CN112403484B - Sulfur-tolerant shift catalyst protective agent and preparation method thereof - Google Patents
Sulfur-tolerant shift catalyst protective agent and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of sulfur-tolerant shift, and particularly relates to a sulfur-tolerant shift catalyst protective agent and a preparation method thereof. The active component of the protective agent is a tungsten, nickel and iron ternary component, the waste iron oxide desulfurizer is used as a main raw material, the preparation process is simple, the production cost is low, particularly, the strength is high, the structural stability is good, the protective agent can adapt to severe conversion process conditions such as high pressure, high airspeed and high water-gas ratio, has good physical and chemical adsorption capacity on ash and poison in the synthesis gas prepared from heavy raw materials such as residual oil, heavy oil, petroleum coke and coal, can play an effective protection role on the subsequent main transformer sulfur-tolerant shift catalyst, relieves the huge pressure of the waste iron oxide desulfurizer on the ecological environment, and has good economic benefit and environmental protection benefit.
Description
Technical Field
The invention belongs to the technical field of sulfur-tolerant shift, and particularly relates to a sulfur-tolerant shift catalyst protective agent and a preparation method thereof.
Background
At present, natural gas of domestic oil and gas fields contains hydrogen sulfide (H) 2 S) gas, in order to ensure smooth operation of the natural gas treatment plant, and in order to reduce hydrogen sulfide (H) 2 S) corrosion of pipeline equipment by gas, and a desulfurization unit is built in a natural gas treatment device.
Hydrogen sulfide (H) in natural gas 2 S) gas content less than 500mg/m 3 In general, the desulfurization unit adopts an iron oxide dry desulfurization technology. Desulfurizing agents generally refer to agents that remove free sulfur or sulfur compounds from fuels, feedstocks, or other materials. The iron oxide normal-temperature fine desulfurizer is a solid normal-temperature fine desulfurizer frequently adopted by a desulfurization unit of a domestic natural gas treatment device, and the active ingredient of the iron oxide normal-temperature fine desulfurizer is iron oxide Fe 2 O 3 Hydrogen sulfide (H) in natural gas 2 S) gas and iron oxide (Fe) 2 O 3 ) The chemical reaction is carried out to generate ferrous sulfide (FeS) and trace elemental sulfur (S), and the FeS (sulfurous sulfur) is generated through the desulfurization processIron) belongs to sulfides which are extremely easy to spontaneously combust under certain conditions, and the ignition point is only 40 ℃, so the waste desulfurizer discharged from the desulfurizing tower can cause great harm to the environment and personal safety if not subjected to safety treatment. The prior disposal method of the waste ferric oxide normal-temperature fine desulfurizer comprises the following steps: (1) Simply stacking in open air for a long time, and oxidizing the simple substance S to generate SO 2 (Sulfur dioxide) gas escapes into the atmosphere and forms H in rainy days 2 SO 3 (sulfurous acid), which can make the grass around grow fast and affect the underground water when immersed in the surrounding soil; (2) Oxidizing S to SO by common burning method 2 (sulfur dioxide) is released into the atmosphere, forming secondary pollution. However, the two existing methods for disposing the desulfurizing agent cause environmental pollution and waste of resources. The invention is a very good solution when being applied to the field of the manufacture of the sulfur-resistant transformation process protective agent.
