CN106316810B - A kind of preparation method improving 1,1,3- trichloroacetone synthesis yields - Google Patents
A kind of preparation method improving 1,1,3- trichloroacetone synthesis yields Download PDFInfo
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- CN106316810B CN106316810B CN201610590411.XA CN201610590411A CN106316810B CN 106316810 B CN106316810 B CN 106316810B CN 201610590411 A CN201610590411 A CN 201610590411A CN 106316810 B CN106316810 B CN 106316810B
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- 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
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- 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 present invention discloses a kind of preparation method improving 1,1,3 trichloroacetone synthesis yield, belongs to technical field of organic synthesis.This method is to prepare support type amines catalyst first, then a certain amount of ultrapure acetone is added into reactor, support type amines catalyst is slowly added under stirring, after support type amines catalyst and ultrapure acetone are sufficiently mixed uniformly, increase temperature, the temperature in reactor is controlled at 25~30 DEG C, starts to be passed through chlorine into reactor under agitation, after being passed through chlorine, controlling reaction temperature is constant, 1,1,3 trichloroacetone is made after continuing stirring, insulation reaction 2h.The present invention uses support type amines catalyst, not only increase the contact area with reactant, improve the selectivity of 1,1,3 trichloroacetones, and further improve 1, the yield of 1,3 trichloroacetone, support type amines catalyst of the present invention, load by covalent bond connection type is secured, and catalyst can be recycled for multiple times.
Description
Technical field：
The invention belongs to technical field of organic synthesis, and in particular to a kind of system improving 1,1,3- trichloroacetone synthesis yield
Preparation Method.
Background technology：
1,1,3- trichloroacetone is the important intermediate for producing folic acid, and folic acid is also Vitamin B9, is a kind of water soluble vitamin
Raw element, it is object necessary to necessary material and body cell growth and breeding of the human body when using sugar and amino acid
Matter.There are many food containing folic acid, but since natural folic acid is extremely unstable, is easily influenced and occurred by factors such as sunlight, temperature
Oxidation, so folic acid that human body can really be obtained from food and few；And synthesize folic acid can stable for extended periods of time, Yi Beiren
Body absorbs and availability is higher.
Currently, 1,1,3- trichloroacetone main method of domestic production is acetone direct chlorination method, the production process of this method
In catalyst need not be added, but the production cycle needs 48h, the poor selectivity of reaction to lead to the yield of 1,1,3- trichloroacetone
Low, the content of 1,1,3- trichloroacetone only accounts for 17% or so in the reaction product, and causes to produce due to its difficulty isolates and purifies
Of high cost, product purity is low.Chinese patent CN90105852.1 discloses a kind of 1,1,3- trichloroacetone of chlorinated with chlorine method synthesis,
Make catalyst using single diethylamine or triethylamine in the synthetic method, although improving 1, the selection of 1,3- trichloroacetone
Property, but the yield of 1,1,3- trichloroacetone is still relatively low.Currently, the cost of domestic production folic acid is higher, yield is also difficult to
To raising, these problems cause folic acid product to lose corresponding competitiveness in the international market.Therefore, in order to solve 1,1,3-
Trichloroacetone series of technical present in large-scale industrial production, the present invention propose a kind of 1,1,3- trichlorine third
The novel method for synthesizing of ketone, the object of the present invention is to provide it is a kind of it is easy to operate, reaction time is short, selectivity is good, high income and
The good synthetic method of purity.
Invention content：
The present invention for present in existing 1,1,3- trichloroacetones synthesis technology reaction time length, poor selectivity, yield
Low many technical problems provide a kind of preparation method improving 1,1,3- trichloroacetone synthesis yield.The method of the present invention is from urging
Agent angle is set out, and uses the good support type amines catalyst of selectivity instead, and the preparation method of such catalyst is to use infusion process
Amine organic compound is loaded on nanometer porous silicon, support type amines catalyst is prepared into, porous silica material generally selects
With mesoporous material, pore diameter range in 2~50nm, such as：SBA-15, MCM-41 etc..Reaction raw materials select ultrapure acetone, certain
Working condition under, synthesize 1,1,3- trichloroacetones.
