A method for preparing activated carbon desulfurizer

Abstract

The present invention belongs to the technical field of coal gas desulfurization and purification, and specifically relates to a method for preparing an activated carbon desulfurizer. The activated carbon desulfurizer obtained by the preparation method provided by the present invention has the advantages of both a hydrolysis catalyst and an activated carbon desulfurizer. 2 S is completely removed, and it has very good removal performance for hydrogen chloride, sulfur dioxide, etc. COS, CS 2 First, it is hydrolyzed by a catalyst to generate H 2 S, then H 2 S reacts with trace oxygen in the gas to generate elemental S which is stored in the micropores of activated carbon, removing sulfur from the coal gas at one time. The addition of active ingredients also enhances the desulfurization activity of the desulfurizer. At the same time, the desulfurizer can also remove hydrogen chloride and sulfur dioxide, has very good chlorine and sulfur resistance, and effectively alleviates the catalyst deactivation caused by hydrogen chloride and sulfur dioxide.

Description

Technical Field

[0001] The invention belongs to the technical field of coal gas desulfurization and purification, and particularly relates to a method for preparing an activated carbon desulfurizer. Background Art

[0002] Activated carbon desulfurizer is widely used in synthetic ammonia, hydrogen production, methanol production, coal chemical industry, petroleum refining and other industries. It has the advantages of high desulfurization accuracy, easy use and stable performance. It occupies an important position in the field of industrial fine desulfurization.

[0003] Activated carbon desulfurizer is mainly used to remove H at room temperature (10-50℃). 2 S. At present, the main sulfide in blast furnace gas is H 2 S and COS, and a small amount of CS 2 Activated carbon desulfurizer can convert H 2 S is removed to below 0.1ppm. Ordinary activated carbon desulfurizers can also remove a small amount of COS, but the desulfurization accuracy and sulfur capacity are very low.

[0004] In the process of blast furnace gas desulfurization, activated carbon desulfurizer is generally used in conjunction with organic sulfur hydrolysis catalyst to convert COS into H 2 S, and then removed by activated carbon desulfurizer to achieve H 2 The desulfurization requirement is that the total sulfur of S and COS is less than 0.1ppm. The operating temperature of COS hydrolysis catalyst is generally 60-150℃, while the operating temperature of activated carbon desulfurizer is generally 10-40℃. The operation requires heating and cooling, which is complicated. The heating and cooling back and forth are easy to bring liquid water into the desulfurization tower and damage the desulfurizer. There are small amounts of HCl and SO in blast furnace gas. 2 The toxic gases such as COS and H2 can easily poison the organic sulfur hydrolysis catalyst, resulting in a significant reduction in the service life of the hydrolysis catalyst. Therefore, it is urgent to develop a catalyst that can remove COS and H2 simultaneously. 2 S, for CS 2 It also has a trace removal effect, high precision, high sulfur capacity, and can remove HCl and SO 2 It is a temperature-resistant desulfurizer suitable for blast furnace gas working environment and other toxic gases. Summary of the invention

[0005] The purpose of the present invention is to provide a method for preparing an activated carbon desulfurizer. The desulfurizer obtained by the method provided by the present invention is 2 It has ultra-high precision removal effect on both S and organic sulfur.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] The present invention provides a method for preparing an activated carbon desulfurizer, comprising the following steps:

[0008] The activated carbon, the catalyst carrier, the active component, the modifier, the additive and the binder are mixed and calcined to obtain a calcined material;

[0009] The calcined material is immersed in a solution containing a supporting material, and then dried to obtain an activated carbon desulfurization agent;

[0010] The catalyst carrier comprises aluminum oxide;

[0011] The load material in the solution containing the load material includes one or more of potassium hydroxide, potassium carbonate, sodium carbonate and sodium hydroxide.

[0012] Preferably, the catalyst carrier comprises fast de-powdering and / or pseudo-diamond stone.

[0013] Preferably, the active ingredient includes one or more of iron oxide, zinc oxide and copper oxide.

[0014] Preferably, the modifier comprises titanium dioxide and / or magnesium oxide.

