阅读说明：本技术 一种1，1，2，3-四氯丙烯的制备方法 (A kind of preparation method of 1,1,2,3- tetrachloropropylenes ) 是由 王金明 吕杨 于 2019-08-16 设计创作，主要内容包括：本发明公开了一种1,1,2,3-四氯丙烯的制备方法,包括：(1)制备含钕增效剂,备用；(2)制备四氯化碳混合液,备用；(3)将四氯化碳混合液及乙烯连续通入第二反应器中进行反应,得到反应产物；(4)将反应产物分离得到第一物流和第二物流,将第二物流分离后得到第三物流和第四物流；(5)将第一物流和第三物流精馏,得到1,1,1,3-四氯丙烷和回收的四氯化碳；(6)将1,1,1,3-四氯丙烷进行裂解反应,经冷凝分离尾气后得到裂解产物；(7)将裂解产物进行气相氯化,经冷凝分离尾气后得到气相氯化产物；(8)将气相氯化产物进行裂解,收集反应产物并冷凝分离尾气后,获得1,1,2,3-四氯丙烯产品。本发明具有工艺简单,效率高,成本低,绿色环保的优点。(The invention discloses a kind of preparation methods of 1,1,2,3- tetrachloropropylene, comprising: (1) synergist containing neodymium is prepared, it is spare；(2) carbon tetrachloride mixed liquor is prepared, it is spare；(3) carbon tetrachloride mixed liquor and ethylene are continuously passed through in second reactor and are reacted, obtain reaction product；(4) by isolated first logistics of reaction product and the second logistics, third―party logistics and the 4th logistics will be obtained after the second logistics separation；(5) by the first logistics and third―party logistics rectifying, the carbon tetrachloride of 1,1,1,3- tetra- chloropropane and recycling is obtained；(6) 1,1,1,3- tetra- chloropropane is subjected to cracking reaction, obtains pyrolysis product after condensing and separating tail gas；(7) pyrolysis product is subjected to gas phase chlorination, obtains gas phase chlorination product after condensing and separating tail gas；(8) gas phase chlorination product is cracked, collecting reaction product and after condensing and separating tail gas obtains 1,1,2,3- tetrachloropropylene products.The present invention has simple process, high-efficient, at low cost, environmentally protective advantage.)

1. the preparation method of 1,1,2,3- tetrachloropropylene of one kind, which comprises the following steps:

(1) by weight, 100 parts of molecular sieve is added in the first reactor, adds water and stirs to obtain slurries, adds methanol-water 150-300 parts of solution, filtering, washing filter cake to neutrality is dried, then three (1,10- phenanthroline) hexafluorophosphoric acid iron are added in roasting 0.05-0.7 parts, 200-500 parts of acetone, 0.02-0.5 parts of (III) dihydrate of hexafluoro -2,4- acetylacetone,2,4-pentanedione neodymium, bis- (double front threes Base silicon substrate) 1-8 parts of amine zinc, 5-20 parts of alkyl imidazoline phosphate, 2-6h is reacted, is filtered, drying obtains synergist containing neodymium, standby With；

(2) synergist containing neodymium, tributyl phosphate, the iron powder obtained step (1) is added in carbon tetrachloride, is uniformly mixing to obtain four Chlorination carbon mixed liquor, the content of the synergist containing neodymium is 0.5-2.5wt% in the carbon tetrachloride mixed liquor, and tributyl phosphate contains Amount is 0.5-1.0wt%, and the content of iron powder is 0.5-1.0wt%, spare；

(3) the carbon tetrachloride mixed liquor that step (2) obtains continuously is passed through in second reactor with ethylene and is reacted, it is described anti- The temperature answered is 90-120 DEG C, residence time 1-2h, system pressure 0.5-1.0Mpa, and carbon tetrachloride is with ethylene molar ratio 1-4:1 obtains the first reaction product；

(4) the first reaction product that step (3) obtains is passed through in the first membrane separator, the first logistics and second is obtained after separation Logistics, the second logistics is passed through in the second membrane separator, and third―party logistics and the 4th logistics are obtained after separation；

(5) the first logistics and third―party logistics obtained step (4) carries out rectifying, obtains 1,1,1,3- tetra- chloropropane and recycling Carbon tetrachloride；

