Synthesis method and application of carbonyl sulfide low-temperature hydrolysis catalyst

Abstract

The invention discloses a synthesis method and application of a carbonyl sulfide low-temperature hydrolysis catalyst, and the synthesis method comprises the following steps: mixing pseudo-boehmite, ammonium bicarbonate, sodium carbonate and a binder, and granulating to obtain a granular mixture; sequentially drying and calcining the granular mixture, so as to obtain gamma-Al2O3 carrier pellets; and placing the gamma-Al2O3 pellets in an impregnation liquid, carrying out impregnation treatment under pressure, drying, and calcining to obtain the carbonyl sulfide hydrolysis catalyst. According to the invention, gamma-Al2O3 balls are prepared as a carrier, then zirconium, sodium and potassium are loaded on the gamma-Al2O3 balls, gamma-Al2O3 has strong adsorbability to carbonyl sulfide, ZrO2 has good acid resistance and water resistance, and plays a role in protecting the catalyst; the metal such as Na, K and the like exists in the blast furnace gas in the form of carbonate, and the weakly alkaline center reduces the activation energy of the reaction, so that carbonyl sulfide is hydrolyzed into H2S and CO2, and the standard emission of SO2 at the user side of the blast furnace gas is realized by matching with an H2S removal technology.

Description

Technical Field

[0001] The invention relates to the technical field of wastewater resource utilization, and in particular to a synthesis method and application of a carbonyl sulfide low-temperature hydrolysis catalyst. Background Art

[0003] Problems with traditional end-of-pipe treatment: desulfurization by-products are difficult to handle. The sulfur content in terminal flue gas from heating furnaces, gas boilers, hot blast furnaces, etc. is not high, and sodium-based desulfurization such as SDS is generally used. Currently, solid wastes such as sodium sulfate and sodium sulfite are also difficult to handle, and some places even define them as hazardous wastes. Management costs increase, and there are many end-of-pipe treatment facilities. On the one hand, the difficulty of plant management increases, and the cost of maintenance increases; on the other hand, the difficulty of environmental monitoring increases. Material consumption increases, there are many end-of-pipe treatment facilities, and there are many operating power equipment. The consumption of energy such as electricity increases, which is not conducive to carbon reduction. Summary of the invention

[0004] In view of the shortcomings existing in the above problems, the present invention provides a synthesis method and application of a carbonyl sulfide low-temperature hydrolysis catalyst.

[0005] To achieve the above object, the present invention provides a method for synthesizing a carbonyl sulfide low-temperature hydrolysis catalyst, comprising:

[0006] The pseudo-boehmite, ammonium bicarbonate, sodium carbonate and a binder are mixed and granulated to obtain a granular mixture;

[0007] The granular mixture is dried and calcined in sequence to obtain γ-Al2O3 carrier pellets;

[0008] The γ-Al2O3 pellets are placed in an impregnation solution and impregnated under pressure, and then dried and calcined to obtain a carbonyl sulfide hydrolysis catalyst.

[0009] Preferably, the binder includes at least one of hydroxymethyl cellulose, sodium carbonate, ammonium bicarbonate, and dilute nitric acid.

[0010] Preferably, the mass ratio of the pseudo-boehmite, the ammonium bicarbonate, the sodium carbonate and the binder is 70-97:1-10:1-10:1-10.

[0011] Preferably, the diameter of the granular mixture is 3-5 mm.

[0012] Preferably, the granular mixture is cured at a temperature of 20-50°C for 12-18 hours; dried at a temperature of 30-200°C for 12-18 hours; and calcined at a temperature of 400-700°C under inert gas protection for 1-6 hours.

[0013] Preferably, the impregnation solution is an aqueous solution of zirconium nitrate, sodium hydroxide and potassium hydroxide, and the molar ratio of zirconium ions, sodium ions and potassium ions in the impregnation solution is 1-2:1-2:1; the mass ratio of the γ-Al2O3 balls to the active components in the impregnation solution is 80-100:0-20.

