A method for regenerating and converting inert substances for preparing methanol from coke oven gas

Abstract

The invention discloses a method for regenerating and converting inert substances for preparing methanol from coke oven gas, belongs to the technical field of coke oven gas treatment, and is used to solve the technical problem in the prior art that during the regeneration and conversion of coke oven gas, a catalyst is easily blocked by carbon decomposed from methane, resulting in low regeneration and conversion efficiency of methane. The invention comprises the following steps: taking a quartz tube reactor, sequentially filling the quartz tube reactor with modified activated carbon and a supported catalyst, forming an activated carbon bed layer and a catalyst bed layer in the quartz tube reactor, and placing the quartz tube in a constant temperature furnace at a temperature of 480-520 DEG C. The invention optimizes the regeneration and conversion process of coke oven gas by preparing a porous supported catalyst and using the supported catalyst and modified activated carbon supported by nickel oxide as fillers, effectively avoiding blockage of filler pores, and reducing the circulation amount of inert gas in a methanol synthesis circulation system.

Description

Technical Field

[0001] The invention relates to the technical field of coke oven gas treatment, and in particular to a method for regenerating and converting inert substances used for preparing methanol from coke oven gas. Background Art

[0002] Coke oven gas contains carbon monoxide and a small amount of toxic substances. In the production process of coke oven gas to methanol, the raw materials must first be pretreated. The raw gas enters the gas holder for buffering and pressure stabilization, and then enters the gas compressor, where it is pressurized to 2.5MPa to reach the pressure required for desulfurization. It then enters the fine desulfurization device to desulfurize the raw gas. After completing the rough desulfurization and fine desulfurization steps, the total sulfur content in the gas is greatly reduced, avoiding catalyst poisoning and corrosion of instruments and equipment.

[0003] The coke oven gas in the prior art contains a large amount of methane gas, which is an inert gas and does not participate in the reaction in the next step of the methanol synthesis reaction. Methanol circulates as an inert gas in the synthesis cycle system, which will increase unnecessary power consumption of the compressor, reduce power consumption per unit methanol output, increase the partial pressure of effective components, promote the forward reaction, improve synthesis efficiency, and increase methanol production. The prior art usually requires converting it into hydrogen and carbon monoxide under a catalyst and a high temperature environment. However, traditional methane gas will produce carbon during the high-temperature decomposition process. The carbon attached to the catalyst surface will cause the catalyst bed to be blocked and the catalyst activity to be reduced, resulting in low regeneration conversion efficiency of methane in the coke oven gas. The circulation amount of inert gas in the methanol synthesis cycle system needs to be further reduced.

[0004] In view of the technical defects in this aspect, a solution is now proposed. Summary of the invention

[0005] The object of the present invention is to provide a method for regenerating and converting coke oven gas to methanol using an inert substance, so as to solve the technical problem in the prior art that during the regeneration and conversion of coke oven gas, the catalyst is easily blocked by carbon decomposed from methane, resulting in low regeneration and conversion efficiency of methane.

[0006] The object of the present invention can be achieved by the following technical scheme: A method for regenerating and converting inert substances for preparing methanol from coke oven gas, comprising the following steps:

[0007] S1, taking a quartz tube reactor, sequentially loading modified activated carbon and a supported catalyst into the quartz tube reactor, and forming an activated carbon bed and a catalyst bed in the quartz tube reactor;

[0008] S2, placing the quartz tube in a constant temperature furnace at a temperature of 480-520°C;

[0009] S3, preheating the desulfurized coke oven gas to 200-260°C, and mixing it with water vapor to obtain a mixed gas;

[0010] S4. The mixed gas is transported from the top of the quartz tube reactor to the quartz tube reactor, and after being catalytically treated in the catalyst bed and the activated carbon bed in sequence, it is discharged from the bottom of the quartz tube reactor to obtain regenerated converted coke oven gas.

[0011] Further, the modified activated carbon is processed by the following steps:

[0012] A1. Dissolve nickel nitrate in deionized water, add activated carbon to the reaction system, perform ultrasonic dispersion for 40-60 min, adjust the pH of the reaction system to 10-11, raise the temperature, complete the reaction, and perform post-treatment to obtain a modified activated carbon precursor;

[0013] A2. Place the modified activated carbon precursor in a muffle furnace and roast it for 3-5 hours, cool it down and discharge it to obtain modified activated carbon.

[0014] The synthetic reaction mechanism of modified activated carbon is:

[0015] Activated carbon is used as a carrier material. Under the action of ultrasonic dispersion, the contact between the activated carbon and the nickel nitrate solution is promoted. By adjusting the pH of the reaction system, the nickel nitrate is converted into nickel hydroxide precipitation attached to the activated carbon. Through long-term high-temperature treatment, it is helpful for the further deposition and solidification of nickel hydroxide on the surface of the activated carbon, and the interaction between the nickel hydroxide and the activated carbon is promoted. At high temperature, the nickel hydroxide undergoes a thermal decomposition reaction to generate nickel oxide, and the modified activated carbon is prepared.

[0016] Furthermore, in step S1, the inner diameter of the quartz tube reactor is 9 cm, the outer diameter is 12 cm, the tube length is 550 cm, the height of the activated carbon bed is 450 cm, and the height of the catalyst bed is 100 cm; in step S3, the volume ratio of desulfurized coke oven gas and water vapor is 100:0.8-1.2; in step S4, the flow rate of the mixed gas is 8-10L / min.