(6) 1,1,1,3- tetra- chloropropane for obtaining step (5) carries out cracking reaction, and the temperature of the cracking reaction is 350- 500 DEG C, residence time 1-8s, pyrolysis product is obtained after condensing and separating tail gas；

(7) pyrolysis product for obtaining step (6) carries out gas phase chlorination, and the temperature of the gas phase chlorination is 140-170 DEG C, stops Time is 0.5-5.5s, and the molar ratio of chlorine and pyrolysis product is 1-4:1, and gas phase chlorination is obtained after condensing and separating tail gas and is produced Object；

(8) the gas phase chlorination product that step (7) obtains is cracked, the temperature of the cracking is 350-500 DEG C, the residence time For 2-15s, collecting reaction product condensation, rectifying obtain 1,1,2,3- tetrachloropropylene products.

2. according to claim 11, the preparation method of 1,2,3- tetrachloropropylene, which is characterized in that described in step (1) Methanol aqueous solution mass concentration be 20-40%.

3. according to claim 11, the preparation method of 1,2,3- tetrachloropropylene, which is characterized in that described in step (1) Roasting temperature be 400-600 DEG C, time 2-6h.

4. according to claim 11, the preparation method of 1,2,3- tetrachloropropylene, which is characterized in that described in step (1) Molecular sieve be ZSM-5 molecular sieve.

5. according to claim 11, the preparation method of 1,2,3- tetrachloropropylene, which is characterized in that described in step (2) Iron powder be 80-200 mesh.

6. according to claim 11, the preparation method of 1,2,3- tetrachloropropylene, which is characterized in that described in step (4) First membrane separator operating pressure is 0.5-1.0Mpa, and operation temperature is 15-40 DEG C, and the second membrane separator operating pressure is 1.0- 1.5Mpa, operation temperature are 25-60 DEG C.

7. according to claim 11, the preparation method of 1,2,3- tetrachloropropylene, which is characterized in that obtain step (4) The 4th logistics carry out rectifying, to recycle synergist containing neodymium therein.

8. according to claim 11, the preparation method of 1,2,3- tetrachloropropylene, which is characterized in that described in step (5) Rectifying temperature be 120-160 DEG C, reflux ratio 2-6.

9. according to claim 11, the preparation method of 1,2,3- tetrachloropropylene, which is characterized in that by institute in step (5) The carbon tetrachloride for the recycling stated is returned in step (2) and is recycled.

10. according to claim 11, the preparation method of 1,2,3- tetrachloropropylene, which is characterized in that described in step (7) Residence time be 0.5-1s.

Technical field

The present invention relates to the preparation methods containing chloro-alkenes, belong to organic synthesis field, and in particular to a kind of 1,1,2,3- tetrachloros The preparation method of propylene.

Background technique

1,1,2,3- tetrachloropropylene (TCP, also known as HCC-1230xa) is to prepare chemical herbicide wheat to fear the main of missible oil One of intermediate and the primary raw material of Pesticidal products tri-allate.1,1,2,3- tetrachloropropylene can also be used to produce as raw material CFC-1233xf, HFO-1234ze, HFC-245eb, HCFC-244bb, HFO-1234yf, 2,3- bis- chloro- 1,1,1 ,-trifluoropropyl Alkane (HCFC-243db) etc., wherein HFO-1234yf is new generation of environment protection fluorinated refrigerant, typical feature be have it is lower GWP value (its value is 4), the car air conditioner refrigerant for current large-scale use are a kind of potential, economical and direct Alternative solution.The production method of HFO-1234yf mainly has using trifluoro propene as raw material, by raw material of hexafluoropropene and with 1,1, 2,3- tetrachloropropylenes are the production technology of raw material, and raw materials for production of 1,1,2, the 3- tetrachloropropylene as HFO-1234yf, production Simple process, industrialized production easy to accomplish.Therefore, 1,1,2,3- tetrachloropropylene is as new generation of environment protection fluorinated refrigerant HFO- The raw materials for production of 1234yf, preparation method become research hotspot.

As China Patent Publication No. CN101754941A provides the method for the chloro- 1- propylene of preparation 1,1,2,3- tetra-, including In the gas phase, in the presence of the first catalyst, make CH₂ClCCl₂CH₂Cl dehydrochlorination is to generate including CHCl=CClCH₂Cl The first intermediate product；Make the CHCl=CClCH of first intermediate product₂At least part chlorination of Cl, with formed include CHCl₂CCl₂CH₂The second intermediate product of Cl；In the gas phase, in the presence of the second catalyst, make to produce among described second The CHCl of object₂CCl₂CH₂At least part dehydrochlorination of Cl includes CCl to be formed₂=CClCH₂The final product of Cl.Deficiency Place is that raw material is not easy to obtain, catalyst can not recycle, is at high cost.