Considering the energy status of rich coal resources and high residual oil content in raw oil in China, the development of the sulfur-tolerant shift process for producing synthetic gas or synthetic ammonia by using coal or residual oil as raw material has wide application prospect, which promotes the research and application of related processes and catalysts, and meanwhile, along with the rising of the price of the raw oil, the coal chemical industry is greatly developed and the gasification process is continuously promoted to be new in recent years, because of the diversity of the coal gasification process at home and abroad and the gradual tightening of the coal resources, the type and quality of coal also have great influence on the subsequent coal gasification process, and a small amount of impurities contained in the process gas are as follows: arsenic (As), hydrocyanic acid, carbonyl compound, etc. get into the transform system after washing preliminary desorption, cause very big influence to the life of transform catalyst long-pending long-term, especially the great inferior coal of ash content brings huge challenge to follow-up desorption technology, and sulfur-tolerant transform catalyst is inevitable simultaneously and is faced the problem that the ash was taken to the area, and its service condition further worsens. Therefore, in recent years, many research units develop a protective agent or a detoxifying agent for protecting the cobalt-molybdenum sulfur-tolerant shift catalyst, and a process design unit also adds a detoxifying tank in front of a shift system so as to protect the shift catalyst and prolong the service life of the catalyst. However, most of the currently used catalysts are mainly magnesium-aluminum systems and alumina, and the active components are more cobalt and molybdenum, so that the catalysts have the defects of high price, poor antitoxic and protective properties and the like.
Disclosure of Invention
The technical problem solved by the invention is as follows: overcomes the defects of the prior art, provides a sulfur-resistant shift catalyst protective agent, has high strength and good structural stability, improves the physical and chemical adsorption capacity to the impurities such as poison, ash content and the like, and effectively protects the function of a subsequent shift catalyst. The preparation method is also provided, the iron oxide desulfurizer waste agent with wide source and low cost is used as the main raw material, the preparation process is simple, the production cost is low, the huge pressure of the waste agent on the ecological environment is relieved, and the preparation method has good economic benefit and environmental protection benefit.
The sulfur-tolerant shift catalyst protective agent comprises the active components of tungsten, nickel and iron, and the weight percentage content of tungsten metal oxide is 4.5-24%, preferably 9-18% on the basis of the mass of the protective agent; the percentage content of the nickel metal oxide is 6 to 21 percent, preferably 9 to 18 percent; the mass percentage of the iron metal oxide is 30-90%, preferably 45-80%. Wherein the total content of tungsten and nickel is not more than 36%. The iron metal oxide is mainly from waste iron oxide desulfurizer.
The preparation method of the sulfur-tolerant shift catalyst protective agent comprises the following steps:
(1) Naturally airing the waste ferric oxide desulfurizer at the temperature of 30 ℃ below room temperature in the dark, crushing and sieving, and taking the sieved substances as the treated waste ferric oxide desulfurizer;
(2) Solution preparation
Dissolving ammonium tungstate and nickel nitrate in deionized water to obtain a solution A;
dissolving a binder, a soluble pore-expanding agent and an active additive in deionized water to obtain a solution B;
(3) Shaping of the protective agent
And (2) uniformly mixing the iron oxide desulfurizer waste agent treated in the step (1) with a magnesium-containing compound and an insoluble pore-expanding agent dry material, adding the solution B, uniformly kneading, adding the solution A, uniformly kneading, forming, drying, and roasting at 400-600 ℃ to obtain a protective agent finished product.
The preparation method comprises the following steps:
the total content of ferric oxide and ferrous sulfide in the waste ferric oxide desulfurizer in the step (1) is not less than 90%, preferably not less than 95%, wherein the content of ferrous sulfide is 15-20%.
The magnesium-containing compound is one or more of magnesium oxide, magnesium oxalate, magnesium carbonate or magnesium stearate, preferably magnesium oxide, and the mass percentage of the magnesium-containing compound in terms of magnesium oxide is 1-15% on the basis of the mass of the protective agent.
The hole expanding agent is one or more of polyvinyl alcohol, glucose sesbania powder, citric acid, starch or cane sugar, sesbania powder is preferred, and the hole expanding agent accounts for 1-6% by mass and preferably 2-4% by mass based on the mass of the protective agent.
The binder is one or more of acetic acid, citric acid, oxalic acid or nitric acid, preferably citric acid and/or oxalic acid, and the mass percentage of the binder is 1-6%, preferably 2-4% based on the mass of the protective agent.
