A metal-carbon composite catalyst and method for the continuous preparation of 1,1,1,3-tetrachloropropane

Abstract

This invention discloses a metal-carbon composite catalyst and method for the continuous preparation of 1,1,1,3-tetrachloropropane. The main component of the catalyst is Cu-Ni-Cl-C / Fe, and the catalyst preparation process includes four steps: mixing, carbonization, displacement, and loading. The catalyst of this invention can efficiently catalyze the telomerization reaction of carbon tetrachloride and ethylene, generating the target product 1,1,1,3-tetrachloropropane with high selectivity. The catalyst exhibits stable performance, maintaining good catalytic effect even after five repeated uses. The conversion rate of carbon tetrachloride and ethylene reaches over 95%, and the selectivity of 1,1,1,3-tetrachloropropane is greater than 98.5%.

Description

Technical Field

[0001] This invention belongs to the field of catalysis technology and relates to a method for preparing chloroalkanes via telomerization reaction, specifically a metal-carbon composite catalyst and method for the continuous preparation of 1,1,1,3-tetrachloropropane. Background Technology

[0002] 1,1,1,3-Tetrachloropropane is an important fine chemical product with wide applications in pesticides, pharmaceuticals, and dyes. It is a crucial raw material for the preparation of 1-chloro-3,3,3-trifluoropropane and 3,3,3-trifluoropropene. 1-Chloro-3,3,3-trifluoropropane is an environmentally friendly cleaning solvent with the potential to replace traditional environmentally unfriendly cleaning agents, thus attracting considerable attention. 3,3,3-trifluoropropene is a basic raw material for the synthesis of fluorosilicone rubber, fluorosilicone oil, and fluorosilicone coatings. It can also serve as a pesticide and pharmaceutical intermediate and a substitute for Freon, possessing significant market potential. With the large-scale application of 1-chloro-3,3,3-trifluoropropane and 3,3,3-trifluoropropene, higher demands are placed on the production capacity and quality of the raw material 1,1,1,3-tetrachloropropane. Therefore, actively researching and developing synthetic methods for 1,1,1,3-tetrachloropropane has significant practical and application value.

[0003] Chinese Patent 202010337171.9 discloses a method for preparing 1,1,1,3-tetrachloropropane, specifically employing a forced circulation method in an enhanced reactor to react carbon tetrachloride and ethylene to produce 1,1,1,3-tetrachloropropane. The process has low energy consumption and is easy to control, improving material utilization through the circulation of carbon tetrachloride and ethylene. To further improve the single-pass conversion rate of carbon tetrachloride and ethylene, it is still necessary to focus on the catalyst, accelerating the reaction rate and enhancing the reaction depth. Chinese Patent 201911249445.2 discloses a method for the continuous preparation of 1,1,1,3-tetrachloropropane, using a traditional fixed-bed tubular reactor to achieve continuous synthesis of 1,1,1,3-tetrachloropropane, obtaining a product yield of 97% after distillation separation. Although this method achieves continuous production, it still uses a traditional iron-based catalyst, which itself has room for improvement; the conversion rate of ethylene and the selectivity of the target product need to be improved. Similarly, Chinese patent 201510130347.2 also discloses a continuous method for preparing 1,1,1,3-tetrachloropropane. This method solves the coking problem from the perspective of process improvement, but does not further optimize the (traditional iron-based) catalyst.

[0004] Chinese patent 202110143120.7 improves upon the catalyst, disclosing a method for preparing 1,1,1,3-tetrachloropropane. This method provides an approach to supported iron catalysts, overcoming the problem of agglomeration in traditional iron powder catalysts, and also adds a second catalyst to ensure efficient reaction operation. However, the catalyst contains precious metals, resulting in higher costs. Furthermore, supported catalysts are prone to loss under the described batch reaction conditions, leading to reduced catalyst activity, especially the potential loss of precious metals. Therefore, further optimization of the catalyst is still needed. Summary of the Invention

[0005] To address the problems and shortcomings of existing technologies, this invention provides a metal-carbon composite catalyst for the continuous preparation of 1,1,1,3-tetrachloropropane, and a method for the continuous preparation of 1,1,1,3-tetrachloropropane using this catalyst.

