A dechlorination agent for deep removal of organic chlorine in raw gas at normal temperature and a preparation method thereof

Abstract

The present application is a kind of raw material gas organic chlorine removal at room temperature and its preparation method.The dechlorination agent includes the following raw materials: 60-80% carrier, 5-15% active component one, 5-10% active component two, 1-5% active additive, 5-10% structural additive, 1-5% molding additive, the total weight percentage is 100%.In the dechlorination agent, the metal in the active component one is embedded in the molecular sieve framework structure, so that the metal active component is more uniformly dispersed on the surface of the molecular sieve, forming a framework catalytic strong absorption effect, the M-O-Al and M-O-Si structure of the obtained molecular sieve makes the molecular sieve have M δ+ (0≤δ≤2), the surface of which has stronger electron-accepting ability, and by loading other components, a dechlorination agent with stronger catalytic and absorption activity is obtained, which is suitable for deep removal of organic chlorine in raw material gas.

Description

Technical Field

[0001] This invention relates to the field of organochlorine purification, specifically to a dechlorinating agent for deep removal of organochlorine from raw gas at room temperature and its preparation method. Background Technology

[0002] Organochlorine compounds (chlorinated alkanes, chlorinated alkenes, chlorinated aromatics, etc.) are serious industrial pollutants. In chemical reactions, under conditions of hydrogen and high temperatures, organochlorine compounds can be hydrogenated by certain dechlorinating agents to form hydrogen chloride, causing severe corrosion to reaction equipment and pipelines. Therefore, deep removal of organochlorine compounds is necessary in the preceding purification processes. For example, syngas is an important chemical synthesis feedstock gas. Its chlorides mainly originate from the chlorine contained in coal, petroleum, or carbonaceous raw materials. During high-temperature gasification reactions, this chlorine is converted into organic and inorganic chlorine compounds, which enter the system along with the feedstock gas. Even after purification processes such as low-temperature methanol washing and pressure swing adsorption separation, the organochlorine content in the syngas can still reach 10 mg / Nm³. 3 This can lead to poisoning of dechlorinating agents in important subsequent processes such as conversion, reforming, transformation, and synthesis, reducing the service life of the dechlorinating agents and decreasing the capacity load of the unit. Organic chlorine in the syngas is mainly removed by catalytic hydrogenation and physical adsorption. In dechlorination, high-temperature hydrogenation converts organic chlorine into hydrogen chloride, which is then removed by a calcium-based dechlorinating agent.

[0003] Catalytic hydrodechlorination typically uses activated carbon (CN 112547093 A, CN 112206801 A, CN115364888A, CN 114367296A, CN 111013604A, CN 111514849A) or alumina (CN 114984986 A) as carriers to load precious metals for the hydrogenation conversion of specific organochlorine compounds. This method is suitable for organochlorine compounds with relatively simple feed gas compositions. However, the purified coal chemical syngas contains complex organochlorine components and small amounts of impurities such as sulfur and arsenic, which can cause poisoning of the precious metal dechlorinating agent. At the same time, the hydrogenation process may also cause changes in the content of CO, CO2, and H2 in the syngas. The hydrogenation process is energy-intensive, complex, requires high-level equipment, involves large-scale investment, and uses expensive dechlorinating agents. Adsorption dechlorination is a simple process, and the adsorbent can be recycled and regenerated. The process is easy to operate and has low operating costs. The core of this method is the adsorbent that can efficiently and deeply remove organic chlorine.

[0004] Patents CN107008221A and CN107096379A respectively describe dechlorinating agents prepared by loading Cu oxides, salts, and alkanolamines onto silica and activated carbon as carriers. These dechlorinating agents are mainly used for the removal of chlorine-containing substances such as Cl2 and HCl. CN109248708A discloses a room-temperature dechlorinating agent and its preparation method. This method uses activated carbon and molecular sieves as carriers to load active metals such as Cu, Zn, and Fe, achieving a chlorine penetration capacity of over 30% at room temperature. While these patents utilize molecular sieves or activated carbon as carriers to load active metals, resulting in dechlorinating agents with high precision and high chlorine capacity, the development of these dechlorinating agents did not consider regeneration and reuse, increasing the cost of dechlorination and failing to verify their applicability for deep removal of organochlorines.

[0005] Patent CN 103611495 A describes an adsorbent for removing organochlorines from hydrocarbon streams. This adsorbent uses X or Y-type zeolite molecular sieves as a carrier, transferring Zn to the zeolite molecular sieve via ion exchange, and then molding it by adding inorganic macroporous materials and clay. The adsorbent prepared by this method has a wide range of applicable temperatures and pressures. Patent CN111514849 A provides a dechlorination adsorbent and its preparation method. This method uses alumina added to a molecular sieve as a carrier to support zinc oxide as the active component. The adsorbent prepared by this method shows good dechlorination performance in alkylated oils and can be repeatedly regenerated and reused. While the above patents demonstrate good adsorption of organochlorines using metal-supported molecular sieves, in some feed gases containing complex components such as CO2, olefins, and alkanes, CO2 in the molecular sieve forms an adsorption structure MO=C=O⊥Oz with the cation M and the framework oxygen atom Oz. The molecular sieve has a high adsorption capacity for weakly acidic CO2. Simultaneously, weakly polar olefins and alkanes also compete with organochlorines for adsorption, reducing dechlorination efficiency.

[0006] Patent CN 114433018 A uses activated coke as raw material and processes it through steps such as high temperature, washing, drying, and oxidation modification to obtain an Ag / activated carbon adsorbent. This process forms a weak chemical bond between silver and organic chlorine, enabling the adsorbent to achieve efficient dechlorination and regeneration. However, this method uses precious metal silver as the active component, which increases the cost of using the adsorbent.

[0007] Conventional adsorbents exhibit a significant decrease in organochlorine adsorption capacity with increasing regeneration cycles. Furthermore, existing adsorbents cannot reduce the total chlorine concentration at the outlet to below 10 ppb. Therefore, there is an urgent need to develop an organochlorine dechlorinating agent with high adsorption depth and stronger molecular bonds. Summary of the Invention

[0008] The purpose of this invention is to address the shortcomings of current organochlorine dechlorination agents by providing a dechlorination agent for deep removal of organochlorine from raw gas at room temperature, as well as a method for preparing the dechlorination agent. The dechlorination agent prepared using this method has advantages such as CO2 repellency, high dechlorination efficiency, high chlorine capacity, low energy consumption, simple operation, and no secondary pollution, thus effectively solving the problems existing in the dechlorination agents of the background art.

[0009] To achieve the above-mentioned objectives, the specific technical solution of the present invention is as follows:

[0010] A dechlorinating agent for deep removal of organochlorine from raw gas at room temperature, comprising the following raw materials by weight percentage: 60-80% carrier, 5-15% active component one, 5-10% active component two, 1-5% active additive, 5-10% structural additive, and 1-5% molding additive, with the total weight percentage being 100%.

[0011] In a preferred embodiment of this application, the carrier is a molecular sieve carrier synthesized by adding an aluminum source using one or more silicon-rich and aluminum-poor materials as raw materials.

[0012] In a preferred embodiment of this application, the active component is one or a combination of any one or more of Cu, Zn, and Ni.

[0013] In a preferred embodiment of this application, the active component two is any one or a combination of several of Cr2O3, MnO2, Co2O3, Fe2O3, Bi2O3, and MoO3.

[0014] In a preferred embodiment of this application, the active agent is any one or a combination of several of CeO2, ZrO2, and La2O3.

[0015] In a preferred embodiment of this application, the structural additive is any one or a combination of several of TiO2, Sb2O3, and Al2O3.

[0016] In a preferred embodiment of this application, the molding aid is any one or a combination of several of sodium cellulose, magnesium stearate, calcium stearate, graphite, guar gum powder, etc.

[0017] As a preferred embodiment of this application, the preparation method of the dechlorinating agent for deep removal of organochlorine from raw gas at room temperature described above includes the following steps:

[0018] (1) Weigh an appropriate amount of silicon-rich and aluminum-poor material, add a certain amount of aluminum source to obtain mixture 1; place mixture 1 in a high-speed ball mill for ball milling, and then place it in a three-necked flask; then add non-metallic alkali solution, and then place the three-necked flask in an oil bath at 80-150℃, and stir and mix at a speed of 100-400r / min for 1-5h to obtain solid-liquid mixed slurry A;

[0019] (2) Weigh a certain amount of the soluble salt of active component one and dissolve it in an appropriate amount of deionized water to prepare a salt solution. Then add the in-situ synthesized metal nano-additive. The molar ratio of active component one to the in-situ synthesized metal nano-additive is 1:0.2-2. Then stir and mix the material in a water bath at 60-80℃ for 2-6 hours to obtain precursor solution B.

