Preparation method of composite high-temperature deaminating agent

Abstract

For ammonia odor, especially the purification removal of industrial flue gas escape ammonia, the application provides a preparation method of a composite high-temperature ammonia removal agent. The active carbon and zeolite are mixed by ball milling, and acid is added as an ammonia removal performance enhancer during the ball milling process, the high-temperature ammonia adsorption capacity is strengthened, and an active carbon-zeolite composite high-temperature powder ammonia removal agent product is obtained; further, the powder ammonia removal agent is added with a clay structure aid, mixing and extrusion molding, a screen mesh mold or a honeycomb body mold is used, and the renewable active carbon-zeolite high-temperature ammonia removal particle product and the honeycomb body product can be obtained respectively. The active carbon and the zeolite are compounded, which can not only promote the adsorption and internal diffusion of low-concentration escape ammonia, but also promote the internal diffusion ammonia to be fixed on the strong acid site of the zeolite, and finally realize the efficient removal of ammonia odor, especially high-temperature flue gas escape ammonia. The prepared active carbon-zeolite composite high-temperature ammonia removal agent has excellent normal temperature and high-temperature ammonia removal capacity, and also has a strong removal effect on flue gas dioxin, heavy metal and other flue gas pollutants. The technical products of the active carbon-zeolite powder, particle and honeycomb body high-temperature ammonia removal agent product can be applied to the removal and purification field of industrial flue gas escape ammonia, chemical fertilizer industrial ammonia pollution gas, indoor ammonia odor and other ammonia-containing pollution gas, and can also be used as a high-temperature ammonia storage material.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of purification of ammonia-containing contaminated gas, and particularly relates to a preparation method of a composite high-temperature deamination agent product for ammonia dry adsorption purification of flue gas escape and application technology thereof. BACKGROUND

[0002] Ammonia is a ubiquitous gaseous pollutant, widely produced in agricultural, industrial and other production processes, and has significant harm to the ecological environment and human health, and is an important gaseous pollutant. In particular, the flue gas denitration purification SNCR, PNCR and SCR processes, and the flue gas ammonia desulfurization process, due to incomplete denitration and desulfurization reactions or changes in boiler processes, are very prone to produce a large amount of escape ammonia. With the continuous improvement of people's requirements for environmental quality, the monitoring of escape ammonia by the state and local governments will become increasingly stringent. Although the current optimization of flue gas desulfurization and denitration processes and the increase of real-time online automatic ammonia injection control systems can reduce some escape ammonia, it is still difficult to effectively and completely avoid escape ammonia exceeding the standard. Therefore, how to effectively remove the end-of-pipe escape ammonia has become an important technical problem to be solved in the current flue gas purification field.

[0003] Current ammonia removal technologies mainly include wet acid washing removal, ammonia selective catalytic oxidation removal, complex deamination, adsorption removal, membrane separation and biological deamination. Wet acid washing ammonia removal may produce secondary wastewater pollution or a large amount of white plume (CN202110663927.3, CN201020239689.0), and this process is currently less used. Ammonia selective catalytic oxidation technology (CN200810103870.6, CN201110069424.X, CN201610368846.X) catalytically oxidizes ammonia into harmless nitrogen, which has the advantages of high catalytic efficiency and selectivity, but the ammonia selective oxidation catalyst is very sensitive to sulfur, and the residual SO2 in the end-of-pipe flue gas will easily poison and deactivate the catalyst, making it difficult to ensure the stability and economy of the application process. The complex deamination method uses alkaline earth metal halides such as CaCl2 and MgCl2 as active components, which are supported on activated carbon, molecular sieves or metal organic compounds, and has a high sulfur capacity under certain pressure, which can realize pressure swing adsorption of ammonia-containing industrial gas (CN202110155556.8), but the flue gas emission is usually very large, and the escape ammonia concentration is very low, so the pressurization or pressure swing adsorption process is difficult to apply to the field of flue gas escape ammonia removal and purification. The adsorption method for deamination usually uses high specific surface activated carbon as the carrier, and uses acid modification or loading of transition metal salts to increase its ammonia adsorption performance (CN202011234848.2, CN101935032A, CN201811496626.0), which has a very large ammonia adsorption capacity at room temperature and is usually used as an ammonia and odor removal agent at room temperature, but the high-temperature deamination effect of the activated carbon deamination agent is significantly reduced, making it difficult to be applied to the removal of flue gas escape ammonia.