[0006] The metal-carbon composite catalyst provided by this invention has an elemental composition of Cu-Ni-Cl-C / Fe, and the catalyst support is iron foam. The mass contents of Cu, Ni, Cl and C are 1.2%–2.3%, 0.8%–1.3%, 3.2%–6.1% and 0.1%–0.4%, respectively.

[0007] The method for preparing the metal-carbon composite catalyst of the present invention includes the following steps:

[0008] Step 1: Immerse the foamed iron completely in a saturated monosaccharide aqueous solution for 2-5 minutes, remove it, dry it at 100-150°C for 1-3 hours, and then repeat the immersion in the saturated monosaccharide aqueous solution. Repeat the above operation 2-5 times.

[0009] Step 2: Place the foamed iron obtained in Step 1 into a carbonization furnace and carbonize it at 550-650℃ for 3-5 hours in a nitrogen atmosphere;

[0010] Step 3: Completely immerse the carbonized foamed iron from Step 2 in a nickel chloride aqueous solution for 10-30 minutes, remove it, dry it at 100-150℃ for 1-3 hours, and then completely immerse it in a copper chloride aqueous solution for 10-30 minutes, remove it, and dry it at 100-150℃ for 1-3 hours.

[0011] Step 4: Immerse the foamed iron obtained in Step 3 completely in alkyl phosphate for 2-5 minutes, remove it, and dry it at 100-150℃ for 1-3 hours to obtain the metal-carbon composite catalyst.

[0012] In step one above, the foamed iron has a size of 2.4–4.7 mm, is irregularly shaped granules, has a pore size of 0.1–0.2 mm, a porosity of 95%–97%, a permeability ≥97%, and a bulk density of 0.13–0.20 g / cm³.3 .

[0013] Furthermore, in step one above, the monosaccharide is preferably one or two of D-glucose, D-galactose, and D-mannose.

[0014] Furthermore, in step three above, the preferred mass concentration of the nickel chloride aqueous solution and the copper chloride aqueous solution is 5.0% to 10.0%.

[0015] Furthermore, in step four above, the alkyl phosphate is preferably one or two of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, and tributyl phosphate.

[0016] The method for continuous preparation of 1,1,1,3-tetrachloropropane using a metal-carbon composite catalyst of the present invention is as follows: the metal-carbon composite catalyst is loaded into a fixed-bed reactor, the reaction system is replaced with nitrogen, ethylene is then introduced, and after setting the reaction temperature and pressure, carbon tetrachloride is introduced. Ethylene and carbon tetrachloride undergo a telomerization reaction on the catalyst. The reacted material is then subjected to gas-liquid separation and purification to obtain 1,1,1,3-tetrachloropropane.

[0017] Furthermore, in the above-described method for the continuous preparation of 1,1,1,3-tetrachloropropane, the preferred reaction temperature is 90–130°C, the pressure is 0.5–1.2 MPa, and the volume hourly space velocity (VHSV) of carbon tetrachloride is 0.1–0.15 h⁻¹. -1 The molar ratio of nitrogen to ethylene is 1:0.5 to 2, and the molar ratio of ethylene to carbon tetrachloride is 1.2 to 2:1.

[0018] The beneficial effects of this invention are as follows:

[0019] 1. The catalyst of this invention has stable performance, high catalytic efficiency, and high utilization rate of carbon tetrachloride and ethylene. Under optimal conditions, the conversion rate of carbon tetrachloride and ethylene reaches over 95%, and the selectivity of 1,1,1,3-tetrachloropropane is greater than 98.5%.