If China Patent Publication No. CN101955414A discloses a kind of 1,1,2,3- tetrachloropropylene production technology, including 1, 2,3- trichloropropanes dehydrochlorination in the presence of aqueous slkali, obtains 2,3- dichloropropylene；2,3- dichloropropylene chlorinations generate 1, 2,2,3- tetra- chloropropanes；1,2,2,3- tetra- chloropropane dehydrochlorination in the presence of aqueous slkali, obtains 1,2,3- tri chloropropenes；1, 2,3- tri chloropropene chlorinations generate 1,1,2,2,3- pentachloropropanes；Rectification and purification resulting 1,1,2,2,3- pentachloropropane；1,1, 2,2,3- pentachloropropanes dehydrochlorination in the presence of aqueous slkali obtains 1,1,2,3- tetrachloropropylene.Shortcoming be yield it is low, Energy consumption is high, " three wastes " discharge amount is big.

It, should if China Patent Publication No. CN102911006A is related to a kind of method for preparing the low moisture content tetrachloropropylene of high-purity After rectifying column rectifying, liquid alkaline and phase transfer catalyst (quaternary ammonium salt) is added in pentachloropropane by method thereto, and reaction obtains four Chloropropene crude product controls water content in 80ppm hereinafter, then obtaining purity by rectifying column rectifying is 99.5% by dehydration More than, water content is in the low moisture content tetrachloropropylene of 30ppm high-purity below.Shortcoming be catalyst can not recycle, " three wastes " Discharge amount is big.

In conclusion currently preparing 1, the method for 1,2,3- tetrachloropropylene is although more, but there are raw materials to be not easy to obtain, yield Low, such or such problem such as energy consumption is high, catalyst can not recycle, " three wastes " discharge amount is big.Therefore, develop a green, Low cost, 1,1,2,3- tetrachloropropylene preparation method of low energy consumption meet needed for industry.

Summary of the invention

It is high-efficient in view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of simple process, it is at low cost, it is green The preparation method for 1,1,2, the 3- tetrachloropropylene that colour circle is protected, this method have great market application prospect.

The technical solution that the present invention uses to achieve the above object are as follows: a kind of preparation method of 1,1,2,3- tetrachloropropylenes, The following steps are included:

(1) by weight, 100 parts of molecular sieve is added in the first reactor, adds water and stirs to obtain slurries, adds first 150-300 parts of alcohol solution, filtering, washing filter cake to neutrality is dried, then three (1,10- phenanthroline) hexafluoro phosphorus are added in roasting It is sour iron 0.05-0.7 parts, 200-500 parts of acetone, 0.02-0.5 parts of (III) dihydrate of hexafluoro -2,4- acetylacetone,2,4-pentanedione neodymium, bis- (double Trimethyl silicon substrate) 1-8 parts of amine zinc, 5-20 parts of alkyl imidazoline phosphate, 2-6h is reacted, is filtered, drying obtains synergy containing neodymium Agent, it is spare；

(2) synergist containing neodymium, tributyl phosphate, the iron powder obtained step (1) is added in carbon tetrachloride, stirs evenly To carbon tetrachloride mixed liquor, the content of the synergist containing neodymium is 0.5-2.5wt% (wt%, quality in the carbon tetrachloride mixed liquor Percentage composition), the content of tributyl phosphate is 0.5-1.0wt%, and the content of iron powder is 0.5-1.0wt%, spare；

(3) the carbon tetrachloride mixed liquor that step (2) obtains continuously is passed through in second reactor with ethylene and is reacted, institute The temperature for stating reaction is 90-120 DEG C, residence time 1-2h, system pressure 0.5-1.0Mpa, carbon tetrachloride and ethylene molar Than obtaining the first reaction product for 1-4:1；

(4) the first reaction product that step (3) obtains is passed through in the first membrane separator, obtained after separation the first logistics and Second logistics, the second logistics is passed through in the second membrane separator, and third―party logistics and the 4th logistics are obtained after separation；

