CN100340341C - Carbon deposit cleaning agent and its application in reproduction process of deactivation catalyst thereof - Google Patents

Abstract

The invention discloses a carbon deposit cleaning agent and its application in the regeneration process of deactivated catalysts. The carbon deposit cleaning agent comprises the following components: 5-95v% of propylene glycol ether, and 5-95v% of vinyl chloride. Using the carbon deposit cleaning agent of the present invention to treat the deactivated catalyst before regeneration, and then performing regeneration treatment, can greatly reduce the carbon deposit content on the deactivated catalyst, which is beneficial to control the temperature during its regeneration and reduce the impact on catalyst performance. Improve the activity of the regenerated catalyst. The carbon deposit cleaning agent of the present invention is suitable for catalysts with obvious exothermic heat during regeneration, and is especially suitable for deactivated hydrogenation catalysts and methane aromatization catalysts that need to be regenerated by oxidative burning of carbon deposits.

Description

Coke Cleaning Agent and Its Application in Regeneration of Deactivated Catalyst

technical field

The invention relates to a carbon deposit cleaning agent and its application in the regeneration process of deactivated catalysts, especially suitable for the regeneration of deactivated hydrogenation catalysts.

Background technique

Catalysts (such as hydrogenation catalysts) used in refining and chemical processes will gradually lose their activity during long-term operation. The reason is largely due to the deposition of carbon deposits on the surface of the catalyst. These coke-deactivated catalysts are regenerated by oxidizing and burning off the coke, and the activity can be partially or completely restored, and they can still be used in industrial production. Some catalysts can even be regenerated multiple times to achieve the purpose of saving energy and increasing efficiency.

When the carbon deposition deactivation catalyst is regenerated by burning carbon, the carbon deposition will react with oxygen and be removed, and a large amount of heat will be generated at the same time. If the heat release is too much or too concentrated, the atmosphere cannot take away the generated heat, which will cause the overheating reaction of the catalyst, resulting in changes in the properties of the catalyst and negatively affecting the properties of the catalyst.

However, among the existing patents related to the regeneration of carbon-deposited deactivated catalysts, most of the patents focus on how to prevent the deactivated catalyst from concentrating or excessively releasing heat during the regeneration process. For example, USP 5,037,785 suggests using laser irradiation to decoke the catalyst under an oxygen-containing gas; USP 4,202,865 suggests intermittent oxygen injection; USP 4,780,195 and USP 4,417,975, etc. consider adding a certain amount of water to the atmosphere to prevent catalyst sintering wait. However, there are few patents about solving the problem of excessive heat release during the regeneration of the deactivated catalyst by treating the deactivated catalyst with carbon deposits.

There was a patent USP 5,916,835 to treat the titanium-containing heterogeneous deactivated catalyst used for ethylene epoxidation reaction with water, alcohol, ester, nitrile, ether, aromatic hydrocarbon, ketone and other substances to restore the activity of the catalyst. The non-molecular sieve titanium-silicon catalyst involved in this patent, in the ethylene epoxidation reaction process (about 100-200 ° C and 10-500 psi), often generates two or three polymers or with the ethylene oligomerization reaction process Oxides generate two and three polyethers. Due to their large molecules, the diffusion rate in the catalyst pores is slow, and the pores are easily blocked, so that the reactants cannot reach the active sites, resulting in a decrease in catalyst activity. The used catalyst is treated with water, alcohol, ester, nitrile, ether, aromatic hydrocarbon, ketone and other substances to restore most of the activity of the catalyst. However, the reason for the deactivation of the catalyst deactivated by carbon deposition is obviously different from that of the titanium-containing heterogeneous catalyst used in the ethylene epoxidation reaction in the above-mentioned patent, so the reaction principle of the above method cannot be applied to the catalyst deactivated by carbon deposition.

Contents of the invention

Aiming at the deficiencies of the prior art, the invention provides a carbon deposit cleaning agent and its application in the regeneration process of deactivated catalysts, especially suitable for the regeneration of deactivated hydrogenation catalysts. After being treated with the carbon deposit cleaning agent, the heat released by the catalyst during the carbon burning regeneration process can be reduced, and the activity of the regenerated catalyst can be improved.

Carbon deposit cleaning agent of the present invention comprises following components:

Propylene glycol ether 5-95v%, preferably 54-80v%;

Vinyl chloride 5-95v%, preferably 20-46v%;

The total volume percentage of propylene glycol ether and vinyl chloride is 100%.