[0004] In summary of the current deamination technology, in addition to catalytic oxidation and complex pressure swing deamination technology, only for the removal of normal temperature ammonia-containing contaminated gas. For the escape of ammonia flue gas, the flue gas temperature is usually 100-200℃, the ammonia content is usually less than 10ppm, and there are SO2 and other catalyst poisons, which makes it difficult to apply catalytic oxidation and complex pressure swing deamination technology to the removal of flue gas escape ammonia. In view of the characteristics of high temperature and low concentration of escape ammonia flue gas, the development of new type of high temperature adsorption material for escape ammonia flue gas and its application technology is an important technical route to effectively control the escape of ammonia flue gas. SUMMARY

[0005] In view of the technical difficulties of the above-mentioned existing deamination technology for purifying flue gas escape ammonia, the present application provides a kind of activated carbon-zeolite high temperature composite deamination agent, realizes high temperature flue gas escape ammonia dry removal purification. Activated carbon has rich pore structure and large specific surface area, which is very beneficial to the internal diffusion and initial capture of low concentration escape ammonia in flue gas when using activated carbon as substrate; natural zeolite is low in price and has abundant strong acid sites, which can realize high temperature deamination. However, due to the low specific surface area of zeolite, the ammonia adsorption process is easily controlled by internal diffusion, and it is difficult to quickly capture low concentration escape ammonia in flue gas. The combination of activated carbon and zeolite can not only promote the internal diffusion of low concentration escape ammonia, but also promote the fixation of internal diffusion ammonia on the strong acid sites of zeolite, so as to realize the efficient removal of high temperature flue gas escape ammonia. The activated carbon and zeolite are ball milled, and acid is added as a deamination performance enhancer during ball milling to obtain an activated carbon-zeolite composite high temperature deamination agent. The powder after ball milling can continue to add clay as a structure aid, mix and extrude into a strip or honeycomb structure adsorbent. The prepared activated carbon-zeolite composite high temperature deamination agent not only has excellent high temperature deamination capacity, but also has strong removal effect on dioxin, heavy metal and other flue gas pollutants.

[0006] In order to achieve the purpose of the application, the application adopts the following technical scheme to provide a preparation method of a high-efficiency high-temperature ammonia removal agent, which comprises the following steps:

[0007] (1) A certain proportion of activated carbon and zeolite is added to a drum ball mill, and ball milled at a certain speed for a certain time. The activated carbon can be coal-based coke or biomass activated carbon. The zeolite used is natural zeolite or modified natural zeolite, including but not limited to analcime, laumontite, stellerite, natrolite, mordenite, phillipsite, epidote, chabazite, faujasite, etc.

[0008] (2) A certain proportion of activated carbon and zeolite are ball milled in a ball mill for a period of time, then a certain amount of different types of acid is added to the ball mill, and the ball milling is continued for a period of time to obtain an acid-modified activated carbon and zeolite composite powder high-temperature deaminating agent product. The acids that can be used include but are not limited to liquid acids such as sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, nitric acid, or solid acids such as niobic acid.

[0009] (3) The acid-modified activated carbon and zeolite composite powder is transferred to a kneader, a certain proportion of clay and water are added, the moisture content is maintained at 15%-30%, and the mixing is continued for a period of time.

[0010] (4) The activated carbon-zeolite mud obtained by mixing is further extruded under a certain extrusion pressure and rate, and different diameter activated carbon-zeolite composite deaminating agent particles can be obtained by using different mesh sieves, and an activated carbon-zeolite deaminating honeycomb body can be obtained by using a honeycomb tool.