[0015] Preferably, the additive includes one or more of nickel oxide, cobalt oxide, cerium oxide, molybdenum oxide and manganese oxide.

[0016] Preferably, the binder comprises carboxymethyl cellulose and / or sesbania powder.

[0017] Preferably, the mass ratio of the activated carbon, the catalyst carrier and the active ingredient is 40-60:10-20:10-15;

[0018] The mass ratio of the activated carbon to the modifier is 40-60:5-10;

[0019] The mass ratio of the activated carbon, the additive and the binder is 40-60:1-3:1-5.

[0020] Preferably, the calcination temperature is 400-500° C., and the holding time is 2-4 hours.

[0021] Preferably, the calcination is carried out in a protective atmosphere.

[0022] Preferably, the mass concentration of the solution containing the support material is 10-30%.

[0023] The present invention provides a method for preparing an activated carbon desulfurizer, comprising the following steps: mixing activated carbon, a catalyst carrier, an active ingredient, a modifier, an additive and a binder, and calcining to obtain a calcined material; immersing the calcined material in a solution containing a load material, and drying to obtain the activated carbon desulfurizer; the catalyst carrier comprises alumina; the load material in the solution containing the load material comprises one or more of potassium hydroxide, potassium carbonate, sodium carbonate and sodium hydroxide. The activated carbon desulfurizer obtained by the preparation method provided by the present invention has the advantages of both a hydrolysis catalyst and an activated carbon desulfurizer, and COS, H 2 S is completely removed, and it has very good removal performance for hydrogen chloride, sulfur dioxide, etc. COS, CS 2 First, it is hydrolyzed by a catalyst to generate H 2 S, then H 2 S reacts with trace oxygen in the gas to generate elemental S which is stored in the micropores of the activated carbon, removing sulfur from the coal gas at one time. The addition of active ingredients also enhances the desulfurization activity of the desulfurizer. At the same time, the desulfurizer can also remove hydrogen chloride and sulfur dioxide, has very good chlorine and sulfur resistance, and effectively alleviates the catalyst deactivation caused by hydrogen chloride and sulfur dioxide. According to the test, the H 2 The penetration sulfur capacity (mass sulfur capacity) of S and COS can reach more than 40%, and the desulfurization accuracy can reach 0.1ppm; at the same time, CS 2 The penetration sulfur capacity (mass sulfur capacity) can reach 5%, which is effective for CS 2 The removal accuracy can reach 1ppm. The desulfurizer can also remove HCl and SO in coal gas. 2 Toxic gases such as HCl and SO 2 The removal accuracy can also reach 0.1ppm, and the removal capacity (mass capacity) can reach more than 20%. DETAILED DESCRIPTION

[0024] The present invention provides a method for preparing an activated carbon desulfurizer, comprising the following steps:

[0025] The activated carbon, the catalyst carrier, the active component, the modifier, the additive and the binder are mixed and calcined to obtain a calcined material;

[0026] The calcined material is immersed in a solution containing a supporting material, and then dried to obtain an activated carbon desulfurization agent;

[0027] The catalyst carrier comprises aluminum oxide;

[0028] The load material in the solution containing the load material includes one or more of potassium hydroxide, potassium carbonate, sodium carbonate and sodium hydroxide.

[0029] In the present invention, unless otherwise specified, all preparation raw materials are commercially available products well known to those skilled in the art.

[0030] The invention mixes activated carbon, a catalyst carrier, an active component, a modifier, an additive and a binder, and roasts them to obtain a roasted material.

[0031] In the present invention, the catalyst carrier comprises alumina. In the present invention, the catalyst carrier preferably comprises fast de-powdering and / or pseudo-diaspore. In the present invention, the catalyst comprises alumina, which generates catalytically active γ-Al after calcination. 2 O 3 , further improving the catalytic performance of the desulfurizer.

[0032] In the present invention, the active ingredient preferably includes one or more of iron oxide, zinc oxide and copper oxide. In the present invention, the active ingredient has very good desulfurization performance, reacts with hydrogen sulfide to generate iron sulfide, zinc sulfide or copper sulfide, and has the characteristics of high removal accuracy and fast reaction speed; at the same time, the added active ingredient also has very good dechlorination performance.

