Method for preparing 1,1,2,3-tetrachloropropene by mixing 1,3-dichloropropene and 3-chloropropene

Abstract

The present application relates to a method for producing 1,1,2,3-tetrachloropropane from a mixture of 1,3-dichloropropene and 3-chloropropene. The method comprises the following steps: a) subjecting a raw material comprising a mixture of 1,3-dichloropropene and 3-chloropropene, and Cl2 to a first chlorine addition reaction at a temperature T1, so as to obtain a first product; b) subjecting the first product to a first chlorine substitution reaction under UV at a temperature T2, so as to obtain a second product; and c) subjecting the second product to a second chlorine addition reaction at a temperature T3, so as to obtain a third product, which comprises 1,1,2,3-tetrachloropropane. A second aspect of the present application relates to a method for producing 1,1,2,3-tetrachloropropene from a mixture of 1,3-dichloropropene and 3-chloropropene. The present application further relates to a 1,1,2,3-tetrachloropropane product and a 1,1,2,3-tetrachloropropene product produced by using the methods described in the first and second aspects.

Description

A process for the preparation of 1,1,2,3-tetrachloropropene from a mixture of 1,3-dichloropropene and 3-chloropropene TECHNICAL FIELD

[0001] The present invention belongs to the field of fine chemical organic synthesis, and relates to a process for the preparation of 1,1,2,3-tetrachloropropene from a crude dichloropropene feed stream comprising 1,3-dichloropropene and 3-chloropropene. BACKGROUND

[0002] 1,1,2,3-tetrachloro-propene (HCC-1230xa or TCP for short, CAS No.: 10436-39-2) is an important chemical intermediate, which can be used to produce herbicide trichloroalkyl diisopropyl thiocarbamate, commonly known as "Lasso", or as a starting material to produce fourth-generation environmentally friendly refrigerant 2,3,3,3-tetrafluoropropene (HFO-1234yf), and can also be used as a monomer component to produce various fluorocarbon materials and various polymers. With the continuous expansion of the application field and demand of 1,1,2,3-tetrachloropropene, the optimization and development of its preparation process have become a difficult problem that researchers need to further overcome, especially the need to produce such compounds by simplified process.

[0003] Currently, according to the classification of starting materials, the synthesis routes mainly include: (1) using carbon tetrachloride, ethylene and chlorine as raw materials in the presence of a free radical initiator to prepare 1,1,2,3-tetrachloropropene through free radical addition, chlorination, dehydrochlorination and isomerization; (2) using tetrachloroethylene and dichloromethane as raw materials to prepare 1,1,1,2,2,3-hexachloropropane through free radical coupling, and then eliminating chlorine to obtain 1,1,2,3-tetrachloropropene; (3) 1,2,3-trichloropropane is an artificially synthesized organic solvent, which is a main by-product of the production of epichlorohydrin. Industrially, it is generally used as a raw material to synthesize 2,3-dichloropropene through dehydrochlorination reaction, and then to synthesize 1,2,2,3-tetrachloropropane after chlorination. However, the dehydrochlorination reaction conversion rate of 1,2,2,3-tetrachloropropane is low, and the product selectivity is poor, which affects the yield of 1,1,2,3-tetrachloropropene synthesis and causes waste of raw materials.

[0004] From the current preparation methods, there are generally problems such as long synthesis route, low production efficiency, more by-products and "three wastes", harsh operating conditions, high cost, and the need for a large number of separation and purification equipment.

[0005] Patent CN106458799B discloses a method for producing 1,1,2,3-tetrachloropropene with high yield, which is a known four-step method, including the following steps:

[0006] (1) CCl4 + CH2=CH2→ CCl3-CH2-CH2Cl (HCC-250fb);

[0007] (2) CCl3-CH2-CH2Cl (HCC-250fb) → CCl2=CH-CH2Cl (HCC-1240za) + HCl;

[0008] (3) CCl2=CH-CH2Cl (HCC-1240za) + Cl2→ CCl3-CHCl-CH2Cl (HCC-240db) and

[0009] (4) CCl3-CHCl-CH2Cl (HCC-240db) → CCl2=CCl-CH2Cl (HCC-1230xa) + HCl.

[0010] The patent mentions that the amount of HCC-1240za and HCC-250fb in the starting material has a significant impact on the conversion of HCC-240db to HCC-1230xa in step (4). Using crude HCC-240db containing HCC-1240za and HCC-250fb with a concentration of less than 0.5% by weight directly as the starting material for step 4, an 85% to 98% yield of HCC-1230xa can be obtained. This process has multiple synthesis steps, requires carcinogenic and teratogenic raw material CCl4, has high risk, causes serious environmental pollution, and is limited by the relevant regulations of the "China Carbon Tetrachloride Production and Processing Aid Industry Elimination Plan".

[0011] Patent CN107285992B discloses a method for preparing 1,1,2,3-tetrachloropropene by free radical coupling of 1,2-dichloroethylene and chloroform as starting materials, in the presence of anhydrous aluminum chloride, anhydrous ferric chloride, and anhydrous zinc chloride catalyst, followed by gas-phase dehydrochlorination using AlCl3 / C, NiCl2 / C, and FeCl3 / C catalysts. Chloroform is a chemical that is easy to make and carcinogenic, and has high environmental pollution and occupational health hazards. Although this method has fewer reaction steps, the amount of metal catalysts is large, and residual metal ions can cause HCC-1230xa to decompose. The high-temperature gas-phase dehydrochlorination method has high energy consumption. The free radical reaction easily produces by-products, which need to be quenched with water, resulting in high acidity and water content in the product, making purification difficult in the entire process, and complicating storage and transportation.

[0012] Patent CN104817425A discloses a method for synthesizing 1,1,2,3-tetrachloropropene. The reaction steps include: (1) adding catalyst, auxiliary and solvent acetonitrile in a pressure reactor under nitrogen protection, continuously stirring for 1 to 2 hours, then adding tetrachloroethylene and dichloromethane at 120 to 130°C under nitrogen atmosphere protection, stirring for 14 to 16 hours, and obtaining 1,1,1,2,2,3-hexachloropropane by reduced pressure distillation; (2) adding the obtained 1,1,1,2,2,3-hexachloropropane, activated zinc powder with hydrochloric acid and dioxane into a closed container at 45°C under nitrogen atmosphere protection, stirring for 48 to 50 hours, and obtaining 1,1,2,3-tetrachloropropene by reduced pressure distillation. Although the method has short reaction steps, it has long reaction time, low production efficiency, large amount of reagents, large amount of "three wastes", complex operation and high cost, which is not conducive to large-scale industrial production.

[0013] Patent application CN102911006A relates to a method for preparing high-purity low-water tetrachloropropene. The method includes distilling pentachloropropane through a rectifying column, adding liquid alkali and phase transfer catalyst (quaternary ammonium salt) into the column, obtaining tetrachloropropene crude product by reaction, controlling water content below 80 ppm after water removal, and obtaining high-purity low-water tetrachloropropene with purity above 99.5% and water content below 30 ppm by distillation through a rectifying column. The disadvantage is that the catalyst cannot be recovered and the amount of "three wastes" discharged is large.

[0014] CN101955414A discloses a production process of 1,1,2,3-tetrachloropropene, which includes dehydrochlorination of 1,2,3-trichloropropane in the presence of alkali solution to obtain 2,3-dichloropropene; chlorination of 2,3-dichloropropene to generate 1,2,2,3-tetrachloropropane; dehydrochlorination of 1,2,2,3-tetrachloropropane in the presence of alkali solution to obtain 1,2,3-trichloropropene; chlorination of 1,2,3-trichloropropene to generate 1,1,2,2,3-pentachloropropane; rectification and purification of the obtained 1,1,2,2,3-pentachloropropane; and dehydrochlorination of 1,1,2,2,3-pentachloropropane in the presence of alkali solution to obtain 1,1,2,3-tetrachloropropene.

[0015] WO2010123148A1 discloses a method for preparing 1,1,1,2,3-pentachloropropane (HCC-240db) with purity of 99.6% by using ethylene and carbon tetrachloride as raw materials to prepare 1,1,1,3-tetrachloropropane, then removing one molecule of hydrogen chloride by dehydrochlorination and chlorination, and the 1,1,1,2,3-pentachloropropane can continue to add 40% potassium hydroxide and Aliquat336 quaternary ammonium salt to remove one molecule of hydrogen chloride, and the reaction obtains a mixture of 1,1,2,3-tetrachloropropene and 2,3,3,3-tetrachloropropene (molar ratio of 38:62). The process uses liquid alkali to remove hydrogen chloride, and a large amount of waste salt containing organic matter is produced in the process.

[0016] US4650914A discloses a method for preparing 1,1,2,3-tetrachloropropene using ethylene + carbon tetrachloride as raw material, through multi-step preparation of 1,1,1,2,3-pentachloropropane, 1,1,1,2,3-pentachloropropane can be directly dehydrochlorinated pyrolysis to obtain 1,1,2,3-tetrachloropropene product using FeCl3 as catalyst under high temperature heating condition of 164℃, but the preparation process of 1,1,1,2,3-pentachloropropane in the early stage is too complex.

[0017] Patent US8084653 discloses a method for preparing 1,1,2,3-tetrachloropropene, wherein the steps include: (1) 1,2,3-trichloropropane is saponified to eliminate hydrogen chloride at 73℃ by 25% sodium hydroxide solution to obtain 2,3-dichloropropene, with a yield of 95.4% and a selectivity of 97.5%, and the product purity is 93% after rectification purification; (2) then 2,3-dichloropropene is added with chlorine gas at 10℃-30℃ to obtain 1,2,2,3,3-pentachloropropane, with a yield of 54.4% and a selectivity of 87%, and the product purity is 99% after purification; (3) finally, 1,2,2,3,3-pentachloropropane is saponified to eliminate hydrogen chloride by 25% sodium hydroxide solution to obtain 1,1,2,3-tetrachloropropene, with a yield of 96%. The disadvantage of this method is that the reaction time is long, the yield is low, the content of by-products is high, and a large amount of separation and purification equipment is needed, which is not conducive to industrial production.