The chlorinated ethylene is one or more of tetrachlorethylene, trichlorethylene and dichloroethylene.

The above-mentioned carbon deposit cleaning agent has an excellent ability to reduce the carbon deposit content in the deactivated catalyst, but the cost of the above-mentioned components is relatively high. In order to reduce the cost of the carbon deposit cleaning agent, one or more of lower-cost benzene, ethanol, gasoline, and kerosene can also be added in the described carbon deposit cleaning agent, and its content is the total volume of propylene glycol ether and vinyl chloride 2-40 times, preferably 5-20 times. The use of a carbon deposit cleaning agent containing one or more components of benzene, ethanol, gasoline and kerosene not only makes the cost of the organic solution relatively low, reduces the regeneration cost, but also has a good effect of removing carbon deposits.

The carbon deposit cleaning agent of the present invention may also contain other organic substances, selected from one or more of organic alcohols, esters, ethers, aromatic hydrocarbons, phenols, alcohol amines, alcohol ethers, alcohol esters, ketones and carboxylic acids. The content is 0.2-5 times, preferably 0.5-2 times of the total volume of propylene glycol ether and vinyl chloride.

The organic alcohol can be aliphatic alcohol or aralkyl alcohol. The fatty alcohols are C ₁ -C ₁₂ carbon atoms, preferably one or more of C ₂ -C ₁₀ , including straight chain, branched chain and cyclic alcohols, including monoalcohols, Diols, etc., such as n-hexanol, isohexanol, cyclohexanol, hexanediol, etc.; the aralkyl alcohol has a carbon number of C ₇ -C ₁₄ , preferably one of C ₇ -C ₁₂ or more, such as benzyl alcohol, phenylpropanol, etc. Esters, ethers, aromatics, phenols, alcohol amines, alcohol ethers, alcohol esters, ketones and carboxylic acids are carbon atoms ranging from the number of carbon atoms required to form the simplest structure to C ₁₄ (ie below C ₁₄ ), preferably C One or more of the following ₁₂ , which covers linear, branched and cycloalkane compounds, including monofunctional groups, difunctional groups, etc., such as butyl butyrate, diisobutyl ether, ethylene glycol dimethyl ether, Butylbenzene, butylphenol, butanone, 2,3-pentanedione, butyric acid, ethanolamine succinate, ethylene glycol monobutyl ether, etc.

The application of the carbon deposit cleaning agent of the present invention in the regeneration process of the carbon deposit deactivation catalyst comprises the following process: the carbon deposit deactivation catalyst is first treated with the above carbon deposit cleaning agent, the carbon deposit is removed as much as possible, and then the regeneration process is performed.

In the present invention, the deactivated catalyst is treated with a carbon deposit cleaning agent, which can be combined with one or more methods of soaking, distillation and heating, preferably soaking and distillation. The soaking method is to use the above-mentioned carbon deposit cleaning agent to cover the deactivated catalyst bed for a long time, and the time is more than 2 hours, preferably 10-20 hours. The distillation method is to raise the temperature of the above-mentioned carbon deposit cleaning agent to its azeotropic temperature, and use its steam to steam the deactivated catalyst for more than 1 hour, preferably 1.5-5 hours. The heating method refers to raising the temperature of the carbon deposit cleaning agent solution soaked in the catalyst to a temperature higher than room temperature but lower than the azeotropic temperature. The solution temperature is preferably 10-50°C lower than the azeotropic temperature, preferably 20-30°C. For more than 1h, preferably 3-5h.

The regeneration can adopt the conventional deactivated catalyst regeneration method in the prior art, and generally depends on the nature of the catalyst and the nature of the carbon deposit on the catalyst, and various regeneration methods can be used. It is most common to regenerate deactivated catalysts by thermostatting at different temperatures under an oxygen-containing atmosphere. Among them, a four-step regeneration method can be selected, and the specific steps are as follows: put the cleaned catalyst into the regeneration device, first replace the device with an inert gas, and then gradually increase the oxygen content to 0.5-10.0v%, preferably 0.5-10.0v%. 1.0-5.0v%, the catalyst is regenerated by burning charcoal step by step. Generally, regeneration can be carried out in four stages. The main control conditions of each stage are: constant temperature for 1-3 hours at 100-140°C, preferably 110-120°C; constant temperature for 1 hour at 150-240°C, preferably 170-220°C -3 hours; 1-2 hours at 250-350°C, preferably 260-320°C; 2-4 hours at 450-550°C, preferably 480-510°C.

