CN105669359A - Preparation method of 1-chloropropylene - Google Patents
Preparation method of 1-chloropropylene Download PDFInfo
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- CN105669359A CN105669359A CN201610077749.5A CN201610077749A CN105669359A CN 105669359 A CN105669359 A CN 105669359A CN 201610077749 A CN201610077749 A CN 201610077749A CN 105669359 A CN105669359 A CN 105669359A
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- chloropropene
- dichloropropane
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
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Abstract
The invention provides a preparation method of 1-chloropropylene. The method comprises the following steps of 1, solvent preparing, wherein an alcohol solvent containing one or more of methyl alcohol, ethyl alcohol and isopropyl alcohol is prepared, and the mass fraction of alcohol ranges from 75% to 100%; 2, alcohol alkali elimination reacting, wherein 1,2-dichloropropane serves as the raw material and is mixed with an alcoholic solution of alkali metal hydroxides, the mass ratio of 1,2-dichloropropane to alkali metal hydroxides to the solvent is 1:(0.3-3):(0.5-5), the alkali metal hydroxides are one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide, the mixture is put into a reaction kettle for reacting, the reaction pressure ranges from 0 to 0.5 MPa (gage pressure), the reaction temperature ranges from 40 DEG C to 150 DEG C, and the reaction time ranges from 1 h to 4h; 3, product separating, wherein the reaction product is subjected to normal temperature distillation and separation, and 1-chloropropylene, 2-chloropropylene and the alcohol solvent are obtained. The method is simple in technology, low in environmental pollution, short in operation time, low in energy consumption and low in cost, the conversion rate of 1,2-dichloropropane ranges from 85% to 100%, and the selectivity of 1-chloropropylene is larger than 60%.
Description
Technical field
This Technology design is a kind of, and with 1,2-dichloropropane (by-product in production expoxy propane), as low cost initiation material, alcohol alkali eliminates dehydrochlorination and produces 1-chloropropene method, belongs to chemical field.
Background technology
1,2-dichloropropane is the Main By product in epoxychloropropane and expoxy propane industrial processes. The method of commercial production expoxy propane mainly has chlorohydrination, altogether catalysis method and isopropylbenzene catalysis method in the world, and nowadays the production capacity of expoxy propane about 48% is chlorohydrination in the world. Then by-product 1,2-dichloropropane 0.1～0.15 ton when adopting chlorohydrination often to produce 1 ton of expoxy propane when producing expoxy propane. Owing to chlorohydrination technique is simple, fixed assets investment is few, and cost of material is relatively low, and what major part enterprise of China adopted is that chlorohydrination produces expoxy propane. Within 2010, China becomes the maximum production and marketing state in the expoxy propane whole world, produces 143.76 ten thousand tons per year, by-product 1,2-dichloropropane about 200,000 tons; China's product propylene demand is still in fast development, it is predicted that the year two thousand twenty consumption figure quickly can reach 275.6 ten thousand tons, and 1,2-dichloropropane of by-product also will be more and more.
In addition, 1,2-dichloropropane or the Main By product of epoxychloropropane, the production method of industrial epoxychloropropane mainly has propylene high-temperature chloridising and acetate propylene ester process two kinds, and on our times, the epoxychloropropane of more than 90% adopts acrylonitrile-chlorinated method to produce. The amount of annual overall consumption epoxychloropropane is about 1,200,000 tons in the world at present, and epoxychloropropane by-product 1, the 2-dichloropropane often producing 1 ton is about 0.14 ton. Not yet finding suitable approach to utilize 1,2-dichloropropane at present, only have extremely least a portion of 1,2-dichloropropane to be used as solvent and fumigant at home, all the other overwhelming majority are used as fuel and burn, and cause environmental pollution and the wasting of resources. Therefore utilizing 1,2-dichloropropane rationally and effectively is a technical problem with bigger economic benefit and social benefit.