The active auxiliary agent is one or more of zinc oxide, chromium oxide, zirconium oxide or corresponding soluble salts thereof, and the mass percentage of the active main agent is 0.5-3%, preferably 1-2% based on the mass of the protective agent.
The drying time of the waste iron oxide desulfurizer in the step (1) is 5-15 hours, preferably 7-12 hours, and the waste iron oxide desulfurizer is crushed to be over 160 meshes, wherein the grain size content of the 160 meshes and over is not less than 95%, preferably not less than 98%, and the grain size content of the 180 meshes and over is not less than 85%, preferably not less than 90%.
The calcination temperature in the step (3) is preferably 500 ℃.
The appearance of the protective agent in the step (3) is in a strip shape, a clover shape or a hollow strip shape, and the strip shape is preferred.
The technical indexes of the sulfur-resistant shift catalyst protective agent are as follows:
the shape is strip-shaped;
the strength should be more than 170N/cm;
the pore volume should be greater than 0.3cm 3 A/g, preferably greater than 0.4cm 3 /g；
The specific surface area should be more than 120m 2 A/g, preferably greater than 130m 2 /g。
The invention fully utilizes the characteristics of the waste iron oxide desulfurizer, and provides a material structure basis for preparing the high-efficiency sulfur-tolerant shift catalyst protective agent with high strength, large specific surface area and large pore volume. The sulfur-resistant shift catalyst is prepared by adding a certain amount of tungsten and nickel active components and adopting a kneading method, has simple preparation process and low cost, and has good adsorption and detoxification effects on toxic substances such As arsenic (As), hydrocyanic acid, carbonyl compounds and the like of the sulfur-resistant shift catalyst. And a proper active auxiliary agent and a proper active component adding mode are selected, so that the active component is well dispersed on the surface of the carrier. And the proper adhesive and pore-expanding agent are selected according to the preparation process, and the compatibility of the adhesive and the pore-expanding agent with the main protective agent is good, so that the protective agent is ensured to have proper strength, pore structure and structural stability.
Compared with the prior art, the invention has the following beneficial effects:
the sulfur-tolerant shift catalyst protective agent prepared by the invention has high strength and good structural and structural stability, can be used for harsh conditions of high pressure, high airspeed and high water-gas ratio, has long service life, has strong physical and chemical adsorption capacity on ash and poison in synthesis gas prepared from heavy raw materials such as residual oil, heavy oil, petroleum coke, coal and the like, can effectively protect a main shift catalyst, and prolongs the service life of the main shift catalyst. The used raw materials adopt the iron oxide desulfurizer waste agent with wide source and low cost, the preparation process is simplified, the preparation cost of the catalyst is greatly reduced, and a more effective way is found for the comprehensive utilization of the iron oxide desulfurizer waste agent, so that the method has good economic benefit and environmental protection benefit.
Drawings
FIG. 1 is a schematic view of a pressurized activity evaluation apparatus;
in the figure: 1. a raw material purifier; 2. a pressure reducer; 3. a mixer; 4. a pressure gauge; 5. a shutdown valve; 6. a heating furnace; 7. a reaction tube; 8. a thermocouple tube inside the tube; 9. a condenser; 10. a separator; 11. a liquid discharge device; 12. a wet flow meter; 13. a vaporizer; 14. a water tank; 15. a water metering pump.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Firstly, naturally airing the waste iron oxide desulfurizer for 7 hours at the temperature of 30 ℃ below room temperature in a dark condition, and then crushing and sieving the waste iron oxide desulfurizer by a 180-mesh sieve with the sieving rate of more than or equal to 90 percent.
Weighing 10.6g of ammonium tungstate and 34.9g of nickel nitrate, and dissolving in 50mL of deionized water to obtain a solution A; 1.4g of zirconium oxychloride, 1.0g of citric acid and 3.0g of oxalic acid were weighed into 25mL of deionized water to obtain solution B.