The formation of carbon on the catalyst surface is a complex chemical process. The composition of the carbon deposit depends on the type of catalyst, the composition of the raw material being processed, the temperature, the processing time, the extent of the carbon deposit and the conditions for subsequent purging of the carbon deposit catalyst, etc. For example, in the hydrogenation process, because the reaction is usually carried out under high temperature and pressure, the carbon deposit itself is relatively high, and there are more dense graphite-like structures in the carbon deposit, so regeneration is difficult, and the regeneration technology has been constantly improving. researching. Among the carbon deposits of deactivated hydrogenation catalysts, in addition to graphite-like structure carbon deposits, some are attached to the surface of the catalyst, and some have poor bonding ability with the catalyst. These carbon deposits are amorphous carbon deposits. The invented cleaning agent for carbon deposits can be removed before regeneration, so that the purpose of effectively reducing the content of carbon deposits on the deactivated catalyst can be achieved.

Structurally speaking, the carbon deposits on deactivated catalysts include X-ray amorphous and graphite-like structures. With the harsh processing conditions, the proportion of graphite-like structure in the carbon deposit increases. When performing thermogravimetric experiments under simulated regeneration conditions, it was found that the weight loss at 150-320°C can be used to characterize the amount of amorphous carbon deposits, while the contribution of graphite-like carbon deposits at 450-550°C. The amount of carbon deposition of different structures on the catalyst can be characterized by the amount of weight loss in the two temperature ranges.

The feature of the present invention is that the deactivated catalyst is treated with a carbon deposit cleaning agent of a specific composition, and then regenerated, which can greatly reduce the carbon deposit content on the deactivated catalyst, which is beneficial to control the temperature during regeneration, and reduces the impact on the performance of the catalyst. influence and improve the activity of the regenerated catalyst.

In the present invention, the solvent used can not only reduce the carbon deposition on the deactivated catalyst, but also has no influence on the properties of the catalyst and has low toxicity.

Detailed ways

The carbon deposit cleaning agent of the present invention is suitable for carbon deposit deactivation catalysts with obvious heat release during regeneration, such as hydrogenation catalysts and methane aromatization catalysts, and is especially suitable for deactivated hydrogenation catalysts that need to be regenerated by oxidative combustion to remove carbon deposits . The hydrogenation catalyst is generally supported by inorganic refractory oxides or inorganic refractory oxides and zeolite, and the inorganic refractory oxides are generally selected from alumina, silicon oxide, aluminum silicate and the like. The active metal in the hydrogenation catalyst is selected from one or more of VIB, VIIB, and VIII group metals. The shape of the hydrogenation catalyst is generally cylindrical, spherical or multilobal, with a diameter of 0.5-3.5 mm and a length of 1.5-10.0 mm. Hydrogenation catalysts are generally used in oil hydrorefining, hydrocracking and residual oil hydrotreating processes.

The method of the present invention is further described in detail below by way of examples.

The mensuration of the coke content in the embodiment of the present invention is to measure on the elemental analyzer of German ELEMENFAV VARIOEL type, and experimental condition is: get 5mg catalyst powder sample and Ar/ _O Under airflow heating to 1100 ℃, the gas that produces carries out C, S analysis.

The determination of the content of amorphous carbon deposit and graphite-like carbon deposit in the embodiment of the present invention is carried out on a 951 type thermogravimetric analyzer produced by DuPont Company of the United States. The experimental conditions are: in an air atmosphere of 50ml/min, the temperature is raised at 10°C/min.

The XRD analysis and relative crystallinity in the examples of the present invention were carried out on a D/max2500 X-ray diffractometer produced by Rigaku Corporation, with a voltage of 40kV, a current of 80mA, and a scan of 6°/min.

The DSC experiment in the embodiment of the present invention is carried out on the DSC951 type DSC instrument that DuPont Company produces, and experimental condition is: 15mg catalyst powder, in the air atmosphere of 30ml/min with the speed of 10 ℃/min heating up.

Example 1

In the flask of 1000ml, add carbon deposit cleaning agent (its concrete composition and its content are shown in Table 1) to the 100ml residual oil hydrodesulfurization MoNiP/Al ₂ O ₃ deactivation catalyst (numbering is A, carbon deposit content) after an industrial operation 11.45wt%) were processed respectively, the treated catalyst continued to be treated with absolute ethanol for 30min, and then the content changes of amorphous and graphite-like carbon deposits were measured with a thermogravimeter, and the results are shown in Table 1.