[0018] Patent applications CN116444339A and CN116194430A report a method for preparing tetrachloropropene by using 1,3-dichloropropene as raw material, through two chlorination and dehydrochlorination reactions, isomerization, rectification and other reaction and separation processes. After the first chlorination and dehydrochlorination process, mixed trichloropropene is obtained from 1,3-dichloropropene. The mixed trichloropropene is chlorinated for the second time to obtain pentachloropropane, and the pentachloropropane is subjected to the second dehydrochlorination process to obtain a mixture of 1,1,2,3-tetrachloropropene and 2,3,3,3-tetrachloropropene, which is subjected to isomerization reaction by adding Lewis acid catalyst to convert 2,3,3,3-tetrachloropropene to 1,1,2,3-tetrachloropropene. Due to the use of alkaline solution in the second dehydrochlorination process, emulsified oil-water wrapping and entrainment may occur, resulting in 0.05-0.5% water in the oil phase. In the Lewis acid catalyzed isomerization reaction process, polychloropropene may undergo side reactions to produce 2,3,3-trichloropropene aldehyde impurities, which has a boiling point of 164℃, close to the boiling point of the desired product 1,1,2,3-tetrachloropropene 167℃. In the process of vacuum rectification separation, the relative volatility of the two is similar, so it is difficult to separate them. In addition, after the isomerization reaction is completed, part of the catalyst is dissolved and remains in the system, which causes the continuous increase of trichloropropene aldehyde and heavy component impurities in the subsequent rectification process as the column bottom temperature increases, and the tar amount increases, which significantly affects the product quality and reduces the total yield of the finished product.

[0019] Therefore, there is a need in the art for a process that overcomes the above-mentioned drawbacks.

[0020] Since many chlorinated propenes are in limited supply and / or can only be obtained at higher cost, both 1,3-dichloropropene and 3-chloropropene are products in the chloropropene industry. Developing a process for the industrial reuse of these as raw materials for the manufacture of high value-added materials whose demand is steadily growing can increase the added value and economic benefits of the products.

[0021] Therefore, it is of great significance to develop a process for the preparation of 1,1,2,3-tetrachloropropene from a mixture stream of 1,3-dichloropropene and 3-chloropropene as starting material, and to overcome the drawbacks of the prior art described above. SUMMARY

[0022] The object of the present application is to provide a process for the preparation of 1,1,2,3-tetrachloropropene from a mixture stream of 1,3-dichloropropene and 3-chloropropene as starting material.

[0023] The applicant has proposed a two-kettle series continuous chlorination process by analyzing the reaction system of 1,3-dichloropropene and 3-chloropropene for the preparation of 1,1,2,3-tetrachloropropene.

[0024] The applicant has unexpectedly found that by controlling the reaction conditions of each stage, especially the reaction temperature, the 1,3-dichloropropene and 3-chloropropene in the raw material can be made to react separately, so that their reactions do not interfere with each other, thereby effectively controlling the addition and substitution chlorination of 1,3-dichloropropene and 3-chloropropene, and controlling the chlorination depth.

[0025] Further, the applicant has unexpectedly found that by the process of the present application, 1,3-dichloropropene and 3-chloropropene can be converted into 1,1,2,3-tetrachloropropane with high selectivity, especially 1,1,2,3-tetrachloropropane is formed with high selectivity relative to 1,2,2,3-tetrachloropropane which is not prone to dehydrochlorination. 1,1,2,3-tetrachloropropane can be subsequently converted into 1,1,2,3-tetrachloropropene.

[0026] The first aspect of the present application relates to a process for producing 1,1,2,3-tetrachloropropane from a mixture of 1,3-dichloropropene and 3-chloropropene, the process comprising the following steps:

[0027] a) subjecting a raw material comprising a mixture of 1,3-dichloropropene and 3-chloropropene and Cl2 to a first chloro-addition reaction at a temperature T1 to obtain a first product,

[0028] wherein T1 ranges from 15 to 50°C, the first product comprising 1,3-dichloropropene and 1,2,3-trichloropropane;

[0029] b) subjecting the first product to a first chloro-substitution reaction under UV at a temperature T2, wherein T2 ranges from -20 to 15 °C, to obtain a second product comprising 1,3-dichloropropene and 1,1,2,3-tetrachloropropane;

[0030] c) subjecting the second product to a second chloro-addition reaction at a temperature T3, wherein T3 ranges from 50 to 75 °C, to obtain a third product comprising 1,1,2,3-tetrachloropropane.

[0031] The second aspect of the present application relates to a process for producing 1,1,2,3-tetrachloropropane from a mixture of 1,3-dichloropropene and 3-chloropropene, said process comprising the steps of:

[0032] a) subjecting a feedstock comprising a mixture of 1,3-dichloropropene and 3-chloropropene and Cl2 to a first chloro-addition reaction at a temperature T1, wherein T1 ranges from 15 to 50 °C, to obtain a first product;

[0033] b) subjecting the first product to a first chloro-substitution reaction under UV at a temperature T2, wherein T2 ranges from -20 to 15 °C, to obtain a second product;

[0034] c) subjecting the second product to a second chloro-addition reaction at a temperature T3, wherein T3 ranges from 50 to 75 °C, to obtain a third product comprising 1,1,2,3-tetrachloropropane;

[0035] f) subjecting the third product to a first conversion sub-system, thereby forming 1,1,2,3-tetrachloropropene.

[0036] The third aspect of the present application relates to a 1,1,2,3-tetrachloropropane product produced by the process of the first aspect of the present application.

[0037] The fourth aspect of the present application relates to a 1,1,2,3-tetrachloropropene product produced by the process of the second aspect of the present application. DETAILED DESCRIPTION

[0038] The ranges disclosed herein are defined by their lower and upper endpoints, given that a range is defined by selecting a lower endpoint and an upper endpoint, the selected lower and upper endpoints define the boundaries of the particular range. Ranges defined by endpoints can be inclusive or exclusive without specific recitation, and can be arbitrarily combined, i.e., any lower endpoint can be combined with any upper endpoint to form a range. For example, if ranges of 60 to 120 and 80 to 110 are listed, it is understood that ranges of 60 to 110 and 80 to 120 are also contemplated. Furthermore, if a minimum range value of 1 and 2 is listed, and if a maximum range value of 3, 4, and 5 is listed, then the following ranges are all contemplated: 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4, and 2 to 5. In this application, unless otherwise specified, a numerical range "a to b" indicates a range of any integers between a and b, in which a and b are real numbers. For example, the numerical range "0 to 5" indicates that all real numbers between "0 to 5" have been listed herein, and "0 to 5" is merely a shorthand for listing all of these numerical combinations. Also, when a parameter is stated to be an integer > 2, it is equivalent to disclose that the parameter is, for example, an integer 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0039] In this application, all the embodiments and preferred embodiments mentioned herein can be combined with each other to form new technical solutions, unless otherwise specified.

[0040] In this application, all the technical features and preferred features mentioned herein can be combined with each other to form new technical solutions, unless otherwise specified.

[0041] In this application, all the steps mentioned herein can be performed in sequence or randomly, but preferably in sequence, unless otherwise specified. For example, the method comprises steps (a) and (b), which means that the method can comprise steps (a) and (b) in sequence, or steps (b) and (a) in sequence. For example, the method can further comprise step (c), which means that step (c) can be added to the method in any order, for example, the method can comprise steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), etc.

[0042] In this application, "including" and "containing" mentioned herein means open or closed, unless otherwise specified. For example, "including" and "containing" can mean that other components not listed can also be included or contained, or only the listed components can be included or contained.

[0043] In the description herein, it is to be understood that, unless otherwise indicated, "above" and "below" are inclusive of the number, and "one or more" of "more" means two or more.

[0044] In the description herein, the term "or" is inclusive, unless otherwise indicated. For example, the phrase "A or B" means "A, B, or both A and B." More specifically, any one of the following conditions fulfills the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0045] In the present description, unless otherwise specified, percentages (%) or parts are weight percentages or parts by weight relative to the composition.

[0046] In the present description, unless otherwise specified, the sum of the amounts of the components in the composition is 100%.

[0047] In the present description, unless otherwise specified, the sum of the parts of the components in the composition can be 100 parts by weight.

[0048] In the present description, unless otherwise specified, "combination thereof" means a multi-component mixture of the elements mentioned, for example two, three, four and up to the maximum possible multi-component mixture.

[0049] In the present description, unless otherwise specified, the term "one" means "at least one".

[0050] In the present description, unless otherwise specified, each reaction is carried out at normal temperature and pressure.

[0051] In the context of the present application, the term "selectivity" has the same meaning as understood by the person skilled in the art.

[0052] In the context of the present application, the expression "Cl2" means chlorine provided in gaseous form.

[0053] Process for the production of 1,1,2,3-tetrachloropropane

[0054] The first aspect of the present application relates to a process for the production of 1,1,2,3-tetrachloropropane from a mixture of 1,3-dichloropropene and 3-chloropropene, said process comprising the steps of:

[0055] a) subjecting a feedstock comprising a mixture of 1,3-dichloropropene and 3-chloropropene and Cl2 to a first chloro-addition reaction at a temperature T1, obtaining a first product,

[0056] wherein T1 ranges from 15 to 50°C, said first product comprising 1,3-dichloropropene and 1,2,3-trichloropropane;

[0057] b) subjecting the first product to a first chloro-substitution reaction under UV at a temperature T2, wherein T2 ranges from -20 to 15 °C, to obtain a second product comprising 1,3-dichloropropene and 1,1,2,3-tetrachloropropane;

[0058] c) subjecting the second product to a second chloro-addition reaction at a temperature T3, wherein T3 ranges from 50 to 75 °C, to obtain a third product comprising 1,1,2,3-tetrachloropropane.

[0059] Starting material

[0060] The starting material according to the first aspect of the present application comprises a mixture of 1,3-dichloropropene and 3-chloropropene.

[0061] According to an embodiment, the molar ratio of 1,3-dichloropropene and 3-chloropropene in the starting material is from 5:95 to 95:5, or from 10:90 to 90:10, or from 20:80 to 80:20, or from 30:70 to 70:30, or from 40:60 to 60:40, for example the molar ratio of 1,3-dichloropropene and 3-chloropropene can be 5:95, or 10:90, or 15:85, or 20:80, or 25:75, or 30:70, or 35:65, or 40:60, or 45:55, or 50:50, or 55:45, or 60:40, or 65:35, or 70:30, or 75:25, or 80:20, or 85:15, or 90:10, or 95:5.

[0062] According to an embodiment, the molar amount N 0；Cl2 of Cl2 in step a) is in a ratio N 0；Cl2 :(N 0；1,3-二氯丙烯 +N 0；3-氯丙烯 ) of from 0.1 to 10, or from 0.1 to 9, or from 0.1 to 8, or from 0.1 to 7, or from 0.1 to 6, or from 0.1 to 5, or from 0.1 to 4, or from 0.1 to 3, or from 0.1 to 2, or from 0.1 to 1.5, wherein N 0；1,3-二氯丙烯 is the molar amount of 1,3-dichloropropene in the starting material and N 0；3-氯丙烯 is the molar amount of 3-chloropropene in the starting material.