[0011] (5) The activated carbon-zeolite composite deaminating agent particles or honeycomb body is first pre-dried at a certain temperature for a period of time, then calcined at a certain temperature for a period of time to shape and increase the strength, and an activated carbon-zeolite composite particle or honeycomb high-temperature deaminating agent is obtained.

[0012] (6) The activated carbon-zeolite powder deaminating agent prepared by the present application can be directly applied to the front end of a bag dust collector for the end purification of flue gas, and is directly sprayed in the form of powder, the deaminating agent dust is captured by the bag dust collector, and the spraying temperature range is 120-250℃. The activated carbon-zeolite composite particle or honeycomb high-temperature deaminating agent can be applied to fixed bed deamination, and is filled in the SCR reactor after the bag dust collector, and the application temperature is 120-250℃. The activated carbon-zeolite powder or particle deaminating agent prepared by the present application can also be made into a bagged deodorizing agent for deamination and deodorization in a closed space.

[0013] (7) The activated carbon-zeolite powder deaminating agent is not regenerated and recycled after use, and the activated carbon-zeolite composite particle or honeycomb high-temperature deaminating agent can be regenerated in situ at a certain temperature or be recycled and calcined for regeneration.

[0014] The application adopts activated carbon and zeolite composite material to prepare high-temperature ammonia removal agent, which plays the advantages of rapid ammonia adsorption of activated carbon, realizes ammonia fixation by strong acid sites of zeolite, and loads acid modified activated carbon and zeolite material to strengthen high-temperature ammonia adsorption capacity, so as to obtain activated carbon-zeolite powder high-temperature ammonia removal agent. Further adding clay structure additives, the renewable activated carbon-zeolite particle or honeycomb high-temperature ammonia removal agent is obtained. Both activated carbon and zeolite are environmentally friendly materials, and ammonia fixed in the activated carbon and zeolite composite material can be used as nitrogen fertilizer, which is not only low in price but also free of secondary pollution. The application provides a renewable, green, pollution-free and efficient high-temperature ammonia removal agent, which is expected to be applied to efficient adsorption and purification of ammonia escaping from industrial boiler flue gas such as glass, steel, cement, biomass and waste incineration, purification of ammonia pollution gas in chemical fertilizer industry, purification of indoor or landfill ammonia-containing malodor, or ammonia storage at room temperature or high temperature.

[0015] Preferably, the mass ratio of the activated carbon to the zeolite in step (1) ranges from 0.1 to 10, for example, can be 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc., but is not limited to the listed values, and other values not listed in the above value range are also applicable.

[0016] Preferably, the rotating speed of the roller ball mill in step (1) ranges from 100 to 500 r / min, for example, can be 100 r / min, 150 r / min, 200 r / min, 250 r / min, 300 r / min, 350 r / min, 400 r / min, 450 r / min, 500 r / min, etc., but is not limited to the listed values, and other values not listed in the above value range are also applicable.

[0017] Preferably, the ball milling time of the ball mill in step (1) ranges from 2 to 8 h, for example, can be 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h, 6 h, 6.5 h, 7 h, 7.5 h, 8 h, etc., but is not limited to the listed values, and other values not listed in the above value range are also applicable.

[0018] Preferably, the acid in step (2) includes hydrochloric acid, nitric acid, concentrated sulfuric acid, phosphoric acid, etc.

[0019] Further preferably, the acid in step (2) is hydrochloric acid.

[0020] Further preferably, the concentration of the hydrochloric acid ranges from 4.0% to 12.0%, for example, can be 4.0%, 5.0%, 6.0%, 7.0%, 8.0%, 9.0%, 10.0%, 11.0%, 12.0%, etc., but is not limited to the listed values, and other values not listed in the above value range are also applicable.

[0021] Preferably, the ball milling time of step (2) is 2-8h, for example, it can be 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, etc.; but not limited to the listed values, other values not listed in the above range are also applicable.