Table 1 Change results of coke content after treatment of MoNiP/Al ₂ O ₃ deactivated catalyst for residual oil hydrodesulfurization Composition of carbon deposit cleaning agent processing conditions Remaining carbon content, wt% Thermogravimetric results: the content of remaining carbon deposits, wt% amorphous graphite-like - 287ml ethanol 287ml benzene Direct distillation 2h 9.56 56 44 - 431ml kerosene 144ml gasoline Soak for 16h, then distill for 2h 8.87 55 45 30ml propylene glycol ethyl ether 45ml ethylene chloride 489ml kerosene Direct distillation 2h 7.66 42 58 40ml propylene glycol ether 25ml ethylene chloride 200ml ethanol 200ml benzene 7.50 41 59 20ml propylene glycol ethyl ether 35ml ethylene chloride 2000ml benzene 7.72 43 57 70ml propylene glycol ether 30ml ethylene chloride 489ml gasoline Soak for 16h, then distill for 2h 7.21 39 61 40ml propylene glycol ether 25ml ethylene chloride 750ml kerosene 250ml gasoline 7.25 39 61 400ml propylene glycol ether 100ml ethylene chloride - 6.89 37 63 350ml propylene glycol ether 150ml ethylene chloride - 6.78 37 63

As can be seen from Table 1, compared with the deactivated catalyst that only ethanol and benzene or kerosene and gasoline are processed, with the catalyst that the carbon deposit cleaning agent solution of the present invention is processed, the amount of carbon deposits all significantly reduces, especially without The relative content of stereotyped carbon deposits has been significantly reduced.

It can also be seen from Table 1 that when benzene, ethanol, gasoline, and kerosene are not added, the effect of the carbon deposit cleaning agent is better, but there is a problem of higher cost and increased catalyst regeneration cost. When benzene, ethanol, gasoline, kerosene and other solvents are added to the carbon deposit cleaning agent, the cost of regeneration can be greatly reduced, and the cleaning effect of carbon deposits is also very good.

The above 100ml deactivated residual oil hydrogenation catalyst A was subjected to differential scanning calorimetry (DSC) analysis, and the results are shown in Table 2.

Put the above 100ml deactivated residual oil hydrogenation catalyst A into a flask, add 750ml gasoline and 250ml kerosene, soak for 16h and then distill for 2h to obtain catalyst A1. Then DSC analysis was carried out, and the results are shown in Table 2.

Put the above 100ml deactivated residual oil hydrogenation catalyst A into a flask, add 750ml gasoline, 250ml kerosene, 40ml propylene glycol ether, 25ml ethylene chloride, soak for 16h and then distill for 2h to obtain catalyst A2. Then DSC analysis was carried out, and the results are shown in Table 2.

Table 2 DSC results of catalysts A, A1 and A2 Catalyst number A A1 A2 exothermic peak temperature, ℃ 235 354 509 230 348 510 215 328 512 Exothermic peak area, W/g 0.33 0.65 0.44 0.30 0.59 0.40 0.17 0.58 0.39

In the DSC spectrum of the deactivated hydrogenation catalyst, two kinds of exothermic peaks of carbon deposits can be clearly seen. The exothermic peak at 200-280°C is the contribution of amorphous carbon deposits, while the peak at 450-550°C is Exothermic for graphite-type carbon deposits. In addition, the exotherm between 300-400°C is the exotherm of the active metal sulfidation state. As can be seen from Table 2, through the catalyst A1 that 750ml gasoline, 250ml kerosene are processed, the heat release during regeneration is less than that of the catalyst that is not processed by this solution, but it is different from that of the catalyst that is processed by the carbon deposit cleaning agent of the present invention. Compared with catalyst A2, the heat release during regeneration, especially the heat release of amorphous carbon deposits, is significantly more. Illustrate that the deactivated catalyst can be treated by the carbon deposit cleaning agent of the present invention, and the purpose of reducing the exothermic heat during regeneration of the deactivated catalyst can indeed be achieved. This means that A2 can reduce the constant temperature time in the low temperature section during regeneration, thereby speeding up the regeneration speed of the catalyst.

Example 2

In the flask of 1000ml, add carbon deposit cleaning agent (its concrete composition and its content are shown in Table 3) to the 100ml Mo/HZSM-5 methane aromatization catalyst (numbering is B, and carbon deposit content is 10.84wt% after an industrial operation) ) were processed respectively, and the treated catalyst continued to be processed with absolute ethanol for 30 min, and then the content changes of amorphous and graphite-like carbon deposits were measured with a thermogravimeter, and the results are shown in Table 3.