[0020] 2. The catalyst of this invention exhibits good selectivity in catalytic polymerization, high yield of the target product, and less than 1.5% byproducts;

[0021] 3. The catalyst of this invention has a hierarchical porous structure. The abundant hierarchical pores are beneficial to diffusion and mass transfer, and can significantly reduce the diffusion effect.

[0022] 4. The Fe, Ni, Cu and C species on the catalyst of this invention are uniformly dispersed and have strong interaction forces, which is beneficial to improving the catalyst activity.

[0023] 5. This invention uses foamed iron as a base material and cleverly loads carbon, nickel and copper elements onto the catalyst through carbonization and displacement reactions, and also achieves the redistribution of ferric chloride. Detailed Implementation

[0024] The present invention will be further described in detail below with reference to the embodiments, but the scope of protection of the present invention is not limited to these embodiments.

[0025] Example 1

[0026] The catalyst in this embodiment has an elemental composition of Cu-Ni-Cl-C / Fe, and the catalyst support is iron foam. The mass contents of Cu, Ni, Cl, and C are 1.4%, 0.8%, 4.3%, and 0.3%, respectively, with the remainder being iron foam. The preparation method of this catalyst is as follows:

[0027] Step 1: Take block-shaped foamed iron (irregular particles, size 2.4-4.7mm, pore diameter 0.1mm, porosity 96%, open porosity ≥97%, bulk density 0.14g / cm³) 3 Completely immerse the sample in a saturated D-glucose aqueous solution for 2 minutes, remove it, and dry it in an oven at 120°C for 1 hour. Then repeat the immersion in the saturated D-glucose aqueous solution four times to complete the mixing step.

[0028] Step 2: Place the foamed iron obtained in Step 1 into a carbonization furnace and carbonize it at 550℃ for 5 hours in a nitrogen atmosphere. After cooling, remove it to complete the carbonization step.

[0029] Step 3: Completely immerse the carbonized foamed iron from Step 2 in a 5.0% nickel chloride aqueous solution for 10 minutes, remove it, and dry it in an oven at 120°C for 1 hour. Then, completely immerse it in a 6.0% copper chloride aqueous solution for 12 minutes, remove it, and dry it in an oven at 120°C for 1 hour to complete the replacement step.

[0030] Step 4: Immerse the foamed iron after replacement in Step 3 in a mixed solution of trimethyl phosphate and triethyl phosphate (mass ratio of trimethyl phosphate to triethyl phosphate is 1:1) for 2 minutes, remove it, and dry it in an oven at 120°C for 1 hour to obtain the catalyst.

[0031] Catalyst performance evaluation: The catalyst was loaded into a fixed-bed reactor, the reaction system was purged with nitrogen, and then ethylene was introduced. The reaction temperature was set to 90℃ and the pressure to 0.9MPa, and the reaction was carried out at a volume hourly space velocity (VHSV) of 0.12h⁻¹. -1 Carbon tetrachloride was introduced, and the molar ratio of nitrogen to ethylene was controlled at 1:1, and the molar ratio of ethylene to carbon tetrachloride at 1.2:1. Ethylene and carbon tetrachloride underwent a telomerization reaction on a catalyst to produce 1,1,1,3-tetrachloropropane. The reactants were then subjected to gas-liquid separation and purification to obtain the 1,1,1,3-tetrachloropropane product. Testing showed a carbon tetrachloride conversion rate of 92%, an ethylene conversion rate of 91%, and a selectivity of 98.5% for 1,1,1,3-tetrachloropropane.

[0032] Example 2

[0033] The catalyst in this embodiment has an elemental composition of Cu-Ni-Cl-C / Fe, and the catalyst support is iron foam. The mass contents of Cu, Ni, Cl, and C are 2.0%, 1.0%, 3.8%, and 0.2%, respectively, with the remainder being iron foam. The preparation method of this catalyst is as follows:

[0034] Step 1: Take block-shaped foamed iron (irregular granules, size 2.4-4.7mm, pore diameter 0.2mm, porosity 95%, open porosity ≥97%, bulk density 0.18g / cm³) 3 Completely immerse the sample in a saturated D-galactose aqueous solution for 3 minutes, remove it, and dry it in an oven at 100°C for 3 hours. Then repeat the immersion in the saturated D-galactose aqueous solution three times to complete the mixing step.