[0017] Furthermore, in step A1, the nickel nitrate, deionized water and activated carbon are used in a ratio of 1-3g:20mL:7-11g, the heating temperature is 70-80°C, and the insulation reaction time is 20-22h. The post-treatment includes: after the reaction is completed, the temperature of the reactor is lowered to room temperature, filtered, the filter cake is washed with purified water until it is neutral and then dried, and the filter cake is transferred to a drying oven at a temperature of 70-80°C, and dried to constant weight to obtain a loaded nickel oxide precursor; in step A2, the calcination temperature is 780-840°C, and the calcination time is 3-5h.

[0018] Further, the supported catalyst is processed by the following steps:

[0019] B1. Add sodium hydroxide, sodium aluminate and deionized water into a reactor, stir at room temperature until the system is clear, add n-butylamine dropwise into the reactor, add modified supported nickel oxide into the reactor after the addition is complete, keep warm and stir for 100-120 minutes, transfer the reaction solution into a high-pressure reactor at a temperature of 140-150° C., keep warm and crystallize for 2 days, and obtain crystal nuclei through post-treatment;

[0020] The synthesis reaction mechanism of the crystal nucleus is:

[0021] Sodium hydroxide, sodium aluminate and deionized water are mixed and stirred until the system is clarified to form an alkaline solution. n-Butylamine is used as a structure-directing agent. The modified loaded nickel oxide not only serves as a catalytic active center, but also interacts with the sodium aluminate and sodium hydroxide in the solution through the silicon-modified layer on its surface during the high-temperature crystallization process, thereby guiding the orderly arrangement and crystallization of the aluminum-oxygen network structure. While the n-butylamine is removed by high-temperature calcination, the crystal structure is further stabilized to prepare a crystal nucleus.

[0022] B2, adding aluminum sulfate 18hydrate, sodium hydroxide and deionized water to a reaction kettle, stirring at room temperature until the system is dissolved, adding silica sol, tetrahydropyrrole and crystal nuclei to the reaction kettle, stirring at room temperature for 2 hours to obtain a mixed solution;

[0023] B3, transferring the mixed solution to a high pressure reactor at a temperature of 140-150° C. for crystallization for 3 days, and post-treating to obtain a catalyst precursor;

[0024] B4. Add the catalyst precursor and ammonium chloride solution into the reactor and stir. Raise the temperature of the reactor to 80-90°C, keep warm and stir for 4-6 hours, and perform post-treatment to obtain the supported catalyst.

[0025] The synthetic reaction mechanism of the supported catalyst is:

[0026] Aluminum sulfate 18hydrate and sodium hydroxide are mixed and stirred in deionized water to generate a neutralization reaction to generate aluminum hydroxide, sodium aluminate and sodium sulfate. Silica sol is a colloidal solution containing nanometer-sized silica particles. The silica particles in the silica sol are adsorbed on the surface of aluminum hydroxide or sodium aluminate to form a preliminary composite structure with a crystal nucleus as a nucleation center and tetrahydropyrrole as a structure directing agent. During the high-temperature crystallization process, sodium aluminate and silica particles form a coating structure on the outside of the crystal nucleus through a dissolution-recrystallization mechanism. Through a calcination treatment, organic impurities such as tetrahydropyrrole are decomposed and removed at high temperature, thereby assembling into a catalyst precursor. During the high-temperature heat preservation process, ammonium chloride and inorganic salts in the precursor undergo ion exchange, resulting in exposure of the catalytic active center on the catalyst surface, thereby preparing a supported catalyst.

[0027] Further, in step B1, the amount ratio of sodium hydroxide, sodium aluminate, deionized water, n-butylamine and modified supported nickel oxide is 1g:7g:200mL:6g:50g, and the post-treatment includes: after the reaction is completed, the temperature of the reactor is lowered to room temperature, filtered, the filter cake is placed in a drying oven at a temperature of 70-80°C, dried to constant weight, and then transferred to a muffle furnace at a temperature of 500-600°C, roasted for 6-8h to obtain a crystal nucleus; in step B2, the amount ratio of aluminum sulfate 18hydrate, sodium hydroxide, deionized water, silica sol, tetrahydropyrrole and crystal nucleus is 3g:2g:50mL:15g:4g:1g; in step B3, the post-treatment includes: reacting After the reaction is completed, the temperature of the reactor is lowered to room temperature, the filter is filtered, the filter cake is placed in a drying oven at a temperature of 70-80°C, dried to constant weight, and then transferred to a muffle furnace at a temperature of 500-600°C, roasted for 6-8h, and discharged after cooling to obtain a catalyst precursor; in step B4, the amount ratio of the catalyst precursor to the ammonium chloride solution is 1g:10mL, and the ammonium chloride solution is composed of ammonium chloride and purified water at a ratio of 1g:10mL. The post-treatment includes: after the reaction is completed, the temperature of the reactor is lowered to room temperature, the filter is filtered, the filter cake is washed with purified water 3-5 times and then dried, and the filter cake is placed in a drying oven at a temperature of 70-80°C, and dried to constant weight to obtain a supported catalyst.

[0028] Furthermore, the preparation method of modified loaded nickel oxide is: add loaded nickel oxide, anhydrous ethanol and tetraethyl orthosilicate into a reactor and stir, increase the temperature of the reactor to 50-60°C, add ammonia water to the reactor, keep warm and stir for 4-6 hours, and post-treat to obtain modified loaded nickel oxide.