A kind of preparation method improving 1,1,3- trichloroacetone synthesis yield provided by the invention, specific reaction equation is such as
Shown in lower：
A kind of preparation method improving 1,1,3- trichloroacetone synthesis yields provided by the present invention is as follows：
(1) support type amines catalyst is prepared：
1. activated 120mg molecular sieve SBA-15s are added into the eggplant type bottle of 50mL, and (concentrated hydrochloric acid activation modification is mesoporous
Molecular sieve), eggplant type bottle is put into oil bath pan heating, controls the temperature in oil bath pan at 120 DEG C, lasting stirring keeps the temperature activation 6h,
Molecular sieve SBA-15 after being activated.
2. under N2 protections, gamma-aminopropyl-triethoxy-silane 12mg (structural formulas are added into the round-bottomed flask of 50mL：) and deoxygenation absolute ethyl alcohol 5mL, or be added γ-aminoethyl amino propyl trimethoxy silane 12mg (structures
Formula：) and deoxygenation absolute ethyl alcohol 5mL, stir to obtain gamma-aminopropyl-triethoxy-silane
With deoxygenation absolute ethyl alcohol or the mixed solution of γ-aminoethyl amino propyl trimethoxy silane and deoxygenation absolute ethyl alcohol.
3. in N2Under protection, under stirring by step 2. described in mixed solution be slowly added to what 1. step obtained
In molecular sieve SBA-15 after the activation, control temperature is sufficiently stirred, insulation reaction 20h at 80 DEG C；It, will after heat preservation
The solid being obtained by filtration obtains support type amines catalyst after fully being washed with ether, will not load to molecular sieve mesopore surfaces
Organic component washes clean, dry, the support type amines catalyst to be synthesized 1,1,3- trichloroacetone react when use.
(2) 1,1,3- trichloroacetones are synthesized：
1. a certain amount of ultrapure acetone is added into reactor, be slowly added to that step (1) obtains under stirring is negative
Load type amines catalyst, the addition of the support type amines catalyst are 5~10wt% of ultrapure acetone, wait for support type amine
After catalyst is sufficiently mixed uniformly with ultrapure acetone, temperature is increased, controls the temperature in reactor at 25~30 DEG C.
2. when the temperature in reactor is stablized at 25~30 DEG C, start to be passed through chlorine into reactor under agitation
The molar ratio of gas, the ultrapure acetone and the chlorine is 1:3, after being passed through chlorine, controlling reaction temperature is constant, continues to stir
It mixes, 1,1,3- trichloroacetones is made after insulation reaction 2h.
According to the difference for testing each elementary reaction speed, logical chlorine process is divided into three phases：Preceding 1~2h is that reaction is first
Phase；2~6h is reaction mid-term；6~18h is the reaction later stage.In its initial reaction stage and later stage, reaction speed is slower, so logical
The speed for entering chlorine is also relatively slow, controls in 6~8L/h；And in the reaction the phase when, reaction speed is very fast, so needing to increase
It is passed through the speed of chlorine, is controlled in 30~32L/h.According to the difference of each elementary reaction speed, we are logical by controlling each stage
The speed for entering chlorine can reach the time for shortening and being passed through chlorine, inhibit the generation of side reaction, improve the choosing of 1,1,3- trichloroacetones
Selecting property.
The present invention has following technical characterstic：
(1) compared with original single catalyst, support type amines catalyst is used in this experiment instead, is not only increased and is reacted
The contact area of object, improves the selectivity of 1,1,3- trichloroacetones, and further improves 1, the yield of 1,3- trichloroacetone；
(2) for porous silicon loaded catalyst, which stablizes the catalyst used, easily stores, to behaviour
Make workshop and is not necessarily to excessively high requirement；
(3) 1,1,3- trichloroacetone synthetic reaction condition is mild, typically carries out, avoids under 25~30 DEG C, normal pressure
The problem of reaction under high pressure causes too big burden to reaction kettle；
(4) the support type amines catalyst that the present invention uses, the load by covalent bond connection type is secured, and catalyst can
It is recycled for multiple times.