[0014] Preferably, the immersion treatment is performed at a pressure of 0.2-0.4 MPa, a rotation speed of 50-100 r / min, and a time of 0.5-1 hour.

[0015] Preferably, after the impregnation treatment, the drying temperature of the γ-Al2O3 pellets is 80-120°C, and the drying time is 12-18 hours; the calcination temperature is 600-800°C, and the calcination time is 2-6 hours.

[0016] The present application also provides an application of a carbonyl sulfide low-temperature hydrolysis catalyst. The carbonyl sulfide low-temperature hydrolysis catalyst prepared by the above-mentioned synthesis method is applied to the treatment of blast furnace gas desulfurization.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] The present invention first prepares γ-Al2O3 balls as a carrier, and then loads zirconium, sodium and potassium on the γ-Al2O3 balls, wherein γ-Al2O3 has strong adsorption for carbonyl sulfide, and ZrO2 has good acid resistance and water resistance, and plays a role in protecting the catalyst; metals such as Na and K exist in the form of carbonates in blast furnace gas, and the weak alkaline center reduces the activation energy of the reaction, thereby achieving the hydrolysis of carbonyl sulfide into H2S and CO2, and cooperates with the H2S removal technology to achieve the standard emission of SO2 at the blast furnace gas user end. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 is a SEM image of γ-Al2O3 of the present invention;

[0020] Figure 2 is the BET data of γ-Al2O3 of the present invention;

[0021] Figure 3 is a SEM image of the hydrolysis catalyst of the present invention;

[0022] Figure 4 It is the BET data of the hydrolysis catalyst of the present invention. DETAILED DESCRIPTION

[0023] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not 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.

[0024] The present invention provides a method for synthesizing a carbonyl sulfide low-temperature hydrolysis catalyst, comprising:

[0025] The pseudo-boehmite, ammonium bicarbonate, sodium carbonate and a binder are mixed and granulated to obtain a granular mixture;

[0026] The granular mixture is dried and calcined in sequence to obtain γ-Al2O3 carrier beads, such as Figure 1 and Figure 2 As shown;

[0027] The γ-Al2O3 pellets are placed in an impregnation solution and impregnated under pressure, and then dried and calcined to obtain a carbonyl sulfide hydrolysis catalyst, such as Figure 3 and Figure 4 shown.

[0028] In this embodiment, the binder includes at least one of hydroxymethyl cellulose, sodium carbonate, ammonium bicarbonate, and dilute nitric acid.

[0029] Furthermore, the mass ratio of pseudo-boehmite, ammonium bicarbonate, sodium carbonate and binder is 70-97:1-10:1-10:1-10.

[0030] Specifically, a mixture of pseudo-boehmite, ammonium bicarbonate, sodium carbonate and a binder is fully mixed and poured into a disc granulator. Water is injected into the granulator at a ratio of mixture: water = 1-3:1, and stirred for about 30 minutes to obtain a γ-Al2O3 carrier pellet precursor.

[0031] In this embodiment, the diameter of the granular mixture is 3-5 mm. The granular mixture is cured at a temperature of 20-50° C. for 12-18 hours, dried at a temperature of 30-200° C. for 12-18 hours, and calcined at a temperature of 400-700° C. for 1-6 hours under inert gas protection.

[0032] In this embodiment, the carrier and the impregnation solution are placed according to the saturated impregnation method. The impregnation solution is an aqueous solution of zirconium nitrate, sodium hydroxide and potassium hydroxide. The molar ratio of zirconium ions, sodium ions and potassium ions in the impregnation solution is 1-2:1-2:1; the mass ratio of γ-Al2O3 balls to the active components in the impregnation solution is 80-100:0-20.

[0033] Specifically, the immersion treatment adopts a pressure of 0.2-0.4 MPa, a rotation speed of 50-100 r / min, and a time of 0.5-1 hour.