[0029] The synthetic reaction mechanism of modified supported nickel oxide is:

[0030] The modified loaded nickel oxide is prepared by hydrolyzing ethyl orthosilicate under alkaline conditions and reacting with the active reaction sites on the surface of the loaded nickel oxide to form a polysiloxane coating on the outside of the loaded nickel oxide.

[0031] Furthermore, the amount ratio of the loaded nickel oxide, anhydrous ethanol, tetraethyl orthosilicate and ammonia water is 3g:15mL:1g:5mL, the concentration of the ammonia water is 0.3mol / L, and the post-treatment includes: after the reaction is completed, the temperature of the reactor is lowered to room temperature, filtered, the filter cake is washed with purified water until it is neutral and then dried, the filter cake is transferred to a drying oven at a temperature of 70-80°C, and dried to constant weight to obtain modified loaded nickel oxide.

[0032] Further, the supported nickel oxide is processed by the following steps:

[0033] C1. Add nickel nitrate, lanthanum nitrate, zirconium nitrate and deionized water into a reactor and stir. Raise the temperature of the reactor to 45-55°C and stir until the system is dissolved. Add sodium hydroxide solution into the reactor and adjust the pH value of the system to 10-11. Raise the temperature of the reactor to 70-80°C and stir for 20-22h. Post-treat to obtain a loaded nickel oxide precursor.

[0034] C2. The loaded nickel oxide precursor is placed in a muffle furnace and calcined for 3-5 hours, cooled, discharged, crushed, and passed through an 80-mesh sieve to obtain loaded nickel oxide.

[0035] The synthetic reaction mechanism of supported nickel oxide is:

[0036] After dissolving nickel nitrate, lanthanum nitrate and zirconium nitrate in water, the pH of the system is adjusted to alkaline, so that the nickel nitrate, lanthanum nitrate and zirconium nitrate form a co-precipitate in the reaction system in the form of metal hydroxides. By continuous stirring at high temperature, the nickel, lanthanum and zirconium elements in the reaction system are promoted to further transform into precipitates. By high-temperature treatment, the metal hydroxide is further decomposed to generate metal oxides through high-temperature treatment, forming a ternary mixed metal oxide of nickel oxide, lanthanum oxide and zirconium oxide, and obtained loaded nickel oxide.

[0037] Furthermore, in step C1, the amount ratio of the nickel nitrate, lanthanum nitrate, zirconium nitrate and deionized water is 3g:6-8g:12-14g:120mL, and the post-treatment includes: after the reaction is completed, the temperature of the reactor is lowered to room temperature, filtered, the filter cake is washed with purified water until it is neutral and then dried, and the filter cake is transferred to a drying oven at a temperature of 70-80°C, and dried to constant weight to obtain a loaded nickel oxide precursor; in step C2, the calcination temperature is 780-840°C.

[0038] The present invention has the following beneficial effects:

[0039] 1. The inert substance regeneration and conversion method for preparing methanol from coke oven gas provided by the present invention comprises the following steps: using a ternary metal oxide composed of nickel, lanthanum and zirconium as loaded nickel oxide, modifying the loaded nickel oxide, preparing a crystal nucleus, and using the crystal nucleus as a nucleation center to prepare a porous loaded catalyst, and using the loaded catalyst and modified activated carbon loaded with nickel oxide as fillers to form a catalyst bed and an activated carbon bed in a quartz tube reactor; after the desulfurized coke oven gas passes through the catalyst bed to catalyze the decomposition of methane in a high temperature environment, the coke oven gas is reprocessed through the activated carbon bed to further reduce the carbon dioxide and oxygen content in the coke oven gas; by adding water vapor to the desulfurized coke oven gas, the carbon produced by the thermal decomposition of low-carbon alkanes such as methane is promoted to react with water, and the carbon is converted into carbon monoxide and hydrogen, so as to avoid the carbon produced by the decomposition from clogging the catalyst bed, thereby maintaining good gas permeability and catalytic performance of the catalyst bed.

[0040] 2. The inert substance regeneration and conversion method for preparing methanol from coke oven gas provided by the present invention uses zirconium oxide as a carrier, nickel oxide as a main catalyst, and lanthanum oxide as a co-catalyst. NiO reacts with low-carbon alkanes to generate H2O, CO, CO2 or carbon powder, and is reduced to metallic Ni. As the reaction proceeds, the metallic Ni aggregates on the surface of the catalyst. When it reaches a certain aggregation state, it will continue to catalyze unreacted CH4 to generate H2. The addition of lanthanum can improve the microstructure of the catalyst, promote the uniform dispersion of nickel on the carrier, and prevent the agglomeration of nickel particles, thereby increasing the surface area and the number of active sites of the catalyst. Lanthanum can also form an alloy or solid solution with nickel and zirconium, change the electronic structure and chemical properties of nickel, and improve its catalytic activity and stability. By loading nickel oxide on activated carbon, it can catalyze the reaction of oxygen and carbon dioxide in coke oven gas with carbon, reduce the content of oxygen and carbon dioxide in the regenerated converted coke oven gas, and further reduce the circulation amount of inert gas in the methanol synthesis cycle system.