Specific implementation mode：
Embodiment 1：232.0g (4.0mol) ultrapure acetone is added into the reaction bulb of 1000mL, under stirring slowly
The more amines catalysts of 11.6g support types are added, temperature is increased with water-bath after stirring evenly, wait for that the temperature in reaction bulb is stablized
At 25 DEG C, starting to be passed through chlorine progress chlorination reaction into reaction bulb, the speed that 1~2h of initial reaction stage leads to chlorine is 6.0L/h,
The speed that 2~6h of mid-term leads to chlorine is 30.0L/h, and the speed that 6~20h of later stage leads to chlorine is 6.0L/h.To the end of logical chlorine reacts
Afterwards, it keeps temperature-resistant in reaction bulb, continues 1~2h of stirring.After insulation reaction, the temperature in holding reaction bulb is not
Become, a certain amount of special solvent is added into reaction bulb, persistently stirs 1h.After stirring, by obtained mixture ice
Water reduces temperature to 10 DEG C, crystallisation by cooling, the solid filtered, i.e., 1,1,3- trichloroacetone product.Using special solvent into
Row crystallization and purification, product purity 90.7%, yield 46.8%.
Embodiment 2：232.0g (4.0mol) ultrapure acetone is added into the reaction bulb of 1000mL, under stirring slowly
The more amines catalysts of 14.0g support types are added, temperature is increased with water-bath after stirring evenly, wait for that the temperature in reaction bulb is stablized
At 30 DEG C, starting to be passed through chlorine progress chlorination reaction into reaction bulb, the speed that 1~2h of initial reaction stage leads to chlorine is 6.0L/h,
The speed that 2~6h of mid-term leads to chlorine is 32.0L/h, and the speed that 6~18h of later stage leads to chlorine is 6.0L/h.To the end of logical chlorine reacts
Afterwards, it keeps temperature-resistant in reaction bulb, continues 1~2h of stirring.After insulation reaction, the temperature in holding reaction bulb is not
Become, a certain amount of special solvent is added into reaction bulb, persistently stirs 1h.After stirring, by obtained mixture ice
Water reduces temperature to 10 DEG C, crystallisation by cooling, the solid filtered, i.e., 1,1,3- trichloroacetone product.Using special solvent into
Row crystallization and purification, product purity 94.3%, yield 47.4%.
Embodiment 3：232.0g (4.0mol) ultrapure acetone is added into the reaction bulb of 1000mL, under stirring slowly
The more amines catalysts of 21.0g support types are added, temperature is increased with water-bath after stirring evenly, wait for that the temperature in reaction bulb is stablized
At 30 DEG C, starting to be passed through chlorine progress chlorination reaction into reaction bulb, the speed that 1~2h of initial reaction stage leads to chlorine is 8.0L/h,
The speed that 2~6h of mid-term leads to chlorine is 28.0L/h, and the speed that 6~18h of later stage leads to chlorine is 8.0L/h.To the end of logical chlorine reacts
Afterwards, it keeps temperature-resistant in reaction bulb, continues 1~2h of stirring.After insulation reaction, the temperature in holding reaction bulb is not
Become, a certain amount of special solvent is added into reaction bulb, persistently stirs 1h.After stirring, by obtained mixture ice
Water reduces temperature to 10 DEG C, crystallisation by cooling, the solid filtered, i.e., 1,1,3- trichloroacetone product.Using special solvent into
Row crystallization and purification, product purity 90%, yield 48.1%.