[0063] For example N 0；Cl2 and N 0；1,3-二氯丙烯 +N 0；3-氯丙烯The ratio of 1,3-dichloropropene to 3-chloropropene can be 0.5, or 0.6, or 0.7, or 0.8, or 0.9, or 1.0, or 1.1, or 1.2, or 1.3, or 1.4, or 1.5, or 1.6, or 1.7, or 1.8, or 1.9, or 2.0, or 2.1, or 2.2, or 2.3, or 2.4, or 2.5, or 2.6, or 2.7, or 2.8, or 2.9, or 3.0, or 3.2, or 3.4, or 3.6, or 3.8, or 4.0, or 4.5, or 5.0, or 5.5, or 6.0, or 6.5, or 7.0, or 7.5, or 8.0, or 8.5, or 9.0, or 9.5.

[0064] N 0；Cl2 and N 0；1,3-二氯丙烯 +N 0；3-氯丙烯 The ratio of Cl2to 1,3-dichloropropene and 3-chloropropene can be obtained by measuring the flow rate (for continuous reactions) or the amount charged (for batch reactions) of Cl2and the flow rate (for continuous reactions) or the amount charged (for batch reactions) of 1,3-dichloropropene and 3-chloropropene in step a). For continuous reactions, the methods for measuring the flow rate of Cl2and the molar flow rate of 1,3-dichloropropene and 3-chloropropene are well known to those skilled in the art, for example, the readings of metering pumps, gas flow meters, or liquid flow meters can be used.

[0065] First chloro-addition reaction

[0066] The method of the first aspect of the present application comprises step a) of carrying out a first chloro-addition reaction at T1 of 15 to 50 °C to obtain a first product.

[0067] The first chloro-addition reaction comprises the following reaction:

[0068] CH2=CH-CH2Cl + Cl2→ CH2Cl-CHCl-CH2Cl (1,2,3-trichloropropane) (Reaction 1)

[0069] According to an embodiment, T1 ranges from 15 to 50 °C, from 15 to 45 °C, or from 15 to 40 °C, or from 15 to 35 °C, or from 15 to 30 °C, or from 15 to 25 °C. In non-limiting examples, T1 can be 15 °C, or 16 °C, or 17 °C, or 18 °C, or 19 °C, or 20 °C, or 21 °C, or 22 °C, or 23 °C, or 24 °C, or 25 °C, or 26 °C, or 27 °C, or 28 °C, or 29 °C, or 30 °C, or 31 °C, or 32 °C, or 33 °C, or 34 °C, or 35 °C, or 36 °C, or 37 °C, or 38 °C, or 39 °C, or 40 °C, or 41 °C, or 42 °C, or 43 °C, or 44 °C, or 45 °C, or 46 °C, or 47 °C, or 48 °C, or 49 °C, or 50 °C.

[0070] According to a preferred embodiment, the duration of step a) is 0.1 to 10 hours, or 0.1 to 9 hours, or 0.1 to 8 hours, or 0.1 to 7 hours, or 0.1 to 6 hours, or 0.1 to 5 hours, or 0.1 to 4 hours, or 0.5 to 3 hours, or 0.5 to 2.5 hours. For example, the duration of step a) can be 0.1 hour, or 0.2 hour, or 0.4 hour, or 0.6 hour, or 0.8 hour, or 1.0 hour, or 1.2 hour, or 1.4 hour, or 1.6 hour, or 1.8 hour, or 2.0 hour, or 2.2 hour, or 2.4 hour, or 2.6 hour, or 2.8 hour, or 3.0 hour, or 3.2 hour, or 3.4 hour, or 3.6 hour, or 3.8 hour, or 4.0 hour, or 4.5 hour, or 5.0 hour, or 5.5 hour, or 6.0 hour, or 6.5 hour, or 7.0 hour, or 7.5 hour, or 8.0 hour, or 8.5 hour, or 9.0 hour, or 9.5 hour.

[0071] Step a) can be carried out in any reactor well known to the person skilled in the art, without being particularly limited.

[0072] The pressure of step a) is not particularly limited. In an exemplary embodiment, step a) can be carried out at normal pressure.

[0073] The present application avoids the addition reaction of 1,3-dichloropropene by controlling T1 so that reaction 1 mainly occurs:

[0074] CHCI=CH-CH2CI + CI2→ CHCI2-CHCI-CH2CI (1,1,2,3-tetrachloropropane) (reaction 3)

[0075] According to a preferred embodiment, the conversion of 3-chloropropene in step a) is greater than 80%, or greater than 90%, or greater than 95%, or greater than 99%. According to an embodiment, the conversion of 3-chloropropene in step a) is less than 99.999%, or less than 99.99%, or less than 99.9%. For example, the conversion of 3-chloropropene in step a) can be 80%, or 82%, or 84%, or 86%, or 88%, or 90%, or 92%, or 94%, or 96%, or 98%, or 99%, or 99.5%, or 99.9%, or 99.95%.

[0076] In the context of the present application, the conversion of 3-chloropropene in step a) is Conv a；3-氯丙烯 The conversion of 3-chloropropene in step a) can be calculated by formula 1:

[0077] where N% Conv 0；3-氯丙烯 refers to the mole fraction of 3-chloropropene in the feedstock, i.e. the mole fraction of 3-chloropropene in all C3 components, and

[0078] A 0；3-氯丙烯 and A 0；1,3-二氯丙烯 normalized content of 3-chloropropene and 1,3-dichloropropene in the starting material as measured by chromatography.

[0079] N% a；3-氯丙烯 molar fraction of 3-chloropropene in all C3 components in the first product as measured at the end of step a), which can be calculated by the following formula:

[0080] wherein A a；3-氯丙烯 , A a；1,3-二氯丙烯 , A a；1,2,3-三氯丙烷 , A a；四氯丙烷 respectively represent the normalized content of 3-chloropropene, the normalized content of 1,3-dichloropropene, the normalized content of 1,2,3-trichloropropane, the total normalized content of all tetrachloropropanes (e.g. 1,1,2,3-tetrachloropropane, 1,2,2,3-tetrachloropropane) in the first product obtained after step a) as measured by chromatography.

[0081] According to a preferred embodiment, the conversion of 1,3-dichloropropene in step a) is less than 10%, or less than 8%, or less than 7%, or less than 6%, or less than 5%. According to an embodiment, the conversion of 1,3-dichloropropene in step a) is more than 0.0001 %, or more than 0.001 %, or more than 0.01 %, or more than 0.1 %.

[0082] In the context of the present application, the conversion of 1,3-dichloropropene in step a) Conva; 1,3-dichloropropene can be calculated by formula 2:

[0083] wherein N%o; 1,3-dichloropropene represents the molar fraction of 1,3-dichloropropene in all C3 components in the starting material, which can be calculated by the following formula:

[0084] N%a; 1,3-dichloropropene represents the molar fraction of 1,3-dichloropropene in all C3 components in the first product as measured at the end of step a), which can be calculated by the following formula:

[0085] wherein A 0；3-氯丙烯 , A 0；1,3-二氯丙烯 , A a；3-氯丙烯 , A a；1,3-二氯丙烯 , A a；1,2,3-三氯丙烷 , A a；四氯丙烷 as described above.

[0086] According to a preferred embodiment, the selectivity to 1,2,3-trichloropropane in step a) is greater than 80%, or greater than 85%, or greater than 90, or greater than 95%. According to an embodiment, the selectivity to 1,2,3-trichloropropane in step a) is less than 99.9%, or less than 99%, or less than 98%, or less than 97%. For example, the selectivity to 1,2,3-trichloropropane in step a) can be 81%, or 82%, or 83%, or 84%, or 85%, or 86%, or 87%, or 88%, or 89%, or 90%, or 91%, or 92%, or 93%, or 94%, or 95%, or 96%, or 97%.

[0087] In the context of the present application, the selectivity to 1,2,3-trichloropropane in step a) is Selecta; the 1,2,3-trichloropropane can be calculated by formula 3:

[0088] where N%a;1,2,3-trichloropropane is the molar fraction of 1,2,3-trichloropropane in the first product measured at the end of step a, N% 0；3-氯丙烯 is the molar fraction of 3-chloropropene in the starting material. a；3-氯丙烯 is the molar fraction of 3-chloropropene in the first product.

[0089] N%a;1,2,3-trichloropropane is calculated by formula: 0；3-氯丙烯 The calculation of N%a;1,2,3-trichloropropane is described above.

[0090] N%a;1,2,3-trichloropropane is calculated by formula:

[0091] where A 0；3-氯丙烯 , A 0；1,3-二氯丙烯 , A a；3-氯丙烯 , A a；1,3-二氯丙烯 , A a；1,2,3-三氯丙烷 , A a；四氯丙烷 are defined as described above.

[0092] It is understood that the method for determining the conversion, selectivity of the various components is not limited to the chromatographic analysis described above. The skilled person can also obtain the selectivity and conversion results of the various components in the starting material and the product at the end of each step by other methods well known to him.

[0093] First chloro-substitution reaction

[0094] The method of the first aspect of the present application comprises a step b) of subjecting the first product to a first chloro-substitution reaction under UV at a temperature T2, wherein T2 ranges from -20 to 15°C, to obtain a second product comprising 1,3-dichloropropene and 1,1,2,3-tetrachloropropane.

[0095] In one embodiment, T2 ranges from -20 to 15°C, or from -18 to 14°C, or from -16 to 13°C, or from -14 to 12°C, or from -12 to 11°C. For example, T2 can be -20°C, or -18°C, or -16°C, or -14°C, or -12°C, or -10°C, or -8°C, or -6°C, or -4°C, or -2°C, or 0°C, or 2°C, or 4°C, or 6°C, or 8°C, or 10°C, or 12°C, or 14°C.

[0096] Step b) of the second aspect of the application is performed under UV conditions. According to a non-limiting embodiment, the UV power used in step b) is less than or equal to 500 W, preferably from 5 to 50 W. For example, the UV power used in step b) is 5 W, or 10 W, or 15 W, or 20 W, or 25 W, or 30 W, or 35 W, or 40 W, or 45 W, or 50 W.