[0041] 3. The inert substance regeneration and conversion method for preparing methanol from coke oven gas provided by the present invention forms a crystal nucleus with a specific structure and pores through the reaction of sodium hydroxide, sodium aluminate and n-butylamine, and subsequent high-temperature crystallization and calcination. The silica sol introduces additional silicon sources, which react with the aluminum source at high temperature to form composite oxides such as silicate aluminates with a large specific surface area and rich pore structure outside the crystal nucleus with the crystal nucleus as the nucleation center, so that the pore structure of the crystal nucleus itself is retained and further expanded to play a role in the final catalyst. The reaction of ammonium chloride solution with the catalyst precursor expands the original pores on the surface or inside of the catalyst through ion exchange, further improving the porosity and specific surface area of ​​the catalyst. In addition, the large specific surface area and rich pore structure are conducive to the dispersion and deposition of carbon particles, reducing the coverage and blockage of the active sites of the catalyst by carbon. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0043] Figure 1 This is the XRD diagram of the nickel oxide loaded in the present invention. DETAILED DESCRIPTION

[0044] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0045] The silica sol used in this application is selected from Donghao Chemical (Shandong) Co., Ltd., the model is DH-silica sol, and the effective content is 40%.

[0046] Example 1

[0047] This embodiment provides a method for preparing modified activated carbon for regeneration and conversion of inert substances for preparing methanol from coke oven gas, comprising the following steps:

[0048] Weigh: 100 g of nickel nitrate and 2000 mL of deionized water are added to a reactor and stirred. The temperature of the reactor is raised to 45°C and stirred until the system is dissolved. 700 g of activated carbon is added to the reactor and ultrasonically dispersed for 40 min. Sodium hydroxide solution is added to the reactor to adjust the pH of the system to 10. The temperature of the reactor is raised to 70°C and stirred for 20 h. The temperature of the reactor is lowered to room temperature and filtered. The filter cake is washed with purified water until it is neutral and then dried. The filter cake is transferred to a drying oven at a temperature of 70°C and dried to constant weight to obtain a loaded nickel oxide precursor.

[0049] The modified activated carbon precursor was placed in a muffle furnace at a temperature of 780° C. and calcined for 3 hours, and then the temperature was lowered and the material was discharged to obtain the modified activated carbon.

[0050] Example 2

[0051] This embodiment provides a method for preparing modified activated carbon for regeneration and conversion of inert substances for preparing methanol from coke oven gas, comprising the following steps:

[0052] Weigh: 200 g of nickel nitrate and 2000 mL of deionized water are added to a reactor and stirred. The temperature of the reactor is raised to 50°C and stirred until the system is dissolved. 900 g of activated carbon is added to the reactor and ultrasonically dispersed for 50 min. Sodium hydroxide solution is added to the reactor to adjust the pH of the system to 10.5. The temperature of the reactor is raised to 75°C and stirred for 21 h. The temperature of the reactor is lowered to room temperature and filtered. The filter cake is washed with purified water until it is neutral and then dried. The filter cake is transferred to a drying oven at a temperature of 75°C and dried to constant weight to obtain a loaded nickel oxide precursor.

[0053] The modified activated carbon precursor was placed in a muffle furnace at a temperature of 810° C. and calcined for 4 hours, and then the temperature was lowered and the material was discharged to obtain the modified activated carbon.

[0054] Example 3

[0055] This embodiment provides a method for preparing modified activated carbon for regeneration and conversion of inert substances for preparing methanol from coke oven gas, comprising the following steps:

[0056] Weigh: 300g of nickel nitrate and 2000mL of deionized water are added to a reactor and stirred. The temperature of the reactor is raised to 55°C and stirred until the system is dissolved. 1100g of activated carbon is added to the reactor and ultrasonically dispersed for 60min. Sodium hydroxide solution is added to the reactor to adjust the pH of the system to 11. The temperature of the reactor is raised to 80°C and stirred for 22h. The temperature of the reactor is lowered to room temperature and filtered. The filter cake is washed with purified water until it is neutral and then dried. The filter cake is transferred to a drying oven at 80°C and dried to constant weight to obtain a loaded nickel oxide precursor.

[0057] The modified activated carbon precursor was placed in a muffle furnace at a temperature of 840° C. and calcined for 5 hours, then the temperature was lowered and the material was discharged to obtain the modified activated carbon.

[0058] Example 4

[0059] This embodiment provides a method for preparing a supported catalyst for inert substance regeneration conversion of coke oven gas to methanol, comprising the following steps:

[0060] S1. Preparation of loaded nickel oxide

[0061] Weigh: 300 g of nickel nitrate hexahydrate, 600 g of lanthanum nitrate hexahydrate, 1200 g of zirconium nitrate hexahydrate and 12000 mL of deionized water, add to a reactor and stir, raise the temperature of the reactor to 45°C, stir until the system is dissolved, add sodium hydroxide solution to the reactor, adjust the pH of the system to 10, raise the temperature of the reactor to 70°C, stir for 20 hours, lower the temperature of the reactor to room temperature, filter, wash the filter cake with purified water until it is neutral and then dry, transfer the filter cake to a drying oven at a temperature of 70°C, dry to constant weight, and obtain a loaded nickel oxide precursor;

[0062] The loaded nickel oxide precursor was placed in a muffle furnace at a temperature of 780° C. and calcined for 3 hours, cooled, discharged, crushed, and passed through an 80-mesh sieve to obtain the loaded nickel oxide.

[0063] S2. Preparation of modified loaded nickel oxide

[0064] Weigh: 300 g of loaded nickel oxide, 1500 mL of anhydrous ethanol and 100 g of tetraethyl orthosilicate, add into a reactor and stir, raise the temperature of the reactor to 50°C, add 500 mL of 0.3 mol / L ammonia water into the reactor, after the addition is complete, keep warm and stir for 4 hours, lower the temperature of the reactor to room temperature, filter, wash the filter cake with purified water until it is neutral and then drain, transfer the filter cake to a drying oven at a temperature of 70°C, dry to constant weight, and obtain modified loaded nickel oxide.