Claims (1)
1. a kind of preparation method improving 1,1,3- trichloroacetone synthesis yield, it is characterised in that this method is as follows：
(1) support type amines catalyst is prepared：
1. activated 120mg molecular sieve SBA-15s are added into the eggplant type bottle of 50mL, the molecular sieve SBA-15 is dense salt
Eggplant type bottle is put into oil bath pan heating, controls the temperature in oil bath pan at 120 DEG C, persistently stir by acid activation modified mesoporous molecular sieve
It mixes, heat preservation activation 6h, the molecular sieve SBA-15 after being activated；
2. under N2 protections, gamma-aminopropyl-triethoxy-silane 12mg and the anhydrous second of deoxygenation are added into the round-bottomed flask of 50mL
γ-aminoethyl amino propyl trimethoxy silane 12mg and deoxygenation absolute ethyl alcohol 5mL is added in alcohol 5mL, stirs to obtain
The mixed solution of gamma-aminopropyl-triethoxy-silane or γ-aminoethyl amino propyl trimethoxy silane and deoxygenation absolute ethyl alcohol；
3. in N2Under protection, under stirring by step 2. described in mixed solution be slowly added to described in 1. step obtains
In molecular sieve SBA-15 after activation, control temperature is sufficiently stirred, insulation reaction 20h at 80 DEG C；After heat preservation, it will filter
Obtained solid obtains support type amines catalyst after fully being washed with ether；
(2) 1,1,3- trichloroacetones are synthesized：
1. a certain amount of ultrapure acetone is added into reactor, the support type that step (1) obtains is slowly added under stirring
Amines catalyst, the addition of the support type amines catalyst are 5~10wt% of ultrapure acetone, wait for support type amines catalysis
After agent is sufficiently mixed uniformly with ultrapure acetone, temperature is increased, controls the temperature in reactor at 25~30 DEG C；
2. when the temperature in the reactor is stablized at 25~30 DEG C, start to be passed through chlorine into reactor under agitation
The molar ratio of gas, the ultrapure acetone and the chlorine is 1:3, after being passed through chlorine, controlling reaction temperature is constant, continues to stir
It mixes, 1,1,3- trichloroacetones is made after insulation reaction 2h.
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| CN108727173B (en) * | 2017-04-19 | 2021-01-01 | 江西天新药业股份有限公司 | Method for preparing 1,1, 3-trichloroacetone |
| CN106946676B (en) * | 2017-04-28 | 2020-07-17 | 常州市新鸿医药化工技术有限公司 | Purification method of high-purity trichloroacetone for preparing folic acid |
| CN113548949B (en) * | 2021-08-27 | 2023-04-18 | 常州新东化工发展有限公司 | Production method of 1,1,3-trichloroacetone |
| CN115784861A (en) * | 2022-11-04 | 2023-03-14 | 南通市常海食品添加剂有限公司 | Method for producing trichloroacetone by continuous microchannel technology |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0234503B1 (en) * | 1986-02-20 | 1990-09-12 | Wacker-Chemie GmbH | Process for the preparation of 1,1,3-trichloroacetone |
| CN1047853A (en) * | 1990-07-10 | 1990-12-19 | 中国科学院成都有机化学研究所 | 1,1,3-trichloroacetone preparation method |
| CN101497024A (en) * | 2009-01-15 | 2009-08-05 | 华东理工大学 | CO2 sorbent and preparation method thereof |
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2016
- 2016-07-25 CN CN201610590411.XA patent/CN106316810B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0234503B1 (en) * | 1986-02-20 | 1990-09-12 | Wacker-Chemie GmbH | Process for the preparation of 1,1,3-trichloroacetone |
| CN1047853A (en) * | 1990-07-10 | 1990-12-19 | 中国科学院成都有机化学研究所 | 1,1,3-trichloroacetone preparation method |
| CN101497024A (en) * | 2009-01-15 | 2009-08-05 | 华东理工大学 | CO2 sorbent and preparation method thereof |
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Effective date of registration: 20201225 Address after: Room 602, unit 1, building 9, Hexi community, Hexi District, Tanzhong West Road, Liunan District, Liuzhou City, Guangxi Zhuang Autonomous Region Patentee after: Ye Xiulan Address before: 243000 No.5 workshop in demonstration park of undertaking industrial transfer in Maanshan City, Anhui Province Patentee before: ANHUI QIANHE NEW MATERIAL SCIENCE & TECHNOLOGY DEVELOPMENT Co.,Ltd. |
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