[0097] The duration of step b) can be adapted according to the reaction. In a non-limiting embodiment, the duration of step b) is from 0.1 to 10 hours, or from 0.1 to 9 hours, or from 0.1 to 8 hours, or from 0.1 to 7 hours, or from 0.1 to 6 hours. For example, the duration of step b) can be 0.1 hour, or 0.2 hour, or 0.4 hour, or 0.6 hour, or 0.8 hour, or 1.0 hour, or 1.2 hour, or 1.4 hour, or 1.6 hour, or 1.8 hour, or 2.0 hour, or 2.2 hour, or 2.4 hour, or 2.6 hour, or 2.8 hour, or 3.0 hour, or 3.2 hour, or 3.4 hour, or 3.6 hour, or 3.8 hour, or 4.0 hour, or 4.2 hour, or 4.4 hour, or 4.6 hour, or 4.8 hour, or 5.0 hour, or 5.5 hour, or 6.0 hour, or 6.5 hour, or 7.0 hour, or 7.5 hour, or 8.0 hour, or 8.5 hour, or 9.0 hour, or 9.5 hour.

[0098] According to a preferred embodiment, in step b), the equivalent ratio of Cl2 to the first product is from 0.1 to 10, or from 0.1 to 9, or from 0.1 to 8, or from 0.1 to 7, or from 0.1 to 6, or from 0.1 to 5, or from 0.1 to 4, or from 0.1 to 3, or from 0.5 to 2.5, or from 1 to 2. In the context of the present application, the expression "equivalent ratio of Cl2 to the first product" is understood to mean the molar ratio of Cl2 fed in step b) to 1,3-dichloropropene in the raw material, i.e. N b；Cl2 : N 0；1,3-二氯丙烯 .

[0099] The equivalent ratio of Cl2 to the first product can be determined by means well known to those skilled in the art.

[0100] For example, if the process according to the first aspect of the present application is carried out in a batch mode, the equivalent ratio of Cl2to the first product in step b) can be calculated by the amount of Cl2fed in step b) and the amount of 1,3-dichloropropene in the feedstock.

[0101] If the process according to the first aspect of the present application is carried out in a continuous mode, the equivalent ratio of Cl2to the first product in step b) can be calculated by the mass flow rate R b；Cl2 of Cl2fed in step b) and the mass flow rate R 0；1,3-二氯丙烯 of 1,3-dichloropropene in the feedstock flow. Wherein

[0102] wherein R0is the mass flow rate of the feedstock. M 1,3-二氯丙烯 and M 3-氯丙烯 are the molar mass of 1,3-dichloropropene and 3-chloropropene, respectively.

[0103] The reaction taking place in step b) comprises:

[0104] CH2Cl-CHCl-CH2Cl + Cl2→ CH2Cl-CHCl-CHCl2(1,1,2,3-tetrachloropropane) + HC1 (reaction 2)

[0105] The present application avoids the addition of 1,3-dichloropropene, i.e. reaction 3 above, by controlling the temperature T2such that in step b) mainly reaction 2 above takes place.

[0106] Furthermore, the formation of 1,2,2,3-tetrachloropropane is not desired in the present application, thus reaction 4 below is not desired to take place in step b):

[0107] CH2Cl-CHCl-CH2Cl + Cl2→ CH2Cl-CHCl2-CH2Cl (1,2,2,3-tetrachloropropane) + HC1 (reaction 4)

[0108] According to an embodiment, the conversion of 1,3-dichloropropene in step b) of the first aspect of the present application is less than 10%, or less than 8%, or less than 7%, or less than 6%, or less than 5%. According to an embodiment, the conversion of 1,3-dichloropropene in step b) of the first aspect of the present application is more than 0.0001%, or more than 0.001%, or more than 0.01%, or more than 0.1%.

[0109] In the context of the present application, the conversion of 1,3-dichloropropene in step b) Convb;1,3-dichloropropene can be calculated by formula 4:

[0110] wherein N%a; 1,3-dichloropropene refers to the molar fraction of 1,3-dichloropropene in the first product as measured at the end of step a), and N%b; 1,3-dichloropropene refers to the molar fraction of 1,3-dichloropropene in the second product as measured at the end of step b).

[0111] N%a; 1,3-dichloropropene can be calculated by the following formula:

[0112] wherein A a；3-氯丙烯 , A a；1,3-二氯丙烯 , A a；1,2,3-三氯丙烷 , A a；四氯丙烷 are as described above.

[0113] N%b; 1,3-dichloropropene can be calculated by the following formula:

[0114] wherein A b；3-氯丙烯 , A b；1,3-二氯丙烯 , A b；1,2,3-三氯丙烷 , A b；四氯丙烷 , A b；五氯丙烷 respectively refer to the normalized content of 3-chloropropene, the normalized content of 1,3-dichloropropene, the normalized content of 1,2,3-trichloropropane, the total normalized content of all tetrachloropropanes (e.g. 1,1,2,3-tetrachloropropane, 1,2,2,3-tetrachloropropane), and the total normalized content of all pentachloropropanes (e.g. 1,1,1,2,3-pentachloropropane, 1,1,2,2,3-pentachloropropane) in the second product obtained after step b) as measured by chromatography.

[0115] According to one embodiment, the conversion of total 1,3-dichloropropene at the end of step b) of the first aspect of the present application is less than 10%, or less than 8%, or less than 7%, or less than 6%, or less than 5%. According to one embodiment, the conversion of total 1,3-dichloropropene at the end of step b) of the first aspect of the present application is more than 0.0001%, or more than 0.001%, or more than 0.01%, or more than 0.1%.

[0116] In the context of the present application, the conversion of total 1,3-dichloropropene at the end of step b) is referred to as Conv b总；1,3-二 氯丙烯 can be calculated by formula 4:

[0117] wherein N%o; 1,3-dichloropropene refers to the molar fraction of 1,3-dichloropropene in the starting material, and N%b; 1,3-dichloropropene refers to the molar fraction of 1,3-dichloropropene in the second product as measured at the end of step b), which is calculated as described above.

[0118] Furthermore, the present application allows to control the temperature T2 in such a way that in step b) 1,1,2,3-tetrachloropropane is selectively produced, in particular with respect to 1,2,2,3-tetrachloropropane which is not easily dehydrochlorinated.

[0119] According to a preferred embodiment, at the end of step b) the molar ratio of 1,1,2,3-tetrachloropropane and 1,2,2,3-tetrachloropropane (N%b; 1,1,2,3-tetrachloropropane : N%b; 1,2,2,3-tetrachloropropane) is greater than 50:50, or greater than 55:45, or greater than 60:40, or greater than 65:35, or greater than 70:30, or greater than 75:25, or greater than 80:20, or greater than 85:15, or greater than 90:10, or greater than 95:5. According to an embodiment, at the end of step b) the molar ratio of 1,1,2,3-tetrachloropropane and 1,2,2,3-tetrachloropropane is less than 99.9:0.1, or less than 99:1, or less than 98.5:1.5, or less than 98:2, or less than 97:3, or less than 96:4.

[0120] At the end of step b) the molar ratio of 1,1,2,3-tetrachloropropane and 1,2,2,3-tetrachloropropane (N%b; 1,1,2,3-tetrachloropropane : N%b; 1,2,2,3-tetrachloropropane) in the second product can be calculated by the following formula: b； 1,1,2,3-tetrachloropropane : N%b; 1,2,2,3-tetrachloropropane) in the second product can be calculated by the following formula:

[0121] wherein A b；1,1,2,3-四氯丙烷 and A b；1,2,2,3-四氯丙烷 respectively represent the normalized content of 1,1,2,3-tetrachloropropane and 1,2,2,3-tetrachloropropane in the second product obtained at the end of step b) as measured by chromatography.

[0122] It is understood that the method for determining the conversion, the selectivity of the various components is not limited to the chromatographic analysis described above. The skilled person can also obtain the selectivity and conversion results of the various components in the starting material and at the end of each step by other methods well known to him.

[0123] Second chlorination reaction

[0124] The method according to the first aspect of the present application comprises a step c) of subjecting the second product to a second chloro-addition reaction at a temperature T3, wherein T3 ranges from 50 to 75 °C, and the third product comprises 1,1,2,3-tetrachloropropane.

[0125] According to an embodiment, said T3 ranges from 50 to 75°C, preferably from 55 to 70°C, preferably from 55 to 65°C. For example, T3 can be 50°C, or 51 °C, or 52°C, or 53°C, or 54°C, or 55°C, or 56°C, or 57°C, or 58°C, or 59°C, or 60°C, or 61 °C, or 62°C, or 63°C, or 64°C, or 65°C, or 66°C, or 67°C, or 68°C, or 69°C, or 70°C, or 71 °C, or 72°C, or 73°C, or 74°C, or 75°C.

[0126] The duration of step c) can be adapted according to the reaction.

[0127] According to a non-limiting embodiment, the duration of step c) ranges from 0.1 to 10 hours, or from 0.1 to 9 hours, or from 0.1 to 8 hours, or from 0.1 to 7 hours, or from 0.1 to 6 hours, or from 0.1 to 5 hours, for example it can be 0.1 hour, or 0.5 hour, or 1 hour, or 1.5 hour, or 2 hours, or 2.5 hours, or 3 hours, or 3.5 hours, or 4 hours, or 4.5 hours, or 5 hours, or 5.5 hours, or 6 hours, or 6.5 hours, or 7 hours, or 7.5 hours, or 8 hours, or 8.5 hours, or 9.0 hours, or 9.5 hours.

[0128] The reaction that occurs in step c) comprises reaction 3 described above:

[0129] CHCI=CH-CH2CI + CI2→ CHCI2-CHCI-CH2CI (1,1,2,3-tetrachloropropane)

[0130] According to one embodiment, the equivalent ratio of Cl2to the second product in step c) is from 0.1 to 10, or from 0.1 to 9, or from 0.1 to 8, or from 0.1 to 7, or from 0.1 to 6, or from 0.1 to 5, or from 0.1 to 4, or from 0.1 to 3, or from 0.5 to 2.5, or from 1 to 2. For example, the equivalent ratio of Cl2to the second product in step c) can be 0.10, or 0.15, or 0.20, or 0.25, or 0.30, or 0.35, or 0.40, or 0.45, or 0.50, or 0.55, or 0.60, or 0.65, or 0.70, or 0.75, or 0.80, or 0.85, or 0.90, or 0.95, or 1.0, or 1.05, or 1.10, or 1.15, or 1.20, or 1.25, or 1.30, or 1.35, or 1.40, or 1.45, or 1.50, or 1.55, or 1.60, or 1.65, or 1.70, or 1.75, or 1.80, or 1.9, or 2, or 2.2, or 2.4, or 2.6, or 2.8, or 3.0, or 3.5, or 4, or 4.5, or 5, or 5.5, or 6, or 6.5, or 7, or 7.5, or 8, or 8.5, or 9, or 9.5, or 10.