1,2-dichloropropane dehydrochlorination generates 1-chloropropene in early days with high temperature dehydrochlorination in the inorganic base aqueous solution such as potassium hydroxide, sodium hydroxide. Research concentrated on and added a small amount of organic base in inorganic base the nineties in 20th century: (C8H17)3The Organic substances such as N (JP. day JP 17139,1990), epoxy resin-ninth of the ten Heavenly Stems phenol mixture, dodecanol (JP. day JP 22302,1979) improve reaction efficiency. This kind of typically causing substantial amounts of chlorinated organics waste water with aqueous alkali dehydrochlorination, the process to this waste water is costly and time-consuming. Japan Patent report (JP, day JP 22302,1979) 1,2-dichloropropane passes under nitrogen protection equipped with BiMo12PO40/Al2O3The fixed bed reactors of heteropolyacid catalyst, under the effect of catalyst, dehydrochlorination generates 1-chloropropene, and reaction temperature is 350 DEG C, and the selectivity of 1-chloropropene is 90.1%. This patent also reports that 1,2-dichloropropane is at metal fluoride (AlF3、MgF2、CaF2) etc. solid super acid catalyst effect under dehydrochlorination generate 1-chloropropene, reaction temperature is 250～300 DEG C, mainly generates 1-chloropropene, 2-chloropropene, chlorallylene and propylene, thus has relatively low 1-chloropropene selectivity. Domestic and international research worker (JP. day JP 22828,1989) also utilizes the laser of different wave length to irradiate 1,2-dichloropropane so that it is optionally dehydrochlorination. Using KrF laser (λ=249nm) to irradiate 1,2-dichloropropane, quick dehydrochlorination at 500 DEG C, the conversion ratio of 1,2-dichloropropane is 70%, and the selectivity of 1-chloropropene is lower than 20%.
Summary of the invention
It is an object of the invention to provide a kind of low stain, low energy consumption, the method for preparing 1-chloropropene at low cost, its basic concept is: utilize the epichlorohydrin by-products 1 of low cost, 2-dichloropropane is raw material, it is mixed with alkali metal hydroxide alcoholic solution, eliminate reaction dehydrochlorination by alcohol alkali and generate 1-chloropropene, by-product 2-chloropropene simultaneously.
To achieve these goals, technical scheme is as follows:
The preparation method that the invention provides a kind of 1-chloropropene, it is characterised in that comprise the following steps:
1) preparation of solvent: preparation is containing the alcoholic solvent of one or more than one in methanol, ethanol, isopropanol, and its mass fraction is 75～100%. Preferably, alcoholic solvent contains methanol and/or ethanol, its preferred content respectively: the methanol of 85～100%wt, the ethanol of 85～100%wt or the methanol of 80～100%wt and ethanol mixed alcohol solvent.
2) with 1, the alcohol alkali that 2-dichloropropane is raw material eliminates reaction: with 1,2-dichloropropane is raw material, it is mixed with alkali metal hydroxide alcoholic solution, wherein, the mass ratio of 1,2-dichloropropane, alkali metal hydroxide and solvent is 1:0.3～3:0.5～5, and described alkali metal hydroxide is one or more in Lithium hydrate, sodium hydroxide, potassium hydroxide; Being put by mixture and react in a kettle., reaction pressure 0～0.5MPa (gauge pressure), reaction temperature is 40～150 DEG C, and the response time is 0.01h～4h.
In step 2) in, it is preferable that the mass ratio of described 1,2-dichloropropane, alkali metal hydroxide and solvent is 1:0.3～2.5:0.5～4.
In step 2) in, it is preferable that described alkali metal hydroxide is sodium hydroxide and/or potassium hydroxide.
In step 2) in, it is preferable that described reaction temperature is 70～120 DEG C.
In step 2) in, it is preferable that the described response time is 0.01h～3h.
3) product separates: product, through room temperature rectification, separates and obtains 1-chloropropene, 2-chloropropene and alcoholic solvent. Wherein alcoholic solvent is reusable.
Invention achieves following beneficial effect:
Using 1-chloropropene preparation method provided by the invention, the conversion ratio of 1,2-dichloropropane is between 85%～100%, and the selectivity of 1-chloropropene is more than 60%; Additionally, this method technique is simple; Avoid a large amount of chlorination organic wastewaters typically carried out in aqueous alkali because of dehydrochlorination steps and produce, reduce contaminated environment; Operating time is short, energy consumption is low, cost is low.
Detailed description of the invention
In order to illustrate technical scheme and technical purpose, below in conjunction with detailed description of the invention, the present invention is described further.
Embodiment 1
Adding 9kg absolute methanol, 1kg water in a kettle., obtain the methanol aqueous solution that quality is 90%, be simultaneously introduced sodium hydroxide 7.5kg, raw material 1,2-dichloropropane 10kg, namely the mass ratio of 1,2-dichloropropane, alkali metal hydroxide and solvent is 1:0.75:1. Water bath heating temperature be 80 DEG C, pressure is 0.1MPa in reactor when reaction 0.5h, 1,2-dichloropropane conversion ratio be 96.3%, the selectivity of 1-chloropropene is 62.8%.
