Using organic amine as catalyst, chloroethyl positive propyl ether is synthesized, since organic solvent is added, product must carry out distilation, to lead
Cause product yield lower, energy consumption is high, and processing step is more, while bis- (trichloromethyl) carbonic ester (abbreviation triphosgene) prices compared with
Height is unfavorable for industrialization promotion.
2- propoxyl group chloroethanes abbreviation chlorine ether, the also known as chloro- 2- propoxyethane of chlorine ether positive propoxy ethyl chloride, 1-, 2- chlorine
Ethyl propyl ether is an important intermediate for synthesizing herbicide pretilachlor.
ZL200810061878.0 discloses a kind of preparation method of intermediate epichlorophdrin of herbicide pretilachlor, with ethylene glycol list
Positive ether and bis- (trichloromethyl) carbonic esters are that raw material is reacted under conditions of organic amine catalyst using organic solvent, are produced
Product purity 98.5%, yield 88.5%.
Zhejiang chemical industry fourth phase " synthesis and exploitation of 2- positive propoxy chloroethanes " of volume 30, with ethylene glycol propyl ether and
Thionyl chloride is that raw material uses composite catalyst, and product content is greater than 97%, and yield is greater than 97%.ZL200920292880.9 is public
A kind of chlorine ether production technology Dropping feeder of cloth.
With the fast development of pesticide industry, on the one hand, the demand of chloroethyl positive propyl ether constantly increases；On the other hand right
The quality of chloroethyl positive propyl ether and environmental friendly higher requirements are also raised.The preparation process of traditional chloroethyl positive propyl ether, is deposited
Unstable product quality, yield is low, wastewater flow rate is big, technique is cumbersome the problems such as, be no longer satisfied requirement of the market to product.
Therefore efficient, the safe and environment-friendly chloroethyl positive propyl ether synthesis technology of one kind is developed to have important practical significance.
Summary of the invention
For this purpose, being generated the object of the present invention is to provide a kind of simple process, safe operation, without waste water, product purity and receipts
Rate promotes the preparation method of significant chloroethyl positive propyl ether.
The preparation method of chloroethyl positive propyl ether of the present invention, comprising the following steps:
Chlorination reaction system is imported after the Cu-Zn/MCM-22 catalyst of 2- positive propoxy ethyl alcohol and support type is mixed, with
Hydrogen chloride carries out chlorination reaction, and chlorination reaction system is that multitower is connected continuous production processes, after chlorination reaction, chlorated liquid warp
It crosses and steams chloroethyl positive propyl ether, catalyst, 2- positive propoxy ethyl alcohol and heavy constituent circulating and recovering.
The operation temperature be 60~130 DEG C, preferably 100~110 DEG C, operating pressure be 20~100kPa, preferably 40~
60kPa.Disposably add the catalyst of 2- positive propoxy ethyl alcohol quality 0.5~7% when driving for the first time, preferably 1~2%, normally
Mode of operation circulating and recovering, is no longer added.
In the case of, according to the invention it is preferred to, the additional amount of the compound containing Cu, compound containing Zn and carrier MCM-22 makes
In the catalyst of the obtained 2- positive propoxy ethyl alcohol chlorination 2- allyloxyethanol, with the 2- positive propoxy ethyl alcohol chlorination
On the basis of the total weight of the catalyst of 2- allyloxyethanol processed, the content of Cu is that the content of 1-25 weight %, Zn are 5-25 weight
The content for measuring % and carrier is 50-94 weight %；Preferably, it is 5-20 weight that the content of Cu, which is the content of 7-23 weight %, Zn,
The content for measuring % and carrier is 57-88 weight %.