Weighing 81.1g of waste iron oxide desulfurizer, 1.0g of magnesium oxide and 3.0g of sesbania powder, uniformly mixing, adding the solution A, and uniformly kneading; and adding the solution B, kneading, molding, naturally drying, roasting at 530 ℃ for 3 hours, and naturally cooling to room temperature. Thus obtaining the finished product of the sulfur-tolerant shift catalyst protective agent C-1. The strength and strength stability thereof are shown in Table 1.
Example 2
Firstly, naturally airing the waste ferric oxide desulfurizer at the temperature of 30 ℃ below room temperature for 7 hours in the dark, then crushing and sieving by a 160-mesh sieve, wherein the sieving rate is more than or equal to 98 percent.
Weighing 21.2g of ammonium tungstate and 69.8g of nickel nitrate, and dissolving the ammonium tungstate and the nickel nitrate in 90mL of deionized water to obtain a solution A; 2.9g of zirconium oxychloride, and 3.0g of oxalic acid were weighed into 30mL of deionized water to obtain solution B.
Weighing 47.7g of waste iron oxide desulfurizer, 15.0g of magnesium oxide and 6.0g of sesbania powder, uniformly mixing, adding the solution A, and uniformly kneading; adding the solution B, kneading, molding, naturally drying, roasting at 420 ℃ for 4 hours, and naturally cooling to room temperature. Thus obtaining the finished product of the sulfur-tolerant shift catalyst protective agent C-2. The strength and strength stability thereof are shown in Table 1.
Example 3
Firstly, naturally airing the waste ferric oxide desulfurizer at the temperature of 30 ℃ below room temperature for 10 hours in the dark, then crushing and sieving by a 160-mesh sieve, wherein the sieving rate is more than or equal to 98 percent.
Weighing 16.5g of ammonium tungstate and 58.2g of nickel nitrate, and dissolving in 80mL of deionized water to obtain a solution A; 3.7g of zinc nitrate, and 3.0g of oxalic acid were weighed into 30mL of deionized water to obtain solution B.
Weighing 62.9g of waste iron oxide desulfurizer, 8.0g of magnesium oxide and 3.0g of sesbania powder, uniformly mixing, adding the solution A, and uniformly kneading; adding the solution B, kneading, molding, naturally drying, roasting at 500 ℃ for 3h, and naturally cooling to room temperature. And obtaining the finished product of the sulfur-resistant shift catalyst protective agent C-3. The strength and strength stability thereof are shown in Table 1.
Example 4
Firstly, naturally airing the waste iron oxide desulfurizer for 10 hours at the temperature of 30 ℃ below room temperature in a dark condition, and then crushing and sieving the waste iron oxide desulfurizer by a 180-mesh sieve with the sieving rate of more than or equal to 90 percent.
Weighing 7.1g of ammonium tungstate and 27.2g of nickel nitrate, and dissolving in 40mL of deionized water to obtain a solution A; 2.2g of zirconium oxychloride, 4.0g of sucrose and 3.0g of citric acid were weighed into 35mL of deionized water to obtain solution B.
Weighing 77.6g of waste iron oxide desulfurizer, 9.0g of magnesium oxide and 4.0g of sesbania powder, uniformly mixing, adding the solution A, and uniformly kneading; and adding the solution B, kneading, forming, naturally drying, roasting at 600 ℃ for 2 hours, and naturally cooling to room temperature. And obtaining the finished product of the sulfur-resistant shift catalyst protective agent C-4. The strength and strength stability thereof are shown in Table 1.
Example 5
Firstly, naturally airing the waste ferric oxide desulfurizer at the temperature of 30 ℃ below room temperature for 10 hours in the dark, then crushing and sieving by a 160-mesh sieve, wherein the sieving rate is more than or equal to 98 percent.
Weighing 14.2g of ammonium tungstate and 50.4g of nickel nitrate, and dissolving in 100mL of deionized water to obtain a solution A; 5.3g of chromium nitrate, 3.0g of lemon and 3.0g of oxalic acid were weighed into 35mL of deionized water to obtain solution B.