[0065] S3. Preparation of crystal nuclei

[0066] Weigh: 10 g of sodium hydroxide, 70 g of sodium aluminate and 2000 mL of deionized water, add them to a reactor, stir at room temperature until the system is clear, add 60 g of n-butylamine dropwise to the reactor, add 500 g of modified loaded nickel oxide to the reactor after the addition is complete, keep warm and stir for 100 minutes, transfer the reaction solution to a high-pressure reactor at a temperature of 140°C, keep warm and crystallize for 2 days, lower the temperature of the high-pressure reactor to room temperature, filter, place the filter cake in a drying oven at a temperature of 70°C, dry to constant weight, then transfer it to a muffle furnace at a temperature of 500°C, and calcine for 6 hours to obtain a crystal nucleus.

[0067] S4. Preparation of supported catalyst

[0068] Weigh: 300 g of aluminum sulfate 18hydrate, 200 g of sodium hydroxide and 5000 mL of deionized water, add them into a reactor, stir at room temperature until the system is dissolved, add 1500 g of silica sol, 400 g of tetrahydropyrrole and 100 g of crystal nuclei into the reactor, stir at room temperature for 2 h to obtain a mixed solution;

[0069] The mixed solution was transferred to a high-pressure reactor at a temperature of 140° C. for crystallization for 3 days, the temperature of the high-pressure reactor was lowered to room temperature, and the filter cake was placed in a drying oven at a temperature of 70° C. and dried to constant weight, and then transferred to a muffle furnace at a temperature of 500° C. and calcined for 6 hours. After cooling, the material was discharged to obtain a catalyst precursor;

[0070] Mix ammonium chloride and purified water in a ratio of 1 g:10 mL to obtain an ammonium chloride solution;

[0071] The catalyst precursor and ammonium chloride solution were added to the reactor at a ratio of 1g:10mL and stirred. The temperature of the reactor was raised to 80°C and stirred for 4 hours. The temperature of the reactor was lowered to room temperature and filtered. The filter cake was washed with purified water for 3 times and then dried. The filter cake was placed in a drying oven at 70°C and dried to constant weight to obtain a supported catalyst.

[0072] Example 5

[0073] This embodiment provides a method for preparing a supported catalyst for inert substance regeneration conversion of coke oven gas to methanol, comprising the following steps:

[0074] S1. Preparation of loaded nickel oxide

[0075] Weigh: 300 g of nickel nitrate hexahydrate, 700 g of lanthanum nitrate hexahydrate, 1300 g of zirconium nitrate hexahydrate and 12000 mL of deionized water, add to a reactor and stir, raise the temperature of the reactor to 50°C, stir until the system is dissolved, add sodium hydroxide solution to the reactor, adjust the pH of the system to 10.5, raise the temperature of the reactor to 75°C, stir for 21 hours, lower the temperature of the reactor to room temperature, filter, wash the filter cake with purified water until it is neutral and then dry, transfer the filter cake to a drying oven at a temperature of 75°C, dry to constant weight, and obtain a loaded nickel oxide precursor;

[0076] The loaded nickel oxide precursor was placed in a muffle furnace at a temperature of 810° C. and calcined for 4 hours. The material was cooled, discharged, crushed, and passed through an 80-mesh sieve to obtain the loaded nickel oxide.

[0077] S2. Preparation of modified loaded nickel oxide

[0078] Weigh: 300 g of loaded nickel oxide, 1500 mL of anhydrous ethanol and 100 g of tetraethyl orthosilicate, add into a reactor and stir, raise the temperature of the reactor to 55°C, add 500 mL of 0.3 mol / L ammonia water dropwise into the reactor, after the addition is complete, keep warm and stir for 5 hours, lower the temperature of the reactor to room temperature, filter, wash the filter cake with purified water until it is neutral and then drain, transfer the filter cake to a drying oven at a temperature of 75°C, and dry to constant weight to obtain modified loaded nickel oxide.

[0079] S3. Preparation of crystal nuclei

[0080] Weigh: 10 g of sodium hydroxide, 70 g of sodium aluminate and 2000 mL of deionized water, add them to a reactor, stir at room temperature until the system is clear, add 60 g of n-butylamine dropwise to the reactor, add 500 g of modified loaded nickel oxide to the reactor after the addition is complete, keep warm and stir for 110 minutes, transfer the reaction solution to a high-pressure reactor at a temperature of 145°C, keep warm and crystallize for 2 days, lower the temperature of the high-pressure reactor to room temperature, filter, place the filter cake in a drying oven at a temperature of 75°C, dry to constant weight, then transfer it to a muffle furnace at a temperature of 550°C, and calcine for 7 hours to obtain a crystal nucleus.