The Cu-Zn/MCM-22 catalyst of the support type uses base metal Cu and Zn as active component, can be effective
Ground improves 2- positive propoxy ethanol conversion, 2- allyloxyethanol selectivity and receipts in 2- positive propoxy ethyl alcohol chlorination reaction
Rate.Under preferable case, the weight ratio of Cu and Zn are 1:0.1-10；Preferably, the weight ratio of Cu and Zn is 1:0.3-8.Particularly,
In the catalyst content of Cu and Zn within the above range when, catalyst imitates the improvement of 2- positive propoxy ethyl alcohol chlorination reaction
Fruit is more preferable.
2- positive propoxy ethyl alcohol chlorination 2- allyloxyethanol provided by the invention is prepared the present invention also provides a kind of
The method of catalyst is catalyzed this method comprises: (1) introduces compound containing Cu and compound containing Zn in carrier MCM-22
Agent precursor；(2) catalyst precarsor is restored under hydrogen atmosphere, obtains 2- positive propoxy ethyl alcohol chlorination 2- propoxyl group
The catalyst of ethyl alcohol.
What is provided in method provided by the invention introduces compound containing Cu and compound containing Zn, purpose in carrier MCM-22
It is finally in order to introduce active component into the catalyst of the 2- positive propoxy ethyl alcohol chlorination 2- allyloxyethanol of preparation, specifically
For Cu and Zn.
According to the present invention, the compound containing Cu can obtain catalyst precarsor and in step for carrier MCM-22 can be added
Suddenly it can be changed into the substance of Cu under conditions of the reduction in (2)；Under preferable case, the compound containing Cu is copper nitrate, chlorine
Change at least one of copper, stannous chloride, cuprous nitrate.
According to the present invention, the compound containing Zn can obtain catalyst precarsor and in step (2) for carrier can be added
In reduction under conditions of can be changed into the substance of Zn.Under preferable case, the compound containing Zn is zinc chloride.
The regeneration method of the Cu-Zn/MCM-22 catalyst of the support type is off into ethyl acetate raw material, continues to lead to
Enter hydrogen, is 100~1000h in 300 DEG C~600 DEG C of temperature, 0.8~6.0MPa of pressure, hydrogen volume air speed-1Under the conditions of to mistake
Catalyst living carries out in reactor plus hydrogen regeneration 3~for 24 hours.
Further, the reaction is carried out in the reactor of two or more serial or parallel connections, each reactor
The identical or different catalyst of interior filling.
A kind of beneficial effect master of the method for 2- positive propoxy ethyl alcohol chlorination synthesis chloromethyl positive propyl ether of the present invention
Be embodied in: the Cu-Zn/MCM-22 catalyst price of support type synthesizes chloromethane compared with low activity height, 2- positive propoxy ethyl alcohol chlorination
Base positive propyl ether high catalytic efficiency, hydrogen chloride utilization rate is high, and selectivity is high, and product yield is high；Disposably investment is urged when need to only drive
Agent, so that it may be recycled, reduce the expenses such as dosage and the recycling of catalyst, do not generate harmful waste water or waste residue, green ring
It protects.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
[embodiment 1]
A certain amount of copper nitrate and zinc chloride and deionized water are mixed evenly, the dipping solution containing Cu-Zn is obtained；
A certain amount of MCM-22 carrier is added in above-mentioned dipping solution, stands aging for 24 hours at room temperature, then through 80 DEG C of dry 4h, 700 DEG C
4h is roasted, catalyst precarsor is made；
Catalyst precarsor is restored, reduction temperature is 400 DEG C, recovery time 10h, and hydrogen contains in hydrogen atmosphere
Amount is 15 volume %, and the volume space velocity of hydrogen atmosphere is 2000h-1, obtain catalyst I.By adjusting active component and carrier
Dosage so that the composition of catalyst I are as follows: the content of content 5.6 the weight %, MCM-22 of content 10.5 the weight %, Zn of Cu
83.9 weight %.