[0035] Step 2: Place the foamed iron obtained in Step 1 into a carbonization furnace and carbonize it at 600℃ for 4 hours in a nitrogen atmosphere. After cooling, remove it to complete the carbonization step.

[0036] Step 3: Completely immerse the carbonized foamed iron from Step 2 in a 7.0% nickel chloride aqueous solution for 20 minutes, remove it, and dry it in an oven at 100°C for 3 hours. Then, completely immerse it in a 9.0% copper chloride aqueous solution for 20 minutes, remove it, and dry it in an oven at 100°C for 3 hours to complete the replacement step.

[0037] Step 4: The foamed iron replaced in Step 3 is completely immersed in a mixed solution of trimethyl phosphate and triethyl phosphate (mass ratio of trimethyl phosphate to triethyl phosphate is 1:1) for 4 minutes, then removed and dried in an oven at 100°C for 3 hours to obtain the catalyst.

[0038] Catalyst performance evaluation: The catalyst was loaded into a fixed-bed reactor, the reaction system was purged with nitrogen, and then ethylene was introduced. The reaction temperature was set to 100℃ and the pressure to 0.5MPa, and the reaction was carried out at a volume hourly space velocity (VHSV) of 0.11h. -1 Carbon tetrachloride was introduced, and the molar ratio of nitrogen to ethylene was controlled at 1:0.8, and the molar ratio of ethylene to carbon tetrachloride at 1.4:1. Ethylene and carbon tetrachloride underwent a telomerization reaction on a catalyst to produce 1,1,1,3-tetrachloropropane. The reactants were then subjected to gas-liquid separation and purification to obtain the 1,1,1,3-tetrachloropropane product. Testing showed a carbon tetrachloride conversion rate of 95%, an ethylene conversion rate of 95%, and a selectivity of 98.5% for 1,1,1,3-tetrachloropropane.

[0039] Example 3

[0040] The catalyst in this embodiment has an elemental composition of Cu-Ni-Cl-C / Fe, and the catalyst support is iron foam. The mass contents of Cu, Ni, Cl, and C are 2.3%, 0.9%, 3.2%, and 0.1%, respectively, with the remainder being iron foam. The preparation method of this catalyst is as follows:

[0041] Step 1: Take block-shaped foamed iron (irregular particles, size 2.4-4.7mm, pore diameter 0.1mm, porosity 97%, open porosity ≥97%, bulk density 0.13g / cm³) 3 Completely immerse the sample in a saturated D-mannose aqueous solution for 4 minutes, remove it, and dry it in an oven at 140°C for 2 hours. Then repeat the immersion in the saturated D-mannose aqueous solution twice to complete the mixing step.

[0042] Step 2: Place the foamed iron obtained in Step 1 into a carbonization furnace and carbonize it at 650℃ for 3 hours in a nitrogen atmosphere. After cooling, remove it to complete the carbonization step.

[0043] Step 3: Completely immerse the carbonized foamed iron from Step 2 in a 6.0% nickel chloride aqueous solution for 30 minutes, remove it, and dry it in an oven at 140°C for 3 hours. Then, completely immerse it in a 10.0% copper chloride aqueous solution for 10 minutes, remove it, and dry it in an oven at 140°C for 2 hours to complete the replacement step.

[0044] Step 4: Immerse the foamed iron replaced in Step 3 completely in tripropyl phosphate for 5 minutes, remove it, and dry it in an oven at 140°C for 2 hours to obtain the catalyst.

