CN112316987A - Desulfurization method of carbon deposition low-carbon alkane dehydrogenation catalyst - Google Patents
Desulfurization method of carbon deposition low-carbon alkane dehydrogenation catalyst Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/06—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using steam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/42—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using halogen-containing material
Abstract
A desulfurization method of a carbon deposition low-carbon alkane dehydrogenation catalyst comprises the steps of feeding the carbon deposition low-carbon alkane dehydrogenation catalyst into a desulfurization remover (20) from the top, introducing a mixed gas containing hydrogen, water and HCl into the desulfurization remover from the bottom, carrying out countercurrent contact with the dehydrogenation catalyst at 400-650 ℃ to remove sulfur in the catalyst, discharging the desulfurized catalyst from a discharge pipe (21) at the bottom of the desulfurization remover, discharging a sulfur-containing mixed gas from a pipeline (28) at the top of the desulfurization remover (20), and feeding water into the desulfurization remover in an amount of 0.3-2.0 mass percent/hour of the catalyst in the desulfurization remover. The method can greatly remove sulfur in the carbon deposition catalyst, reduce the amount of sulfur converted into sulfate in the regeneration and burning process, and improve the regeneration performance of the catalyst.
Description
Technical Field
The invention relates to a desulfurization method of a low-carbon alkane dehydrogenation catalyst, in particular to a desulfurization method of a low-carbon alkane dehydrogenation catalyst after carbon deposition inactivation.
Background
The catalytic dehydrogenation of light alkane to prepare corresponding olefin is an important chemical process. The low-carbon olefin is a very important chemical raw material and has wide application in the chemical industry, for example, propylene is widely applied to the production of various chemical products such as polypropylene, acetone, acrylonitrile, propylene oxide, acrylic acid and the like; isobutylene is the primary feedstock for the production of Methyl Tertiary Butyl Ether (MTBE); the butylene is mainly used in the fuel fields of synthesizing useful gasoline components and synthesizing MTBE and ETBE gasoline additives by alkylation, superposition, isomerization and dimerization processes, and is widely applied to the chemical field. In recent years, propane/isobutane catalytic dehydrogenation processes have evolved rapidly and have become an important source of propylene/isobutylene. The propane/isobutane catalytic dehydrogenation processes that have been commercialized at present mainly include the Oleflex process using UOP in a moving bed, and the Catofin process using ABB Lummus in a fixed bed.
For the moving bed process, 3 or 4 reactors are generally adopted, the catalyst generally adopts a supported platinum-based catalyst, alumina is taken as a carrier, and modification is carried out by adding other components so as to improve the activity and the selectivity of the catalyst. The dehydrogenation reaction of the light alkane is very high in severity, and is generally carried out at a high temperature of over 600 ℃. In order to passivate the metal reactor walls and the initial activity of the catalyst, it is necessary to inject a certain amount of a sulfur-containing compound, such as dimethyl disulfide, into the feed. During the dehydrogenation reaction, injected sulfur accumulates on the catalyst as the reaction proceeds, and the catalyst is deactivated by gradual carbon deposition, requiring regeneration of the catalyst. Conventional catalyst regeneration processes typically include four steps of coking, oxychlorination, drying, and reduction.
The purpose of the coke burning is to burn off coke on the catalyst, and the coke and oxygen are burnt at a certain temperature to generate carbon dioxide and water, and a large amount of heat is released. The Pt crystal grains on the catalyst can be sintered and aggregated in the process of burning, and Pt needs to be redispersed through an oxychlorination process. During the course of the coke burning, the sulfur accumulated in the catalyst will also react with oxygen to form sulfate radicals. The generated sulfate radicals can enter an oxychlorination area to influence the redispersion of Pt crystal grains on the catalyst, thereby influencing the dehydrogenation reaction performance after the catalyst is regenerated. It is therefore desirable to remove the sulfur from the catalyst prior to regeneration of the coke.
CN104203410B discloses a method for regenerating spent catalyst from a reactor by feeding spent catalyst with sulfur to a sulfur stripper, feeding a hydrogen-rich gas stream to the sulfur stripper to remove sulfur from the spent catalyst at an elevated temperature, and then feeding the stripped catalyst stream to a cooling section to pass cold gas through the catalyst before feeding the catalyst to a regenerator for regeneration.