[0131] In the context of the present application, the expression "equivalent ratio of Cl2to the second product" means the molar ratio of Cl2fed in step c) to 1,3-dichloropropene in the feedstock, i.e. N c；Cl2 : N 0；1,3-二氯丙烯 .

[0132] The equivalent ratio of Cl2to the second product can be calculated in a manner well known to the person skilled in the art.

[0133] For example, if the process according to the first aspect of the present application is carried out in batch mode, the equivalent ratio of Cl2to the second product in step c) can be calculated from the amount of Cl2fed in step c) and the amount of 1,3-dichloropropene in the feedstock.

[0134] If the process according to the first aspect of the present application is carried out in continuous mode, the equivalent ratio of Cl2to the second product in step c) can be calculated from the mass flow rate of Cl2fed in step c) r c；Cl2 and the mass flow rate of 1,3-dichloropropene in the feedstock flow rate r0;1,3-dichloropropene calculated (the manner of calculating r0;1,3-dichloropropene is described above).

[0135] According to an embodiment, the conversion of 1,3-dichloropropene in step c) Convc;1,3-dichloropropene is at least 80%, or at least 85%, or at least 90%, or at least 95%, or at least 99%. According to an embodiment, the conversion of 1,3-dichloropropene in step c) Convc;1,3-dichloropropene is less than 99.999%, or less than 99.99, or less than 99.9%. For example, the conversion of 1,3-dichloropropene in step c) can be 80%, or 81 %, or 82%, or 83%, or 84%, or 85%, or 86%, or 87%, or 88%, or 89%, or 90%, or 91 %, or 92%, or 93%, or 94%, or 95%, or 96%, or 97%, or 98%, or 99%, or 99.5%.

[0136] In the context of the present application, the conversion of 1,3-dichloropropene in step c) Convc;1,3-dichloropropene can be calculated by formula 6:

[0137] wherein N%b;1,3-dichloropropene refers to the molar fraction of 1,3-dichloropropene in the second product at the end of step b) and N%c;1,3-dichloropropene refers to the molar fraction of 1,3-dichloropropene in the third product measured at the end of step c).

[0138] N%b;1,3-dichloropropene is calculated as described above.

[0139] N%c;1,3-dichloropropene can be calculated by formula 7:

[0140] wherein A c；3-氯丙烯 , A c；1,3-二氯丙烯 , A c；1,2,3-三氯丙烷 , A c；四氯丙烷 , A c；五氯丙烷 respectively represent the normalized content of 3-chloropropene, the normalized content of 1,3-dichloropropene, the normalized content of 1,2,3-trichloropropane, the total normalized content of all tetrachloropropanes (e.g. 1,1,2,3-tetrachloropropane, 1,2,2,3-tetrachloropropane) and the total normalized content of all pentachloropropanes (e.g. 1,1,1,2,3-pentachloropropane, 1,1,2,2,3-pentachloropropane) in the third product obtained at the end of step c) measured by chromatography.

[0141] The present application provides for setting T1, T2 and T3 such that at the end of step c) the starting material is selectively converted to 1,1,2,3-tetrachloropropane.

[0142] According to an embodiment, the sum of the contents of 1,1,2,3-tetrachloropropane and 1,2,2,3-tetrachloropropane in the third product at the end of step c) is greater than 50 mol%, or greater than 60%, or greater than 70%, or greater than 80%, or greater than 90%, relative to the total number of moles of C3 to C5 halogenated hydrocarbons in the third product.

[0143] According to an embodiment, the sum of the contents of 1,1,2,3-tetrachloropropane and 1,2,2,3-tetrachloropropane in the third product at the end of step c) is less than 99.9%, or less than 99%, or less than 98%, or less than 97%, or less than 96%, or less than 95%, or less than 94%, or less than 93%, or less than 92%, or less than 91%, relative to the total number of moles of C3 to C5 halogenated hydrocarbons in the third product.

[0144] According to a preferred embodiment, the content of 1,1,2,3-tetrachloropropane in the third product at the end of step c) is greater than 50 mol%, or greater than 60 mol%, or greater than 70 mol%, or greater than 80 mol%, or greater than 90 mol%, relative to the total number of moles of C3 to C5 halogenated hydrocarbons in the third product.

[0145] According to an embodiment, the content of 1,1,2,3-tetrachloropropane in the third product at the end of step c) is less than 99.9%, or less than 99%, or less than 98%, or less than 97%, or less than 96%, or less than 95%, or less than 94%, or less than 93%, or less than 92%, or less than 91%, relative to the total number of moles of C3 to C5 halogenated hydrocarbons in the third product.

[0146] For example, the content of 1,1,2,3-tetrachloropropane in the third product at the end of step c) can be 50 mol%, or 52 mol%, or 54 mol%, or 56 mol%, or 58 mol%, or 60 mol%, or 62 mol%, or 64 mol%, or 66 mol%, or 68 mol%, or 70 mol%, or 72 mol%, or 74 mol%, or 76 mol%, or 78 mol%, or 80 mol%, or 82 mol%, or 84 mol%, or 86 mol%, or 88 mol%, or 90 mol%, or 92 mol%, or 94 mol%, or 96 mol%, or 98 mol%, or 99 mol%, relative to the total number of moles of C3 to C5 halogenated hydrocarbons in the third product.

[0147] According to a preferred embodiment, at the end of step c), the molar ratio of 1,1,2,3-tetrachloropropane to 1,2,2,3-tetrachloropropane in the third product (N% c; 1,1,2,3-tetrachloropropane : N% c; 1,2,2,3-tetrachloropropane) is greater than 50:50, or greater than 55:45, or greater than 60:40, or greater than 65:35, or greater than 70:30, or greater than 75:25, or greater than 80:20, or greater than 85:15, or greater than 90:10, or greater than 95:5. According to one embodiment, at the end of step c), the molar ratio of 1,1,2,3-tetrachloropropane to 1,2,2,3-tetrachloropropane in the third product is less than 99.9:0.1, or less than 99:1, or less than 98.5:1.5, or less than 98:2, or less than 97:3, or less than 96:4.

[0148] The molar ratio of 1,1,2,3-tetrachloropropane to 1,2,2,3-tetrachloropropane in the third product at the end of step c) (N% c; 1,1,2,3-tetrachloropropane : N% c; 1,2,2,3-tetrachloropropane) can be calculated by the following formula:

[0149] wherein A c；1,1,2,3-四氯丙烷 and A c；1,2,2,3-四氯丙烷 respectively represent the normalized content of 1,1,2,3-tetrachloropropane and 1,2,2,3-tetrachloropropane in the third product obtained at the end of step c) as measured by chromatography.

[0150] First purification

[0151] According to a preferred embodiment, the process of the first aspect of the present application further comprises a step d) of submitting the third product to a first purification device, thereby forming a fourth product and a fifth product, wherein the fourth product comprises 1,1,2,3-tetrachloropropane and the fifth product comprises 1,2,3-trichloropropane.

[0152] The first purification device used in step d) can be any device known to the person skilled in the art. In a non-limiting embodiment, the first purification device can be a distillation column or a rectification column.

[0153] According to one embodiment, the content of 1,1,2,3-tetrachloropropane in the fourth product is greater than 60 mol%, or greater than 70 mol%, or greater than 80 mol%, or greater than 90 mol% relative to the total number of moles of C3 to C5 halogenated hydrocarbons in the fourth product.

[0154] According to an embodiment, the content of 1,1,2,3-tetrachloropropane in the fourth product is less than 99.9%, or less than 99%, or less than 98%, or less than 97%, or less than 96%, or less than 95%, or less than 94%, or less than 93%, or less than 92%, or less than 91%, relative to the total number of moles of C3 to C5 halogenated hydrocarbons in the fourth product.

[0155] For example, the content of 1,1,2,3-tetrachloropropane in the fourth product can be 60 mol%, or 62 mol%, or 64 mol%, or 66 mol%, or 68 mol%, or 70 mol%, or 72 mol%, or 74 mol%, or 76 mol%, or 78 mol%, or 80 mol%, or 82 mol%, or 84 mol%, or 86 mol%, or 88 mol%, or 90 mol%, or 92 mol%, or 94 mol%, or 96 mol%, or 98 mol%, or 99 mol%, or 99.5 mol%, relative to the total number of moles of C3 to C5 halogenated hydrocarbons in the fourth product.

[0156] The present application enables the production of 1,1,2,3-tetrachloropropene with high selectivity and avoids the formation of 1,2,2,3-tetrachloropropene by the selection of T1, T2 and T3 and the use of a combination of specific T1, T2 and T3.

[0157] According to an embodiment, the molar ratio of 1,1,2,3-tetrachloropropane and 1,2,2,3-tetrachloropropane in the fourth product is greater than 50:50, or greater than 55:45, or greater than 60:40, or greater than 65:35, or greater than 70:30, or greater than 75:25, or greater than 80:20, or greater than 85:15, or greater than 90:10, or greater than 95:5.

[0158] According to an embodiment, the molar ratio of 1,1,2,3-tetrachloropropane and 1,2,2,3-tetrachloropropane in the fourth product is less than 99.9:0.1, or less than 99:1, or less than 98.5:1.5, or less than 98:2, or less than 97:3, or less than 96:4.

[0159] The content of each component in the fourth product and the molar ratio of two components can be calculated according to the calculation method described above.

[0160] A fifth product is also formed in step d). The fifth product comprises 1,2,3-trichloropropane.

[0161] According to an embodiment, the content of 1,2,3-trichloropropane in the fifth product is greater than 60 mol%, or greater than 70 mol%, or greater than 80 mol%, or greater than 90 mol%, relative to the total number of moles of C3 to C5 halogenated hydrocarbons in the fifth product.

[0162] According to an embodiment, the content of 1,2,3-trichloropropane in the fifth product is less than 99.9 mol%, or less than 99 mol%, or less than 98 mol%, or less than 97 mol%, or less than 96 mol%, or less than 95 mol%, or less than 94 mol%, or less than 93 mol%, or less than 92 mol%, or less than 91 mol%, relative to the total moles of C3 to C5 halogenated hydrocarbons in the fifth product.