[0020] (3) Add precursor solution B to precursor slurry A and stir in a water bath at 60-80℃ for 3-12 hours. Then, disperse and emulsify the mixture in an ultrasonic water bath at 60-80℃ at a frequency of 50-80kHz for 2-8 hours. Then, pour the mixture into a high-temperature and high-pressure reactor and set the stirring speed at 200-1000r / min. Set the temperature program to age the mixture to obtain precursor slurry C.

[0021] (4) The precursor slurry C is filtered, pulped and washed three times, then dried at 100-150℃ for 3-12h, and calcined at 400-600℃ in air for 2-8h to obtain the precursor D.

[0022] (5) Weigh a certain amount of molding aid, structural aid, pore-forming agent and precursor D and mechanically mix them with precursor D in a closed ply mill for 1-3 hours to obtain precursor E.

[0023] (6) Weigh a certain amount of the soluble salt of active component II and the soluble salt of active auxiliary agent and dissolve them in a certain amount of deionized water and stir to mix well. Then add an acid of the same molar amount as the structural auxiliary agent to obtain the precursor solution F.

[0024] (7) Add the precursor solution F to the vacuum ply mill and mix it thoroughly with the precursor E. Then, perform vacuum ply milling, extrusion molding, and dry and calcin the extruded material to obtain the precursor G.

[0025] (8) Place the precursor G in a tube furnace and reduce it for 4 to 12 hours in a mixed atmosphere of N2 and H2 at 200 to 400°C; then reduce it to room temperature and passivate it for 4 to 12 hours in a mixed atmosphere of N2 and O2 to obtain the finished dechlorination agent.

[0026] As a preferred embodiment of this application, the silicon-rich and aluminum-poor material in step (1) is coal gangue powder, montmorillonite, or kaolin; the aluminum source is any one or a combination of aluminum oxide, aluminum nitrate, and aluminum hydroxide; the non-metallic alkali in the non-metallic alkali solution is any one or a combination of ethylenediamine, phenylethylamine, and ammonia water; the rotation speed of the high-speed ball mill is 200-600 r / min, and the ball milling time is 1-10 h; the ball milled material is passed through a 200-600 mesh sieve; the mass concentration of the non-metallic alkali solution is 10-25%; the non-metallic alkali solution is added at a solid-liquid ratio of 1 g / 2 ml to 1 g / 10 ml.

[0027] In a preferred embodiment of this application, the soluble salt of the active component in step (2) is any one or a combination of several of nickel nitrate, zinc nitrate, copper nitrate, nickel sulfate, zinc sulfate, copper sulfate, copper oxalate, zinc oxalate, and nickel oxalate; the in-situ synthesis metal nanoparticle aid is any one or a combination of several of ethylene glycol, 1,2-propanediol, glycerol, polyethylene glycol, and polypropylene glycol; and the mass concentration of the soluble salt solution of the active component is 10-40%.

[0028] As a preferred embodiment of this application, the conditions for heating and aging in step (3) are as follows: heating to 100°C within 1 hour and maintaining at 100°C for 2 to 12 hours; then heating to 180°C within 1 hour and maintaining at 180°C for 2 to 12 hours; then heating to 300°C within 1 hour and maintaining at 300°C for 2 to 12 hours; finally cooling to obtain precursor slurry C.

[0029] As a preferred embodiment of this application, the pore-forming agent in step (5) is any one or a combination of several of polyvinyl alcohol, urea, ammonium bicarbonate, ammonium carbonate, polycaprolactone, etc.; the amount of pore-forming agent added is 1 to 4% of the weight of the dechlorinating agent.

[0030] In a preferred embodiment of this application, the soluble salt of the active component II in step (6) is any one or a combination of several of chromium nitrate, manganese nitrate, cobalt nitrate, bismuth nitrate, ferric nitrate, and ammonium heptamolybdate, more preferably chromium nitrate, manganese nitrate, cobalt nitrate, and ferric nitrate; the soluble salt of the active additive is any one or a combination of several of cerium nitrate, zirconium nitrate, and lanthanum nitrate, more preferably cerium nitrate, zirconium nitrate, and lanthanum nitrate; and the acid is any one or a combination of several of nitric acid, sulfuric acid, hydrochloric acid, oxalic acid, and phosphoric acid, more preferably nitric acid and oxalic acid.

[0031] In a preferred embodiment of this application, in step (7), the absolute pressure in the vacuum plow is 0.001-0.01 MPa, the plowing time is 3-6 h; the specification of the round hole die extruder is 2-6 mm; the drying temperature of the extruded material is 100-150℃, the drying time is 2-12 h; the calcination temperature in the muffle furnace is 400-550℃, and the calcination time is 4-12 h.

[0032] In a preferred embodiment of this application, in step (8), the volume percentage of H2 in the N2 and H2 mixed atmosphere is 1 to 10%; and the volume percentage of O2 in the N2 and O2 mixed atmosphere is 0.1 to 5%.

[0033] A dechlorinating agent for deep removal of organochlorine from raw gas at room temperature is prepared by any of the methods or combinations of the above-described methods. The dechlorinating agent product is cylindrical, prismatic, or spherical in shape. The radial dimension of the dechlorinating agent is 3-5 mm, the axial dimension is 6-50 mm, and the radial strength is ≥60 N / cm.

[0034] As a preferred embodiment of this application, the dechlorination agent product described above is used under the following conditions: temperature 0–200°C, and volume hourly space velocity (HSV) 100–8000 h⁻¹. -1 The total organic chlorine content in the feed gas is ≤200ppm, and the pressure is 0.2~10MPa. The main types of organic chlorine are chlorinated alkanes, chlorinated alkenes, and chlorinated aromatics.

[0035] As a preferred embodiment of this application, the regeneration conditions for the dechlorination agent product described above are: regeneration temperature 200–350°C, space velocity 100–3000 h⁻¹. -1 The pressure is at atmospheric pressure, and the regeneration gas is an inert gas or a gas after deep dechlorination.

[0036] This invention embeds the active component into the molecular sieve framework structure, allowing it to be more uniformly dispersed on the surface of the molecular sieve and forming a strong absorption effect through framework catalysis. The resulting MO-Al and MO-Si structures give the molecular sieve the characteristics of M... δ+ (0≤δ≤2), its surface has a stronger ability to gain electrons, and its catalytic and absorption activities are stronger.

[0037] The dechlorinating agent prepared by this invention has a dual-function deep purification function of catalysis and absorption. In order to avoid the strong adsorption effect of the presence of alkali metals in ordinary molecular sieves on weak acid gases, alkanes and olefins in the raw gas, inorganic non-metallic alkalis are selected as the synthesis raw material, so that the dechlorinating agent has better adsorption performance for organic chlorine. It can be directly used for selective deep removal of organic chlorine in the raw gas of coal chemical, petrochemical and other chemical synthesis reactions. Its dechlorination accuracy can reach below 10 ppb, the chlorine penetration capacity can reach more than 5%, and it can be regenerated and used multiple times, which fully meets the requirements of subsequent process catalysts. It reduces production energy consumption and equipment requirements, and has the advantages of simple production process, low cost, high chlorine capacity and high dechlorination accuracy.

[0038] Compared with existing technologies, the beneficial effects of this invention are as follows:

[0039] (i) In this invention, metal nano-sizing aids are added during the hydrothermal synthesis of molecular sieves as in-situ metal nano-sizing synthesis. Metal oxide defect sites are formed by calcination and reduction, which increases the exposure of active metal oxides on the surface of dechlorinating agent, thereby realizing in-situ dechlorinating agent absorption of organic chlorine and improving the absorption performance of organic chlorine.

[0040] (ii) In this invention, during the hydrothermal synthesis of molecular sieves, special additives are added to improve the dispersion of active metal components and the specific surface area of ​​dechlorinating agents. During the molding process of the prepared molecular sieve precursor, pore-forming agents, structural aids and molding agents are added and dried and calcined to obtain a porous material with rich pore structure, which greatly improves the adsorption capacity of organochlorine.

[0041] (iii) No alkali metals are introduced in the synthesis process of this invention. At the same time, acid is added during the molding process to reduce the surface active adsorption sites of CO2, olefins and alkanes, thereby improving the selective adsorption capacity of organic chlorine and realizing the selective removal of organic chlorine from complex component raw gas.

[0042] (iv) The organochlorine-specific molecular sieve composite adsorbent prepared by this method adopts the catalytic in-situ absorption mechanism, realizes the absorption and conversion of organochlorines at room temperature and pressure, and achieves deep dechlorination at room temperature. The dechlorination accuracy and efficiency reach the international advanced level.

[0043] (V) In this invention, inexpensive raw materials such as coal gangue powder, kaolin, and montmorillonite, which are low in aluminum and rich in silicon, are used as raw materials for the synthesis of molecular sieves, which greatly reduces the production cost of dechlorination agents. Moreover, the dechlorination agents can be regenerated and reused multiple times in practical applications, and have good industrial application prospects. Attached Figure Description

[0044] Figure 1 This is a schematic diagram of the structure of an evaluation device for a dechlorinating agent for deep removal of organic chlorine from raw gas at room temperature, as described in this invention.