[0034] Furthermore, after the impregnation treatment, the drying temperature of the γ-Al2O3 pellets is 80-120°C, and the drying time is 12-18 hours; the calcination temperature is 600-800°C, and the calcination time is 2-6 hours.

[0035] The present application also provides an application of a carbonyl sulfide low-temperature hydrolysis catalyst. The carbonyl sulfide low-temperature hydrolysis catalyst prepared by the above-mentioned synthesis method is applied to the treatment of blast furnace gas desulfurization.

[0036] In the present invention, γ-Al2O3 has well-developed capillaries and a large specific surface area, and has strong adsorption for carbonyl sulfide, providing a reaction site for hydrolysis catalysis; ZrO2 has good acid resistance and water resistance, and plays a role in protecting the catalyst; metals such as Na and K exist in the form of carbonates in blast furnace gas, and the weak alkaline center reduces the activation energy of the reaction, thereby achieving the hydrolysis of carbonyl sulfide into H2S and CO2, and cooperating with H2S removal technology to achieve the standard emission of SO2 at the blast furnace gas user end. At the same time, the catalyst synthesized by the method of the present invention is used for the fine desulfurization of blast furnace gas, and the desulfurization product is sulfur that can be reused, while reducing equipment investment and floor space, truly achieving safety, reliability, high efficiency, stability, energy saving and carbon reduction.

[0037] Example 1

[0038] This embodiment relates to a method for synthesizing a carbonyl sulfide low-temperature hydrolysis catalyst, comprising the following steps:

[0039] (1) Preparation of γ-Al2O3 carrier beads

[0040] 850g of pseudo-boehmite powder, 50g of ammonium bicarbonate, 50g of sodium carbonate and 50g of sodium hydroxymethylcellulose were weighed and poured into a disc granulator. 400g of deionized water was weighed and poured into the granulator. After stirring for 30 minutes, a γ-Al2O3 carrier precursor with a particle size of 3-5mm was obtained.

[0041] The catalyst carrier precursor is placed in a constant temperature and humidity oven with a tray, 20-50°C, and the curing time is 12-18 hours; the tray is taken out and placed in an oven, the drying temperature is 30-200°C, and the drying time is 12-18 hours; the catalyst carrier precursor is placed in a muffle furnace and the calcination temperature is 400-700°C, and the calcination time is 1-6 hours. Nitrogen protection is introduced, and the calcination product is a γ-Al2O3 carrier pellet.

[0042] Take 100g of synthesized γ-Al2O3 carrier beads, take 100ml of deionized water and put it into a beaker, weigh 18g of zirconium nitrate, 0.8g of sodium hydroxide and 0.56g of potassium hydroxide and dissolve them in water, place the beaker on a magnetic stirrer, stir at a constant speed for 15 minutes, and the impregnation solution is ready.

[0043] The carrier and the impregnation liquid are placed in an impregnation tank, compressed air is introduced, the pressure is set to 0.4 MPa, the rotation speed of the impregnation tank is 80 r / min, and the impregnation time is (0.5-1) h.

[0044] Take out the impregnated catalyst precursor, put it into the oven with a tray, dry it at (80-120)°C for (12-18)h, then put the catalyst precursor into the electric furnace with a dry pot, calcine it at (600-800)°C for (2-6)h, and the catalyst is manufactured.

[0045] Blast furnace gas was simulated, and nitrogen, water vapor, and carbonyl sulfide gas lines were configured. The carbonyl sulfide concentration was 100 ppm, and the flow rate was designed to be 100 ml / min. 90 ml of catalyst was placed in the catalytic reaction tower, and the gas entered from the bottom of the catalytic reaction tower. The reaction temperature was 60-100°C, and the gas after the reaction was connected to an ion chromatograph. The carbonyl sulfide concentration was detected to be 8.5 ppm, and the carbonyl sulfide removal rate was as high as 91.5%. The results are shown in Table 1.