Table 3 Change results of coke content in methane aromatization Mo/HZSM-5 catalyst after treatment Carbon cleaning agent processing conditions Remaining carbon content, wt% Thermogravimetric results: the content of remaining carbon deposits, wt% amorphous graphite-like - 287ml ethanol 287ml benzene Soak for 16h, distill for 2h 10.21 86 14 350ml Propylene Glycol Ether 150ml Ethylene Chloride 150ml Isohexanol - 6.75 76 twenty four 40ml propylene glycol ethyl ether 15ml vinyl chloride 12ml isohexyl alcohol 489ml kerosene 7.25 80 20 30ml propylene glycol ether 25ml vinyl chloride 150ml phenol 15ml butyric acid 200ml ethanol 200ml benzene Heating for 3h 7.15 80 20 35ml propylene glycol ethyl ether 20ml ethylene chloride 100ml butyl butyrate 431ml kerosene 144ml gasoline 7.04 78 twenty two

As can be seen from Table 3, the carbon deposit cleaning agent of the present invention contains other at least An organic substance, which is more conducive to reducing the carbon deposition on non-hydrogenation catalysts, especially has a special effect on the removal of amorphous structure carbon deposition.

The above-mentioned 100ml deactivated methane aromatization catalyst B is regenerated in the following way:

First, put the catalyst into the regeneration device, replace the device with _N2 , then adjust the oxygen content to 2.0v%, and regenerate the catalyst step by step by burning charcoal. The main control conditions at each stage are: 120°C, constant temperature for 3h; 200°C constant temperature for 2h; 300°C constant temperature for 1.5h; 500°C constant temperature for 3h. Catalyst B1 is obtained. Then carry out X-ray diffraction (XRD) analysis, the results are shown in Table 4.

Put the above 100ml deactivated methane aromatization catalyst B into a flask, add 35ml propylene glycol ether, 20ml ethylene chloride, 100ml butyl butyrate, then add 575ml of kerosene:gasoline=3:1 (v%), soak for 16h , and then distilled for 2h to obtain catalyst B2. Then carry out XRD analysis, and the results are shown in Table 4.

Table 4 XRD analysis results of catalysts B1 and B2 Catalyst number crystal phase Relative crystallinity of ZSM-5 molecular sieve, % B1 MoO3, ZSM-5 100 B2 ZSM-5 114

The relative crystallinity of the ZSM-5 molecular sieve in Table 4 defines the crystallinity of the ZSM-5 molecular sieve in the catalyst B1 as 100%, and the crystallinity of the ZSM-5 molecular sieve in the catalyst B2 is relative to the crystallinity of the catalyst B1.

As can be seen from Table 4, through the deactivated catalyst processed by the carbon deposit cleaning agent of the present invention, there is no aggregation of active metals on the catalyst after regeneration, and the crystallinity of the ZSM-5 type molecular sieve remains better simultaneously, indicating that the catalyst is adopted Method treatment can reduce the loss of active centers on the catalyst. This is of considerable significance for maintaining the activity of the regenerated catalyst.

Example 3

The 100ml hydrotreating MoNiP/ _Al2O3 deactivated catalyst (coded as C, carbon deposit content is 10.21wt%) after an industrial operation is regenerated in the following _way :

First, put the catalyst into the regeneration device, replace the device with _N2 , then adjust the oxygen content to 2.0v%, and regenerate the catalyst step by step by burning charcoal. The main control conditions at each stage are: 120°C, constant temperature for 3h; 200°C constant temperature for 2h; 300°C constant temperature for 1.5h; 500°C constant temperature for 3h.

The 15ml catalyst that regenerates like this is packed in microreactor, carry out activity evaluation according to following condition:

Raw material oil: 950 μg/g pyridine/kerosene; volumetric space velocity: 2.0h ^-1 ; temperature: 360°C; reaction pressure: 4.0MPa; hydrogen flow rate: 100ml/min. Samples were taken for analysis after 12 hours of stabilization. The nitrogen content in the treated oil sample was 185 μg/g.