CN1065902C discloses a method for removing sulfate radicals on a reforming catalyst, hydrogen and organic chloride capable of decomposing hydrogen chloride under the condition are introduced into a catalyst bed layer at 400-600 ℃, the introduction amount of the hydrogen per hour is 200-4000 times of the volume of the catalyst, the introduction amount of the organic chloride is 0.2-8.0% of the mass of the catalyst calculated by elemental chlorine, and the decomposed hydrogen chloride penetrates through the catalyst bed layer. The process is suitable for the regeneration of reforming catalysts contaminated with sulfate.
CN102166534A discloses a method for removing sulfate radicals from a continuous reforming catalyst, wherein under the conditions of continuous reforming reaction and normal operation of a catalyst circulation system, organic chloride which decomposes hydrogen chloride at a reduction temperature is injected into a hydrogen flow entering a catalyst reduction zone, the decomposed hydrogen chloride penetrates a catalyst bed layer, gas discharged from the reduction zone is dechlorinated and then discharged out of a reaction zone of a reforming device, and the injection amount of the organic chloride is 0.02-0.5 mass% of the catalyst circulation amount calculated by elemental chlorine. The method carries out desulfurization in a reduction zone, and the catalyst does not contain carbon deposition.
Disclosure of Invention
The invention aims to provide a desulfurization method of a carbon deposition low-carbon alkane dehydrogenation catalyst, which can greatly remove sulfur in the carbon deposition catalyst, reduce the amount of sulfur converted into sulfate in the regeneration and scorching process and improve the regeneration performance of the catalyst.
The invention provides a desulfurization method of a carbon deposition low-carbon alkane dehydrogenation catalyst, which comprises the steps of feeding the carbon deposition low-carbon alkane dehydrogenation catalyst into a desulfurization remover from the top, introducing a mixed gas containing hydrogen, water and HCl into the desulfurization remover from the bottom, removing sulfur in the catalyst by countercurrent contact with the dehydrogenation catalyst at 400-650 ℃, discharging the desulfurized catalyst from a discharge pipe at the bottom of the desulfurization remover, discharging the sulfur-containing mixed gas from a pipeline at the top of the desulfurization remover, and feeding water into the desulfurization remover in an amount of 0.3-2.0 mass%/h of the catalyst in the desulfurization remover.
According to the invention, water-containing hydrogen is injected into the carbon-deposited low-carbon alkane dehydrogenation catalyst to form a mixed gas containing water, hydrogen chloride and hydrogen, and the sulfur adsorbed by the catalyst can be rapidly removed through hot hydrogen desulfurization and the action of chlorine and sulfur in the presence of water vapor, so that the amount of sulfate generated in a scorching zone in the catalyst regeneration process is greatly reduced, the redispersion of platinum in an oxychlorination zone is improved, and the activity stability of the regenerated catalyst is further improved.
Drawings
FIG. 1 is a schematic diagram of a desulfurization method of a carbon-deposited low-carbon alkane dehydrogenation catalyst provided by the invention.
Detailed Description
In the moving bed catalytic dehydrogenation process, during the catalytic dehydrogenation reaction of low-carbon alkanes such as propane and/or isobutane, a certain amount of sulfur-containing compounds capable of decomposing at high temperature to generate hydrogen sulfide need to be injected into a reactor, the generated hydrogen sulfide can be adsorbed and accumulated on a dehydrogenation catalyst, and the sulfur content of the catalyst flowing out of the last reactor is usually 0.1-0.5 mass%. If the sulfur adsorbed by the catalyst is not removed before the regeneration of the carbon deposition catalyst, the sulfur adsorbed by the catalyst can react with the introduced oxygen-containing gas in a coking zone to generate sulfate and form sulfate in the regeneration and coking process. After the catalyst enters the oxychlorination area, the existence of sulfate radicals can affect the redispersion of Pt crystal grains, thereby affecting the regeneration performance of the catalyst.