[0045] Figure labels: 1 is a pressure reducing valve for chlorine gas cylinders, 2 is a pressure reducing valve for nitrogen gas cylinders, 3 and 4 are flow meters, 5, 6, 8, 10, 15, 17, 19, and 22 are ball valves, 7 is a gas buffer tank, 9, 16, 18, and 20 are needle valves, 11 is a fixed-bed direct-flow reactor, 12 is a tubular heater, 13 is a constant-temperature water bath heat exchanger, 14 is a back pressure valve, 21 is a gas chromatograph, and 23 and 24 are chloride absorption tanks. Detailed Implementation

[0046] All features disclosed in this specification, or all steps in all disclosed methods or processes, may be combined in any way, except for mutually exclusive features and / or steps.

[0047] Any feature disclosed in this specification (including the claims and abstract) may be replaced by other equivalent or similar features, unless specifically stated otherwise. That is, unless specifically stated otherwise, each feature is merely one example of a series of equivalent or similar features.

[0048] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0049] All ingredients listed below are commercially available products; unless otherwise specified, percentages (%) indicate their mass percentage (wt%).

[0050] The kaolin used in this application is a commercially available product, with its main components being 68% SiO2 and 31% Al2O3, and the total content of effective components being ≥99%.

[0051] The coal gangue powder in this application is commercially available gangue powder that has been calcined at high temperature. Its main components are 75% SiO2 and 24% Al2O3, and the total content of effective components is ≥99%.

[0052] Example 1:

[0053] A method for preparing a dechlorinating agent for deep removal of organochlorine from raw gas at room temperature, wherein the dechlorinating agent comprises a carrier accounting for 70%, active component one accounting for 10%, and active component two accounting for 8%.

[0054] The active additives account for 3%, the structural additives account for 6%, and the molding additives account for 3%, with a total mass percentage of 100%.

[0055] The specific preparation steps are as follows:

[0056] (1) Weigh 100g of kaolin and add 53.6g of alumina to obtain mixture 1. Place mixture 1 in a high-speed ball mill and ball mill at 400r / min for 4h. Pass it through a 400-mesh sieve and then place it in a three-necked flask. Add 15% ethylenediamine at a solid-liquid ratio of 1g / 10ml. Then place the three-necked flask in a 120℃ oil bath and stir at 300r / min for 3h to obtain solid-liquid mixed slurry A1.

[0057] (2) Weigh 82.30 g of copper nitrate trihydrate and dissolve it in 149.11 g of deionized water, then add 21.12 g of ethylene glycol and stir and mix in an 80°C water bath for 4 h to obtain precursor solution B1.

[0058] (3) Add precursor solution B1 to precursor slurry A1 and stir at 70°C for 4 hours. Then, disperse and emulsify the mixture in an ultrasonic water bath at 70°C at a frequency of 60kHz for 4 hours. Then, pour the mixture into a high-temperature and high-pressure reactor and set it to a stirring speed of 600r / min. Heat the mixture to 100°C in 1 hour and keep it at 100°C for 3 hours. Heat the mixture to 180°C in 1 hour and keep it at 180°C for 3 hours. Heat the mixture to 300°C in 1 hour and keep it at 300°C for 6 hours. Cool the mixture to obtain precursor slurry C1.

[0059] (4) The precursor slurry C1 was filtered, pulped and washed three times, then dried at 120°C for 8 hours and calcined at 350°C in air for 4 hours to obtain the precursor D1.

[0060] (5) Weigh 18.69 g of boehmite (loss on ignition of 30%), 6.54 g of guar gum powder, and 4.36 g of polyvinyl alcohol and mechanically dry mix them with precursor D1 in a closed ply mill for 2 h to obtain precursor E1.

[0061] (6) Weigh 91.79 g of chromium nitrate nonahydrate and 16.5 g of cerium nitrate hexahydrate and dissolve them in 60.27 g of deionized water. Then add 13.46 g of nitric acid with a mass concentration of 60% and stir to obtain precursor solution F1. (7) Add precursor solution F1 to a vacuum ply mill and mix it thoroughly with precursor E1. Ply the ply mill for 4 h under an absolute pressure of 0.005 MPa. Then extrude it into strips on a 4 mm round hole die extruder. Dry the extruded material at 120 °C for 8 h and then calcine it in a muffle furnace at 350 °C for 4 h to obtain precursor G1.

[0062] (8) The precursor G1 was placed in a tube furnace and reduced for 10 h at 300 °C and 2% H2 in N2. Then it was cooled to room temperature and passivated for 8 h in a 0.5% O2 atmosphere in N2 to obtain the finished dechlorination agent H1.

[0063] Example 2:

[0064] A method for preparing a dechlorinating agent for deep removal of organochlorine from raw gas at room temperature, wherein,

[0065] In this dechlorination agent, the carrier accounts for 60%, active component one accounts for 15%, active component two accounts for 10%, active additives account for 4%, structural additives account for 10%, and molding additives account for 1%, with a total mass percentage of 100%.

[0066] The specific preparation steps are as follows:

[0067] (1) Weigh 84.85 g of kaolin and add 45.94 g of alumina to obtain mixture 1. Place mixture 1 in a high-speed ball mill and ball mill at 400 r / min for 6 h. Pass it through a 400 mesh sieve and then place it in a three-necked flask. Add 25% ethylenediamine at a solid-liquid ratio of 1 g / 10 ml. Then place the three-necked flask in a 120℃ oil bath and stir at 300 r / min for 3 h to obtain solid-liquid mixed slurry A2.

[0068] (2) Weigh 123.44 g of copper nitrate trihydrate and dissolve it in 183.46 g of deionized water, then add 51.45 g of ethylene glycol and stir and mix in an 80°C water bath for 4 h to obtain precursor solution B2.

[0069] (3) Add precursor solution B2 to precursor slurry A2 and stir at 70°C for 4 hours. Then, disperse and emulsify the mixture in an ultrasonic water bath at 70°C at a frequency of 60kHz for 4 hours. Then, pour the mixture into a high-temperature and high-pressure reactor and set it to a stirring speed of 600r / min. Heat the mixture to 100°C in 1 hour and keep it at 100°C for 3 hours. Heat the mixture to 180°C in 1 hour and keep it at 180°C for 3 hours. Heat the mixture to 300°C in 1 hour and keep it at 300°C for 6 hours. Cool the mixture to obtain precursor slurry C2.

[0070] (4) The precursor slurry C2 was filtered, pulped and washed three times, then dried at 120°C for 8 hours and calcined at 350°C in air for 6 hours to obtain the precursor D2.

[0071] (5) Weigh 31.14 g of boehmite (loss on ignition of 30%), 2.18 g of guar gum powder, and 6.54 g of urea and mechanically dry mix them with precursor D2 in a closed plow mill for 2 h to obtain precursor E2.

[0072] (6) Weigh 114.74 g of chromium nitrate nonahydrate and 22.00 g of cerium nitrate hexahydrate and dissolve them in 45.50 g of deionized water. Then add 22.44 g of nitric acid with a mass concentration of 60% and stir to obtain precursor solution F2. (7) Add precursor solution F2 to a vacuum ply mill and mix it thoroughly with precursor E2. Ply the ply mill for 4 h under an absolute pressure of 0.001 MPa. Then extrude it into strips on a 4 mm round hole die extruder. Dry the extruded material at 120 °C for 8 h and then calcine it in a muffle furnace at 350 °C for 6 h to obtain precursor G2.

[0073] (8) The precursor G2 was placed in a tube furnace and reduced for 10 h at 300 °C and 2% H2 in N2. Then it was cooled to room temperature and passivated for 8 h in a 0.5% O2 atmosphere in N2 to obtain the finished dechlorination agent H2.

[0074] Example 3:

[0075] A method for preparing a dechlorinating agent for deep removal of organochlorine from raw gas at room temperature, wherein,

[0076] In this dechlorination agent, the carrier accounts for 79%, active component one accounts for 5%, and active component two accounts for 5%.

[0077] The active additives account for 1%, the structural additives account for 5%, and the molding additives account for 5%, with a total mass percentage of 100%.

[0078] The specific preparation steps are as follows:

[0079] (1) Weigh 111.73 g of kaolin and add 60.49 g of alumina to obtain mixture 1. Place mixture 1 in a high-speed ball mill and ball mill at 400 r / min for 6 h. Pass it through a 400 mesh sieve and then place it in a three-necked flask. Add 10% ethylenediamine at a solid-liquid ratio of 1 g / 10 ml. Then place the three-necked flask in a 100℃ oil bath and stir at 300 r / min for 3 h to obtain solid-liquid mixed slurry A3.

[0080] (2) Weigh 41.15 g of copper nitrate trihydrate and dissolve it in 103.46 g of deionized water, then add 8.77 g of ethylene glycol. Stir and mix in an 80°C water bath for 4 h to obtain precursor solution B3. Add precursor solution B3 to precursor slurry A3.