[0022] Preferably, the weight ratio of clay and water in step (3) is 5-15% and 10-25%, respectively, for example, it can be 5% and 10%, 6% and 12%, 7% and 14%, 8% and 16%, 9% and 18%, 10% and 20%, 11% and 22%, 12% and 24%, 13% and 25%, etc.; but not limited to the listed values, other values not listed in the above range are also applicable.

[0023] Preferably, the mixing and kneading time of step (3) is 30-90min, for example, it can be 30min, 35min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80min, 90min, etc.; but not limited to the listed values, other values not listed in the above range are also applicable.

[0024] Preferably, the extrusion pressure of step (4) is 1.5-6Mpa, for example, it can be 1.5map, 2map, 2.5map, 0.3map, 3.5map, 4map, 4.5map, 5map, 5.5map, 6map, etc.; but not limited to the listed values, other values not listed in the above range are also applicable.

[0025] Preferably, the extrusion rate of step (4) is 0.1-0.5m / min, for example, it can be 0.1m / min, 0.15m / min, 0.2m / min, 0.25m / min, 0.3m / min, 0.35m / min, 0.4m / min, 0.45m / min, 0.5m / min, etc.; but not limited to the listed values, other values not listed in the above range are also applicable.

[0026] Preferably, the particle size of the activated carbon-zeolite composite deaminating agent obtained by sieving in step (4) is 3mm, 6mm, 9mm, 12mm.

[0027] Preferably, the pre-drying temperature of step (5) is 80-150℃, for example, it can be 80℃, 85℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, etc.; but not only limited to the listed values, other values not listed in the above range are also applicable.

[0028] Preferably, the pre-drying time of step (5) is 12-24h, for example, it can be 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, etc.; but not only limited to the listed values, other values not listed in the above range are also applicable.

[0029] Preferably, the calcination temperature of step (5) is 200-400℃, for example, it can be 200℃, 220℃, 240℃, 260℃, 280℃, 300℃, 320℃, 340℃, 360℃, 380℃, 400℃, etc.; but not only limited to the listed values, other values not listed in the above range are also applicable.

[0030] Preferably, the calcination time of step (5) is 12-36h, for example, it can be 12h, 16h, 20h, 24h, 28h, 32h, 36h, etc.; but not only limited to the listed values, other values not listed in the above range are also applicable.

[0031] Preferably, the regeneration temperature of step (7) is 200-400℃, for example, it can be 200℃, 220℃, 240℃, 260℃, 280℃, 300℃, 320℃, 340℃, 360℃, 380℃, 400℃, etc.; but not only limited to the listed values, other values not listed in the above range are also applicable.

[0032] As a preferred technical solution of the present application, the preparation method comprises the following steps:

[0033] (1) The activated carbon and zeolite with a mass ratio of 0.1-10 are added to a drum ball mill, and ball milling is carried out at a speed of 100-500r / min for 2-8h.

[0034] (2) After the activated carbon and zeolite with a mass ratio of 0.1-10 are ball milled in the ball mill for 2-8h, hydrochloric acid with a concentration of 4.0%-12.0% is continuously added to the ball mill, and the ball milling is continued for 2-8h to obtain an acid-modified activated carbon and zeolite composite powder high-temperature deamination agent.

[0035] (3) Transfer the acid-modified activated carbon and zeolite composite powder to a kneader, add clay and water at a weight ratio of 5-15% and 10-25% respectively, keep the moisture content between 15% and 30%, and mix for 30-90 minutes.

[0036] (4) The activated carbon-zeolite mud obtained by mixing is further extruded and shaped under an extrusion pressure of 1.5-6 MPa and an extrusion rate of 0.1-0.5 m / min. Different diameter activated carbon-zeolite composite deammonigenizer particles can be obtained by using screens with different pore sizes. Activated carbon-zeolite deammonigenizer honeycomb can be obtained by using honeycomb molds.