[0033] In the present invention, the modifier preferably includes titanium dioxide and / or magnesium oxide. In the present invention, the addition of the modifier can effectively improve the pore structure and physical properties of alumina, and improve the sulfur and oxygen resistance of alumina; at the same time, the modifier can also be used as a catalyst carrier to further improve the catalytic performance.

[0034] In the present invention, the additive preferably includes one or more of nickel oxide, cobalt oxide, cerium oxide, molybdenum oxide and manganese oxide. In the present invention, by adding additives, the corresponding metal is generated after roasting and loaded in the activated carbon desulfurizer, and the obtained metal has excellent reduction performance, which can significantly improve the low-temperature catalytic activity of the desulfurizer, improve the organic sulfur conversion efficiency, and improve the sulfur and oxygen resistance of the desulfurizer, and effectively alleviate the deactivation caused by sulfation of the desulfurizer.

[0035] In the present invention, the binder preferably includes carboxymethyl cellulose and / or sesbania powder.

[0036] In the present invention, the mass ratio of the activated carbon, catalyst carrier and active ingredient is preferably 40-60:10-20:10-15; the mass ratio of the activated carbon and modifier is preferably 40-60:5-10; the mass ratio of the activated carbon, additive and binder is preferably 40-60:1-3:1-5.

[0037] The present invention has no particular limitation on the mixing process, and any method known to those skilled in the art may be used.

[0038] In the present invention, the mixed raw materials preferably further include water. The present invention has no particular limitation on the amount of water added, and any amount known to those skilled in the art may be used. In the present invention, when the mixed raw materials further include water, after the mixing, the obtained mixed liquid is preferably subjected to extrusion molding and drying.

[0039] In the present invention, the calcination temperature is preferably 400-500° C., and the holding time is preferably 2-4 hours; the calcination is preferably carried out in a protective atmosphere; and the protective atmosphere is preferably nitrogen.

[0040] After obtaining the calcined material, the present invention immerses the calcined material in a solution containing a supporting material and then dries it to obtain the activated carbon desulfurizer.

[0041] In the present invention, the load material in the solution containing the load material includes one or more of potassium hydroxide, potassium carbonate, sodium carbonate and sodium hydroxide. In the present invention, the mass concentration of the solution containing the load material is preferably 10-30%. In the present invention, the mass percentage of the load material in the activated carbon desulfurizer is preferably 8-20%. The present invention can effectively improve the conversion capacity of the desulfurizer to organic sulfur by loading the above components on the desulfurizer. At the same time, the above components can also react with hydrogen chloride and sulfur dioxide, and have very good dechlorination and deacidification performance.

[0042] In the present invention, the use temperature of the activated carbon desulfurizer is preferably 50-120°C.

[0043] In order to further illustrate the present invention, the preparation method of an activated carbon desulfurizer provided by the present invention is described in detail below in combination with examples, but they should not be construed as limiting the scope of protection of the present invention.

[0044] Example 1

[0045] 45g of activated carbon, 15g of pseudo-diatomite, 10g of zinc oxide, 5g of magnesium oxide, 1g of cerium oxide, 1g of nickel oxide, 1g of molybdenum oxide and 3g of carboxymethyl cellulose were mixed, and extruded into strips after adding water. After drying, the mixture was heated to 450°C in a nitrogen atmosphere for calcination, and kept warm for 3h to obtain a calcined material.

[0046] The obtained roasted material is immersed in a potassium carbonate solution with a mass concentration of 20%, taken out and dried to obtain the activated carbon desulfurizer, wherein the mass percentage of potassium carbonate in the obtained activated carbon desulfurizer is 14%.

[0047] Example 2

[0048] 40g of activated carbon, 15g of quick-de-powder, 10g of iron oxide, 5g of copper oxide, 5g of titanium dioxide, 1g of cerium oxide, 0.5g of nickel oxide, 0.5g of cobalt oxide, 1g of molybdenum oxide and 3g of sesbania powder were mixed, and extruded into strips after adding water. After drying, the mixture was heated to 400°C in a nitrogen atmosphere for calcination, and kept warm for 4h to obtain a calcined material;

[0049] The obtained roasted material is immersed in a solution containing 3wt% sodium hydroxide and 15wt% potassium carbonate, taken out and dried to obtain the activated carbon desulfurizer, wherein the mass percentages of sodium hydroxide and potassium carbonate in the obtained activated carbon desulfurizer are 2.1% and 10.5% respectively.