Put the above 500ml deactivated hydrotreating catalyst C into a flask, add 600ml gasoline, 400ml kerosene, 35ml propylene glycol ethyl ether, 20ml ethylene chloride, 80ml butyl butyrate, soak for 16h and then distill for 2h, then use catalyst C Regeneration and activity evaluation were carried out under the same conditions, and the nitrogen content in the oil sample was found to be 141 μg/g.

This shows that the activity of the regenerated catalyst can be improved by treating the deactivated catalyst with a carbon cleaning agent containing propylene glycol ether and ethylene chloride.

Claims (13)

1, a kind of carbon deposit cleaner comprises following component:

Propylene-glycol ethyl ether 54～95v%

Ethlyene dichloride 5～46v%

Wherein said propylene-glycol ethyl ether and ethlyene dichloride total volume percent are 100%.

2, according to the described carbon deposit cleaner of claim 1, it is characterized in that comprising following component:

Propylene-glycol ethyl ether 54-80v%;

Ethlyene dichloride 20-46v%;

Wherein said propylene-glycol ethyl ether and ethlyene dichloride total volume percent are 100%.

3, according to claim 1 or 2 described carbon deposit cleaners, it is characterized in that containing in this carbon deposit cleaner in benzene, ethanol, gasoline, the kerosene one or more, its content be propylene-glycol ethyl ether and ethlyene dichloride cumulative volume 2-40 doubly.

4, according to the described carbon deposit cleaner of claim 3, the content that it is characterized in that described benzene, ethanol, gasoline, kerosene is propylene-glycol ethyl ether and ethlyene dichloride cumulative volume 5-20 times.

5, according to the described carbon deposit cleaner of claim 3, it is characterized in that also containing in the described carbon deposit cleaner and be selected from one or more other organic matters except propylene-glycol ethyl ether, ethlyene dichloride, benzene and ethanol in organic alcohol, ester, ether, aromatic hydrocarbons, phenol, hydramine, alcohol ether, alcohol ester, ketone, carboxylic acid and the ethlyene dichloride, its content be propylene-glycol ethyl ether and ethlyene dichloride cumulative volume 0.2-5 doubly.

6,, it is characterized in that described organic content is propylene-glycol ethyl ether and ethlyene dichloride cumulative volume 0.5-2 times according to the described carbon deposit cleaner of claim 5.

7,, it is characterized in that described organic alcohol is fatty alcohol and/or aralkyl alcohol according to the described carbon deposit cleaner of claim 5; It is C that described fatty alcohol is selected from carbon atom number ₁-C ₁₂In one or more, wherein contain the alcohols of straight chain, side chain and band; It is C that described aralkyl alcohol is selected from carbon atom number ₇-C ₁₄In one or more; It is C that ester, ether, aromatic hydrocarbons, phenol, hydramine, alcohol ether, alcohol ester, ketone and carboxylic acid are selected from carbon atom number ₁₄Below in one or more, wherein contain straight chain, side chain and cycloalkane compound.

8, the application of the arbitrary described carbon deposit cleaner of claim 1～7 in the coking deactivation catalyst regeneration process comprises following process: the coking deactivation catalyst is handled the processing of regenerating then earlier with described carbon deposit cleaner.

9,, it is characterized in that method that carbon deposit cleaner is handled decaying catalyst is selected from one or more in infusion method, the way of distillation and the heating according to the described application of claim 8.

10,, it is characterized in that the method that carbon deposit cleaner is handled decaying catalyst is the method for soaking and distillation combines according to the described application of claim 8.

11,, it is characterized in that in the described infusion method processing time 2h-20h according to the described application of claim 9; In the described way of distillation, the processing time is 1h-5h; In the described heating, the temperature of carbon deposit cleaner is lower than azeotropic temperature, and the processing time is 1h-5h.

12, according to the described application of claim 8, it is characterized in that described regeneration process is as follows: the regenerating unit of packing into of the catalyst after will cleaning with carbon deposit cleaner, with inert gas device is replaced earlier, then oxygen content is progressively increased and be 0.5-10.0v% catalyst to be carried out the substep coke-burning regeneration; Described substep coke-burning regeneration divides four-stage, and each stage major control condition is as follows, first section: constant temperature is 1-3 hour in the time of 100-140 ℃; Second section: constant temperature is 1-3 hour in the time of 150-240 ℃; The 3rd section: constant temperature is 1-2 hour in the time of 250-350 ℃; The 4th section: constant temperature is 2-4 hour in the time of 450-550 ℃.

13,, it is characterized in that described coking deactivation catalyst is hydrogenation catalyst or methane aromatization catalyst according to the described application of claim 8.