[0045] Catalyst performance evaluation: The catalyst was loaded into a fixed-bed reactor, the reaction system was purged with nitrogen, and then ethylene was introduced. The reaction temperature was set to 110℃ and the pressure to 0.8MPa, and the reaction was carried out at a volume hourly space velocity (VHSV) of 0.10h⁻¹. -1 Carbon tetrachloride was introduced, and the molar ratio of nitrogen to ethylene was controlled at 1:0.5, and the molar ratio of ethylene to carbon tetrachloride at 1.6:1. Ethylene and carbon tetrachloride underwent a telomerization reaction on a catalyst to produce 1,1,1,3-tetrachloropropane. The reactants were then subjected to gas-liquid separation and purification to obtain the 1,1,1,3-tetrachloropropane product. Testing showed a carbon tetrachloride conversion rate of 93%, an ethylene conversion rate of 94%, and a selectivity of 98% for 1,1,1,3-tetrachloropropane.

[0046] Example 4

[0047] The catalyst in this embodiment has an elemental composition of Cu-Ni-Cl-C / Fe, and the catalyst support is iron foam. The mass contents of Cu, Ni, Cl, and C are 1.8%, 1.2%, 5.5%, and 0.2%, respectively, with the remainder being iron foam. The preparation method of this catalyst is as follows:

[0048] Step 1: Take block-shaped foamed iron (irregular particles, size 2.4-4.7mm, pore diameter 0.2mm, porosity 96%, open porosity ≥97%, bulk density 0.15g / cm³) 3 Completely immerse the sample in a saturated D-glucose aqueous solution for 4 minutes, remove it, and dry it in an oven at 120°C for 1 hour. Then repeat the immersion in the saturated D-glucose aqueous solution three times to complete the mixing step.

[0049] Step 2: Place the foamed iron obtained in Step 1 into a carbonization furnace and carbonize it at 600℃ for 4 hours in a nitrogen atmosphere. After cooling, remove it to complete the carbonization step.

[0050] Step 3: Completely immerse the carbonized foamed iron from Step 2 in a 9.0% nickel chloride aqueous solution for 20 minutes, remove it, and dry it in an oven at 120°C for 1 hour. Then, completely immerse it in an 8.0% copper chloride aqueous solution for 30 minutes, remove it, and dry it in an oven at 120°C for 1 hour to complete the replacement step.

[0051] Step 4: Immerse the foamed iron replaced in Step 3 completely in trimethyl phosphate for 3 minutes, remove it, and dry it in an oven at 120°C for 1 hour to obtain the catalyst.

[0052] Catalyst performance evaluation: The catalyst was loaded into a fixed-bed reactor, the reaction system was purged with nitrogen, and then ethylene was introduced. The reaction temperature was set to 120℃ and the pressure to 1.2MPa, and the reaction was carried out at a volume hourly space velocity (VHSV) of 0.14h. -1 Carbon tetrachloride was introduced, and the molar ratio of nitrogen to ethylene was controlled at 1:1.5, and the molar ratio of ethylene to carbon tetrachloride at 1.8:1. Ethylene and carbon tetrachloride underwent a telomerization reaction over a catalyst to produce 1,1,1,3-tetrachloropropane. The reactants were then subjected to gas-liquid separation and purification to obtain the 1,1,1,3-tetrachloropropane product. Testing showed a carbon tetrachloride conversion rate of 95%, an ethylene conversion rate of 97%, and a selectivity of 97.4% for 1,1,1,3-tetrachloropropane.

[0053] Example 5

[0054] The catalyst in this embodiment has an elemental composition of Cu-Ni-Cl-C / Fe, and the catalyst support is iron foam. The mass contents of Cu, Ni, Cl, and C are 2.0%, 1.1%, 6.1%, and 0.4%, respectively, with the remainder being iron foam. The preparation method of this catalyst is as follows:

[0055] Step 1: Take block-shaped foamed iron (irregular granules, size 2.4-4.7mm, pore diameter 0.1mm, porosity 95%, open porosity ≥97%, bulk density 0.20g / cm³) 3 Completely immerse the sample in a saturated D-glucose aqueous solution for 4 minutes, remove it, and dry it in an oven at 130°C for 1 hour. Then repeat the immersion in the saturated D-glucose aqueous solution 5 times to complete the mixing step.