[0081] S4. Preparation of supported catalyst

[0082] Weigh: 300 g of aluminum sulfate 18hydrate, 200 g of sodium hydroxide and 5000 mL of deionized water, add them into a reactor, stir at room temperature until the system is dissolved, add 1500 g of silica sol, 400 g of tetrahydropyrrole and 100 g of crystal nuclei into the reactor, stir at room temperature for 2 h to obtain a mixed solution;

[0083] The mixed solution was transferred to a high-pressure reactor at a temperature of 145°C for crystallization for 3 days, the temperature of the high-pressure reactor was lowered to room temperature, and the filter cake was placed in a drying oven at a temperature of 75°C and dried to constant weight, and then transferred to a muffle furnace at a temperature of 550°C and calcined for 7 hours. After cooling, the material was discharged to obtain a catalyst precursor;

[0084] Mix ammonium chloride and purified water in a ratio of 1 g:10 mL to obtain an ammonium chloride solution;

[0085] The catalyst precursor and ammonium chloride solution were added to the reactor at a ratio of 1g:10mL and stirred. The temperature of the reactor was raised to 85°C and stirred for 5 hours. The temperature of the reactor was lowered to room temperature and filtered. The filter cake was washed with purified water for 4 times and then dried. The filter cake was placed in a drying oven at 75°C and dried to constant weight to obtain a supported catalyst.

[0086] Example 6

[0087] This embodiment provides a method for preparing a supported catalyst for inert substance regeneration conversion of coke oven gas to methanol, comprising the following steps:

[0088] S1. Preparation of loaded nickel oxide

[0089] Weigh: 300 g of nickel nitrate hexahydrate, 800 g of lanthanum nitrate hexahydrate, 1400 g of zirconium nitrate hexahydrate and 12000 mL of deionized water, add to a reactor and stir, raise the temperature of the reactor to 55°C, stir until the system is dissolved, add sodium hydroxide solution to the reactor, adjust the pH of the system to 11, raise the temperature of the reactor to 80°C, stir for 22 hours, lower the temperature of the reactor to room temperature, filter, wash the filter cake with purified water until it is neutral and then dry, transfer the filter cake to a drying oven at 80°C, dry to constant weight, and obtain a loaded nickel oxide precursor;

[0090] The loaded nickel oxide precursor was placed in a muffle furnace at a temperature of 840° C. and calcined for 5 hours. The material was cooled, discharged, crushed, and passed through an 80-mesh sieve to obtain the loaded nickel oxide.

[0091] S2. Preparation of modified loaded nickel oxide

[0092] Weigh: 300 g of loaded nickel oxide, 1500 mL of anhydrous ethanol and 100 g of tetraethyl orthosilicate, add into a reactor and stir, raise the temperature of the reactor to 60°C, add 500 mL of 0.3 mol / L ammonia water dropwise into the reactor, after the addition is complete, keep warm and stir for 6 hours, lower the temperature of the reactor to room temperature, filter, wash the filter cake with purified water until it is neutral and then drain, transfer the filter cake to a drying oven at 80°C, dry to constant weight, and obtain modified loaded nickel oxide.

[0093] S3. Preparation of crystal nuclei

[0094] Weigh: 10 g of sodium hydroxide, 70 g of sodium aluminate and 2000 mL of deionized water, add them to a reactor, stir at room temperature until the system is clear, add 60 g of n-butylamine dropwise to the reactor, add 500 g of modified loaded nickel oxide to the reactor after the addition is complete, keep warm and stir for 120 minutes, transfer the reaction solution to a high-pressure reactor at a temperature of 150°C, keep warm and crystallize for 2 days, lower the temperature of the high-pressure reactor to room temperature, filter, place the filter cake in a drying oven at a temperature of 80°C, dry to constant weight, then transfer it to a muffle furnace at a temperature of 600°C, and calcine for 8 hours to obtain a crystal nucleus.

[0095] S4. Preparation of supported catalyst

[0096] Weigh: 300 g of aluminum sulfate 18hydrate, 200 g of sodium hydroxide and 5000 mL of deionized water, add them into a reactor, stir at room temperature until the system is dissolved, add 1500 g of silica sol, 400 g of tetrahydropyrrole and 100 g of crystal nuclei into the reactor, stir at room temperature for 2 h to obtain a mixed solution;

[0097] The mixed solution was transferred to a high-pressure reactor at a temperature of 150° C. for crystallization for 3 days, the temperature of the high-pressure reactor was lowered to room temperature, and the filter cake was placed in a drying oven at a temperature of 80° C. and dried to constant weight, and then transferred to a muffle furnace at a temperature of 600° C. and calcined for 8 hours. After cooling, the material was discharged to obtain a catalyst precursor;

[0098] Mix ammonium chloride and purified water in a ratio of 1 g:10 mL to obtain an ammonium chloride solution;

[0099] The catalyst precursor and ammonium chloride solution were added to the reactor at a ratio of 1g:10mL and stirred. The temperature of the reactor was raised to 90°C and stirred for 6 hours. The temperature of the reactor was lowered to room temperature and filtered. The filter cake was washed with purified water for 5 times and then dried. The filter cake was placed in a drying oven at 80°C and dried to constant weight to obtain a supported catalyst.

[0100] Example 7

[0101] This embodiment provides a method for regenerating and converting inert substances for preparing methanol from coke oven gas, comprising the following steps:

[0102] Step 1: Take a quartz tube reactor with an inner diameter of 9 cm, an outer diameter of 12 cm, and a tube length of 550 cm, and sequentially load the modified activated carbon of Example 1 and the supported catalyst of Example 4 into the quartz tube reactor to form an activated carbon bed with a thickness of 450 cm and a catalyst bed with a thickness of 100 cm in the quartz tube reactor;

[0103] Step 2: Place the quartz tube in a constant temperature furnace at 480°C;

[0104] Step 3: preheat the desulfurized coke oven gas to 200° C., and mix it with water vapor at a volume ratio of 100:0.8 to obtain a mixed gas;

[0105] Step 4: transport the mixed gas from the top of the quartz tube reactor to the quartz tube reactor at a gas flow rate of 8 L / min, and after catalytic treatment in the catalyst bed and the activated carbon bed in sequence, discharge it from the bottom of the quartz tube reactor to obtain regenerated converted coke oven gas.