[0081] (3) Add precursor solution B3 to precursor slurry A3 and stir at 70°C for 4 hours. Then, disperse and emulsify the mixture in an ultrasonic water bath at 70°C at a frequency of 60kHz for 4 hours. Then, pour the mixture into a high-temperature and high-pressure reactor and set it to a stirring speed of 600r / min. Heat the mixture to 100°C in 1 hour and keep it at 100°C for 3 hours. Heat the mixture to 180°C in 1 hour and keep it at 180°C for 3 hours. Heat the mixture to 300°C in 1 hour and keep it at 300°C for 6 hours. Cool the mixture to obtain precursor slurry C3.

[0082] (4) C3 was filtered, pulped and washed three times, then dried at 120°C for 8 hours and calcined at 350°C in air for 6 hours to obtain precursor D3.

[0083] (5) Weigh 15.57 g of boehmite (loss on ignition of 30%), 10.9 g of guar gum powder, 2.18 g of polyvinyl alcohol and precursor D3 and mechanically dry mix them with precursor D3 in a closed ply mill for 2 h to obtain precursor E3.

[0084] (6) Weigh 57.37 g of chromium nitrate nonahydrate and 5.50 g of cerium nitrate hexahydrate and dissolve them in 78.62 g of deionized water. Then add 11.22 g of nitric acid with a mass concentration of 60% and stir to obtain precursor solution F3. (7) Add precursor solution F3 to a vacuum ply mill and mix it thoroughly with precursor E3. Ply the ply mill for 4 h under an absolute pressure of 0.01 MPa. Then extrude it into strips on a 4 mm round hole die extruder. Dry the extruded material at 120 °C for 8 h and then calcine it in a muffle furnace at 350 °C for 6 h to obtain precursor G3.

[0085] (8) The precursor G3 was placed in a tube furnace and reduced for 10 h at 300 °C and 2% H2 in N2. Then it was cooled to room temperature and passivated for 8 h in a 0.5% O2 atmosphere in N2 to obtain the finished dechlorination agent H3.

[0086] Example 4:

[0087] A method for preparing a dechlorinating agent for deep removal of organochlorine from raw gas at room temperature, wherein,

[0088] In this dechlorination agent, the carrier accounts for 70%, active component one accounts for 8%, and active component two accounts for 8%.

[0089] The active additives account for 3%, the structural additives account for 8%, and the molding additives account for 3%, with a total mass percentage of 100%.

[0090] The specific preparation steps are as follows:

[0091] (1) Weigh 100g of kaolin and add 53.6g of alumina to obtain mixture 1. Place mixture 1 in a high-speed ball mill and ball mill at 400r / min for 6h. Pass it through a 400-mesh sieve and then place it in a three-necked flask. Add 15% ethylenediamine at a solid-liquid ratio of 1g / 5ml. Then place the three-necked flask in a 120℃ oil bath and stir at 300r / min for 3h to obtain solid-liquid slurry A4.

[0092] (2) Weigh 32.92 g of copper nitrate trihydrate and 39.68 g of zinc nitrate hexahydrate and dissolve them in 118.61 g of deionized water. Then add 16.01 g of ethylene glycol and stir and mix in an 80°C water bath for 4 h to obtain precursor solution B4.

[0093] (3) Add precursor solution B4 to precursor slurry A4 and stir at 70°C for 4 hours. Then, disperse and emulsify the mixture in an ultrasonic water bath at 70°C at a frequency of 70kHz for 4 hours. Then, pour the mixture into a high-temperature and high-pressure reactor and set it to a stirring speed of 600r / min. Heat the mixture to 100°C in 1 hour and keep it at 100°C for 3 hours. Heat the mixture to 180°C in 1 hour and keep it at 180°C for 3 hours. Heat the mixture to 300°C in 1 hour and keep it at 300°C for 6 hours. Cool the mixture to obtain precursor slurry C4.

[0094] (4) C4 was filtered, pulped and washed three times, then dried at 120°C for 8 hours and calcined at 350°C in air for 6 hours to obtain precursor D4.

[0095] (5) Weigh 24.91 g of boehmite (loss on ignition of 30%), 6.54 g of graphite, and 4.36 g of urea and mechanically dry mix them with precursor D4 in a closed ply mill for 2 h to obtain precursor E4.

[0096] (6) Weigh 97.79 g of chromium nitrate nonahydrate and 16.5 g of cerium nitrate hexahydrate and dissolve them in 58.47 g of deionized water. Then add 17.95 g of nitric acid with a mass concentration of 60% and stir to obtain precursor solution F4. (7) Add precursor solution F4 to a vacuum ply mill and mix it thoroughly with precursor E4. Ply the ply mill for 4 h under an absolute pressure of 0.005 MPa. Then extrude the ply mill on a 4 mm round die extruder. Dry the extruded material at 120 °C for 8 h and then calcine it in a muffle furnace at 350 °C for 6 h to obtain precursor G4.

[0097] (8) The precursor G4 was placed in a tube furnace and reduced for 10 h at 300 °C and 2% H2 in N2. Then it was cooled to room temperature and passivated for 8 h in a 0.5% O2 atmosphere in N2 to obtain the finished dechlorination agent H4.

[0098] Example 5:

[0099] A method for preparing a dechlorinating agent for deep removal of organochlorine from raw gas at room temperature, wherein,

[0100] In this dechlorination agent, the carrier accounts for 70%, active component one accounts for 8%, and active component two accounts for 8%.

[0101] The active additives account for 3%, the structural additives account for 8%, and the molding additives account for 3%, with a total mass percentage of 100%.

[0102] The specific preparation steps are as follows:

[0103] (1) Weigh 100g of coal gangue powder and add 79.5g of alumina to obtain mixture 1. Place mixture 1 in a high-speed ball mill and ball mill at 400r / min for 6h. Pass it through a 400-mesh sieve and then place it in a three-necked flask. Add 15% ethylenediamine at a solid-liquid ratio of 1g / 10ml. Then place the three-necked flask in a 120℃ oil bath and stir at 300r / min for 3h to obtain solid-liquid mixed slurry A5.

[0104] (2) Weigh 38.51 g of copper nitrate trihydrate and 46.41 g of zinc nitrate hexahydrate and dissolve them in 138.7 g of deionized water. Then add 19.55 g of ethylene glycol and stir and mix in an 80°C water bath for 4 h to obtain precursor solution B5.

[0105] (3) Add precursor solution B5 to precursor slurry A5 and stir at 70°C for 4 hours. Then, disperse and emulsify the mixture in an ultrasonic water bath at 70°C at a frequency of 50kHz for 6 hours. Then, pour the mixture into a high-temperature and high-pressure reactor and set it to a stirring speed of 600r / min. Heat the mixture to 100°C for 1 hour and keep it at 100°C for 3 hours. Heat the mixture to 180°C for 1 hour and keep it at 180°C for 3 hours. Heat the mixture to 300°C for 1 hour and keep it at 300°C for 6 hours. Cool the mixture to obtain precursor slurry C5.

[0106] (4) C5 was filtered, pulped and washed three times, then dried at 120°C for 8 hours and calcined at 350°C in air for 6 hours to obtain precursor D5.

[0107] (5) Weigh 27.2 g of boehmite (loss on ignition of 30%), 7.14 g of guar gum powder, 4.76 g of polyethylene glycol and precursor D5 and mechanically dry mix them in a closed ply mill for 2 h to obtain precursor E5.

[0108] (6) Weigh 107.36 g of chromium nitrate nonahydrate and 19.30 g of cerium nitrate hexahydrate and dissolve them in 68.40 g of deionized water. Then add 21 g of nitric acid with a mass concentration of 60% and stir to obtain precursor solution F5.

[0109] (7) Add the precursor solution F5 to the vacuum plow and mix it thoroughly with the precursor E5. Plow the plow for 4 hours under an absolute pressure of 0.005 MPa. Then, extrude it into strips on a 4 mm round hole die extruder. Dry the extruded material at 120°C for 8 hours. Then, place it in a muffle furnace and calcine it at 350°C for 6 hours to obtain the precursor G5.

[0110] (8) The precursor G5 was placed in a tube furnace and reduced for 10 h at 350 °C and 2% H2 in N2. Then it was cooled to room temperature and passivated for 8 h in a 0.5% O2 atmosphere in N2 to obtain the finished dechlorination agent H5.

[0111] Example 6:

[0112] A method for preparing a dechlorinating agent for deep removal of organochlorine from raw gas at room temperature, wherein,

[0113] In this dechlorination agent, the carrier accounts for 70%, active component one accounts for 8%, and active component two accounts for 8%.

[0114] The active additives account for 3%, the structural additives account for 8%, and the molding additives account for 3%, with a total mass percentage of 100%.

[0115] The specific preparation steps are as follows:

[0116] (1) Weigh 100g of kaolin and add 53.6g of alumina to obtain mixture 1. Place mixture 1 in a high-speed ball mill and ball mill at 400r / min for 6h. Pass it through a 400-mesh sieve and then place it in a three-necked flask. Add 15% ethylenediamine at a solid-liquid ratio of 1g / 10ml. Then place the three-necked flask in a 120℃ oil bath and stir at 300r / min for 3h to obtain solid-liquid mixed slurry A6.