Weighing 64.9g of waste iron oxide desulfurizer, 10.0g of magnesium oxide and 3.0g of glucose, uniformly mixing, adding the solution A, and uniformly kneading; adding the solution B, kneading, molding, naturally drying, roasting at 500 ℃ for 3h, and naturally cooling to room temperature. And obtaining the finished product of the sulfur-resistant shift catalyst protective agent C-5. The strength and strength stability thereof are shown in Table 1.
Example 6
Firstly, naturally airing the waste ferric oxide desulfurizer at the temperature of 30 ℃ below room temperature for 12 hours in the dark, then crushing and sieving by a 160-mesh sieve, wherein the sieving rate is more than or equal to 98 percent.
Weighing 11.8g of ammonium tungstate and 34.9g of nickel nitrate, and dissolving in 80mL of deionized water to obtain a solution A; 10.5g of chromium nitrate and 3.0g of oxalic acid were weighed into 35mL of deionized water to obtain solution B.
Weighing 72.0g of waste iron oxide desulfurizer, 8.0g of magnesium oxide and 4.0g of sesbania powder, uniformly mixing, adding the solution A, and uniformly kneading; and adding the solution B, kneading, forming, naturally drying, roasting at 550 ℃ for 4 hours, and naturally cooling to room temperature. And obtaining the finished product of the sulfur-resistant shift catalyst protective agent C-6. The strength and strength stability thereof are shown in Table 1.
Example 7
Firstly, naturally airing the waste ferric oxide desulfurizer at the temperature of 30 ℃ below room temperature for 9 hours in the dark, then crushing and sieving by a 160-mesh sieve, wherein the sieving rate is more than or equal to 98 percent.
Weighing 10.6g of ammonium tungstate and 38.8g of nickel nitrate, and dissolving in 60mL of deionized water to obtain a solution A; 7.3g of zinc nitrate and 3.0g of oxalic acid were weighed into 35mL of deionized water to obtain solution B.
Weighing 71.0g of waste iron oxide desulfurizer, 9.0g of magnesium oxide and 2.0g of sesbania powder, uniformly mixing, adding the solution A, and uniformly kneading; adding the solution B, kneading, molding, naturally drying, roasting at 520 ℃ for 3 hours, and naturally cooling to room temperature. Thus obtaining the finished product of the sulfur-tolerant shift catalyst protective agent C-7. The strength and strength stability thereof are shown in Table 1.
Example 8
Firstly, naturally airing the waste ferric oxide desulfurizer at the temperature of 30 ℃ below room temperature for 12 hours in the dark, then crushing and sieving by a 160-mesh sieve, wherein the sieving rate is more than or equal to 98 percent.
Weighing 23.6g of ammonium tungstate and 73.7g of nickel nitrate, and dissolving in 120mL of deionized water to obtain a solution A; 5.5g of zinc nitrate, 2.0g of sucrose and 2.0mL of concentrated nitric acid were weighed into 35mL of deionized water to obtain solution B.
Weighing 49.2g of waste iron oxide desulfurizer, 11.0g of magnesium oxide and 2.0g of sesbania powder, uniformly mixing, adding the solution A, and uniformly kneading; adding the solution B, kneading, molding, naturally drying, roasting at 450 ℃ for 4h, and naturally cooling to room temperature. And obtaining the finished product of the sulfur-tolerant shift catalyst protective agent C-8. The strength and strength stability thereof are shown in Table 1.
Comparative example
The sulfur-resistant transformation protective agent D which is used more at present and has the type QBS-05 as a comparative example has the main active components of cobalt and molybdenum and an alumina carrier as a carrier.