(5) the first logistics and third―party logistics obtained step (4) carries out rectifying, obtains 1,1,1,3- tetra- chloropropane (HCC-250fb) and recycling carbon tetrachloride；

(6) 1,1,1,3- tetra- chloropropane for obtaining step (5) carries out cracking reaction, and the temperature of the cracking reaction is 350-500 DEG C, residence time 1-8s, pyrolysis product is obtained after condensing and separating tail gas；

(7) pyrolysis product for obtaining step (6) carries out gas phase chlorination, and the temperature of the gas phase chlorination is 140-170 DEG C, Residence time is 0.5-5.5s, and the molar ratio of chlorine and pyrolysis product is 1-4:1, obtains gas phase chlorination after condensing and separating tail gas Product；

(8) the gas phase chlorination product that step (7) obtains is cracked, the temperature of the cracking is 350-500 DEG C, is stopped Time is 2-15s, and collecting reaction product condensation, rectifying obtain 1,1,2,3- tetrachloropropylene products.

As the preferred embodiment of the present invention, the mass concentration of methanol aqueous solution described in step (1) is 20- 40%.

As the preferred embodiment of the present invention, the temperature of roasting described in step (1) is 400-600 DEG C, and the time is 2-6h。

As the preferred embodiment of the present invention, molecular sieve described in step (1) is ZSM-5 molecular sieve.

As the preferred embodiment of the present invention, iron powder described in step (2) is 80-200 mesh.

As the preferred embodiment of the present invention, the first membrane separator operating pressure described in step (4) is 0.5- 1.0Mpa, operation temperature are 15-40 DEG C, and the second membrane separator operating pressure is 1.0-1.5Mpa, and operation temperature is 25-60 DEG C.

As the preferred embodiment of the present invention, the 4th logistics that step (4) obtain can be subjected to rectifying, to recycle wherein Synergist containing neodymium.

As the preferred embodiment of the present invention, the temperature of rectifying described in step (5) is 120-160 DEG C, reflux ratio For 2-6.

As the preferred embodiment of the present invention, the carbon tetrachloride of recycling described in step (5) can be returned to step (2) it is recycled in.

As the preferred embodiment of the present invention, the residence time described in step (7) is 0.5-1s.

During step (3) liquid phase continuous catalysis telomerisation, ethylene, carbon tetrachloride pass through respectively mass flowmenter, Constant flow pump controls flow.The reaction can be implemented in the reactor of the teflon lined equipped with blender, insertion tube of going to the bottom. Carbon tetrachloride and ethylene gas are continuously passed through in reactor by pass gaseous diffuser according to required molar ratio, and reaction solution is thick Product are drawn by the bottom insertion tube with filter cloth, continuously successively introduce two-stage difference film point by constant flow pump with certain flow velocity From being separated in device.

In step (3) liquid phase continuous catalysis telomerisation, it is catalyst, preferably iron that iron powder, iron filings or iron wire, which can be used, Powder, the iron particle size are slurried less than 200 mesh, preferably 80-200 mesh so as to mix with carbon tetrachloride, continuously enter reaction Device.In step (3) liquid phase continuous catalysis telomerisation, using tributyl phosphate as auxiliary agent.Synergist containing neodymium, tricresyl phosphate fourth Before ester, iron powder reaction start and carbon tetrachloride is configured to mixed liquor according to a certain percentage, then quantitative together to be continuously passed through instead It answers in device.

In step (3) liquid phase continuous catalysis telomerisation, HCC-250fb crude product is passed through into constant flow pump from filter first The bottom insertion tube of cloth is led in the first membrane separator with certain flow rate, operating pressure 0.5-1.0Mpa, operation temperature 15-40 DEG C, introduce flow 10-70ml/min, preferably 40ml/min.Crude product is separated into the non-pole such as carbon tetrachloride after the first membrane separator Property object (logistics 1) and HCC-250fb/ auxiliary agent/catalyst mixture (logistics 2) two streams.Wherein, logistics 1 forms (quality hundred Divide content) are as follows: 85-90% carbon tetrachloride, 5-10%HCC-250fb, 2-3% tetrachloro-ethylene, 0.5-1% carbon trichloride.Logistics 2 It forms (mass percentage) are as follows: 85-93%HCC-250fb, catalyst 1-3%, the 2.3-5% of synergist containing neodymium, 1-6% tetrachloro Change carbon, 1-3% carbon trichloride, 1,1,1,5- tetra- chloropentane 0.5-1.2%.