[0046] Example 2

[0047] This embodiment relates to a method for synthesizing a carbonyl sulfide low-temperature hydrolysis catalyst, comprising the following steps:

[0048] (1) Preparation of γ-Al2O3 carrier beads

[0049] 800g of pseudo-boehmite powder, 50g of ammonium bicarbonate, 50g of sodium carbonate and 50g of sodium hydroxymethylcellulose were weighed and poured into a disc granulator. 300g of deionized water was weighed and poured into the granulator. After stirring for 30 minutes, a γ-Al2O3 carrier precursor with a particle size of 3-5mm was obtained.

[0050] The catalyst carrier precursor is placed in a constant temperature and humidity oven with a tray, 20-50°C, and the curing time is 12-18 hours; the tray is taken out and placed in an oven, the drying temperature is 30-200°C, and the drying time is 12-18 hours; the catalyst carrier precursor is placed in a muffle furnace and the calcination temperature is 400-700°C, and the calcination time is 1-6 hours. Nitrogen protection is introduced, and the calcination product is a γ-Al2O3 carrier pellet.

[0051] Take 100g of synthesized γ-Al2O3 carrier beads, take 100ml of deionized water and put it into a beaker, weigh 18g of zirconium nitrate, 0.4g of sodium hydroxide and 0.56g of potassium hydroxide and dissolve them in water, place the beaker on a magnetic stirrer, stir at a constant speed for 15 minutes, and the impregnation solution is ready.

[0052] The carrier and the impregnation liquid are placed in an impregnation tank, compressed air is introduced, the pressure is set to 0.4 MPa, the rotation speed of the impregnation tank is 80 r / min, and the impregnation time is (0.5-1) h.

[0053] Take out the impregnated catalyst precursor, put it into the oven with a tray, dry it at (80-120)°C for (12-18)h, then put the catalyst precursor into the electric furnace with a dry pot, calcine it at (600-800)°C for (2-6)h, and the catalyst is manufactured.

[0054] Blast furnace gas was simulated, and nitrogen, water vapor, and carbonyl sulfide gas lines were configured. The carbonyl sulfide concentration was 100 ppm, and the flow rate was designed to be 100 ml / min. 90 ml of catalyst was placed in the catalytic reaction tower, and the gas entered from the bottom of the catalytic reaction tower. The reaction temperature was 60-100°C, and the gas after the reaction was connected to an ion chromatograph. The carbonyl sulfide concentration was detected to be 12.3 ppm, and the carbonyl sulfide removal rate was as high as 87.7%. The results are shown in Table 1.

[0055] Comparative Example 1

[0056] This embodiment relates to a method for synthesizing a carbonyl sulfide low-temperature hydrolysis catalyst, comprising the following steps:

[0057] (1) Preparation of γ-Al2O3 carrier beads

[0058] 850g of pseudo-boehmite powder, 50g of ammonium bicarbonate, 50g of sodium carbonate and 50g of sodium hydroxymethylcellulose were weighed and poured into a disc granulator. 400g of deionized water was weighed and poured into the granulator. After stirring for 30 minutes, a γ-Al2O3 carrier precursor with a particle size of 3-5mm was obtained.

[0059] The catalyst carrier precursor is placed in a constant temperature and humidity oven with a tray, 20-50°C, and the curing time is 12-18 hours; the tray is taken out and placed in an oven, the drying temperature is 30-200°C, and the drying time is 12-18 hours; the catalyst carrier precursor is placed in a muffle furnace and the calcination temperature is 400-700°C, and the calcination time is 1-6 hours. Nitrogen protection is introduced, and the calcination product is a γ-Al2O3 carrier pellet.

[0060] Take 100g of synthesized γ-Al2O3 carrier beads, take 100ml of deionized water and put it in a beaker, weigh 0.8g of sodium hydroxide and 0.56g of potassium hydroxide and dissolve them in water, place the beaker on a magnetic stirrer, stir at a constant speed for 15 minutes, and the impregnation solution is ready.