The method injects hydrogen containing water into the chlorine-containing low-carbon alkane dehydrogenation catalyst after carbon deposition to react with the chlorine-containing catalyst to form mixed gas containing water, hydrogen chloride and hydrogen, and the hydrogen can react with sulfur adsorbed in the catalyst to generate H2S is removed, the hydrogen chloride in the S-containing catalyst can chemically react with sulfur in the catalyst to replace sulfur by chlorine, and the water vapor can enhance the effect and promote the replacement of sulfur by chlorine. The method can effectively remove sulfur in the carbon deposition catalyst, so that the sulfur is prevented from being generated in the regeneration and burning processSulfate radical, so that platinum can be better dispersed in the oxychlorination process, and the activity and the stability of the regenerated catalyst are improved.
The HCl in the mixed gas comes from a catalyst or an external chlorine source, and the external chlorine source is selected from hydrochloric acid solution, organic chloride capable of decomposing hydrogen chloride under desulfurization conditions or chlorine.
The organic chloride is preferably chloralkane or chloroalkene, and the carbon number of the organic chloride is preferably 1-3. The chloroalkane is preferably dichloroethane, trichloroethane or carbon tetrachloride, and the chloroalkene is preferably tetrachloroethylene. The chlorine gas is preferably liquid chlorine when in use, so that the chlorine injection amount is easy to control. The chlorine gas can react with hydrogen gas under desulfurization conditions to produce HCl.
After the hydrogen containing water is introduced into the desulfurizing and eliminating device, the hydrogen and the chlorine in the catalyst react to form the mixed gas containing water, hydrogen chloride and hydrogen, and the content of HCl in the mixed gas is calculated by chlorine. Preferably, the added chlorine source is introduced into the desulfurization remover so that the mixed gas contains more HCl, and the amount of the added chlorine source introduced into the desulfurization remover is preferably 0.01 to 0.3 mass percent/hour, preferably 0.05 to 0.25 mass percent/hour of the catalyst in the desulfurization remover based on the amount of chlorine contained in the added chlorine source.
In the method of the present invention, the amount of water introduced into the desulfurization remover is preferably 0.3 to 1.5 mass%/hour of the catalyst in the desulfurization remover.
The hydrogen content in the mixed gas is 80-98.5 mass%, the water content is 1.0-15 mass%, and the chlorine content is 0.2-5 mass%, preferably, the hydrogen content in the mixed gas is 79-94 mass%, the water content is 5.0-20 mass%, and the chlorine content is 0.5-3.5 mass%.
The volume ratio of the mixed gas to the catalyst in the desulfurization remover is 200-2000: 1, preferably 300 to 1000: 1. and the mixed gas enters from the bottom of the desulfurization remover, passes through the whole catalyst bed layer to obtain the sulfur-containing mixed gas, and is discharged from a pipeline at the top of the desulfurization remover, preferably discharged out of the system after dechlorination. The fuel gas system which can be conveyed to the light alkane dehydrogenation device is used as fuel for heating the heating furnace.
The temperature of the dehydrogenation catalyst and mixed gas countercurrent contact desulfurization is preferably 450-630 ℃, and when the desulfurization temperature is higher, the contact time of the catalyst and the mixed gas can be properly shortened; when the desulfurization temperature is low, the contact time of the catalyst and the mixed gas can be properly prolonged. The time for the dehydrogenation catalyst to be subjected to desulfurization treatment in the desulfurization remover is preferably 0.5 to 6.0hr, more preferably 0.5 to 2 hr.
In the method, the hydrogen, the water and the organic chloride or the chlorine which can decompose the hydrogen chloride at high temperature can be from a low-carbon alkane dehydrogenation device and are respectively provided with an independent injection pipeline. Preferably, the organic chloride or chlorine gas which decomposes out hydrogen chloride can be premixed with hydrogen gas and then mixed with water on entering the desulfurizer. The chlorine-containing gas is not premixed with water, so that corrosion to equipment can be avoided.
The hydrogen can be recycled hydrogen generated by a low-carbon alkane dehydrogenation device or high-purity hydrogen generated by a PSA (pressure swing adsorption separation) unit, preferably the PSA hydrogen with the purity of more than 90 volume percent, the organic chloride or chlorine can be led into a sulfur remover by a chlorine injection pipeline separated from a chlorine injection system of an oxychlorination area of a regeneration system, and the water can be low-pressure steam generated by the dehydrogenation device.