[0056] Step 2: Place the foamed iron obtained in Step 1 into a carbonization furnace and carbonize it at 650℃ for 3 hours in a nitrogen atmosphere. After cooling, remove it to complete the carbonization step.

[0057] Step 3: Completely immerse the carbonized foamed iron from Step 2 in an 8.0% nickel chloride aqueous solution for 10 minutes, remove it, and dry it in an oven at 130°C for 1 hour. Then, completely immerse it in a 7.0% copper chloride aqueous solution for 20 minutes, remove it, and dry it in an oven at 130°C for 1 hour to complete the replacement step.

[0058] Step 4: Immerse the foamed iron replaced in Step 3 completely in tributyl phosphate for 4 minutes, remove it, and dry it in an oven at 130°C for 1 hour to obtain the catalyst.

[0059] Catalyst performance evaluation: The catalyst was loaded into a fixed-bed reactor, the reaction system was purged with nitrogen, and then ethylene was introduced. The reaction temperature was set to 130℃ and the pressure to 1.1 MPa, and the reaction was carried out at a volume hourly space velocity (VHSV) of 0.15 h⁻¹. -1 Carbon tetrachloride was introduced, and the molar ratio of nitrogen to ethylene was controlled at 1:2, and the molar ratio of ethylene to carbon tetrachloride at 2:1. Ethylene and carbon tetrachloride underwent a telomerization reaction on a catalyst to produce 1,1,1,3-tetrachloropropane. The reactants were then subjected to gas-liquid separation and purification to obtain the 1,1,1,3-tetrachloropropane product. Testing showed a carbon tetrachloride conversion rate of 97%, an ethylene conversion rate of 98%, and a selectivity of 95.5% for 1,1,1,3-tetrachloropropane.

[0060] Example 6

[0061] The catalyst in this embodiment has an elemental composition of Cu-Ni-Cl-C / Fe, and the catalyst support is iron foam. The mass contents of Cu, Ni, Cl, and C are 1.2%, 1.3%, 4.9%, and 0.3%, respectively, with the remainder being iron foam. The preparation method of this catalyst is as follows:

[0062] Step 1: Take block-shaped foamed iron (irregular particles, size 2.4-4.7mm, pore diameter 0.2mm, porosity 97%, open porosity ≥97%, bulk density 0.17g / cm³) 3 Completely immerse the sample in a saturated aqueous solution of D-galactose and D-mannose for 3 minutes, remove it, and dry it in an oven at 150°C for 1 hour. Then repeat the immersion in the saturated aqueous solution of D-galactose and D-mannose for 4 times to complete the mixing step.

[0063] Step 2: Place the foamed iron obtained in Step 1 into a carbonization furnace and carbonize it at 550℃ for 5 hours in a nitrogen atmosphere. After cooling, remove it to complete the carbonization step.

[0064] Step 3: Completely immerse the carbonized foamed iron from Step 2 in a 10.0% nickel chloride aqueous solution for 30 minutes, remove it, and dry it in an oven at 150°C for 1 hour. Then, completely immerse it in a 5.0% copper chloride aqueous solution for 15 minutes, remove it, and dry it in an oven at 150°C for 1 hour to complete the replacement step.

[0065] Step 4: Immerse the foamed iron replaced in Step 3 completely in triethyl phosphate for 3 minutes, remove it, and dry it in an oven at 150°C for 1 hour to obtain the catalyst.