[0050] Example 3

[0051] 60g of activated carbon, 10g of pseudo-diatomite, 15g of copper oxide, 10g of magnesium oxide, 3g of molybdenum oxide and 5g of carboxymethyl cellulose were mixed, and extruded into strips after adding water. After drying, the strips were heated to 500°C in a nitrogen atmosphere for calcination, and kept warm for 2h to obtain a calcined material.

[0052] The obtained roasted material is immersed in a potassium hydroxide solution with a mass concentration of 15%, taken out and dried to obtain the activated carbon desulfurizer, wherein the mass percentage of potassium hydroxide in the obtained activated carbon desulfurizer is 10.5%.

[0053] Performance Testing

[0054] The removal effect of the activated carbon desulfurizer obtained in Examples 1 to 3 was tested;

[0055] The activated carbon desulfurizer was crushed and a 40-mesh sample was screened out. 3 mL was taken and loaded into a reactor with a diameter of 6 mm and a length of 200 mm. N 2 Check whether the experimental device is leaking. After heating to the reaction temperature of 50-120℃, introduce the gas to be removed at an air velocity of 500-1000h -1 , the outlet uses the TY-2000-TS-A trace sulfur analyzer of Southwest Chemical Research Institute to detect the composition content of the gas at the outlet of the reactor; the test results are shown in Table 1 and Table 2;

[0056] Table 1 Desulfurization effect of activated carbon desulfurizer obtained in Examples 1 to 3

[0057]

[0058] Table 2 Dechlorination and SO removal of activated carbon desulfurizers obtained in Examples 1 to 3 2 Effect

[0059]

[0060] It can be seen from Table 1 and Table 2 that the desulfurizer prepared in the above embodiment has an effective effect on inorganic sulfur H 2 S and organic sulfur COS, CS 2 They all have very good removal effects, and can achieve one-step removal of organic sulfur and inorganic sulfur, while removing HCl, SO 2 It also has a very good removal effect, effectively avoiding the deactivation of the desulfurization catalyst caused by acidic gases such as HCl.

[0061] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for preparing an activated carbon desulfurizer, characterized in that: The following steps are involved: The activated carbon, catalyst carrier, active component, modifier, additive and binder are mixed and roasted to obtain a roasted material; the active component includes one or more of iron oxide, zinc oxide and copper oxide; the modifier includes titanium dioxide and / or magnesium oxide; the additive includes one or more of nickel oxide, cobalt oxide, cerium oxide, molybdenum oxide and manganese oxide; The calcined material is immersed in a solution containing a supporting material, and then dried to obtain the activated carbon desulfurization agent; The catalyst carrier comprises aluminum oxide; The load material in the solution containing the load material includes one or more of potassium hydroxide, potassium carbonate, sodium carbonate and sodium hydroxide.

2. The preparation method according to claim 1, characterized in that: The catalyst carrier includes fast de-powdering and / or pseudo-diamond stone.

3. The preparation method according to claim 1, characterized in that: The binder includes carboxymethyl cellulose and / or sesbania powder.

4. The preparation method according to claim 1, characterized in that: The mass ratio of the activated carbon, the catalyst carrier and the active ingredient is 40-60:10-20:10-15; The mass ratio of the activated carbon to the modifier is 40-60:5-10; The mass ratio of the activated carbon, the additive and the binder is 40-60:1-3:1-5.

5. The preparation method according to claim 1, characterized in that: The calcination temperature is 400-500° C., and the heat preservation time is 2-4 hours.

6. The preparation method according to claim 1 or 5, characterized in that: The calcination is carried out in a protective atmosphere.

7. The preparation method according to claim 1, characterized in that: The mass concentration of the solution containing the loading material is 10-30%.

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