[0037] (5) The activated carbon-zeolite composite deaming agent particles or honeycomb bodies are first pre-dried at 80-150℃ for 12-24h, and then calcined at 200-400℃ for 12-36h to fix the shape and increase the strength, so as to obtain the activated carbon-zeolite composite particles or honeycomb bodies high temperature deaming agent.

[0038] (6) The activated carbon-zeolite powder ammonia removal agent prepared by this invention can be directly applied to the front end of the bag filter for flue gas purification. It is directly sprayed in powder form, and the ammonia removal agent dust is captured by the bag filter. The spraying application temperature range is 120-250℃. The activated carbon-zeolite composite particle or honeycomb high-temperature ammonia removal agent is applied to fixed bed ammonia removal, after filling the SCR reactor and before the bag filter, with an application temperature of 120-250℃.

[0039] (7) The activated carbon-zeolite powder deammoniation agent is not regenerated or recycled after use. The activated carbon-zeolite composite particles or honeycomb high-temperature deammoniation agent can be regenerated in situ in a hot air furnace at 200-400℃, or regenerated by calcination in a furnace.

[0040] Compared with the prior art, the present invention has the following beneficial effects:

[0041] (1) In the composite high-temperature deammoniation agent of the present invention, activated carbon and zeolite are combined, which can not only promote the internal diffusion of low-concentration escaped ammonia, but also promote the fixation of internally diffused ammonia on the strong acidic sites of zeolite, and finally achieve efficient removal of escaped ammonia from high-temperature flue gas.

[0042] (2) In the composite high-temperature deammoniation agent of the present invention, activated carbon and zeolite materials are modified by loading acid as deammoniation performance enhancers to strengthen the high-temperature ammonia adsorption capacity.

[0043] (3) In the composite high-temperature deammoniation agent of the present invention, activated carbon and zeolite are both environmentally friendly materials. Ammonia fixed in the composite material of activated carbon and zeolite can be used as nitrogen fertilizer, which is not only inexpensive but also produces no secondary pollution.

[0044] (4) The composite high-temperature deaminating agent has excellent high-temperature deaminating capacity, and has strong removal effect on flue gas pollutants such as dioxin and heavy metal. BRIEF DESCRIPTION OF DRAWINGS

[0045] Figure 1 The ammonia temperature programmed desorption curve of the active carbon, zeolite and active carbon-zeolite composite material.

[0046] Figure 2 The high-temperature deaminating curve of the typical active carbon, zeolite and active carbon-zeolite composite material. DETAILED DESCRIPTION

[0047] The technical solutions of the present application are further illustrated by specific embodiments. Those skilled in the art should understand that the embodiments are only used to help understand the present application, and should not be regarded as specific limitations on the present application.

[0048] The preparation method of the composite high-temperature deaminating agent specifically includes the following steps:

[0049] (1) A certain proportion of active carbon and zeolite are added to a tumbling ball mill, and ball milled at a certain speed for a certain time.

[0050] (2) After a certain proportion of active carbon and zeolite are ball milled in the ball mill for a period of time, a certain amount of different types of acid is continuously added to the ball mill, and ball milled for a period of time to obtain an acid-modified active carbon and zeolite composite powder high-temperature deaminating agent product.

[0051] (3) The acid-modified active carbon and zeolite composite powder is transferred to a kneader, a certain proportion of clay and water are added, the water content is maintained at 15%-30%, and the mixture is mixed for a certain time.

[0052] (4) The active carbon-zeolite mud obtained by mixing is further extruded at a certain extrusion pressure and rate, and different diameter active carbon-zeolite composite deaminating agent particles can be obtained by using different mesh sieves, and active carbon-zeolite deaminating honeycomb bodies can be obtained by using honeycomb tooling.

[0053] (5) The active carbon-zeolite composite deaminating agent particles or honeycomb bodies are first pre-dried at a certain temperature for a certain time, and then calcined at a certain temperature for a certain time to shape and increase the strength, so that the active carbon-zeolite composite particle or honeycomb body high-temperature deaminating agent can be obtained.