[0117] (2) Weigh 99.77 g of zinc nitrate hexahydrate and dissolve it in 148.29 g of deionized water, then add 20.79 g of ethylene glycol and stir and mix in an 80°C water bath for 4 h to obtain precursor solution B6.

[0118] (3) Add precursor solution B6 to precursor slurry A6 and stir at 70°C for 4 hours. Then, disperse and emulsify the mixture in an ultrasonic water bath at 70°C at a frequency of 60kHz for 6 hours. Then, pour the mixture into a high-temperature and high-pressure reactor and set it to a stirring speed of 600r / min. Heat the mixture to 100°C for 1 hour and keep it at 100°C for 3 hours. Heat the mixture to 180°C for 1 hour and keep it at 180°C for 3 hours. Heat the mixture to 300°C for 1 hour and keep it at 300°C for 6 hours. Cool the mixture to obtain precursor slurry C6.

[0119] (4) C6 was filtered, pulped and washed three times, then dried at 120°C for 8 hours and calcined at 400°C in air for 6 hours to obtain precursor D6.

[0120] (5) Weigh 24.91 g of boehmite (loss on ignition of 30%), 6.54 g of guar gum powder, and 4.36 g of polyvinyl alcohol and mechanically dry mix them with precursor D6 in a closed ply mill for 2 h to obtain precursor E6.

[0121] (6) Weigh 92.71 g of ferric nitrate nonahydrate and 22.79 g of zirconium nitrate pentahydrate and dissolve them in 50.61 g of deionized water. Then add 35.93 g of oxalic acid with a mass concentration of 60% and stir to obtain precursor solution F6. (7) Add precursor solution F6 to a vacuum pumice machine and mix it thoroughly with precursor E6. Pumice for 4 h under an absolute pressure of 0.005 MPa. Then extrude it on a 4 mm round hole die extruder. Dry the extruded material at 120 °C for 8 h and then calcine it in a muffle furnace at 400 °C for 6 h to obtain precursor G6.

[0122] (8) The precursor G6 was placed in a tube furnace and reduced for 10 h at 350 °C and 2% H2 in N2. Then it was cooled to room temperature and passivated for 8 h in a 0.5% O2 atmosphere in N2 to obtain the finished dechlorination agent H6.

[0123] Example 7:

[0124] A method for preparing a dechlorinating agent for deep removal of organochlorine from raw gas at room temperature, wherein the dechlorinating agent comprises a carrier accounting for 70%, active component one accounting for 10%, and active component two accounting for 6%.

[0125] The active additives account for 3%, the structural additives account for 8%, and the molding additives account for 3%, with a total mass percentage of 100%.

[0126] The specific preparation steps are as follows:

[0127] (1) Weigh 100g of kaolin and add 69.36g of aluminum hydroxide trihydrate to obtain mixture 1. Place mixture 1 in a high-speed ball mill and ball mill at 400r / min for 6h. Pass it through a 400-mesh sieve and then place it in a three-necked flask. Add 15% ethylenediamine at a solid-liquid ratio of 1g / 10ml. Then place the three-necked flask in a 120℃ oil bath and stir at 300r / min for 3h to obtain solid-liquid mixed slurry A7.

[0128] (2) Weigh 32.92 g of copper nitrate trihydrate, 39.68 g of zinc nitrate hexahydrate and 21.60 g of nickel nitrate hexahydrate and dissolve them in 150.29 g of deionized water. Then add 26.17 g of 1,2-propanediol and stir in an 80°C water bath for 4 h to obtain precursor solution B7.

[0129] (3) Add precursor solution B7 to precursor slurry A7 and stir at 70°C for 4 hours. Then, disperse and emulsify the mixture in an ultrasonic water bath at 70°C at a frequency of 60kHz for 4 hours. Then, pour the mixture into a high-temperature and high-pressure reactor and set it to a stirring speed of 600r / min. Heat the mixture to 100°C in 1 hour and keep it at 100°C for 3 hours. Heat the mixture to 180°C in 1 hour and keep it at 180°C for 3 hours. Heat the mixture to 300°C in 1 hour and keep it at 300°C for 6 hours. Cool the mixture to obtain precursor slurry C7.

[0130] (4) C7 was filtered, pulped and washed three times, then dried at 120°C for 8 hours and calcined at 350°C in air for 6 hours to obtain precursor D7.

[0131] (5) Weigh 24.91 g of boehmite (loss on ignition of 30%), 6.54 g of guar gum powder, and 4.36 g of urea and mechanically dry mix them with precursor D7 in a closed plow mill for 2 h to obtain precursor E7.

[0132] (6) Weigh 45.91 g of cobalt nitrate hexahydrate and 17.38 g of lanthanum nitrate hexahydrate and dissolve them in 74.20 g of deionized water. Then add 17.95 g of nitric acid with a mass concentration of 60% and stir to obtain precursor solution F7. (7) Add precursor solution F7 to a vacuum ply mill and mix it thoroughly with precursor E7. Ply the ply mill for 4 h under an absolute pressure of 0.005 MPa. Then extrude the ply mill on a 4 mm round die extruder. Dry the extruded material at 120 °C for 8 h and then calcine it in a muffle furnace at 350 °C for 6 h to obtain precursor G7.

[0133] (8) The precursor G7 was placed in a tube furnace and reduced for 10 h at 350 °C and 2% H2 in N2. Then it was cooled to room temperature and passivated for 8 h in a 0.5% O2 atmosphere in N2 to obtain the finished dechlorination agent H7.

[0134] Example 8:

[0135] A method for preparing a dechlorinating agent for deep removal of organochlorine from raw gas at room temperature, wherein the carrier accounts for 70% of the dechlorinating agent, active component one accounts for 10%, and active component two accounts for 5%.

[0136] The active additives account for 3%, the structural additives account for 8%, and the molding additives account for 3%, with a total mass percentage of 100%.

[0137] The specific preparation steps are as follows:

[0138] (1) Weigh 100g of kaolin and add 53.6g of alumina to obtain mixture 1. Place mixture 1 in a high-speed ball mill and ball mill at 400r / min for 6h. Pass it through a 400-mesh sieve and then place it in a three-necked flask. Add 15% phenylethylamine at a solid-liquid ratio of 1g / 10ml. Then place the three-necked flask in a 120℃ oil bath and stir at 300r / min for 3h to obtain solid-liquid mixed slurry A8.

[0139] (2) Weigh 82.30 g of copper nitrate trihydrate and dissolve it in 149.1 g of deionized water, then add 31.37 g of glycerol and stir in an 80°C water bath for 4 h to obtain precursor solution B8.

[0140] (3) Add precursor solution B8 to precursor slurry A8 and stir at 70°C for 4 hours. Then, disperse and emulsify the mixture in an ultrasonic water bath at 70°C at a frequency of 60kHz for 4 hours. Then, pour the mixture into a high-temperature and high-pressure reactor and set it to a stirring speed of 600r / min. Heat the mixture to 100°C in 1 hour and keep it at 100°C for 3 hours. Heat the mixture to 180°C in 1 hour and keep it at 180°C for 3 hours. Heat the mixture to 300°C in 1 hour and keep it at 300°C for 6 hours. Cool the mixture to obtain precursor slurry C8.

[0141] (4) C8 was filtered, pulped and washed three times, then dried at 120°C for 8 hours and calcined at 350°C in air for 6 hours to obtain precursor D8.

[0142] (5) Weigh 24.91 g of boehmite (loss on ignition of 30%), 6.54 g of magnesium stearate, 6.54 g of polyvinyl alcohol and precursor D8 and mechanically dry mix them in a closed ply mill for 2 h to obtain precursor E8.

[0143] (6) Weigh 55.05 g of ferric nitrate nonahydrate and 16.50 g of cerium nitrate hexahydrate and dissolve them in 76.14 g of deionized water. Then add 17.95 g of nitric acid with a mass concentration of 60% and stir to obtain precursor solution F8. (7) Add precursor solution F8 to a vacuum ply mill and mix it thoroughly with precursor E8. Ply the ply mill for 4 h under an absolute pressure of 0.005 MPa. Then extrude the ply mill on a 3 mm round hole die extruder. Dry the extruded material at 120 °C for 8 h and then calcine it in a muffle furnace at 350 °C for 6 h to obtain precursor G8.

[0144] (8) The precursor G8 was placed in a tube furnace and reduced for 10 h at 300 °C and 2% H2 in N2. Then it was cooled to room temperature and passivated for 8 h in a 0.5% O2 atmosphere in N2 to obtain the finished dechlorination agent H8.

[0145] Example 9:

[0146] A method for preparing a dechlorinating agent for deep removal of organochlorine from raw gas at room temperature, wherein,

[0147] In this dechlorination agent, the carrier accounts for 70%, active component one accounts for 8%, and active component two accounts for 8%.