The low-carbon alkane dehydrogenation catalyst comprises an alumina carrier and active components with the following content calculated by taking the carrier as a reference
In the active components, platinum is a dehydrogenation active component, chlorine is an acid component, and the balance is an auxiliary agent, wherein the platinum content of the catalyst is preferably 0.1-0.5 mass%, the IVA group metal content is preferably 0.1-0.5 mass%, the alkali metal content is preferably 0.5-1.5 mass%, and the chlorine content is preferably 0.5-1.5 mass%.
The IVA group metal is preferably tin, the alkali metal is preferably potassium, the alumina carrier is preferably theta-alumina, and the specific surface area measured by a BET method is preferably 50-130 m2/g，The total pore volume is preferably 0.5 to 1.0 mL/g.
The method is suitable for the low-carbon alkane dehydrogenation catalyst to be used for dehydrogenation reaction, and desulfurization before regeneration after carbon deposition inactivation, wherein the regeneration of the inactivated low-carbon alkane dehydrogenation catalyst comprises the steps of burning, oxychlorination, drying and reduction. The dehydrogenation reaction of the low-carbon alkane can use a fixed bed or a moving bed. The dehydrogenation reaction is preferably carried out using a moving bed.
The moving bed dehydrogenation reaction device comprises a reaction part and a catalyst regeneration part, wherein a carbon deposition catalyst in the reaction part flows out of the reactor and is lifted to the regeneration part by a catalyst lifter, and the regenerated catalyst obtained by carbon burning, oxychlorination, drying and reduction returns to the reactor.
Preferably, the carbon-deposited low-carbon alkane dehydrogenation catalyst is taken from a carbon-deposited catalyst flowing out of the last reactor of a moving bed reaction device, the desulfurized carbon-deposited catalyst obtained after desulfurization by the method enters a cooling zone through a catalyst conveying pipeline, is cooled to a temperature below 200 ℃ in the cooling zone and is dried, then enters a catalyst lifter, the catalyst is conveyed into a regenerator by nitrogen, the carbon-deposited catalyst enters a coking zone after catalyst crushed particles and dust are removed, carbon deposits in the catalyst are burned out under the action of oxygen, then enters an oxychlorination zone, the catalyst is subjected to oxychlorination by injecting chlorine-containing gas, Pt crystal grains gathered in the coking process are redispersed, then the catalyst is conveyed to a reduction zone to reduce platinum in the catalyst, and the reduced catalyst is conveyed to the reactor to be reused for dehydrogenation.
The lower alkane in the invention is preferably propane, butane or pentane.
The present invention will be described with reference to the accompanying drawings, which do not show the process of cooling the catalyst and transferring it to the regenerator for regeneration.
In fig. 1, the carbon-deposited low-carbon alkane dehydrogenation catalyst flowing out from the last reactor 10 of the moving bed reaction system enters a sulfur remover 20 from the upper part through a catalyst discharge pipe 11, hydrogen from a pipeline 22, water from a pipeline 24 and a chlorine-containing gas stream from a pipeline 26 are mixed and then enter the sulfur remover 20 from the lower part, and then the mixture upwards passes through a catalyst bed layer to be in countercurrent contact with the carbon-deposited catalyst entering the sulfur remover to remove sulfur in the carbon-deposited catalyst, and a sulfur-containing mixed gas passing through the catalyst bed layer is discharged from a pipeline 28 and discharged out of the system after dechlorination. The desulfurized carbon deposition catalyst enters the cooler 30 through the catalyst discharging pipe 21, the cooling gas-nitrogen from the dehydrogenation device enters the cooler from the lower part of the cooler 30 through the pipeline 32, the cooled tail gas formed after the cooling gas-nitrogen upwards passes through the catalyst bed layer in a countercurrent mode is discharged out of the system through the pipeline 38, the cooled carbon deposition catalyst enters the catalyst lifting system through the catalyst discharging pipe 31, and the desulfurized carbon deposition catalyst is conveyed to the regenerator to be regenerated.
The invention is further illustrated below by way of examples, without being limited thereto.
Example 1
100g of the propane dehydrogenation catalyst after carbon deposition is placed in a fixed bed reactor, the carrier of the catalyst is theta-alumina, and the specific surface area measured by a BET method is 115m2The total pore volume was 0.71mL/g, and based on the support, the catalyst contained 0.30 mass% of platinum, 0.30 mass% of tin, 1.10 mass% of potassium, and 1.20 mass% of chlorine, the carbon content of the catalyst was 1.2 mass%, and the sulfur content of the catalyst was 0.28 mass% (both carbon and sulfur contents based on the support).