[0163] For example, the content of 1,2,3-trichloropropane in the fifth product can be 60 mol%, or 62 mol%, or 64 mol%, or 66 mol%, or 68 mol%, or 70 mol%, or 72 mol%, or 74 mol%, or 76 mol%, or 78 mol%, or 80 mol%, or 82 mol%, or 84 mol%, or 86 mol%, or 88 mol%, or 90 mol%, or 92 mol%, or 94 mol%, or 96 mol%, or 98 mol%, or 99 mol%, or 99.5 mol%, relative to the total moles of C3 to C5 halogenated hydrocarbons in the fifth product.

[0164] The content of each component in the fifth product and the molar ratio of two components can be calculated according to the calculation method described above.

[0165] According to a preferred embodiment, a sixth product is further formed in step d), and the sixth product comprises pentachloropropane.

[0166] According to a preferred embodiment, the content of pentachloropropane in the sixth product is greater than 60 mol%, or greater than 70 mol%, or greater than 80 mol%, or greater than 90 mol%, relative to the total moles of C3 to C5 halogenated hydrocarbons in the sixth product.

[0167] According to an embodiment, the content of pentachloropropane in the sixth product is less than 99.9 mol%, or less than 99 mol%, or less than 98 mol%, or less than 97 mol%, or less than 96 mol%, or less than 95 mol%, or less than 94 mol%, or less than 93 mol%, or less than 92 mol%, or less than 91 mol%, relative to the total moles of C3 to C5 halogenated hydrocarbons in the sixth product.

[0168] For example, the content of pentachloropropane in the sixth product can be 60 mol%, or 62 mol%, or 64 mol%, or 66 mol%, or 68 mol%, or 70 mol%, or 72 mol%, or 74 mol%, or 76 mol%, or 78 mol%, or 80 mol%, or 82 mol%, or 84 mol%, or 86 mol%, or 88 mol%, or 90 mol%, or 92 mol%, or 94 mol%, or 96 mol%, or 98 mol%, or 99 mol%, or 99.5 mol%, relative to the total number of moles of C3 to C5 halogenated hydrocarbons in the sixth product.

[0169] The content of each component in the sixth product and the molar ratio of two components can be calculated according to the calculation method described above.

[0170] According to a preferred embodiment, the method according to the first aspect of the application further comprises a step e) of returning the fifth product to the first chlorination reaction of step a).

[0171] The step e) can be performed by means well known to the person skilled in the art. For example, the step e) can be performed by pumping, for example a metering pump.

[0172] Method for producing 1,1,2,3-tetrachloropropene

[0173] The second aspect of the application relates to a method for producing 1,1,2,3-tetrachloropropane from a mixture of 1,3-dichloropropene and 3-chloropropene, the method comprising the following steps:

[0174] a) subjecting a feedstock comprising a mixture of 1,3-dichloropropene and 3-chloropropene and Cl2 to a first chloro-addition reaction at a temperature T1, wherein T1 ranges from 15 to 50°C, to obtain a first product;

[0175] b) subjecting the first product to a first chloro-substitution reaction under UV at a temperature T2, wherein T2 ranges from -20 to 15°C, to obtain a second product;

[0176] c) subjecting the second product to a second chloro-addition reaction at a temperature T3, wherein T3 ranges from 50 to 75°C, to obtain a third product, and wherein the third product comprises 1,1,2,3-tetrachloropropane;

[0177] f) subjecting the third product to a first conversion sub-system, thereby forming 1,1,2,3-tetrachloropropene.

[0178] According to a preferred embodiment, the method of the second aspect of the present application further comprises a step d) of subjecting the third product to a first purification device, thereby forming a fourth product and a fifth product, wherein the fourth product comprises 1,1,2,3-tetrachloropropane and the fifth product comprises 1,2,3-trichloropropane.

[0179] According to a preferred embodiment, the method of the second aspect of the present application, the step d) further forms a sixth product, the sixth product comprising pentachloropropane.

[0180] According to a preferred embodiment, the method of the second aspect of the present application further comprises a step e) of subjecting the fifth product to the first chlorination reaction of step a).

[0181] The steps a), b), c), d) and e) of the second aspect of the present application, as well as the first product, the second product, the third product, the fourth product, the fifth product and the sixth product of the second aspect, are as described in the first aspect of the present application.

[0182] The step f) of the second aspect of the present application can be performed by means well known to the person skilled in the art.

[0183] According to an exemplary and non-limiting embodiment, the step f) of the second aspect of the present application comprises the following sub-steps:

[0184] f-1) subjecting the third product or the fourth product to a first reactor and introducing a first caustic solution and a first phase transfer catalyst into the first reactor, so that a de-HCl reaction occurs in the first reactor, resulting in a seventh product, the seventh product comprising trichloropropene;

[0185] f-2) subjecting the seventh product to a second reactor and introducing chlorine gas into the second reactor, so that a chlorination reaction occurs in the second reactor, resulting in an eighth product, the eighth product comprising pentachloropropane;

[0186] f-3) optionally subjecting the eighth product to a second purification device, resulting in a ninth product, the ninth product comprising pentachloropropane;

[0187] f-4) subjecting the eighth or the ninth product to a third reactor and introducing a second liquid caustic and a second phase transfer catalyst into the third reactor, so that a dehydrochlorination reaction occurs in the third reactor, thereby resulting in a tenth product, the tenth product comprising 1,1,2,3-tetrachloropropene and 2,3,3,3-tetrachloropropene.

[0188] In a preferred embodiment, the content of 1,1,2,3-tetrachloropropene in the tenth product is at least 60 mol%, or at least 65 mol%, or at least 70 mol%, or at least 75 mol%, or at least 80 mol%, or at least 85 mol%, or at least 90 mol%, or at least 95 mol%, or at least 99 mol%, relative to the total number of moles of C3 to C5 halogenated hydrocarbons in the tenth product. According to an embodiment, the content of 1,1,2,3-tetrachloropropene in the tenth product is less than 99.99 mol%, or less than 99.9 mol%, or less than 99 mol%, relative to the total number of moles of C3 to C5 halogenated hydrocarbons in the tenth product.

[0189] In a preferred embodiment, the step f) further comprises the following sub-step:

[0190] f-5) introducing the tenth product into a fourth reactor, so that an isomerization reaction occurs, obtaining an eleventh product comprising 1,1,2,3-tetrachloropropene.

[0191] According to a preferred embodiment, the isomerization reaction is a photocatalytic isomerization reaction.

[0192] The sub-step f-5) is configured so that the 2,3,3,3-tetrachloropropene contained in the tenth product is converted into 1,1,2,3-tetrachloropropene.

[0193] According to a preferred embodiment, in the step f-5) the conversion of 2,3,3,3-tetrachloropropene into 1,1,2,3-tetrachloropropene is at least 50 mol%, or at least 55 mol%, or at least 60 mol%, or at least 65 mol%, or at least 70 mol%, or at least 75 mol%, or at least 80 mol%, or at least 85 mol%, or at least 90 mol%, or at least 95 mol%, or at least 99 mol%.

[0194] According to an embodiment, in the step f-5) the conversion of 2,3,3,3-tetrachloropropene into 1,1,2,3-tetrachloropropene is less than 99.9 mol%, or less than 99 mol%, or less than 95 mol%, or less than 90 mol%.

[0195] According to a preferred embodiment, in the method of the second aspect of the application, the step c) further comprises introducing the sixth product into the third reactor.

[0196] More specifically, the step f) of the method of the second aspect of the application and each of its sub-steps can be carried out, for example, by using the method described in patent application CN116444339A.

[0197] The third aspect of the present application relates to 1,1,2,3-tetrachloropropane product prepared by the method of the first aspect of the present application. The fourth aspect of the present application relates to 1,1,2,3-tetrachloropropene product prepared by the method of the second aspect of the present application.

[0198] The present application will be further described below in conjunction with specific examples. It should be understood that the following examples are only intended to illustrate the present application, and not to limit the present application in any way.

[0199] Examples

[0200] The equipment and sample information used in the examples of the present application are as follows:

[0201] 1,3-dichloropropene: Jiangsu Congzhong Chemical Co., Ltd.

[0202] 3-chloropropene: Jinan Shiji Tongda Chemical Co., Ltd.

[0203] Cl2: Jiangsu Ruishaoke Electronic Material Co., Ltd.

[0204] NaOH: Jinan Jinhu Chemical Co., Ltd.

[0205] The phase transfer catalyst is one or two or three of hexadecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, and tetradecyl dimethyl benzyl ammonium chloride, which is purchased from Shanghai Ziyi Reagent Factory.

[0206] Chromatograph: Agilent Technology (China) Co., Ltd. 8860GC

[0207] UV light source: CEL-LAM500 long-arc mercury lamp light source purchased from Beijing Zhongjiao Jin Yuan Technology Co., Ltd.

[0208] Rectification device: glass batch rectification device purchased from Aishengke (Jiangsu) Chemical Technology Co., Ltd.

[0209] Example 1: synthesis of 1,1,2,3-tetrachloropropane from 1,3-dichloropropene and 3-chloropropene mixed raw materials

[0210] A 500 mL four-necked round-bottom flask (chlorination reactor) equipped with a cold water condenser, a thermometer, stirring, and a gas inlet tube was charged with 400.7 g of a mixture of 1,3-dichloropropene and 3-chloropropene (molar ratio 1:1). The primary tail gas was absorbed by chloropropene, and the secondary tail gas was absorbed by alkali. The single-pot batch chlorination was monitored by GC.

[0211] Under light shielding environment, the temperature was lowered to T1 = 20℃±3℃, and chlorine gas was bubbled under the liquid surface. The amount of chlorine gas was 1.1 eq, and the reaction was carried out for 2 h. The conversion rate of 3-chloropropene was 99.1%, the conversion rate of 1,3-dichloropropene was 4.3%, and the selectivity of 1,2,3-trichloropropane was 97.2%.(denoted as 1-1 in Table 1)

[0212] The reaction temperature was changed and maintained at T2 = 10°C, and the reaction mixture was further irradiated with the UV lamp, the chlorine amount was 1.5 eq, and the reaction was carried out for 4 h, and the conversion of 1,2,3-trichloropropane was 47.5% (denoted as 1-2, UV in Table 1).

[0213] Subsequently, the UV lamp was turned off, the temperature was adjusted to T3 = 60°C, the chlorine amount was 1.5 eq, and the reaction was carried out for 3 h, and the conversion of 1,3-dichloropropene was 99.8%.