Logistics 2 is flowed into the second membrane separator by pump with certain flow velocity, operating pressure 1.0-1.5Mpa, operation temperature 25-60 DEG C, flow 10-40ml/min, preferably 20ml/min.Be separated into the mixtures such as HCC-250fb (logistics 3) and catalyst/ Synergist containing neodymium etc. mixtures (logistics 4) two streams.Wherein, logistics 3 forms (mass percentage) are as follows: 86-95%HCC- 250fb, 1-15% carbon tetrachloride, 1-4% carbon trichloride.Logistics 4 forms (mass percentage) are as follows: 5-10%HCC-250fb, 1-5% carbon tetrachloride, 2-3% carbon trichloride, 1,1,1,5- tetra- chloropentane 1-5%, catalyst 11-20%, the 70- of synergist containing neodymium 84%.To avoid some such as 1,1,1,5- tetra- chloropentanes of heavy by-product etc. from accumulating, logistics 4 can be subjected to continuously or periodically portion It distinguishes and removes.The material cleared out of can carry out batch fractionating, to recycle useful object therein.Logistics 1 mixed with logistics 3 after together into Enter rectifying column to be separated.

Logistics 1 and logistics 3 are mixed into rectifying column and carry out rectification under vacuum (preferably 30-200mmHg), light group isolated (predominantly carbon tetrachloride) is divided to can return to step (2) for preparing carbon tetrachloride mixed liquor, mainly containing the intermediate of HCC-250fb Logistics can be directly used for step (6) reaction.

In step (6) reaction process, mainly the intermediate containing HCC-250fb is by pump directly with certain flow rate (20- It 40ml/min) imports shell and tube reactor and carries out Pintsch process.350-500 DEG C of cracking temperature, normal pressure, residence time 1-8s is split 1 after solution, 1,3- tri chloropropene/3,3,3- tri chloropropene, after condensing and separating tail gas, obtain pyrolysis product, pyrolysis product without Purification & isolation is needed, can be directly used for step (7) reaction.

In step (7) reaction process, pyrolysis product directly imports shell and tube reactor with certain flow rate and carries out gas phase chlorine Change.140-170 DEG C of chlorination temperature, normal pressure, residence time 0.5-5.5s, chlorine and pyrolysis product molar ratio 1-4:1, chlorine with split It solves product molar ratio and exceeds 1.2:1, then 1,1,1,2,3- pentachloropropane selectively reduces obvious.Contain 1,1,1,2,3- after chlorination The mixture of pentachloropropane is condensed and separated HCl tail gas (a small amount of chlorine for retaining remaining), obtains chlorizate, chlorizate Without purification & isolation, step (8) reaction can be directly used for.

In step (8) reaction process, chlorizate directly imports shell and tube reactor with certain flow rate and carries out high anneal crack Solution.350-500 DEG C of cracking temperature, normal pressure, residence time 2-15s, 1 after cracking, 1,2,3- tetrachloropropylene mixture, through condensing After separating HCl tail gas, 1,1,2,3- tetrachloropropylenes are obtained, 1,1,2,3- tetrachloropropylene is obtained by rectifying column rectifying by dehydration Product.

To all shell and tube reactors and catalytic reactor material, there is no limit any acid corrosion-resistant material is equal in the present invention It can be used for the present invention, preferably Hastelloy, Inconel etc. commonly uses corrosion-resistant material.After HCl, tail gas and separation in the present invention HF, Cl₂It can be further recycled by compressor.

Compared with prior art, advantages of the present invention are as follows:

1, at low cost, HCC-250fb crude product through two-stage UF membrane, catalyst and synergist containing neodymium can realize recovery and Separation costs are cheap, greatly reduce production cost；

2, simple process, step (6)-(8) reaction are gas phase successive reaction, and intermediate reduces separation without purifying The use of equipment；

3, environmentally protective, greatly simplify the preparation process of 1,1,2,3- tetrachloropropylene, reduces equipment, energy makes With reducing the discharge of " three wastes ".

4, high-efficient, synergist containing neodymium significantly improves the efficiency of catalyst telomerization reaction, conversion of ethylene 99% or more, HCC-250fb selectivity is 98% or more.

Specific embodiment

Invention is further described in detail by the following examples, but the present invention is not limited in these following implementations Example.