Heating a reactor to 500 ℃, introducing hydrogen with the purity of 99 volume percent into the reactor from the bottom at the flow rate of 800ml/min, injecting a hydrochloric acid solution into the hydrogen entering the reactor through a syringe pump, wherein the mass concentration of HCl in the injected hydrochloric acid solution is 18 mass percent, forming a mixed gas containing HCl, water and hydrogen, the injection amount of the hydrochloric acid solution is 0.6g/h calculated by chlorine element, namely the amount of chlorine introduced per hour accounts for 0.1 percent of the mass of the catalyst, the amount of water introduced per hour accounts for 0.5 percent of the mass of the catalyst, the content of hydrogen in the mixed gas is 87.7 mass percent, the content of water is 10 mass percent, the content of chlorine is 2.3 mass percent, and the volume ratio of the introduced mixed gas to the catalyst is 500: 1, treating the carbon deposition catalyst at 500 ℃ for 0.5hr to obtain catalyst A, wherein the sulfur content before and after desulfurization of the catalyst A is shown in Table 1.
Example 2
Placing 100g of the carbon-deposited dehydrogenation catalyst described in example 1 in a fixed bed reactor, heating the reactor to 550 ℃, introducing hydrogen with a purity of 99 vol% into the reactor from the bottom at a flow rate of 1600ml/min, and injecting tetrachloroethylene and water into the hydrogen introduced into the reactor by a syringe pump to form a mixed gas containing HCl, water and hydrogen, the amount of tetrachloroethylene injected per hour being 0.12g, the amount of water injected per hour being 0.5g, the hydrogen content in the mixed gas being 93.2 mass%, the water content being 5.5 mass%, the chlorine content being 1.3 mass%, the amount of chlorine introduced per hour being 0.1% of the mass of the catalyst, the amount of water introduced per hour being 0.5% of the mass of the catalyst, and the volume ratio of the introduced mixed gas to the catalyst being 1000: 1, treating the carbon deposition catalyst for 1hr at 600 ℃ to obtain a catalyst B, wherein the sulfur content before and after desulfurization of the catalyst B is shown in Table 1.
Example 3
The desulfurization of the deposited carbon catalyst was carried out by the method of example 2 except that the flow rate of hydrogen gas fed into the fixed bed reactor was 1000ml/min, the organic chloride fed into the reactor was dichloroethane, the feed amount of dichloroethane per hour was 0.2g, the feed amount of water per hour was 0.8g, the hydrogen content of the mixed gas was 84.3 mass%, the water content was 12.6 mass%, the chlorine content was 3.1 mass%, the feed amount of chlorine per hour was 0.15 mass% of the catalyst mass, and the feed amount of water per hour was 0.8 mass% of the catalyst mass, to obtain a desulfurized catalyst C, the sulfur contents before and after the desulfurization of which are shown in table 1.
Example 4
The desulfurization of the deposited carbon catalyst was carried out by the method of example 2 except that hydrogen was fed into the fixed bed reactor at a flow rate of 1200ml/min, liquid chlorine and water were fed into the reactor, the feed amount of liquid chlorine per hour was 0.2g, the feed amount of water per hour was 1.0g, the hydrogen content of the mixed gas was 84.3 mass%, the water content was 13.1 mass%, the chlorine content was 2.6 mass%, the feed amount of chlorine per hour was 0.2 mass% and the feed amount of water per hour was 1.0 mass%, to obtain a desulfurized catalyst D, and the sulfur contents before and after the desulfurization of the catalyst D were shown in table 1.
Example 5
The desulfurization of the deposited carbon catalyst was carried out by the method of example 2 except that hydrogen was fed into the fixed bed reactor at a flow rate of 1200ml/min, water was fed into the hydrogen fed into the reactor through a syringe pump without feeding tetrachloroethylene, the feed amount of water per hour was 1.5g, the hydrogen content in the mixed gas was 81.1 mass%, the water content was 18.7 mass%, the chlorine content was 0.2 mass%, and the water fed per hour accounted for 1.5 mass% of the catalyst, to obtain a desulfurized catalyst E, and the sulfur content before and after the desulfurization of the catalyst E was shown in table 1.