[0061] The carrier and the impregnation liquid are placed in an impregnation tank, compressed air is introduced, the pressure is set to 0.4 MPa, the rotation speed of the impregnation tank is 80 r / min, and the impregnation time is (0.5-1) h.

[0062] Take out the impregnated catalyst precursor, put it into the oven with a tray, dry it at (80-120)°C for (12-18)h, then put the catalyst precursor into the electric furnace with a dry pot, calcine it at (600-800)°C for (2-6)h, and the catalyst is manufactured.

[0063] Blast furnace gas was simulated, and nitrogen, water vapor, and carbonyl sulfide gas lines were configured. The carbonyl sulfide concentration was 100 ppm, and the flow rate was designed to be 100 ml / min. 90 ml of catalyst was placed in the catalytic reaction tower, and the gas entered from the bottom of the catalytic reaction tower. The reaction temperature was 60-100°C, and the gas after the reaction was connected to an ion chromatograph. The carbonyl sulfide concentration was detected to be 40.5 ppm, and the carbonyl sulfide removal rate was as high as 59.5%. The results are shown in Table 1.

[0064] Comparative Example 2

[0065] This embodiment relates to a method for synthesizing a carbonyl sulfide low-temperature hydrolysis catalyst, comprising the following steps:

[0066] (1) Preparation of γ-Al2O3 carrier beads

[0067] 850g of pseudo-boehmite powder, 50g of ammonium bicarbonate, 50g of sodium carbonate and 50g of sodium hydroxymethylcellulose were weighed and poured into a disc granulator. 400g of deionized water was weighed and poured into the granulator. After stirring for 30 minutes, a γ-Al2O3 carrier precursor with a particle size of 3-5mm was obtained.

[0068] The catalyst carrier precursor is placed in a constant temperature and humidity oven with a tray, 20-50°C, and the curing time is 12-18 hours; the tray is taken out and placed in an oven, the drying temperature is 30-200°C, and the drying time is 12-18 hours; the catalyst carrier precursor is placed in a muffle furnace and the calcination temperature is 400-700°C, and the calcination time is 1-6 hours. Nitrogen protection is introduced, and the calcination product is a γ-Al2O3 carrier pellet.

[0069] Take 100g of synthesized γ-Al2O3 carrier beads, take 100ml of deionized water and put it into a beaker, weigh 18g of zirconium nitrate and dissolve it in water, place the beaker on a magnetic stirrer, stir at a constant speed for 15 minutes, and the impregnation solution is ready.

[0070] The carrier and the impregnation liquid are placed in an impregnation tank, compressed air is introduced, the pressure is set to 0.4 MPa, the rotation speed of the impregnation tank is 80 r / min, and the impregnation time is (0.5-1) h.

[0071] Take out the impregnated catalyst precursor, put it into the oven with a tray, dry it at (80-120)°C for (12-18)h, then put the catalyst precursor into the electric furnace with a dry pot, calcine it at (600-800)°C for (2-6)h, and the catalyst is manufactured.

[0072] Blast furnace gas was simulated, and nitrogen, water vapor, and carbonyl sulfide gas lines were configured. The carbonyl sulfide concentration was 100 ppm, and the flow rate was designed to be 100 ml / min. 90 ml of catalyst was placed in the catalytic reaction tower, and the gas entered from the bottom of the catalytic reaction tower. The reaction temperature was 60-100°C, and the gas after the reaction was connected to an ion chromatograph. The carbonyl sulfide concentration was detected to be 85.3 ppm, and the carbonyl sulfide removal rate was as high as 14.7%. The results are shown in Table 1.

[0073] Table 1

[0074]

[0075] It can be seen from Table 1 that under the coordinated treatment of alumina, zirconium oxide and carbonate, carbonyl sulfide can be effectively hydrolyzed, and the hydrolysis efficiency is above 87.7%. The various components of the catalyst work together to achieve the effects of adsorption + catalytic hydrolysis + anti-poisoning. It can be seen from Comparative Example 1 that when zirconium oxide is removed, the removal rate drops to 59.5%. Considering that the catalyst may be poisoned, although the weak alkaline center can still be hydrolyzed normally, the efficiency drops significantly. It can be seen from Comparative Example 2 that when there is no carbonate, the removal rate drops by 14.7%, indicating that the weak alkaline center is the key to the hydrolysis of carbonyl sulfide. If only relying on the adsorption of alumina, the removal efficiency of carbonyl sulfide is basically zero.