[0054] (6) The prepared active carbon-zeolite powder deaminating agent can be directly applied to the front end of a bag dust collector for the end purification of flue gas, and is directly sprayed in powder form. The deaminating agent dust is captured by the bag dust collector, and the application temperature range of the powder spraying is 120-250°C. The active carbon-zeolite composite particles or honeycomb high-temperature deaminating agent can be applied to fixed bed deamination, and is filled in the SCR reactor and before the bag dust collector, and the application temperature is 120-250°C.

[0055] (7) The active carbon-zeolite powder deaminating agent is not regenerated and recovered after use, and the active carbon-zeolite composite particles or honeycomb high-temperature deaminating agent can be regenerated in situ in a hot blast furnace at a certain temperature, or is regenerated by re-furnace calcination.

[0056] The following examples all use the preparation method described above.

[0057] Example 1

[0058] The present embodiment provides a preparation method of a composite high-temperature powder deaminating agent, which comprises the following steps:

[0059] (1) The active carbon and zeolite with a mass ratio of 3 are added to a drum ball mill, and ball milling is performed at a speed of 350 r / min for 4 h.

[0060] (2) After the active carbon and zeolite with a mass ratio of 3 are ball milled in the ball mill for 4 h, hydrochloric acid with a concentration of 8.0% is continuously added to the ball mill, and ball milling is continuously performed for 6 h to obtain an acid-modified active carbon and zeolite composite powder high-temperature deaminating agent.

[0061] (3) The prepared active carbon-zeolite powder deaminating agent has an ammonia desorption capacity of 86 mg / g at room temperature 25°C, and the ammonia desorption capacities at 100°C, 150°C, 200°C, 250°C and 300°C are 75 mg / g, 65 mg / g, 56 mg / g, 37 mg / g and 15 mg / g, respectively.

[0062] Example 2

[0063] The present embodiment provides a preparation method of a composite high-temperature particle deaminating agent, which comprises the following steps:

[0064] (1) The active carbon and zeolite with a mass ratio of 4 are added to a drum ball mill, and ball milling is performed at a speed of 320 r / min for 5 h.

[0065] (2) After the active carbon and zeolite with a mass ratio of 4 are ball milled in the ball mill for 5 h, hydrochloric acid with a concentration of 9.0% is continuously added to the ball mill, and ball milling is continuously performed for 6 h to obtain an acid-modified active carbon and zeolite composite powder high-temperature deaminating agent.

[0066] (3) The acid-modified activated carbon and zeolite composite powder is transferred to a kneader, 12% and 22% of clay and water by weight are added respectively, the moisture content is kept between 15% and 30%, and the mixing is performed for 60 min.

[0067] (4) The activated carbon-zeolite mud obtained by mixing is further extruded at an extrusion pressure of 4.5 Mpa and an extrusion rate of 0.3 m / min, and 3mm screen is used to obtain activated carbon-zeolite composite deaminating agent particles with a diameter of 3mm.

[0068] (5) The activated carbon-zeolite composite deaminating agent particles are first pre-dried at 120℃ for 18h, and then calcined at 300℃ for 28h to be shaped and to increase the strength, so that the activated carbon-zeolite composite particle high-temperature deaminating agent is obtained.

[0069] (6) The activated carbon-zeolite particle deaminating agent prepared in the application has an ammonia desorption capacity of 81mg / g at room temperature of 25℃, and the ammonia desorption capacities at 100℃, 150℃, 200℃, 250℃ and 300℃ are 69mg / g, 57mg / g, 45mg / g, 28mg / g and 7mg / g respectively.

[0070] (7) The activated carbon-zeolite particle deaminating agent is regenerated at 300℃, and the ammonia capacity of the particle deaminating agent after the heat regeneration at 200℃ can reach 43mg / g, and the regeneration efficiency is more than 95%.

[0071] Example 3

[0072] The embodiment provides a preparation method of a composite high-temperature honeycomb body deaminating agent, and the preparation method comprises the following steps:

[0073] (1) Activated carbon and zeolite with a mass ratio of 5 are added to a drum ball mill, and ball milling is performed at a rotating speed of 350r / min for 6h.