Embodiment 2
Add 21.4kg dehydrated alcohol, 0.6kg water in a kettle., obtain the ethanol water that quality is 95%, it is simultaneously introduced potassium hydroxide 5.2kg, raw material 1,2-dichloropropane 11kg, namely the mass ratio of 1,2-dichloropropane, alkali metal hydroxide and solvent is 1:0.47:2. Oil bath heating-up temperature be 120 DEG C, pressure is 0.5MPa in reactor when reaction 0.2h, 1,2-dichloropropane conversion ratio be 97.3%, the selectivity of 1-chloropropene is 66.8%.
Embodiment 3
Adding 12kg absolute methanol, 2kg water, 2kg dehydrated alcohol in a kettle., be simultaneously introduced Lithium hydrate 18.2kg, raw material 1,2-dichloropropane 20kg after to be mixed, namely the mass ratio of 1,2-dichloropropane, alkali metal hydroxide and solvent is 1:0.91:0.7. Water bath heating temperature be 80 DEG C, pressure is 0.2MPa in reactor when reaction 1h, 1,2-dichloropropane conversion ratio be 93.1%, the selectivity of 1-chloropropene is 63.2%.
Embodiment 4
Add 20kg absolute methanol, 4kg water, 2kg dehydrated alcohol in a kettle., sodium hydroxide 7.7kg, potassium hydroxide 0.5kg, raw material 1,2-dichloropropane 20kg it is simultaneously introduced after to be mixed, namely the mass ratio of 1,2-dichloropropane, alkali metal hydroxide and solvent is 1:0.41:1.3. Water bath heating temperature be 85 DEG C, pressure is 0.2MPa in reactor when reaction 0.5h, 1,2-dichloropropane conversion ratio be 97.1%, the selectivity of 1-chloropropene is 65.1%.
Embodiment 5
Add 22kg isopropanol, 4.6kg water in a kettle., obtain the isopropanol water solution that quality is 95.2%, it is simultaneously introduced Lithium hydrate 10kg, potassium hydroxide 5kg, raw material 1,2-dichloropropane 10kg, namely the mass ratio of 1,2-dichloropropane, alkali metal hydroxide and solvent is 1:1.5:2.46. Oil bath heating-up temperature be 100 DEG C, pressure is 0.3MPa in reactor when reaction 0.5h, 1,2-dichloropropane conversion ratio be 93.3%, the selectivity of 1-chloropropene is 61.3%.
Embodiment 6
Adding 15kg isopropanol, 3kg absolute methanol, 5kg water in a kettle., be simultaneously introduced Lithium hydrate 10kg, sodium hydroxide 2kg, raw material 1,2-dichloropropane 10kg, namely the mass ratio of 1,2-dichloropropane, alkali metal hydroxide and solvent is 1:1.2:2.3. Oil bath heating-up temperature be 100 DEG C, pressure is 0.3MPa in reactor when reaction 0.5h, 1,2-dichloropropane conversion ratio be 92.3%, the selectivity of 1-chloropropene is 63.1%.
The ultimate principle of the present invention, principal character and advantages of the present invention have more than been shown and described. Skilled person will appreciate that of the industry; the present invention is not restricted to the described embodiments; described in above-described embodiment and description is that principles of the invention is described; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and claimed scope is defined by appending claims, description and equivalent thereof.
Claims (10)
1. the preparation method of a 1-chloropropene, it is characterised in that comprise the following steps:
1) preparation of solvent: preparation is containing the alcoholic solvent of one or more than one in methanol, ethanol, isopropanol, and its mass fraction is 75～100%;
2) with 1, the alcohol alkali that 2-dichloropropane is raw material eliminates reaction: with 1,2-dichloropropane is raw material, it is mixed with alkali metal hydroxide alcoholic solution, wherein, the mass ratio of 1,2-dichloropropane, alkali metal hydroxide and solvent is 1:0.3～3:0.5～5, and described alkali metal hydroxide is one or more in Lithium hydrate, sodium hydroxide, potassium hydroxide; During reaction, gauge ranges for 0～0.5MPa, and reaction temperature is 40～150 DEG C, and the response time is 0.01h～4h;
3) product separates: product, through room temperature rectification, separates and obtains 1-chloropropene, 2-chloropropene and alcoholic solvent.