Adopting water boiling and hydrothermal treatment strengthening tests to respectively investigate the strength and strength stability of the protective agent after being boiled in water with normal pressure and being subjected to high-temperature and high-pressure hydrothermal treatment;
boiling test conditions: a certain amount of the protective agent is boiled in boiling water for 5 hours, and the change of the strength of the protective agent is measured after drying so as to investigate the strength and the stability of the protective agent after being soaked in hot water under normal pressure.
High-temperature high-pressure hydrothermal treatment test conditions: on a primary particle size pressurization evaluation device, taking nitrogen and water vapor as media, and the dry gas space velocity: 4000h -1 (ii) a Pressure: 6.0MPa; evaluation of inlet temperature: 350 ℃; the loading of the protective agent: 50.0 ml; and (3) treating for 100 hours under the condition that the water-vapor ratio is 1.8, and measuring the change of the strength of the dried protective agent so as to investigate the strength and the stability of the protective agent after the test under severe conditions.
TABLE 1 comparison of strength and strength stability of protective agents prepared by different preparation routes
Evaluation of catalyst pressurizing Activity:
the apparatus and the flow of the evaluation of the pressurized activity are shown in FIG. 1. The device is used for simulating industrial conditions, measuring the concentration and the change of the carbon monoxide of the tail gas of the 'primary particle size' catalyst under different conditions under certain pressure, comparing the performances of the catalyst such as conversion activity, stability and the like, and comprehensively evaluating various performances of the catalyst. The reaction tube is a stainless steel tube with a diameter of 45X 5mm, and a thermocouple tube with a diameter of 8X 2mm is arranged in the center. The process gas before transformation in a certain ammonia synthesis workshop is used as raw material gas, and a proper quantity of H is added 2 S, according toAdding a certain amount of water according to different water-gas ratios, gasifying at high temperature, feeding the mixture and the feed gas into a reaction tube for water-gas shift reaction, and analyzing tail gas after the reaction by chromatography.
The pressurization evaluation conditions were: feed gas composition, CO: 45-49% (V/V), CO 2 5～10％(V/V)，H 2 S is more than 0.05 percent (V/V), and the balance is hydrogen; dry gas space velocity: 3000h -1 (ii) a Pressure: 4.0MPa; evaluation of inlet temperature: 250 ℃; loading of the catalyst: 50mL.
The CO conversion rate is calculated by the formula: x CO ＝(Y CO -Y CO’ )/[YCO(1+Y CO’ )]×100％；
Y CO -mole fraction of reactor inlet gas CO (dry basis);
Y CO’ the mole fraction of reactor outlet gas CO (dry basis).
After the protective agent is adopted, the change rule of the pressurization activity of the same industrial sulfur-resistant shift catalyst after running for 400 hours is shown in the following table 2.
TABLE 2 catalyst run 400h pressurization activity comparison
Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.
Claims (9)
1. A preparation method of a sulfur-tolerant shift catalyst protective agent is characterized by comprising the following steps: the active component of the sulfur-tolerant shift catalyst protective agent is a tungsten, nickel and iron ternary component, and the weight percentage content of tungsten metal oxide is 4.5-24% on the basis of the mass of the protective agent; the percentage content of the nickel metal oxide is 6 to 21 percent; the mass percentage content of the iron metal oxide is 30 to 90 percent; wherein the total content of tungsten and nickel is not more than 36%;
the preparation method of the sulfur-tolerant shift catalyst protective agent comprises the following steps:
(1) Drying the waste ferric oxide desulfurizer, crushing and sieving, and taking undersize as the treated waste ferric oxide desulfurizer;
(2) Solution preparation
Dissolving ammonium tungstate and nickel nitrate in deionized water to obtain a solution A;
dissolving a binder, a soluble pore-expanding agent and an active additive in deionized water to obtain a solution B;
(3) Shaping of the protective agent
And (2) uniformly mixing the iron oxide desulfurizer waste agent treated in the step (1) with a magnesium-containing compound and an insoluble pore-expanding agent dry material, adding the solution B, uniformly kneading, adding the solution A, uniformly kneading, forming, drying, and roasting at 400-600 ℃ to obtain a protective agent finished product.