Comparative example 1
100g of the coked dehydrogenation catalyst described in example 1 was placed in a fixed bed reactor, the reactor was heated to 600 ℃ and hydrogen gas having a purity of 99 vol% was introduced into the reactor from the bottom at a flow rate of 1600ml/min, and the coked catalyst was treated at 600 ℃ for 1hr to obtain catalyst F, the sulfur content before and after desulfurization of which is shown in Table 1.
Comparative example 2
100G of the carbon-deposited dehydrogenation catalyst described in example 1 was placed in a fixed bed reactor, the reactor was heated to 600 ℃, hydrogen gas having a purity of 99 vol% was introduced into the reactor from the bottom at a flow rate of 1000ml/min, dichloroethane was injected into the hydrogen gas introduced into the reactor by means of a syringe pump to form a mixed gas containing HCl and hydrogen gas, the amount of dichloroethane injected per hour was 0.2G, the amount of chlorine introduced per hour accounted for 0.15% of the mass of the catalyst, and the carbon-deposited catalyst was treated at 600 ℃ for 1hr to obtain a catalyst G, the sulfur content before and after desulfurization of which is shown in Table 1.
TABLE 1
As can be seen from Table 1, the process of the present invention can effectively remove sulfur from the deposited carbon catalyst and has a very good desulfurization effect, compared with the process used in the comparative example.
Claims (13)
1. A desulfurization method of a carbon deposition low-carbon alkane dehydrogenation catalyst comprises the steps of feeding the carbon deposition low-carbon alkane dehydrogenation catalyst into a desulfurization remover (20) from the top, introducing a mixed gas containing hydrogen, water and HCl into the desulfurization remover from the bottom, carrying out countercurrent contact with the dehydrogenation catalyst at 400-650 ℃ to remove sulfur in the catalyst, discharging the desulfurized catalyst from a discharge pipe (21) at the bottom of the desulfurization remover, discharging a sulfur-containing mixed gas from a pipeline (28) at the top of the desulfurization remover (20), and feeding water into the desulfurization remover in an amount of 0.3-2.0 mass percent/hour of the catalyst in the desulfurization remover.
2. The process of claim 1, wherein the HCl in the gaseous mixture is derived from a catalyst or an added chlorine source selected from the group consisting of hydrochloric acid solution, organic chlorides capable of dissociating hydrogen chloride under desulfurization conditions, and chlorine gas.
3. The method according to claim 1, wherein the mixed gas contains 78 to 98.5 mass% of hydrogen, 1.0 to 20 mass% of water, and 0.2 to 5 mass% of chlorine.
4. The process according to claim 2, characterized in that the organic chloride is selected from chlorinated alkanes or chlorinated alkenes.
5. The process according to claim 4, characterized in that the chlorinated alkane is selected from dichloroethane, trichloroethane or carbon tetrachloride and the chlorinated alkene is selected from tetrachloroethylene.
6. The method according to claim 1, wherein the dehydrogenation catalyst is subjected to desulfurization treatment in the desulfurization remover for 0.5 to 6.0 hr.
7. The method of claim 2, wherein when HCl in the mixed gas comes from an external chlorine source, chlorine is introduced into the desulfurizer in an amount of 0.01 to 0.3% by mass/hr based on the catalyst in the desulfurizer.
8. The method according to claim 1, wherein the volume ratio of the mixed gas introduced into the desulfurization remover to the catalyst in the desulfurization remover is 200-2000: 1.
9. the method according to claim 8, wherein the volume ratio of the mixed gas to the catalyst in the desulfurization remover is 300-1000: 1.
10. a process according to claim 1, characterized in that the mixture containing sulphur which is discharged from the line (28) at the top of the sulphur remover (20) is discharged from the system after dechlorination.
11. The method of claim 1, wherein the light alkane dehydrogenation catalyst comprises an alumina support and the following active components in the amounts calculated based on the support
12. The method of claim 11 wherein the group IVA metal is tin, the alkali metal is potassium and the alumina support is theta alumina.
13. The process of claim 1, wherein the lower alkane is propane, butane or pentane.
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