[0214] The final target mixture product stream contained 1,1,2,3-tetrachloropropane, 1,2,2,3-tetrachloropropane, 1,1,2,2,3-pentachloropropane, 1,1,1,2,3-pentachloropropane, 1,1,2,3,3-pentachloropropane, and other selectivities of 76.5%, 15.6%, 4.3%, 1.9%, 0.5%, and 1.2%, respectively.

[0215] After the reaction solution was refluxed with nitrogen to chase the chlorine, purified 1,1,2,3-tetrachloropropane (GC normalized content > 99.5%) was obtained by rectification separation.

[0216] Example 2: Example 1 was repeated, except that T2 was -10°C.

[0217] Comparative Example 1: Example 1 was repeated, except that T2 was 60°C.

[0218] Comparative Example 2: Example 1 was repeated, except that T1 was 60°C.

[0219] Comparative Example 3: Example 1 was repeated, except that both T1 and T2 were 60°C, and T3 was 80°C.

[0220] After each reaction, the conversion of 3-chloropropene, the conversion of 1,3-dichloropropene, the conversion of 1,2,3-trichloropropane, the selectivity of 1,1,2,3-tetrachloropropane, the selectivity of 1,2,2,3-tetrachloropropane, the selectivity of pentachloropropane, and the content of other heavy components were summarized in Table 1 below. Each selectivity described in Table 1 is the result calculated after step c) was completed. In Table 1:

[0221] - the conversion of 3-chloropropene Conv c总；3-氯丙烯 which can be calculated by Formula 7:

[0222] where N% is the mole fraction of 3-chloropropene in the raw material 0；3-氯丙烯 which is the mole fraction of 3-chloropropene in the third product measured at the end of step c); c；3-氯丙烯 which is the mole fraction of 3-chloropropene in the third product measured at the end of step c);

[0223] - conversion of 1,3-dichloropropene, Convc totai; 1,3-dichloropropene can be calculated by formula 8:

[0224] wherein N%o; 1,3-dichloropropene refers to the molar fraction of 1,3-dichloropropene in the feedstock, N%c; 1,3-dichloropropene refers to the molar fraction of 1,3-dichloropropene in the third product as measured at the end of step c);

[0225] - conversion of 1,2,3-trichloropropane, Convc totai; 1,2,3-trichloropropane can be calculated by formula 9:

[0226] wherein N%b; 1,2,3-trichloropropane refers to the molar fraction of 1,2,3-trichloropropane in the second product as measured at the end of step b), N%c; 1,2,3-trichloropropane refers to the molar fraction of 1,2,3-trichloropropane in the third product as measured at the end of step c);

[0227] - selectivity of 1,1,2,3-tetrachloropropane, Selectc totai; 1,1,2,3-tetrachloropropane can be calculated by formula 10:

[0228] wherein N%c; 1,1,2,3-tetrachloropropane refers to the molar fraction of 1,1,2,3-tetrachloropropane in the third product as measured at the end of step c), N%o; 1,3-dichloropropene refers to the molar fraction of 1,3-dichloropropene in the feedstock, N%b; 1,2,3-trichloropropane refers to the molar fraction of 1,2,3-trichloropropane in the second product as measured at the end of step b), N%a; 3-chloropropene refers to the molar fraction of 3-chloropropene in the feedstock, N%c; 1,3-dichloropropene refers to the molar fraction of 1,3-dichloropropene in the third product as measured at the end of step c), N%b; 1,2,3-trichloropropane refers to the molar fraction of 1,2,3-trichloropropane in the third product as measured at the end of step c), N%a; 3-chloropropene refers to the molar fraction of 3-chloropropene in the third product as measured at the end of step c). 0；3-氯丙烯 refers to the molar fraction of 3-chloropropene in the feedstock; N%c; 1,3-dichloropropene refers to the molar fraction of 1,3-dichloropropene in the third product, N%b; 1,2,3-trichloropropane refers to the molar fraction of 1,2,3-trichloropropane in the third product. c；3-氯丙烯 refers to the molar fraction of 3-chloropropene in the third product;

[0229] - selectivity of 1,2,2,3-tetrachloropropane, Selectc totai; 1,2,2,3-tetrachloropropane can be calculated by formula 11 :

[0230] wherein N%c; 1,2,2,3-tetrachloropropane refers to the molar fraction of 1,2,2,3-tetrachloropropane in the third product as measured at the end of step c), N%o; 1,3-dichloropropene refers to the molar fraction of 1,3-dichloropropene in the feedstock, N%b; 1,2,3-trichloropropane refers to the molar fraction of 1,2,3-trichloropropane in the second product as measured at the end of step b), N%a; 3-chloropropene refers to the molar fraction of 3-chloropropene in the feedstock, N%c; 1,3-dichloropropene refers to the molar fraction of 1,3-dichloropropene in the third product as measured at the end of step c), N%b; 1,2,3-trichloropropane refers to the molar fraction of 1,2,3-trichloropropane in the third product as measured at the end of step c), N%a; 3-chloropropene refers to the molar fraction of 3-chloropropene in the third product as measured at the end of step c). 0；3-氯丙烯 refers to the molar fraction of 3-chloropropene in the feedstock; N%c; 1,3-dichloropropene refers to the molar fraction of 1,3-dichloropropene in the third product, N%b; 1,2,3-trichloropropane refers to the molar fraction of 1,2,3-trichloropropane in the third product. c；3-氯丙烯 refers to the molar fraction of 3-chloropropene in the third product;

[0231] - selectivity of pentachloropropane, Select c总；五氯丙烷which can be calculated by formula 12:

[0232] wherein N% is the molar fraction of 1,3-dichloropropene in the third product at the end of step c), N%0; N% is the molar fraction of 1,3-dichloropropene in the raw material, N%0 c；五氯丙烷 wherein N% is the molar fraction of 1,3-dichloropropene in the third product at the end of step c), N%0; N% is the molar fraction of 1,3-dichloropropene in the raw material, N%0 0；3-氯丙烯 wherein N% is the molar fraction of 1,3-dichloropropene in the third product at the end of step c), N%0; N% is the molar fraction of 1,3-dichloropropene in the raw material, N%0 c；3-氯丙烯 wherein N% is the molar fraction of 1,3-dichloropropene in the third product at the end of step c), N%0; N% is the molar fraction of 1,3-dichloropropene in the raw material, N%0

[0233] The content of "other chlorinated heavy components" in Table 1 can be calculated by formula 13: c；其他 = 1 - N% c；氯丙烯 N% c；二氯丙烯 N% c；三氯丙烷 N% c；四氯丙烷 N% c；五氯丙烷 N% c；四氯丙烯

[0234] wherein the content of each component is expressed in the same way as in formulae 1 to 12.

[0235] Table 1

[0236] Note: Both the conversion and the selectivity are the total normalized results after the second chlorination is completed.

[0237] Example 3: Synthesis of pentachloropropane from 1,1,2,3-tetrachloropropane

[0238] The 1,1,2,3-tetrachloropropane 959 g (purity 99.5%, 0.55 mol) from Example 1 and a phase transfer catalyst 0.3 wt.% were added to a four-necked flask equipped with a thermometer and a stirrer, and the temperature was raised to 60°C. Then, a 20 wt.% NaOH aqueous solution (molar ratio of NaOH to tetrachloropropane 1.05:1) was added dropwise for 2 h. The reaction was carried out at 60°C for 3 h, and the pH was about 14. After the reaction was completed, the pH was adjusted to about 7, and the oil phase was separated by standing. The conversion of tetrachloropropane was 100%, and the total selectivity of trichloropropene was 98.6%.

[0239] The above trichloropropene isomer reaction solution was chlorinated for 3 h under the conditions of light shielding, chlorine flow 12 to 15 L / h, and temperature 50°C. The conversion of trichloropropene was greater than 99%, and the total selectivity of 1,1,2,2,3-pentachloropropane and 1,1,1,2,3-pentachloropropane was 99%. After the reaction solution was chased with chlorine under nitrogen reflux, purified pentachloropropane (GC normalized content >95%) was obtained by rectification separation.

[0240] Example 4: Synthesis of 1,1,2,3-tetrachloropropene from pentachloropropane

[0241] Purified pentachloropropane 848.02 g from Example 2 and phase transfer catalyst 0.3 wt.% were charged into a four-necked flask equipped with a thermometer and a stirrer, heated to 80 °C, and 20% NaOH solution was added dropwise (molar ratio of NaOH to pentachloropropane was 1.05:1), dropwise addition was completed in 2 h, and the reaction was kept at 80 °C for 2 h. The conversion of pentachloropropane was 96%, and the selectivity of tetrachloropropene product was 98%.

[0242] From the results of Table 1, it can be seen that:

[0243] The method of the first aspect of the present application can highly selectively convert the starting material into 1,1,2,3-tetrachloropropane and avoid the generation of 1,2,2,3-tetrachloropropane. In addition, from the comparison of the results in Example 1 and Example 2, it can be seen that the use of a lower reaction temperature in step b) of the first aspect of the present application can further improve the selectivity of 1,1,2,3-tetrachloropropane and further inhibit the selectivity of 1,2,2,3-tetrachloropropane.

[0244] The formation of 1,1,2,3-tetrachloropropane and the inhibition of the generation of 1,2,2,3-tetrachloropropane with high selectivity requires the joint action of T1, T2 and T3. The results of Comparative Examples 1-3 show that as long as any one of T1, T2 and T3 does not meet the range in the first aspect of the present application, the selectivity of 1,1,2,3-tetrachloropropane will be significantly reduced, and the selectivity of the undesired 1,2,2,3-tetrachloropropane will be significantly increased.

[0245] Therefore, by controlling the reaction conditions of each stage, especially the reaction temperature, the present application controls the reactions of 1,3-dichloropropene and 3-chloropropene in the starting material, respectively, so that the reactions of the two do not interfere with each other, thereby effectively controlling the addition and substitution chlorination of 1,3-dichloropropene and 3-chloropropene and the depth of chlorination. Further, the method of the present application can make 1,3-dichloropropene and 3-chloropropene both highly selectively converted into 1,1,2,3-tetrachloropropane, especially highly selectively form 1,1,2,3-tetrachloropropane relative to 1,2,2,3-tetrachloropropane which is not prone to dehydrochlorination. 1,1,2,3-tetrachloropropane can then be converted into 1,1,2,3-tetrachloropropene.

[0246] The above is only a preferred embodiment of the present application, it should be noted that the above preferred embodiment should not be regarded as limiting the present application, the protection scope of the present application should be limited by the scope defined in the claims. For those skilled in the art, several improvements and refinements can be made without departing from the spirit and scope of the present application, and these improvements and refinements should also be regarded as the protection scope of the present application.