[0148] The active additives account for 3%, the structural additives account for 8%, and the molding additives account for 3%, with a total mass percentage of 100%.

[0149] The specific preparation steps are as follows:

[0150] (1) Weigh 100g of kaolin and add 53.6g of alumina to obtain mixture 1. Place mixture 1 in a high-speed ball mill and ball mill at 400r / min for 6h. Pass it through a 400-mesh sieve and then place it in a three-necked flask. Add 15% ethylenediamine at a solid-liquid ratio of 1g / 20ml. Then place the three-necked flask in a 120℃ oil bath and stir at 300r / min for 3h to obtain solid-liquid mixed slurry A9.

[0151] (2) Weigh 65.84 g of copper nitrate trihydrate and dissolve it in 204.48 g of deionized water, then add 16.89 g of ethylene glycol and stir and mix in an 80°C water bath for 4 h to obtain precursor solution B9.

[0152] (3) Add precursor solution B9 to precursor slurry A9 and stir at 70°C for 4 hours. Then, disperse and emulsify the mixture in an ultrasonic water bath at 70°C at a frequency of 60kHz for 4 hours. Then, pour the mixture into a high-temperature and high-pressure reactor and set it to a stirring speed of 600r / min. Heat the mixture to 100°C in 1 hour and keep it at 100°C for 3 hours. Heat the mixture to 180°C in 1 hour and keep it at 180°C for 3 hours. Heat the mixture to 300°C in 1 hour and keep it at 300°C for 6 hours. Cool the mixture to obtain precursor slurry C9.

[0153] (4) C9 was filtered, pulped and washed three times, then dried at 120°C for 8 hours and calcined at 350°C in air for 6 hours to obtain precursor D9.

[0154] (5) Weigh 24.19 g of boehmite (loss on ignition of 30%), 6.54 g of guar gum powder, 6.54 g of polyvinyl alcohol and precursor D9 and mechanically dry mix them with precursor E9 in a closed ply mill for 2 h to obtain precursor E9.

[0155] (6) Weigh 71.83 g of manganese nitrate solution (50% mass concentration) and 16.50 g of cerium nitrate hexahydrate and dissolve them in 61.79 g of deionized water. Then add 17.95 g of nitric acid with a mass concentration of 60% and stir to obtain precursor solution F9.

[0156] (7) Add the precursor solution F9 to the vacuum ply mill and mix it thoroughly with the precursor E9. Ply the ply for 4 hours under an absolute pressure of 0.005 MPa. Then, extrude the ply into strips on a 3 mm round hole die extruder. Dry the extruded material at 120°C for 8 hours. Then, place it in a muffle furnace and calcine it at 350°C for 6 hours to obtain the precursor G9.

[0157] (8) The precursor G9 was placed in a tube furnace and reduced for 10 h at 300 °C and 2% H2 in N2. Then it was cooled to room temperature and passivated for 8 h in a 0.5% O2 atmosphere in N2 to obtain the finished dechlorination agent H9.

[0158] Example 10:

[0159] A method for preparing a dechlorinating agent for deep removal of organochlorine from raw gas at room temperature, wherein,

[0160] In this dechlorination agent, the carrier accounts for 70%, active component one accounts for 8%, and active component two accounts for 8%.

[0161] The active additives account for 3%, the structural additives account for 10%, and the molding additives account for 1%, with a total mass percentage of 100%.

[0162] The specific preparation steps are as follows:

[0163] (1) Weigh 100g of kaolin and add 50.2g of alumina to obtain mixture 1. Place mixture 1 in a high-speed ball mill and ball mill at 400r / min for 6h. Pass it through a 400-mesh sieve and then place it in a three-necked flask. Add ammonia water with a mass concentration of 15% according to the solid-liquid ratio of 1g / 10ml. Then place the three-necked flask in a 120℃ oil bath and stir at 300r / min for 3h to obtain solid-liquid mixed slurry A10.

[0164] (2) Weigh 65.84 g of copper nitrate trihydrate and dissolve it in 76.68 g of deionized water, then add 16.90 g of ethylene glycol and stir and mix in an 80°C water bath for 4 h to obtain precursor solution B10.

[0165] (3) Add precursor solution B10 to precursor slurry A10 and stir at 70°C for 4 hours. Then, disperse and emulsify the mixture in an ultrasonic water bath at 70°C at a frequency of 60kHz for 4 hours. Then, pour the mixture into a high-temperature and high-pressure reactor and set it to a stirring speed of 600r / min. Heat the mixture to 100°C in 1 hour and keep it at 100°C for 3 hours. Heat the mixture to 180°C in 1 hour and keep it at 180°C for 3 hours. Heat the mixture to 300°C in 1 hour and keep it at 300°C for 6 hours. Cool the mixture to obtain precursor slurry C10.

[0166] (4) C10 was filtered, pulped and washed three times, then dried at 120°C for 8 hours and calcined at 350°C in air for 6 hours to obtain precursor D10.

[0167] (5) Weigh 31.14 g of boehmite (loss on ignition of 30%), 2.18 g of guar gum powder, and 6.54 g of polyvinyl alcohol and mechanically dry mix them with precursor D10 in a closed ply mill for 2 h to obtain precursor E10.

[0168] (6) Weigh 91.79 g of chromium nitrate nonahydrate and 16.50 g of cerium nitrate hexahydrate and dissolve them in 56.68 g of deionized water. Then add 22.44 g of nitric acid with a mass concentration of 60% and stir to obtain precursor solution F10. (7) Add precursor solution F10 to a vacuum ply mill and mix it thoroughly with precursor E10. Ply the ply mill for 4 h under an absolute pressure of 0.005 MPa. Then extrude the ply into strips on a 3 mm round hole die extruder. Dry the extruded material at 120 °C for 8 h and then calcine it in a muffle furnace at 350 °C for 6 h to obtain precursor G10.

[0169] (8) The precursor G10 was placed in a tube furnace and reduced for 10 h at 300 °C and 2% H2 in N2. Then it was cooled to room temperature and passivated for 8 h in a 0.5% O2 atmosphere in N2 to obtain the finished dechlorination agent H10.

[0170] Comparative Example 1:

[0171] A method for preparing a dechlorination agent, wherein,

[0172] In this dechlorination agent, the carrier accounts for 70%, active component one accounts for 4%, and active component two accounts for 11%.

[0173] The active additives account for 0.5%, the structural additives account for 11%, and the molding additives account for 3.5%, with a total mass percentage of 100%.

[0174] The specific preparation steps are as follows:

[0175] (1) Weigh 100g of kaolin and add 53.6g of alumina to obtain mixture 1. Place mixture 1 in a high-speed ball mill and ball mill at 400r / min for 6h. Pass it through a 400-mesh sieve and then place it in a three-necked flask. Add 15% ethylenediamine at a solid-liquid ratio of 1g / 10ml. Then place the three-necked flask in a 120℃ oil bath and stir at 300r / min for 3h to obtain solid-liquid mixed slurry A11.

[0176] (2) Weigh 32.92 g of copper nitrate trihydrate and dissolve it in 59.64 g of deionized water, then add 8.45 g of ethylene glycol and stir and mix in an 80°C water bath for 4 h to obtain precursor solution B11.

[0177] (3) Add precursor solution B11 to precursor slurry A11 and stir at 70°C for 4 hours. Then, disperse and emulsify the mixture in an ultrasonic water bath at 70°C at a frequency of 60kHz for 4 hours. Then, pour the mixture into a high-temperature and high-pressure reactor and set it to a stirring speed of 600r / min. Heat the mixture to 100°C in 1 hour and keep it at 100°C for 3 hours. Heat the mixture to 180°C in 1 hour and keep it at 180°C for 3 hours. Heat the mixture to 300°C in 1 hour and keep it at 300°C for 6 hours. Cool the mixture to obtain precursor slurry C11.

[0178] (4) C11 was filtered, pulped and washed three times, then dried at 120°C for 8 hours and calcined at 350°C in air for 6 hours to obtain precursor D11.

[0179] (5) Weigh 34.26 g of boehmite (loss on ignition of 30%), 7.63 g of guar gum powder, and 6.54 g of polyvinyl alcohol and mechanically dry mix them with precursor D11 in a closed ply mill for 2 h to obtain precursor E11.

[0180] (6) Weigh 126.2 g of chromium nitrate nonahydrate and 19.25 g of cerium nitrate hexahydrate and dissolve them in 40.38 g of deionized water. Then add 22.69 g of nitric acid with a mass concentration of 60% and stir to obtain precursor solution F11. (7) Add precursor solution F11 to a vacuum ply mill and mix it thoroughly with precursor E11. Ply the ply mill for 4 h under an absolute pressure of 0.005 MPa. Then extrude the ply into strips on a 3 mm round hole die extruder. Dry the extruded material at 120 °C for 8 h and then calcine it in a muffle furnace at 350 °C for 6 h to obtain precursor G11.