[0074] (2) After the activated carbon and zeolite with a mass ratio of 5 are ball milled in the ball mill for 6h, hydrochloric acid with a concentration of 10.0% is continuously added to the ball mill, and ball milling is continuously performed for 6h, so that the acid-modified activated carbon and zeolite composite powder high-temperature deaminating agent is obtained.

[0075] (3) The acid-modified activated carbon and zeolite composite powder is transferred to a kneader, 9% and 18% of clay and water by weight are added respectively, the moisture content is kept between 15% and 30%, and the mixing is performed for 80 min.

[0076] (4) The activated carbon-zeolite mud obtained by mixing is further extruded at an extrusion pressure of 3.6 Mpa and an extrusion rate of 0.25 m / min, and a honeycomb body mold is used for extrusion molding, so that the activated carbon-zeolite deaminating honeycomb body is obtained.

[0077] (5) The activated carbon-zeolite composite honeycomb desorber is pre-dried at 120°C for 20h, and then is baked at 350°C for 26h to be shaped and to increase the strength, so that the activated carbon-zeolite honeycomb high-temperature desorber is obtained.

[0078] (6) The activated carbon-zeolite honeycomb desorber prepared by the present application has an ammonia desorption capacity of 74mg / g at normal temperature of 25°C, and ammonia desorption capacities of 62mg / g, 51mg / g, 41mg / g, 38mg / g and 9mg / g at 100°C, 150°C, 200°C, 250°C and 300°C respectively.

[0079] (7) The activated carbon-zeolite honeycomb desorber is regenerated at 350°C, and the ammonia capacity of the granular desorber after the regeneration at 200°C can reach 40mg / g, and the regeneration efficiency is more than 97%.

[0080] Example 4

[0081] The present embodiment provides a composite high-temperature powder desorber and a preparation method thereof. The preparation method is the same as that described in Example 1, except that the mass ratio of the activated carbon to the zeolite in step (1) is 4. The activated carbon-zeolite powder desorber prepared by the present application has an ammonia desorption capacity of 90mg / g at normal temperature of 25°C, and ammonia desorption capacities of 78mg / g, 67mg / g, 60mg / g, 42mg / g and 23mg / g at 100°C, 150°C, 200°C, 250°C and 300°C respectively.

[0082] Example 5

[0083] The present embodiment provides a composite high-temperature granular desorber and a preparation method thereof. The preparation method is the same as that described in Example 2, except that the hydrochloric acid in step (2) is replaced by concentrated sulfuric acid. The activated carbon-zeolite granular desorber prepared by the present application has an ammonia desorption capacity of 78mg / g at normal temperature of 25°C, and ammonia desorption capacities of 64mg / g, 53mg / g, 40mg / g, 26mg / g and 6mg / g at 100°C, 150°C, 200°C, 250°C and 300°C respectively. The activated carbon-zeolite granular desorber is regenerated at 320°C, and the ammonia capacity of the granular desorber after the regeneration at 200°C can reach 36mg / g, and the regeneration efficiency is more than 94%.

[0084] Example 6

[0085] The present embodiment provides a kind of composite high-temperature honeycomb body deaminating agent and its preparation method, with reference to the preparation method described in embodiment 3, the only difference is that the weight ratio of clay and water in step (3) is 12% and 22% respectively.The ammonia desorption capacity of the prepared activated carbon-zeolite honeycomb body deaminating agent at room temperature 25 ℃ is 76 mg / g, and the ammonia desorption capacity at 100 ℃, 150 ℃, 200 ℃, 250 ℃ and 300 ℃ is 67 mg / g, 54 mg / g, 47 mg / g, 41 mg / g and 13 mg / g respectively.The ammonia capacity of the activated carbon-zeolite honeycomb body deaminating agent at 200 ℃ after thermal regeneration at 360 ℃ can reach 45 mg / g, and the regeneration efficiency is more than 98%.