[0106] Example 8

[0107] This embodiment provides a method for regenerating and converting inert substances for preparing methanol from coke oven gas, comprising the following steps:

[0108] Step 1: Take a quartz tube reactor with an inner diameter of 9 cm, an outer diameter of 12 cm, and a tube length of 550 cm, and sequentially load the modified activated carbon of Example 2 and the supported catalyst of Example 5 into the quartz tube reactor to form an activated carbon bed with a thickness of 450 cm and a catalyst bed with a thickness of 100 cm in the quartz tube reactor;

[0109] Step 2: Place the quartz tube in a constant temperature furnace at 500°C;

[0110] Step 3: preheat the desulfurized coke oven gas to 230° C., and mix it with water vapor at a volume ratio of 100:1 to obtain a mixed gas;

[0111] Step 4: transport the mixed gas from the top of the quartz tube reactor to the quartz tube reactor at a gas flow rate of 9 L / min, and after catalytic treatment in the catalyst bed and the activated carbon bed in sequence, discharge it from the bottom of the quartz tube reactor to obtain regenerated converted coke oven gas.

[0112] Example 9

[0113] This embodiment provides a method for regenerating and converting inert substances for preparing methanol from coke oven gas, comprising the following steps:

[0114] Step 1: Take a quartz tube reactor with an inner diameter of 9 cm, an outer diameter of 12 cm, and a tube length of 550 cm, and sequentially load the modified activated carbon of Example 3 and the supported catalyst of Example 6 into the quartz tube reactor to form an activated carbon bed with a thickness of 450 cm and a catalyst bed with a thickness of 100 cm in the quartz tube reactor;

[0115] Step 2: Place the quartz tube in a constant temperature furnace at 520°C;

[0116] Step 3: preheat the desulfurized coke oven gas to 260° C., and mix it with water vapor at a volume ratio of 100:1.2 to obtain a mixed gas;

[0117] Step 4: transport the mixed gas from the top of the quartz tube reactor to the quartz tube reactor at a gas flow rate of 10 L / min, and after catalytic treatment in the catalyst bed and the activated carbon bed in sequence, discharge it from the bottom of the quartz tube reactor to obtain regenerated converted coke oven gas.

[0118] Comparative Example 1

[0119] The difference between this comparative example and Example 9 is that in step 1, the modified activated carbon prepared in Example 3 is replaced by the activated carbon in Example 3.

[0120] Comparative Example 2

[0121] The difference between this comparative example and Example 9 is that in step 1, during the supported catalyst process of Example 6, lanthanum nitrate hexahydrate is not added in step S1.

[0122] Comparative Example 3

[0123] The difference between this comparative example and Example 9 is that in step 1, during the supported catalyst process of Example 6, the supported catalyst is replaced by the catalyst precursor in step S4.

[0124] Comparative Example 4

[0125] The difference between this comparative example and Example 9 is that no water vapor is added to the mixed gas in step 3.

[0126] Performance Testing:

[0127] Referring to the standard GB / T 28901-2012 "Gas Chromatographic Analysis Method for Coke Oven Gas Components", the contents of methane, carbon dioxide and oxygen in the regenerated conversion coke oven gas prepared in Examples 7-9 and Comparative Examples 1-4 were determined;

[0128] The porosity of some supported catalysts near the top of the quartz tube reactor before and after 100 hours of use in Examples 7-9 and Comparative Examples 1-4 was determined with reference to standard GB / T 21650.2-2008 "Mercury Intrusion Porosimetry and Gas Adsorption Method for Pore Size Distribution and Porosity of Solid Materials Part 2: Analysis of Mesopores and Macropores by Gas Adsorption Method". The specific test results are shown in Table 1 below.

[0129] Table 1-Performance test data of samples

[0130] Data Analysis:

[0131] Comparative analysis of the data in Table 1 above shows that the porosity of the supported catalyst prepared by the present invention reaches 68.9%. After 100 hours, the porosity is 67.3%, and the porosity retention rate reaches 97.7%. After regeneration conversion, the methane content in the coke oven gas is reduced to 0.43%, the carbon dioxide content is reduced to 0.14%, and the oxygen content is reduced to 0.07%. All performance data are better than those of the comparative example.

[0132] It is explained that the present invention prepares crystal nuclei after modifying the loaded nickel oxide, and prepares a porous loaded catalyst with the crystal nuclei as the nucleation center, and uses the loaded catalyst and modified activated carbon loaded with nickel oxide as fillers to optimize the regeneration conversion process of coke oven gas, which not only effectively reduces the content of methane, carbon dioxide and oxygen in the coke oven gas, but also avoids the clogging of the filler pores by carbon powder, thereby improving the porosity retention rate of the catalytic filler.