[embodiment 2]
A certain amount of copper nitrate and zinc chloride and deionized water are mixed evenly, the dipping solution containing Cu-Zn is obtained；
A certain amount of MCM-22 carrier is added in above-mentioned dipping solution, stands aging for 24 hours at room temperature, then through 80 DEG C of dry 4h, 700 DEG C
4h is roasted, catalyst precarsor is made；
Catalyst precarsor is restored, reduction temperature is 400 DEG C, recovery time 10h, and hydrogen contains in hydrogen atmosphere
Amount is 15 volume %, and the volume space velocity of hydrogen atmosphere is 2000h-1, obtain catalyst II.By adjusting active component and carrier
Dosage so that the composition of catalyst II are as follows: the content of content 12.1 the weight %, MCM-22 of content 6.6 the weight %, Zn of Cu
81.1 weight %.
[embodiment 3]
A certain amount of copper nitrate and zinc chloride and deionized water are mixed evenly, the dipping solution containing Cu-Zn is obtained；
A certain amount of MCM-22 carrier is added in above-mentioned dipping solution, stands aging for 24 hours at room temperature, then through 80 DEG C of dry 4h, 700 DEG C
4h is roasted, catalyst precarsor is made；
Catalyst precarsor is restored, reduction temperature is 400 DEG C, recovery time 10h, and hydrogen contains in hydrogen atmosphere
Amount is 15 volume %, and the volume space velocity of hydrogen atmosphere is 2000h-1, obtain catalyst III.By adjusting active component and load
The dosage of body, so that the composition of catalyst III are as follows: the 12.1 weight % of content of content 8.6 the weight %, Zn of Cu, MCM-22's
79.3 weight % of content.
[embodiment 4]
A certain amount of copper nitrate and zinc chloride and deionized water are mixed evenly, the dipping solution containing Cu-Zn is obtained；
A certain amount of α-MCM-22 carrier is added in above-mentioned dipping solution, stands aging for 24 hours at room temperature, then through 80 DEG C of dry 4h, 700
DEG C roasting 4h, be made catalyst precarsor；
Catalyst precarsor is restored, reduction temperature is 400 DEG C, recovery time 10h, and hydrogen contains in hydrogen atmosphere
Amount is 15 volume %, and the volume space velocity of hydrogen atmosphere is 2000h-1, obtains catalyst IV.By adjusting active component and load
The dosage of body, so that the composition of catalyst I are as follows: content 8.5 the weight %'s, MCM-22 of content 12.5 the weight %, Zn of Cu contains
Measure 79 weight %.
[embodiment 3]
By the Cu-Zn/MCM-22 catalyst of 2- positive propoxy ethyl alcohol and support type be added in chlorination reaction system with
Hydrogen chloride carries out chlorination reaction, and chlorination reaction system uses caldron process, and operation temperature is 100 DEG C, operating pressure 60kPa；
Disposably add 2% catalyst of 2- positive propoxy ethyl alcohol quality when driving for the first time, after chlorination reaction, chlorated liquid passes through
Steam 2- allyloxyethanol, heavy constituent circulating and recovering.The catalytic performance of catalyst is evaluated, experimental result is listed in table 1.
Table 1
Above description sufficiently discloses a specific embodiment of the invention.It should be pointed out that being familiar with the field
Range of any change that technical staff does a specific embodiment of the invention all without departing from claims of the present invention.
Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.
Claims (7)
1. a kind of method of 2- positive propoxy ethyl alcohol chlorination synthesis chloromethyl positive propyl ether, it is characterised in that: by 2- positive propoxy second
Chlorination reaction system is imported after the Cu-Zn/MCM-22 catalyst mixing of pure and mild support type, carries out chlorination reaction, chlorine with hydrogen chloride
Change reaction system as multitower series connection continuous production processes, after chlorination reaction, chlorated liquid steams chloroethyl positive third by distillation
Ether, catalyst, 2- positive propoxy ethyl alcohol and heavy constituent circulating and recovering.