Claims

1. Process for the production of 1,1,2,3-tetrachloropropane from a mixture of 1,3- dichloropropene and 3-chloropropene, said process comprising the steps of: a) subjecting a feedstock comprising a mixture of 1,3-dichloropropene and 3- chloropropene and Cl2 to a first chloro-addition reaction at a temperature T1, obtaining a first product, wherein T1 ranges from 15 to 50 °C, or from 15 to 45 °C, or from 15 to 40 °C, or from 15 to 35 °C, or from 15 to 30 °C, or from 15 to 25 °C, said first product comprising 1,3- dichloropropene and 1,2,3-trichloropropane; preferably wherein the molar ratio of 1,3-dichloropropene to 3-chloropropene in the feedstock is from 5:95 to 95:5, or from 10:90 to 90:10, or from 20:80 to 80:20, or from 30:70 to 70:30, or from 40:60 to 60:40; and / or The ratio N of the molar amount of Cl2 in step a) to the total molar amount of 1,3-dichloropropene and 3-chloropropene in the raw material 0；Cl2 The ratio N of the molar amount of Cl2 in step a) to the total molar amount of 1,3-dichloropropene and 3-chloropropene in the raw material 0；Cl2 :(N 0；1,3-二氯丙烯 +N 0；3-氯丙烯 0.1 to 10, or 0.1 to 9, or 0.1 to 8, or 0.1 to 7, or 0.1 to 6, or 0.1 to 5, or 0.1 to 4, or 0.1 to 3, or 0.1 to 2, or 0.1 to 1.5; and / or the duration of step a) is from 0.1 to 10 hours, or from 0.1 to 9 hours, or from 0.1 to 8 hours, or from 0.1 to 7 hours, or from 0.1 to 6 hours, or from 0.1 to 5 hours, or from 0.1 to 4 hours, or from 0.5 to 3 hours, or from 0.5 to 2.5 hours; and / or the conversion of 3-chloropropene in step a) is greater than 80%, or greater than 90%, or greater than 95%, or greater than 99%; and / or the conversion of 1,3-dichloropropene in step a) is less than 10%, or less than 8%, or less than 7%, or less than 6%, or less than 5%; and / or the selectivity to 1,2,3-trichloropropane in step a) is greater than 80%, or greater than 85%, or greater than 90, or greater than 95%; b) subjecting said first product to a first chloro-substitution reaction under UV at a temperature T2, obtaining a second product, wherein T2 ranges from -20 to 15 °C, or from -18 to 14 °C, or from -16 to 13 °C, or from -14 to 12 °C, or from -12 to 11 °C, said second product comprising 1,3-dichloropropene and 1,1,2,3-tetrachloropropane; preferably: in step b), the equivalent ratio of Cl2 to said first product is from 0.1 to 10, or from 0.1 to 9, or from 0.1 to 8, or from 0.1 to 7, or from 0.1 to 6, or from 0.1 to 5, or from 0.1 to 4, or from 0.1 to 3, or from 0.5 to 2.5, or from 1 to 2; and / or the UV power used in step b) is less than or equal to 500 W, preferably from 5 to 50 W; and / or the duration of step b) is from 0.1 to 10 hours, or from 0.1 to 9 hours, or from 0.1 to 8 hours, or from 0.1 to 7 hours, or from 0.1 to 6 hours; and / or at the end of step b), the overall conversion of 1,3-dichloropropene is less than 10%, or less than 8%, or less than 7%, or less than 6%, or less than 5%; and / or at the end of step b), the molar ratio of 1,1,2,3-tetrachloropropane to 1,2,2,3- tetrachloropropane is greater than 50:50, or greater than 60:40, or greater than 70:30, or greater than 80:20, or greater than 90:10, or greater than 95:5; c) subjecting the second product to a second chloro-addition reaction at a temperature T3, wherein T3 ranges from 50 to 75 °C, or from 55 to 70 °C, or from 55 to 65 °C, to obtain a third product, and the third product comprises 1,1,2,3-tetrachloropropane; Preferably The duration of step c) is from 0.1 to 10 hours, or from 0.1 to 9 hours, or from 0.1 to 8 hours, or from 0.1 to 7 hours, or from 0.1 to 6 hours, or from 0.1 to 5 hours; and / or In step c), the equivalent ratio of Cl2 to the second product is from 0.1 to 10, or from 0.1 to 9, or from 0.1 to 8, or from 0.1 to 7, or from 0.1 to 6, or from 0.1 to 5, or from 0.1 to 4, or from 0.1 to 3, or from 0.5 to 2.5, or from 1 to 2; and / or In step c), the conversion of 1,3-dichloropropene is at least 80%, or at least 85%, or at least 90%, or at least 95%, or at least 99%; and / or The third product further comprises one or more of 1,2,2,3-tetrachloropropane, 1,3-dichloropropene, 3-chloropropene, 1,2,3-trichloropropane, pentachloropropane; and / or In the third product, the sum of the contents of 1,1,2,3-tetrachloropropane and 1,2,2,3-tetrachloropropane is greater than 50 mole%, or greater than 60%, or greater than 70%, or greater than 80%, or greater than 90%, relative to the total moles of C3 to C5 halogenated hydrocarbons in the third product; and / or In the third product, the content of 1,1,2,3-tetrachloropropane is greater than 50 mole%, or greater than 60 mole%, or greater than 70 mole%, or greater than 80 mole%, or greater than 90 mole%, relative to the total moles of C3 to C5 halogenated hydrocarbons in the third product; and / or In the third product, the molar ratio of 1,1,2,3-tetrachloropropane to 1,2,2,3-tetrachloropropane is greater than 50:50, or greater than 60:40, or greater than 70:30, or greater than 80:20, or greater than 90:10, or greater than 95:

5.

2. The process of claim 1, wherein the process further comprises step d): subjecting the third product to a first purification device, thereby forming a fourth product and a fifth product, wherein the fourth product comprises 1,1,2,3-tetrachloropropane, and the fifth product comprises 1,2,3-trichloropropane; Preferably: In the fourth product, the content of 1,1,2,3-tetrachloropropane is greater than 60 mole%, or greater than 70 mole%, or greater than 80 mole%, or greater than 90 mole%, relative to the total moles of C3 to C5 halogenated hydrocarbons in the fourth product; and / or In the fifth product, the content of 1,2,3-trichloropropane is greater than 60 mole%, or greater than 70 mole%, or greater than 80 mole%, or greater than 90 mole%, relative to the total moles of C3 to C5 halogenated hydrocarbons in the third product; and / or In the step d), a sixth product is further formed, the sixth product comprising pentachloropropane; and / or The fifth product comprises more than 60 mole %, or more than 70 mole %, or more than 80 mole %, or more than 90 mole % of pentachloropropane relative to the total moles of C3 to C5 halogenated hydrocarbons in the third product.

3. The method according to claim 2, wherein the method further comprises step e) returning the fifth product to the first chlorination reaction in step a).

4. A method for producing 1,1,2,3-tetrachloropropane from a mixture of 1,3- dichloropropene and 3-chloropropene, the method comprising the following steps: a) subjecting a feedstock comprising a mixture of 1,3-dichloropropene and 3- chloropropene and Cl2 to a first chloro-addition reaction at a temperature T1, wherein T1 ranges from 15 to 50 °C, to obtain a first product; b) subjecting the first product to a first chloro-substitution reaction under UV at a temperature T2, wherein T2 ranges from -20 to 15 °C, to obtain a second product; c) subjecting the second product to a second chloro-addition reaction at a temperature T3, wherein T3 ranges from 50 to 75 °C, to obtain a third product, and the third product comprises 1,1,2,3-tetrachloropropane; optionally d) subjecting the third product to a first purification device, thereby forming a fourth product and a fifth product, wherein the fourth product comprises 1,1,2,3- tetrachloropropane, and the fifth product comprises 1,2,3-trichloropropane; preferably the step d) further forms a sixth product, the sixth product comprising pentachloropropane; optionally e) returning the fifth product to the first chlorination reaction in step a); f) subjecting the third product to a first conversion sub-system, thereby forming 1,1,2,3- tetrachloropropene.

5. The method according to claim 4, wherein the step f) comprises the following sub-steps: f-1) subjecting the third product or fourth product to a first reactor, and introducing a first caustic solution and a first phase transfer catalyst into the first reactor, such that a de-HCl reaction occurs in the first reactor, to obtain a seventh product, the seventh product comprising trichloropropene; f-2) subjecting the seventh product to a second reactor, and introducing chlorine gas into the second reactor, such that a chlorination reaction occurs in the second reactor, to obtain an eighth product, the eighth product comprising pentachloropropane; f-3) optionally subjecting the eighth product to a second purification device, to obtain a ninth product, the ninth product comprising pentachloropropane; f-4) subjecting the eighth or ninth product to a third reactor, and introducing a second caustic solution and a second phase transfer catalyst into the third reactor, such that a dehydrochlorination reaction occurs in the third reactor, to obtain a tenth product, the tenth product comprising 1,1,2,3-tetrachloropropene and 2,3,3,3- tetrachloropropene; optionally f-5) subjecting the tenth product to a fourth reactor, to undergo an isomerization reaction, to obtain an eleventh product comprising 1,1,2,3-tetrachloropropene; preferably the tenth product, the content of 1,1,2,3-tetrachloropropene is at least 60 mol%, or at least 65 mol%, or at least 70 mol%, or at least 75 mol%, or at least 80 mol%, or at least 85 mol%, or at least 90 mol%, or at least 95 mol%, or at least 99 mol%, relative to the total number of moles of C3 to C5 halogenated hydrocarbons in the tenth product; and / or the isomerization reaction is a photocatalytic isomerization reaction; and / or in step f-5), at least 50 mol%, or at least 55 mol%, or at least 60 mol%, or at least 65 mol%, or at least 70 mol%, or at least 75 mol%, or at least 80 mol%, or at least 85 mol%, or at least 90 mol%, or at least 95 mol%, or at least 99 mol%, or 100 mol% of the 2,3,3,3-tetrachloropropene is converted into 1,1,2,3-tetrachloropropene; and / or step c) comprises passing the sixth product into the third reactor.

6. A 1,1,2,3-tetrachloropropane product prepared by the process of any one of claims 1-3.

7. A 1,1,2,3-tetrachloropropene product prepared by the process of any one of claims 4-5.

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