[0181] (8) The precursor G11 was placed in a tube furnace and reduced for 10 h at 300 °C and 2% H2 in N2. Then it was cooled to room temperature and passivated for 8 h in a 0.5% O2 atmosphere in N2 to obtain the finished dechlorination agent H11.

[0182] Comparative Example 2:

[0183] A method for preparing a dechlorination agent, wherein,

[0184] In this dechlorination agent, the carrier accounts for 58%, active component one accounts for 16%, and active component two accounts for 8%.

[0185] The active additives account for 3%, the structural additives account for 8%, and the molding additives account for 7%, with a total mass percentage of 100%.

[0186] The specific preparation steps are as follows:

[0187] (1) Weigh 82.02 g of kaolin and add 53.6 g of alumina to obtain mixture 1. Place mixture 1 in a high-speed ball mill and ball mill at 400 r / min for 6 h. Pass it through a 400 mesh sieve and then place it in a three-necked flask. Add 15% ethylenediamine at a solid-liquid ratio of 1 g / 10 ml. Then place the three-necked flask in a 120℃ oil bath and stir at 300 r / min for 3 h to obtain solid-liquid mixed slurry A12.

[0188] (2 Weigh 131.67 g of copper nitrate trihydrate and dissolve it in 238.56 g of deionized water, then add 8.45 g of ethylene glycol and stir and mix in an 80°C water bath for 4 h to obtain precursor solution B12.

[0189] (3) Add precursor solution B12 to precursor slurry A12 and stir at 70°C for 4 hours. Then, disperse and emulsify the mixture in an ultrasonic water bath at 70°C at a frequency of 60kHz for 4 hours. Then, pour the mixture into a high-temperature and high-pressure reactor and set it to a stirring speed of 600r / min. Heat the mixture to 100°C in 1 hour and keep it at 100°C for 3 hours. Heat the mixture to 180°C in 1 hour and keep it at 180°C for 3 hours. Heat the mixture to 300°C in 1 hour and keep it at 300°C for 6 hours. Cool the mixture to obtain precursor slurry C12.

[0190] (4) C12 was filtered, pulped and washed three times, then dried at 120°C for 8 hours and calcined at 350°C in air for 6 hours to obtain precursor D12.

[0191] (5) Weigh 24.91 g of boehmite (loss on ignition of 30%), 15.26 g of guar gum powder, and 6.54 g of polyvinyl alcohol and mechanically dry mix them with precursor D12 in a closed ply mill for 2 h to obtain precursor E12.

[0192] (6) Weigh 91.88 g of chromium nitrate nonahydrate and 16.50 g of cerium nitrate hexahydrate and dissolve them in 58.47 g of deionized water. Then add 17.95 g of nitric acid with a mass concentration of 60% and stir to obtain precursor solution F12. (7) Add precursor solution F12 to a vacuum pumice machine and mix it thoroughly with precursor E12. Pumice the pumice for 4 h under an absolute pressure of 0.005 MPa. Then extrude it into strips on a 3 mm round hole die extruder. Dry the extruded material at 120 °C for 8 h and then calcine it in a muffle furnace at 350 °C for 6 h to obtain precursor G12.

[0193] (8) The precursor G12 was placed in a tube furnace and reduced for 10 h at 300 °C and 2% H2 in N2. Then it was cooled to room temperature and passivated for 8 h in a 0.5% O2 atmosphere in N2 to obtain the finished dechlorination agent H12.

[0194] Comparative Example 3:

[0195] A method for preparing a dechlorination agent, wherein,

[0196] In this dechlorination agent, the carrier accounts for 81%, active component one accounts for 8%, and active component two accounts for 5%.

[0197] The active additives account for 1%, the structural additives account for 4%, and the molding additives account for 1%, with a total mass percentage of 100%.

[0198] The specific preparation steps are as follows:

[0199] (1) Weigh 115.97 g of kaolin and add 53.6 g of alumina to obtain mixture 1. Place mixture 1 in a high-speed ball mill and ball mill at 400 r / min for 6 h. Pass it through a 400 mesh sieve and then place it in a three-necked flask. Add 15% ethylenediamine at a solid-liquid ratio of 1 g / 10 ml. Then place the three-necked flask in a 120℃ oil bath and stir at 300 r / min for 3 h to obtain solid-liquid mixed slurry A13.

[0200] (2) Weigh 65.84 g of copper nitrate trihydrate and dissolve it in 119.28 g of deionized water, then add 16.90 g of ethylene glycol and stir and mix in an 80°C water bath for 4 h to obtain precursor solution B13.

[0201] (3) Add precursor solution B13 to precursor slurry A13 and stir at 70°C for 4 hours. Then, disperse and emulsify the mixture in an ultrasonic water bath at 70°C at a frequency of 60kHz for 4 hours. Then, pour the mixture into a high-temperature and high-pressure reactor and set it to a stirring speed of 600r / min. Heat the mixture to 100°C in 1 hour and keep it at 100°C for 3 hours. Heat the mixture to 180°C in 1 hour and keep it at 180°C for 3 hours. Heat the mixture to 300°C in 1 hour and keep it at 300°C for 6 hours. Cool the mixture to obtain precursor slurry C13.

[0202] (4) C13 was filtered, pulped and washed three times, then dried at 120°C for 8 hours and calcined at 350°C in air for 6 hours to obtain precursor D13.

[0203] (5) Weigh 24.91 g of boehmite (loss on ignition of 30%), 2.18 g of guar gum powder, and 6.54 g of polyvinyl alcohol and mechanically dry mix them with precursor D13 in a closed ply mill for 2 h to obtain precursor E13.

[0204] (6) Dissolve 57.37 g of chromium nitrate nonahydrate and 5.50 g of cerium nitrate hexahydrate in 75.92 g of deionized water, then add 17.95 g of nitric acid with a mass concentration of 60%, stir and mix to obtain precursor solution F13.

[0205] (7) Add the precursor solution F13 to the vacuum ply mill and mix it thoroughly with the precursor E13. Ply the ply for 4 hours under an absolute pressure of 0.005 MPa. Then, extrude the ply into strips on a 3 mm round hole die extruder. Dry the extruded material at 120°C for 8 hours. Then, place it in a muffle furnace and calcine it at 350°C for 6 hours to obtain the precursor G13.

[0206] (8) The precursor G13 was placed in a tube furnace and reduced for 10 h at 300 °C and 2% H2 in N2. Then it was cooled to room temperature and passivated for 8 h in a 0.5% O2 atmosphere in N2 to obtain the finished dechlorination agent H13.

[0207] The operation steps of the evaluation device are as follows:

[0208] 1. Dechlorination agent loading: Crush the formed dechlorination agent into particles of 3-4 mm size, weigh 30 mL (m0) and load it into a straight-through (fixed bed) reactor 14 with an inner diameter of 19 mm.

[0209] 2. Air tightness test: After installing reactor 11, close ball valves 5, 8, and 17, open ball valves 10 and 19, open needle valve 20, open nitrogen cylinder pressure reducing valve 2, adjust gas mass flow meter 4 and back pressure valve 14 until the system pressure reaches 3MPa, close gas mass flow meter 4, use soap bubbles to test the air tightness of the system, and after checking that there is no leakage, open back pressure valve 114 to purge nitrogen.

[0210] 3. Test for organochlorine concentration in raw material gas:

[0211] Close ball valves 10 and 17, open ball valve 8, open pressure reducing valve 1 on the chlorine gas cylinder, adjust gas mass flow meter 3, and slowly open needle valve 9 to adjust the airflow so that continuous and uniform bubbles emerge from the washing bottle. The actual concentration of organic chlorine C0 in the gas is obtained by testing with gas colorimeter 21.

[0212] 4. Penetration Chlorine Capacity Test: After step 3 is completed, close ball valve 8, open ball valves 17, 19, and 22, open needle valves 18 and 20, adjust gas mass flow meter 3 and back pressure valve 14 until the system pressure reaches 1 MPa, and when the tail gas absorption bottle can continuously and uniformly bubble, record time t0 and gas flow rate L1. Analyze the outlet concentration and record the bed temperature T1 every hour. When the outlet organic chlorine concentration is higher than 10 ppb, stop the experiment, record time t1, and weigh the dechlorinating agent m1.

[0213] 5. Dechlorinating agent regeneration: After the test, the system pressure is released to atmospheric pressure through the back pressure valve 14, then nitrogen is introduced, and then the temperature of the heating furnace 12 is raised to 300℃. The organic chlorine content at the outlet is analyzed by gas chromatography 21 every 1 hour. When the organic chlorine content is zero, the regeneration can be considered to be over.

[0214] 6. Formula for calculating the penetration chlorine capacity Y1:

[0215]

[0216] L1: Hourly gas flow rate, unit: Nm³ 3 / h.

[0217] t1~t0: running time, in hours.

[0218] C0: The concentration of the feed gas, in mg / Nm³. 3 .

[0219] m0: Initial concentration, in g.

