Patent application EP19727276A (EP), filed 2019-04-30
Publication number: EP3756758A1
Title: CATALYST FOR PREPARING VINYL CHLORIDE BY CRACKING 1,2-DICHLOROETHANE AND PREPARATION AND REGENERATION METHODS THEREFOR
Abstract: [0001]    A catalyst for preparing chloroethylene by cracking 1,2-dichloroethane and a preparation and regeneration method thereof are disclosed in the present application. A catalyst for preparing chloroethylene by cracking 1,2-dichloroethane comprises a carrier and a nitrogen-containing carbon as an active component of the catalyst with the nitrogen-containing carbon being loaded on the carrier. The method for preparing the catalyst comprises the following steps: supporting an organic matter on an inorganic porous carrier and then performing a carbonization-nitridation process by pyrolysis in an atmosphere containing the nitrogen-containing compound. The method for regenerating the catalyst comprises the following steps: calcinating the catalyst with deactivated carbon deposit in an oxidizing atmosphere to remove all the carbonaceous portions on the surface, and repeating the above preparation process of the catalyst. The catalyst could reduce the reaction temperature, greatly reduce energy consumption, reduce the production cost, and improve the selectivity and conversion rate and is inexpensive and reproducible, and has a long service life in comparison with the existing thermal cracking technology.
IPC codes: B01J  27/    24            A I
B01J  27/    28            A I
B01J  37/    02            A I
B01J  37/    08            A I
B01J  38/    02            A I
C07C  17/    25            A I
C07C  21/    06            A I
B01J  21/    12            A I
B01J  21/    20            A I
Claims: number: 1
text: A catalyst for preparing chloroethylene by cracking 1,2-dichloroethane, wherein the catalyst comprises a carrier and a nitrogen-containing carbon material as an active component of the catalyst; and the nitrogen-containing carbon material is loaded on the carrier;
the carrier is at least one selected from inorganic porous materials;
in the nitrogen-containing carbon material, a nitrogen element is doped in the carbon material in a form of covalent bond.
number: 2
text: The catalyst for preparing chloroethylene by cracking 1,2-dichloroethane according to claim 1, wherein the mass percentage of the nitrogen element in the nitrogen-containing carbon material is in a range from 0.1 % to 20%.
number: 3
text: The catalyst for preparing chloroethylene by cracking 1,2-dichloroethane according to claim 1, wherein the mass percentage of the nitrogen element in the nitrogen-containing carbon material is in a range from 1 % to 9%.
number: 4
text: The catalyst for preparing chloroethylene by cracking 1,2-dichloroethane according to claim 1, wherein the mass percentage of the nitrogen-containing carbon material in the catalyst is in a range from 1 % to 40%.
number: 5
text: The catalyst for preparing chloroethylene by cracking 1,2-dichloroethane according to claim 1, wherein the mass percentage of the nitrogen-containing carbon material in the catalyst is in a range from 8 % to 30%.
number: 6
text: The catalyst for preparing chloroethylene by cracking 1,2-dichloroethane according to claim 1, wherein the inorganic porous material is at least one selected from the group consisting of silicon oxide, aluminum oxide, titanium oxide, and zirconium oxide.
number: 7
text: A preparation method of the catalyst for preparing chloroethylene by cracking 1,2-dichloroethane in any one of claims 1 to 6, wherein the method comprises at least the following steps:
firstly, supporting an organic precursor on an inorganic porous material and then carrying out a carbonization-nitridation reaction by pyrolysis in an atmosphere containing the nitrogen-containing compound.
number: 8
text: The preparation method according to claim 7, wherein the pyrolysis conditions are:
a pyrolysis temperature in a range from 400 □ to 1000 □, and a pyrolysis time in a range from 0.2 hour to 10 hours.
number: 9
text: The preparation method according to claim 7, wherein the pyrolysis conditions are:
a pyrolysis temperature in a range from 600 □ to 900 □, and a pyrolysis time in a range from 0.5 hour to 6 hours.
number: 10
text: The preparation method according to claim 7, wherein the nitrogen-containing compound is at least one selected from the group consisting of ammonia gas, hydrazine, an organic compound containing a C-N bond, an organic compound containing C=N, and an organic compound containing C=N.
number: 11
text: The preparation method according to claim 7, wherein the nitrogen-containing compound is at least one selected from the group consisting of ammonia gas, hydrazine, acetonitrile, cyanamide, pyridine, pyrrole, ethylenediamine or methylamine.
number: 12
text: The preparation method according to claim 7, wherein the organic precursor is at least one selected from the group consisting of hydrocarbon compound, polymer, an organic compound containing at least one group of *-CX, *-OH, *-C≡N, *-C=O, *-C-O-* bond, *-C-NH<2>, *-C-NH-C-*, *-C-N=C-*;
wherein X in *-CX represents a halogen, which is at least one selected from the group consisting of F, Cl, Br, and I.
number: 13
text: The preparation method according to claim 7, wherein the organic precursor is at least one selected from the group consisting of acrylonitrile, chloroethylene, dichloroethylene, vinylpyridine, acrylamide, acrylic compounds, vinyl ester compounds, aniline compounds, pyrrolic compounds, urea resin, phenol resin, melamine resin, polyurethane and furan resin in a form of a monomer or polymer, glucose, fructose, xylose, sucrose, dextran, lignin, organic pyrolysis oil and pitch.
number: 14
text: The preparation method according to claim 7, wherein the method for supporting the organic precursor on the inorganic porous material is at least one selected from the following methods:
number: 15
text: A regeneration method of the catalyst for preparing chloroethylene by cracking 1,2-dichloroethane in any one of claims 1 to 6, wherein the regeneration method comprises:
calcinating a deactivated catalyst in an atmosphere containing oxygen after deactivating the catalyst in a catalytic cracking reaction of 1,2-dichloroethane for preparing chloroethylene; using the solid obtained after calcination as a carrier to prepare a regenerated catalyst according to the preparation method in any one of claims 7 to 14.
number: 16
text: The regeneration method according to claim 15, wherein the calcination conditions are: a calcination temperature in a range from 300□ to 800□, and a calcination time in a range from 0.2 hour to 10 hours.
number: 17
text: The regeneration method according to claim 15, wherein the calcination conditions are: a calcination temperature in a range from 450□ to 700□, and a calcination time in a range from 0.5 hour to 6 hours.
number: 18
text: A method for preparing chloroethylene by cracking 1,2-dichloroethane, comprising passing a feed gas containing 1,2-dichloroethane through a fixed bed reactor supported with a catalyst to prepare chloroethylene;
the catalyst is at least one selected from the catalyst for preparing chloroethylene by cracking 1,2-dichloroethane in any one of claims 1 to 6.
Office action: search_report, dated 2020-12-30
Rejection reasons: inventive_step_epc_56
Prior art cited: ref_id: EP1273336
ref_type: patent
severity: obviousness
ref_id: CN109180421
ref_type: patent
severity: obviousness
ref_id: - ZHAO WEI ET AL, "Catalytic dehydrochlorination of 1,2-dichloroethane to produce vinyl chloride over N-doped coconut activated carbon", RSC ADVANCES, vol. 5, no. 126, doi:10.1039/C5RA20916A, (20150101), pages 104071 - 104078, URL: https://pubs.rsc.org/en/content/articlepdf/2015/ra/c5ra20916a, XP055787652 [I] 1,7,15 * see, in particular, entire point 2.2 "Catalyst preparation"; see also entire point 3.1 "Catalytic performance of N-doped coconut activated carbon" * [Y] 1-12,15
ref_type: npl
severity: obviousness
Final disposition: pending (2020-12-30)