[0086] Comparative example 1

[0087] The present comparative example provides the deaminating capacity of activated carbon powder alone, which is 46 mg / g at room temperature 25 ℃, and the ammonia desorption capacity at 100 ℃, 150 ℃, 200 ℃, 250 ℃ and 300 ℃ is 10 mg / g, 2 mg / g, 1 mg / g, 0.5 mg / g and 0.1 mg / g respectively.

[0088] Comparative example 2

[0089] The present comparative example provides the deaminating capacity of zeolite powder alone, which is 66 mg / g at room temperature 25 ℃, and the ammonia desorption capacity at 100 ℃, 150 ℃, 200 ℃, 250 ℃ and 300 ℃ is 54 mg / g, 36 mg / g, 24 mg / g, 15 mg / g and 7 mg / g respectively.

[0090] The deaminating capacity of the activated carbon-zeolite composite high-temperature powder deaminating agent, activated carbon-zeolite particles and honeycomb body high-temperature deaminating agent obtained from the above examples 1-6 and comparative examples 1-2 at room temperature 25 ℃, 100 ℃, 200 ℃ and 300 ℃ is listed in Table 1.

[0091] The deaminating capacity of the activated carbon-zeolite composite high-temperature powder deaminating agent, activated carbon-zeolite particles and honeycomb body high-temperature deaminating agent obtained from the above examples 1-6 and comparative examples 1-2 at 100 ℃, the ammonia capacity after thermal regeneration and the regeneration efficiency are listed in Table 2.

[0092] Table 1 Deaminating capacity of composite high-temperature deaminating agent at different temperatures (mg / g)

[0093] 25℃ 100℃ 200℃ 300℃ Example 1 86 75 56 15 Example 2 81 69 45 7 Example 3 74 62 41 9 Example 4 90 78 60 23 Example 5 78 64 40 6 Example 6 76 67 41 13 Comparative Example 1 46 10 1 0.1 Comparative Example 2 66 54 24 7

[0094] Table 2 Deaminating performance test of composite high-temperature deaminating agent at 100 ℃

[0095]

[0096]

Claims

1. A method for preparing a honeycomb composite high temperature deaminator, characterized in that, The preparation method comprises the following steps: (1) adding activated carbon and zeolite with a mass ratio of 0.1-10 into a tumbling ball mill, and tumbling for 2-8 hours at a rotating speed of 100-500 r / min; (2) after tumbling for 2-8 hours, adding hydrochloric acid with a concentration of 4.0%-12.0% into the ball mill, and continuing tumbling for 2-8 hours to obtain acid-modified activated carbon and zeolite composite high-temperature deaminating agent powder; (3) transferring the acid-modified activated carbon and zeolite composite powder into a kneader, adding clay and water with a weight ratio of 5-15% and 10-25% respectively, keeping the moisture content at 15%-30%, and mixing for 30-90 minutes; (4) further extruding the activated carbon-zeolite mud obtained by mixing under an extrusion pressure of 1.5-6 MPa and an extrusion rate of 0.1-0.5 m / min, and using a honeycomb tool to obtain activated carbon-zeolite deaminating honeycomb; (5) pre-drying the activated carbon-zeolite composite deaminating honeycomb at 80-150 ℃ for 12-24 hours, and then calcining at 200-400 ℃ for 12-36 hours to shape and increase the strength, so as to obtain activated carbon-zeolite composite honeycomb high-temperature deaminating agent; (6) applying the prepared activated carbon-zeolite honeycomb deaminating agent to fixed-bed deamination, filling in the SCR reactor, and then filling in the bag dust collector, and applying at a temperature of 120-250 ℃.

2. The production method according to claim 1, characterized by, The zeolite used is natural zeolite or modified natural zeolite.

3. Application of the activated carbon-zeolite honeycomb high-temperature deaminating agent obtained by the preparation method of any one of claims 1-2 in the field of removal and purification of ammonia-containing contaminated gas, or as a high-temperature ammonia storage material.

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