2. The method for producing a sulfur-tolerant shift catalyst protectant according to claim 1, comprising: the weight percentage content of the tungsten metal oxide is 9 to 18 percent based on the mass of the protective agent; the percentage content of the nickel metal oxide is 9 to 18 percent; the mass percentage of the iron metal oxide is 45 to 80 percent.
3. The method for preparing the sulfur-tolerant shift catalyst protecting agent according to claim 1, characterized in that: the total content of ferric oxide and ferrous sulfide in the waste ferric oxide desulfurizer in the step (1) is not less than 90%, wherein the content of ferrous sulfide is 15-20%.
4. The method for producing a sulfur-tolerant shift catalyst protectant according to claim 1, comprising: the magnesium-containing compound is one or more of magnesium oxide, magnesium oxalate, magnesium carbonate or magnesium stearate, and the mass percentage of the magnesium-containing compound in terms of magnesium oxide is 1-15% on the basis of the mass of the protective agent.
5. The method for producing a sulfur-tolerant shift catalyst protectant according to claim 1, comprising: the hole expanding agent is one or more of polyvinyl alcohol, glucose sesbania powder, citric acid, starch or cane sugar, and the weight percentage of the hole expanding agent is 1-6% based on the weight of the protective agent.
6. The method for producing a sulfur-tolerant shift catalyst protectant according to claim 1, comprising: the binder is one or more of acetic acid, citric acid, oxalic acid or nitric acid, and the mass percentage of the binder is 1-6% based on the mass of the protective agent.
7. The method for producing a sulfur-tolerant shift catalyst protectant according to claim 1, comprising: the active auxiliary agent is one or more of zinc oxide, chromium oxide, zirconium oxide or corresponding soluble salts thereof, and the mass percentage content of the active auxiliary agent is 0.5 to 3 percent based on the mass of the protective agent.
8. The method for producing a sulfur-tolerant shift catalyst protectant according to claim 1, comprising: and (2) naturally airing the waste iron oxide desulfurizer at the temperature of lower than room temperature and 30 ℃ in a dark condition for 5 to 15h, and then crushing to over 160 meshes.
9. The method for producing a sulfur-tolerant shift catalyst protectant according to claim 1, comprising: the appearance of the protective agent is in a strip shape, a clover shape or a hollow strip shape.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3974096A (en) * | 1972-03-16 | 1976-08-10 | Exxon Research And Engineering Company | Water gas shift catalyst |
| DE3228481A1 (en) * | 1982-07-30 | 1984-02-02 | VEG-Gasinstituut N.V., 7300 Apeldoorn | REACTION MEASURES, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| CN102451701A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | High-concentration CO synthesis gas sulfur-tolerant shift pre-conversion treatment method |
| CN103769234A (en) * | 2012-10-22 | 2014-05-07 | 中国石油化工股份有限公司 | Protective agent for sulfur tolerant shift catalyst and preparation method thereof |
| CN109536195A (en) * | 2018-11-30 | 2019-03-29 | 北京三聚环保新材料股份有限公司 | A kind of conversion process of biomass and coal |
-
2019
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3974096A (en) * | 1972-03-16 | 1976-08-10 | Exxon Research And Engineering Company | Water gas shift catalyst |
| DE3228481A1 (en) * | 1982-07-30 | 1984-02-02 | VEG-Gasinstituut N.V., 7300 Apeldoorn | REACTION MEASURES, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| CN102451701A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | High-concentration CO synthesis gas sulfur-tolerant shift pre-conversion treatment method |
| CN103769234A (en) * | 2012-10-22 | 2014-05-07 | 中国石油化工股份有限公司 | Protective agent for sulfur tolerant shift catalyst and preparation method thereof |
| CN109536195A (en) * | 2018-11-30 | 2019-03-29 | 北京三聚环保新材料股份有限公司 | A kind of conversion process of biomass and coal |
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