2. the preparation method of a kind of 1-chloropropene as claimed in claim 1, it is characterised in that step 1) described in alcoholic solvent contain methanol and/or ethanol.
3. the preparation method of a kind of 1-chloropropene as claimed in claim 2, it is characterised in that described alcoholic solvent contains the methanol of 85～100%wt or the ethanol of 85～100%wt.
4. the preparation method of a kind of 1-chloropropene as claimed in claim 2, it is characterised in that described alcoholic solvent contains methanol and the ethanol of 80～100%wt.
5. the preparation method of a kind of 1-chloropropene as described in claim 1 or 2, it is characterised in that step 2) in, the mass ratio of described 1,2-dichloropropane, alkali metal hydroxide and solvent is 1:0.3～2.5:0.5～4.
6. the preparation method of a kind of 1-chloropropene as claimed in claim 5, it is characterised in that step 2) in, described alkali metal hydroxide is sodium hydroxide and/or potassium hydroxide.
7. the preparation method of a kind of 1-chloropropene as described in claim 1 or 6, it is characterised in that step 2) in, described reaction temperature is 70～120 DEG C.
8. the preparation method of a kind of 1-chloropropene as claimed in claim 7, it is characterised in that step 2) in, the described response time is 0.01h～3h.
9. the preparation method of a kind of 1-chloropropene as claimed in claim 1, it is characterised in that step 2) in, described alkali metal hydroxide is sodium hydroxide and/or potassium hydroxide.
10. the preparation method of a kind of 1-chloropropene as claimed in claim 1, it is characterised in that step 2) in, the described response time is 0.01h～3h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610077749.5A CN105669359A (en) | 2016-02-03 | 2016-02-03 | Preparation method of 1-chloropropylene |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610077749.5A CN105669359A (en) | 2016-02-03 | 2016-02-03 | Preparation method of 1-chloropropylene |
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| CN105669359A true CN105669359A (en) | 2016-06-15 |
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| CN201610077749.5A Pending CN105669359A (en) | 2016-02-03 | 2016-02-03 | Preparation method of 1-chloropropylene |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019153774A1 (en) * | 2018-02-09 | 2019-08-15 | 浙江大学 | Method for preparing 2-methylallyl chloride from 1,2-dichlorotert-butane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2378859A (en) * | 1941-08-08 | 1945-06-19 | Distillers Co Yeast Ltd | Splitting-off of hydrogen halide from halogenated hydrocarbons |
| CN102056875A (en) * | 2008-04-09 | 2011-05-11 | 墨西哥化学阿玛科股份有限公司 | Process for preparing 1,1,1-trifluoro-2,3-dichloropropane |
-
2016
- 2016-02-03 CN CN201610077749.5A patent/CN105669359A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2378859A (en) * | 1941-08-08 | 1945-06-19 | Distillers Co Yeast Ltd | Splitting-off of hydrogen halide from halogenated hydrocarbons |
| CN102056875A (en) * | 2008-04-09 | 2011-05-11 | 墨西哥化学阿玛科股份有限公司 | Process for preparing 1,1,1-trifluoro-2,3-dichloropropane |
Non-Patent Citations (2)
| Title |
|---|
| 程能林编著: "《溶剂手册》", 30 November 2002 * |
| 赵新堂等: "1,1,2,3-四氯丙烯制备技术研究进展", 《浙江化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019153774A1 (en) * | 2018-02-09 | 2019-08-15 | 浙江大学 | Method for preparing 2-methylallyl chloride from 1,2-dichlorotert-butane |
| JP2021513537A (en) * | 2018-02-09 | 2021-05-27 | 浙江大学Ｚｈｅｊｉａｎｇ Ｕｎｉｖｅｒｓｉｔｙ | Method for Producing 2-Methylallyl Chloride from 1,2-Dichloro-t-Butane |
| JP7029739B2 (en) | 2018-02-09 | 2022-03-04 | 浙江大学 | Method for Producing 2-Methylallyl Chloride from 1,2-Dichloro-t-Butane |
| US11319267B2 (en) | 2018-02-09 | 2022-05-03 | Zhejiang University | Method for preparing 2-methylallyl chloride from 1,2-dichloroisobutane |
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