2. the method for 2- positive propoxy ethyl alcohol chlorination synthesis chloromethyl positive propyl ether according to claim 1, it is characterised in that:
The operation temperature of the reaction is 60~130 DEG C, preferably 100~110 DEG C；Operating pressure be 20~100kPa, preferably 40~
60kPa；Disposably add the catalyst of 2- positive propoxy ethyl alcohol quality 0.5~7% when driving for the first time, preferably 1~2%, normally
Mode of operation circulating and recovering, is no longer added.
3. the method for 2- positive propoxy ethyl alcohol chlorination synthesis chloromethyl positive propyl ether according to claim 1, which is characterized in that
The Cu-Zn/MCM-22 catalyst of the support type uses base metal Cu and Zn as active component, and the weight ratio of Cu and Zn are
1:0.1-10；Preferably, the weight ratio of Cu and Zn is 1:0.3-8, with the 2- positive propoxy ethyl alcohol chlorination 2- propoxyl group second
On the basis of the total weight of the catalyst of alcohol, the content of Cu is that the content of 1-25 weight %, Zn are 5-25 weight % and carrier
Content is 50-94 weight %；Preferably, it is 5-20 weight % and carrier that the content of Cu, which is the content of 7-23 weight %, Zn,
Content is 57-88 weight %.
4. the method for 2- positive propoxy ethyl alcohol chlorination synthesis chloromethyl positive propyl ether according to claim 3, which is characterized in that
The Cu-Zn/MCM-22 catalyst of the support type the preparation method comprises the following steps: (1) in carrier MCM-22 introduce compound containing Cu with
Compound containing Zn obtains catalyst precarsor；(2) catalyst precarsor is restored under hydrogen atmosphere, obtains positive third oxygen of 2-
The catalyst of base ethyl alcohol chlorination 2- allyloxyethanol.
5. the method for 2- positive propoxy ethyl alcohol chlorination synthesis chloromethyl positive propyl ether according to claim 3, which is characterized in that
The compound containing Cu can obtain the condition of catalyst precarsor and the reduction in step (2) for carrier MCM-22 can be added
The substance of Cu can be changed into down；Under preferable case, the compound containing Cu is copper nitrate, copper chloride, stannous chloride, nitric acid Asia
At least one of copper.
6. the method for 2- positive propoxy ethyl alcohol chlorination synthesis chloromethyl positive propyl ether according to claim 4, it is characterised in that:
The compound containing Zn can under conditions of can obtaining catalyst precarsor and reduction in step (2) for carrier can be added
It is changed into the substance of Zn；Under preferable case, the compound containing Zn is zinc chloride or protochloride zinc.
7. the method for 2- positive propoxy ethyl alcohol chlorination synthesis chloromethyl positive propyl ether according to claim 1, it is characterised in that:
The regeneration method of the Cu-Zn/MCM-22 catalyst of the support type is off into ethyl acetate raw material, continues to be passed through hydrogen,
It is 100~1000h in 300 DEG C~600 DEG C of temperature, 0.8~6.0MPa of pressure, hydrogen volume air speed-1Under the conditions of to inactivation be catalyzed
Agent carry out reactor in plus hydrogen regeneration 3~for 24 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811097900.7A CN109232197A (en) | 2018-09-20 | 2018-09-20 | A kind of method of 2- positive propoxy ethyl alcohol chlorination synthesis chloromethyl positive propyl ether |
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| CN201811097900.7A CN109232197A (en) | 2018-09-20 | 2018-09-20 | A kind of method of 2- positive propoxy ethyl alcohol chlorination synthesis chloromethyl positive propyl ether |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116102408A (en) * | 2022-12-14 | 2023-05-12 | 首建科技有限公司 | Continuous synthesis process of 2-chloroethyl propyl ether and tail gas recovery process thereof |
-
2018
- 2018-09-20 CN CN201811097900.7A patent/CN109232197A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116102408A (en) * | 2022-12-14 | 2023-05-12 | 首建科技有限公司 | Continuous synthesis process of 2-chloroethyl propyl ether and tail gas recovery process thereof |
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