[0133] The above contents are merely examples and explanations of the structure of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the structure of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

[0134] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0135] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only specific implementation methods. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A method for regenerating and converting inert substances for preparing methanol from coke oven gas, characterized in that: The inert material includes methane and the process comprises the following steps: S1, taking a quartz tube reactor, sequentially loading modified activated carbon and a supported catalyst into the quartz tube reactor, and forming an activated carbon bed and a catalyst bed in the quartz tube reactor; S2, placing the quartz tube in a constant temperature furnace at a temperature of 480-520°C; S3, preheating the desulfurized coke oven gas containing inert methane to 200-260° C., and mixing it with water vapor to obtain a mixed gas, wherein the volume ratio of the desulfurized coke oven gas to the water vapor is 100:0.8-1.2; S4, the mixed gas is transported from the top of the quartz tube reactor to the quartz tube reactor, and after being catalytically treated by the catalyst bed and the activated carbon bed in sequence, it is discharged from the bottom of the quartz tube reactor to obtain regenerated converted coke oven gas; Modified activated carbon is processed by the following steps: A1. Dissolve nickel nitrate in deionized water, add activated carbon to the reaction system, ultrasonically disperse for 40-60 min, add sodium hydroxide solution to the reactor, adjust the pH of the reaction system to 10-11, heat up, keep warm until the reaction is complete, and post-treat to obtain a modified activated carbon precursor; A2, calcining the modified activated carbon precursor in a muffle furnace, cooling and discharging the material to obtain modified activated carbon; The supported catalyst is processed by the following steps: B1. Add sodium hydroxide, sodium aluminate and deionized water into a reactor, stir at room temperature until the system is clear, add n-butylamine dropwise into the reactor, add modified supported nickel oxide into the reactor after the addition is complete, keep warm and stir for 100-120 minutes, transfer the reaction solution into a high-pressure reactor at a temperature of 140-150° C., keep warm and crystallize for 2 days, post-treat, and calcine to obtain crystal nuclei; B2, adding aluminum sulfate 18hydrate, sodium hydroxide and deionized water to a reaction kettle, stirring at room temperature until the system is dissolved, adding silica sol, tetrahydropyrrole and crystal nuclei to the reaction kettle, stirring at room temperature for 2 hours to obtain a mixed solution; B3, transferring the mixed solution to a high pressure reactor at a temperature of 140-150° C. for crystallization for 3 days, post-treating, and calcining to obtain a catalyst precursor; B4, adding the catalyst precursor and ammonium chloride solution into the reactor and stirring, raising the temperature of the reactor to 80-90°C, keeping the temperature and stirring for 4-6h, and post-treating to obtain the supported catalyst; The preparation method of the modified loaded nickel oxide is as follows: the loaded nickel oxide, anhydrous ethanol and ethyl orthosilicate are added into a reaction kettle and stirred, the temperature of the reaction kettle is raised to 50-60° C., ammonia water is added dropwise into the reaction kettle, and after the addition is completed, the reaction kettle is stirred for 4-6 hours at the same temperature, and the modified loaded nickel oxide is obtained by post-processing; The supported nickel oxide is processed by the following steps: C1. Add nickel nitrate hexahydrate, lanthanum nitrate hexahydrate, zirconium nitrate hexahydrate and deionized water into a reactor and stir. The temperature of the reactor is raised to 45-55°C. Stir until the system is dissolved. Add sodium hydroxide solution into the reactor and adjust the pH value of the system to 10-11. The temperature of the reactor is raised to 70-80°C. Stir for 20-22h. Post-treat to obtain a supported nickel oxide precursor. C2. The loaded nickel oxide precursor is placed in a muffle furnace and calcined for 3-5 hours, cooled, discharged, crushed, and passed through an 80-mesh sieve to obtain loaded nickel oxide.

2. The method for regenerating and converting inert substances for preparing methanol from coke oven gas according to claim 1, characterized in that: In step S1, the inner diameter of the quartz tube reactor is 9 cm, the outer diameter is 12 cm, the tube length is 550 cm, the height of the activated carbon bed is 450 cm, and the height of the catalyst bed is 100 cm; in step S4, the flow rate of the mixed gas is 8-10 L / min.

3. The method for regenerating and converting inert substances for preparing methanol from coke oven gas according to claim 1, characterized in that: In step A1, the nickel nitrate, deionized water and activated carbon are used in a ratio of 1-3 g:20 mL:7-11 g, the heating temperature is 70-80° C., and the insulation reaction time is 20-22 h; in step A2, the roasting temperature is 780-840° C., and the roasting time is 3-5 h.

4. The method for regenerating and converting inert substances for preparing methanol from coke oven gas according to claim 1, characterized in that: In step B1, the amount ratio of the sodium hydroxide, sodium aluminate, deionized water, n-butylamine and modified supported nickel oxide is 1g:7g:200mL:6g:50g; in step B2, the amount ratio of the aluminum sulfate 18hydrate, sodium hydroxide, deionized water, silica sol, tetrahydropyrrole and crystal nucleus is 3g:2g:50mL:15g:4g:1g; in step B4, the amount ratio of the catalyst precursor and the ammonium chloride solution is 1g:10mL, and the ammonium chloride solution is composed of ammonium chloride and purified water in an amount ratio of 1g:10mL.

5. The method for regenerating and converting inert substances for preparing methanol from coke oven gas according to claim 1, characterized in that: The usage ratio of the loaded nickel oxide, anhydrous ethanol, tetraethyl orthosilicate and ammonia water is 3g:15mL:1g:5mL, and the concentration of ammonia water is 0.3mol / L.

6. The method for regenerating and converting inert substances for preparing methanol from coke oven gas according to claim 1, characterized in that: In step C1, the usage ratio of nickel nitrate hexahydrate, lanthanum nitrate hexahydrate, zirconium nitrate hexahydrate and deionized water is 3g:6-8g:12-14g:120mL; in step C2, the roasting temperature is 780-840°C.

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