[0076] In the present invention, γ-Al2O3 has well-developed capillaries and a large specific surface area, and has strong adsorption for carbonyl sulfide, providing a reaction site for hydrolysis catalysis; ZrO2 has good acid resistance and water resistance, and plays a role in protecting the catalyst; metals such as Na and K exist in the form of carbonates in blast furnace gas, and the weak alkaline center reduces the activation energy of the reaction, thereby achieving the hydrolysis of carbonyl sulfide into H2S and CO2, and with the H2S removal technology, achieving the SO2 emission standard at the blast furnace gas user end. Performance test data show that the present invention meets the development expectations and can be industrialized.

[0077] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for synthesizing a carbonyl sulfide low-temperature hydrolysis catalyst, characterized in that: include: The pseudo-boehmite, ammonium bicarbonate, sodium carbonate and a binder are mixed and granulated to obtain a granular mixture; The granular mixture is dried and calcined in sequence to obtain γ-Al2O3 carrier pellets; The γ-Al2O3 pellets are placed in an impregnation solution and impregnated under pressure, and then dried and calcined to obtain a carbonyl sulfide hydrolysis catalyst.

2. The method for synthesizing the carbonyl sulfide low-temperature hydrolysis catalyst according to claim 1, characterized in that: The binder includes at least one of hydroxymethyl cellulose, sodium carbonate, ammonium bicarbonate, and dilute nitric acid.

3. The method for synthesizing the carbonyl sulfide low-temperature hydrolysis catalyst according to claim 2, characterized in that: The mass ratio of the pseudo-boehmite, the ammonium bicarbonate, the sodium carbonate and the binder is 70-97:1-10:1-10:1-10.

4. The method for synthesizing the carbonyl sulfide low-temperature hydrolysis catalyst according to claim 1, characterized in that: The diameter of the granular mixture is 3-5 mm.

5. The method for synthesizing the carbonyl sulfide low-temperature hydrolysis catalyst according to claim 1, characterized in that: The granular mixture is cured at a temperature of 20-50°C for 12-18 hours; dried at a temperature of 30-200°C for 12-18 hours; and calcined at a temperature of 400-700°C under inert gas protection for 1-6 hours.

6. The method for synthesizing the carbonyl sulfide low-temperature hydrolysis catalyst according to claim 1, characterized in that: The impregnation solution is an aqueous solution of zirconium nitrate, sodium hydroxide and potassium hydroxide, and the molar ratio of zirconium ions, sodium ions and potassium ions in the impregnation solution is 1-2:1-2:1; the mass ratio of the γ-Al2O3 balls to the active components in the impregnation solution is 80-100:0-20.

7. The method for synthesizing the carbonyl sulfide low-temperature hydrolysis catalyst according to claim 6, characterized in that: The immersion treatment is carried out at a pressure of 0.2-0.4 MPa, a rotation speed of 50-100 r / min, and a time of 0.5-1 hour.

8. The method for synthesizing the carbonyl sulfide low-temperature hydrolysis catalyst according to claim 7, characterized in that: After the impregnation treatment, the drying temperature of the γ-Al2O3 pellets is 80-120°C, and the drying time is 12-18 hours; the calcination temperature is 600-800°C, and the calcination time is 2-6 hours.

9. An application of a carbonyl sulfide low-temperature hydrolysis catalyst, characterized in that: The carbonyl sulfide low-temperature hydrolysis catalyst prepared by the synthesis method according to any one of claims 1 to 8 is used in the treatment of blast furnace gas desulfurization.

Images