[0220] 7. Composition of raw gas containing organochlorine:

[0221] (1) 200 ppm of chloromethane, unit, other components: CO2 concentration of 10%, CO content of 15%, CH4 content of 10%, C2-C5 alkanes: 3%, the remainder is nitrogen.

[0222] (2) Trichloroethylene 150ppm, other components: CO2 concentration 10%, CO content 15%, CH4 content 10%, C2~C5 alkanes: 3%, the remainder is nitrogen.

[0223] (3) 100 ppm of monochlorobenzene, the remaining components are: 10% CO2 concentration, 15% CO content, 10% CH4 content, 3% C2-C5 alkanes, and the remainder is nitrogen.

[0224] 8. Test conditions: reaction temperature 30℃, test space velocity 4000h -1 The test pressure was 1 MPa.

[0225] Table 1. Results of Dechlorinating Agent Performance Tests

[0226]

[0227]

[0228] The embodiments described above merely illustrate specific implementation methods of this application, and while the descriptions are detailed and specific, they should not be construed as limiting the scope of protection of this application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the technical solution of this application, and these modifications and improvements all fall within the scope of protection of this application.

[0229] This background section is provided to generally present the context of the invention. The work of the currently named inventors, the work to the extent described in this background section, and aspects of this section that did not constitute prior art at the time of application are neither expressly nor impliedly acknowledged as prior art to the invention.

Claims

1. A method for preparing a dechlorinating agent for deep removal of organochlorine from raw gas at room temperature, characterized in that, The dechlorination agent comprises the following raw materials by weight percentage: 60-80% carrier, 5-15% active component one, 5-10% active component two, 1-5% active additive, 5-10% structural additive, and 1-5% molding additive, with a total weight percentage of 100%. The carrier is a molecular sieve carrier synthesized from any one or more silicon-rich and aluminum-poor materials by adding an aluminum source. Active component one is a composition of any one or more of Cu, Zn, and Ni. Active component two is a composition of any one or more of Cr2O3, MnO2, Co2O3, Fe2O3, Bi2O3, and MoO3. The active additive is a composition of any one or more of CeO2, ZrO2, and La2O3. The structural additive is a composition of any one or more of TiO2, Sb2O3, and Al2O3. The preparation method includes the following steps: (1) Weigh an appropriate amount of silicon-rich and aluminum-poor material, add a certain amount of aluminum source to obtain a mixture; place the mixture in a high-speed ball mill for ball milling, and then place it in a three-necked flask; then add non-metallic alkali solution, and then place the three-necked flask in an oil bath at 80~150℃, and stir and mix at a speed of 100~400r / min for 1~5h to obtain solid-liquid mixed slurry A; (2) Weigh a certain amount of the soluble salt of active component one and dissolve it in an appropriate amount of deionized water to prepare a salt solution. Then add the in-situ synthesized metal nano-additive. The molar ratio of active component one to the in-situ synthesized metal nano-additive is 1:0.2~2. Then stir and mix the material in a water bath at 60~80℃ for 2~6h to obtain precursor solution B. (3) Add precursor solution B to precursor slurry A and stir in a water bath at 60~80℃ for 3~12h. Then, disperse and emulsify in an ultrasonic water bath at 60~80℃ at a frequency of 50~80kHz for 2~8h. Then, pour the mixture into a high-temperature and high-pressure reactor and age it at a stirring speed of 200~1000r / min to obtain precursor slurry C. (4) The precursor slurry C is filtered, pulped and washed three times, then dried at 100~150℃ for 3~12h, and calcined at 400~600℃ in air for 2~8h to obtain the precursor D; (5) Weigh a certain amount of molding aid, structural aid, pore-forming agent and precursor D and mechanically mix them in a closed ply mill for 1-3 hours to obtain precursor E; (6) Weigh a certain amount of the soluble salt of active component II and the soluble salt of active auxiliary agent and dissolve them in a certain amount of deionized water and stir to mix well. Then add an acid of the same molar amount as the structural auxiliary agent to obtain the precursor solution F. (7) Add the precursor solution F to the vacuum ply mill and mix it thoroughly with the precursor E. Then, perform vacuum ply milling, extrusion molding, and dry and calcin the extruded material to obtain the precursor G. (8) Place the precursor G in a tube furnace and reduce it for 4-12 h in a mixed atmosphere of N2 and H2 at 200-400℃; then cool it to room temperature and passivate it for 4-12 h in a mixed atmosphere of N2 and O2 to obtain the finished dechlorination agent.

2. The method for preparing a dechlorinating agent for deep removal of organochlorine from raw gas at room temperature as described in claim 1, characterized in that: The molding aid is any one or a combination of several of sodium cellulose, magnesium stearate, calcium stearate, graphite, and guar gum powder.

3. The method for preparing a dechlorinating agent for deep removal of organochlorine from raw gas at room temperature as described in claim 1, characterized in that: The silicon-rich and aluminum-poor material mentioned in step (1) is coal gangue powder, montmorillonite, or kaolin; the aluminum source is any one or a combination of aluminum oxide, aluminum nitrate, and aluminum hydroxide; the non-metallic alkali in the non-metallic alkali solution is any one or a combination of ethylenediamine, phenylethylamine, and ammonia water; the rotation speed of the high-speed ball mill is 200~600 r / min, and the ball milling time is 1~10 h; after ball milling, it is passed through a 200~600 mesh sieve; the mass concentration of the non-metallic alkali solution is 10~25%; the non-metallic alkali solution is added according to a solid-liquid ratio of 1g / 2ml~1g / 10ml.

4. The method for preparing a dechlorinating agent for deep removal of organochlorine from raw gas at room temperature as described in claim 1, characterized in that: The soluble salt of the active component in step (2) is any one or a combination of several of nickel nitrate, zinc nitrate, copper nitrate, nickel sulfate, zinc sulfate, copper sulfate, copper oxalate, zinc oxalate, and nickel oxalate; the in-situ synthesis metal nano-sizing aid is any one or a combination of several of ethylene glycol, 1,2-propanediol, glycerol, polyethylene glycol, and polypropylene glycol; the mass concentration of the soluble salt solution of the active component is 10-40%.

5. The method for preparing a dechlorinating agent for deep removal of organochlorine from raw gas at room temperature as described in claim 1, characterized in that, The conditions for aging in step (3) are as follows: raise the temperature to 100°C within 1 hour and maintain it at 100°C for 2 to 12 hours; then raise the temperature to 180°C within 1 hour and maintain it at 180°C for 2 to 12 hours; then raise the temperature to 300°C within 1 hour and maintain it at 300°C for 2 to 12 hours; finally, cool down to obtain the precursor slurry C.

6. The method for preparing a dechlorinating agent for deep removal of organochlorine from raw gas at room temperature as described in claim 1, characterized in that: The pore-forming agent mentioned in step (5) is any one or a combination of several of polyvinyl alcohol, urea, ammonium bicarbonate, ammonium carbonate, and polycaprolactone; the amount of pore-forming agent added is 1 to 4% of the weight of the dechlorinating agent.

7. The method for preparing a dechlorinating agent for deep removal of organochlorine from raw gas at room temperature as described in claim 1, characterized in that: In step (6), the active component 2 soluble salt is any one or a combination of several of chromium nitrate, manganese nitrate, cobalt nitrate, bismuth nitrate, ferric nitrate, and ammonium heptamolybdate; the active auxiliary soluble salt is any one or a combination of several of cerium nitrate, zirconium nitrate, and lanthanum nitrate; the acid is any one or a combination of several of nitric acid, sulfuric acid, hydrochloric acid, oxalic acid, and phosphoric acid; in step (7), the absolute pressure in the vacuum pumice machine is 0.001~0.01MPa, and the pumice time is 3~6h; the specification of the round hole die extruder is 2~6mm; the drying temperature of the extruded material is 100~150℃, and the drying time is 2~12h; the calcination temperature in the muffle furnace is 400~550℃, and the calcination time is 4~12h; in step (8), in the mixed atmosphere of N2 and H2, the volume percentage of H2 is 1~10%; in the mixed atmosphere of N2 and O2, the volume percentage of O2 is 0.1~5%.

8. A dechlorinating agent for deep removal of organochlorine from raw gas at room temperature, prepared by any one of claims 1-7, characterized in that: The obtained dechlorination agent product is cylindrical, prismatic, or spherical in shape; the radial dimension of the dechlorination agent is 3~5mm, the axial dimension is 6~50mm, and the radial strength is ≥60N / cm.

9. The dechlorinating agent for deep removal of organochlorine from raw gas at room temperature as described in claim 8, characterized in that, The operating conditions for the dechlorination agent are: temperature 0~200℃, volume hourly space velocity 100~8000h. -1 The raw material gas contains ≤200 ppm organic chlorine and has a pressure of 0.2~10 MPa; the regeneration conditions for the dechlorinating agent are: regeneration temperature 200~350℃, space velocity 100~3000 h⁻¹. -1 The pressure is at atmospheric pressure, and the regeneration gas is an inert gas or a gas after deep dechlorination.

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