[0066] Catalyst performance evaluation: The catalyst was loaded into a fixed-bed reactor, the reaction system was purged with nitrogen, and then ethylene was introduced. The reaction temperature was set to 120℃ and the pressure to 0.9MPa, and the reaction was carried out at a volume hourly space velocity (VHSV) of 0.10h⁻¹. -1 Carbon tetrachloride was introduced, and the molar ratio of nitrogen to ethylene was controlled at 1:1.7, and the molar ratio of ethylene to carbon tetrachloride at 1.5:1. Ethylene and carbon tetrachloride underwent a telomerization reaction on a catalyst to produce 1,1,1,3-tetrachloropropane. The reactants were then subjected to gas-liquid separation and purification to obtain the 1,1,1,3-tetrachloropropane product. Testing showed a carbon tetrachloride conversion rate of 94%, an ethylene conversion rate of 97%, and a selectivity of 96.1% for 1,1,1,3-tetrachloropropane.

Claims

1. A metal-carbon composite catalyst for continuously producing 1,1,1,3-tetrachloropropane, characterized by, The element composition of the catalyst is Cu-Ni-Cl-C / Fe, the carrier of the catalyst is foamed iron, and the mass content of Cu, Ni, Cl and C is 1.2-2.3%, 0.8-1.3%, 3.2-6.1% and 0.1-0.4% respectively; The preparation method of the metal-carbon composite catalyst is as follows: Step one: the foamed iron is completely immersed in a saturated monosaccharide aqueous solution for 2-5 minutes, taken out, dried at 100-150 ℃ for 1-3 hours, and then repeatedly immersed in the saturated monosaccharide aqueous solution for 2-5 times; Step two: the foamed iron obtained in step one is placed in a carbonization furnace and carbonized at 550-650 ℃ for 3-5 hours in a nitrogen atmosphere; Step three: the foamed iron after carbonization in step two is completely immersed in a nickel chloride aqueous solution for 10-30 minutes, taken out, dried at 100-150 ℃ for 1-3 hours, and then completely immersed in a copper chloride aqueous solution for 10-30 minutes, taken out, dried at 100-150 ℃ for 1-3 hours; Step four: the foamed iron obtained in step three is completely immersed in an alkyl phosphate for 2-5 minutes, taken out, dried at 100-150 ℃ for 1-3 hours, and a metal-carbon composite catalyst is obtained.

2. The metal-carbon composite catalyst for continuously producing 1,1,1,3-tetrachloropropane according to claim 1, characterized by: The size of the foamed iron is 2.4-4.7 mm, irregular granular shape, pore size 0.1-0.2 mm, porosity 95%-97%, through-hole rate ≥97%, bulk density 0.13-0.20 g / cm 3 .

3. The metal-carbon composite catalyst for continuously producing 1,1,1,3-tetrachloropropane according to claim 1, characterized by, The monosaccharide is one or two of D-glucose, D-galactose and D-mannose.

4. The metal-carbon composite catalyst for continuously producing 1,1,1,3-tetrachloropropane according to claim 1, characterized by, The mass concentration of the nickel chloride aqueous solution and the copper chloride aqueous solution is 5.0-10.0%.

5. The metal-carbon composite catalyst for continuously producing 1,1,1,3-tetrachloropropane according to claim 1, characterized by, The alkyl phosphate is one or two of trimethyl phosphate, triethyl phosphate, tripropyl phosphate and tributyl phosphate.

6. A method for continuously producing 1,1,1,3-tetrachloropropane using the metal-carbon composite catalyst according to claim 1, characterized by, The metal-carbon composite catalyst is loaded into a fixed bed reactor, the reaction system is replaced with nitrogen, then ethylene is introduced, the reaction temperature and pressure are set, carbon tetrachloride is introduced, and the polycondensation reaction of ethylene and carbon tetrachloride occurs on the catalyst, then the reacted materials are subjected to gas-liquid separation and purification, and 1,1,1,3-tetrachloropropane is obtained.

7. The process for the continuous preparation of 1,1,1,3-tetrachloropropane according to claim 6, characterized in that The reaction temperature is 90-130°C, the pressure is 0.5-1.2 MPa, the volume space velocity of carbon tetrachloride is 0.1-0.15 h -1 , the molar ratio of nitrogen and ethylene is 1:0.5-2, and the molar ratio of ethylene to carbon tetrachloride is 1.2-2:1.