A dechlorinating agent for removing organic chlorine and inorganic chlorine from reformed oil and a preparation method thereof

Abstract

A dechlorinating agent for removing organic chlorine and inorganic chlorine from reformed oil and a preparation method thereof belong to the technical field of dechlorination. The preparation method of the dechlorinating agent for removing organic chlorine and inorganic chlorine from reformed oil includes five steps: preparing a metal-organic framework material MOF-copper-nickel composite molecular sieve, preparing modified activated carbon, preparing a slurry, extrusion molding, and curing and calcining. The dechlorinating agent for removing organic chlorine and inorganic chlorine from reformed oil obtained by the present invention has an organic chlorine removal rate of 95.8-97.2%. In reformed product oil with a chlorine content of about 4 μg / L and a water content of about 25 μg / L, under the conditions of controlling 70 °C, 1 MPa, and a liquid mass space velocity of about 5 h⁻¹, the measured inorganic chlorine breakthrough chlorine capacity is 40.5-42.7%, the crushing strength is 164-173 N·cm⁻¹, and the attrition rate is 0.9-1.2%.

Description

Technical Field

[0001] The invention relates to a dechlorinating agent for removing organic and inorganic chlorine from reformed oil and a preparation method thereof, belonging to the technical field of dechlorination. Background Art

[0002] Catalytic reforming is an important secondary process in the crude oil processing flow, and chlorine corrosion in catalytic reforming units has attracted increasing attention. There are three main sources of chlorine in reforming oil: chlorine in crude oil, chlorine lost from acidic catalysts, and chlorine added to maintain the performance of catalysts. Among them, chlorine in crude oil includes inorganic chlorine and organic chlorine. Inorganic chlorides in crude oil, including magnesium chloride and calcium chloride, can be hydrolyzed to produce hydrogen chloride to corrode equipment; organic chlorine in crude oil mainly comes from chlorine-containing additives added during crude oil extraction. These organic chlorides are neither soluble in water nor easy to remove by electrical desalination. Although organic chlorine does not cause corrosion when it exists alone, it will be converted into inorganic hydrogen chloride in the pre-hydrogenation system of the catalytic reforming unit and enter the reforming oil generated by the reforming reaction, causing corrosion to the reforming equipment. In addition, in the catalytic reforming process, in order to maintain the acidic function of the reforming catalyst, so that it maintains high reactivity, good selectivity and stability, chlorine needs to be continuously added during operation to supplement the chlorine content on the catalyst to keep it stable, and these chlorides will eventually enter the reforming oil after the reforming reaction.

[0003] The hazards of organic and inorganic chlorine in reforming oil can be divided into three main types: corrosion to catalytic reforming equipment, ammonium salt blockage and catalyst poisoning. Among them, the corrosion to the equipment is mainly concentrated on the top of the depentanizer tower and its condensation system of the catalytic reforming unit. The production of ammonium salts will not only destroy the stable operation of the fractionation tower, but also easily cause ammonium salt crystallization in the low-temperature part of the heat exchanger, causing blockage of equipment and pipelines, and forming under-scale corrosion at the ammonium salt coverage, affecting the normal operation of the catalytic reforming equipment. After the organic chlorides in naphtha are hydrogenated, some chlorine will still enter the reforming reaction system with the reforming oil, which will cause the acid activity of the reforming catalyst to be too strong, destroy the water-chlorine balance of the reforming catalyst, and be very unfavorable to the long-term and efficient operation of the catalyst. Therefore, the efficient removal of organic and inorganic chlorine from reforming oil is a major technical problem that must be solved by the secondary processing industry of crude oil.

[0004] At present, the dechlorinating agents used for catalytic reforming of crude oil to remove organic chlorine and inorganic chlorine are mainly divided into two categories. One is the gas-phase dechlorinating agent, which generally operates at a relatively high temperature or the raw material itself is gaseous. The technology of this type of dechlorinating agent is relatively mature, and the chlorine capacity of the dechlorinating agent is relatively large, generally reaching 50% or even higher. The other is the liquid-phase dechlorinating agent, that is, the dechlorinating agent used for liquid-phase materials. Since the mass transfer rate in the liquid phase system is relatively low, the application effect of the liquid-phase dechlorinating agent is poor. Especially for reformed oil with relatively low contents of organic chlorine and inorganic chlorine, the liquid-phase dechlorinating agent relies on two functions, physical adsorption and chemical adsorption, to remove trace chlorine in the reformed oil. The adsorption effect has relatively high requirements for the specific surface area, pore size distribution and operating pressure of the dechlorinating agent. The liquid-phase dechlorinating agent is generally prepared by the kneading method or the impregnation method, and its main reactants are active substances that can adsorb organic chlorine and oxides of alkali metals, alkaline earth metals or transition metals that can react with inorganic chlorine (hydrogen chloride). For example, oxides of Cu, Mg, Fe, and Mn are loaded onto a porous carrier by the impregnation method. These active components of the oxides can adsorb organic chlorine and can also react with inorganic chlorine, thereby realizing the removal of trace organic chlorine and inorganic chlorine. The biggest difference between liquid-phase dechlorination and gas-phase dechlorination is that the diffusion resistance of organic chlorine and inorganic chlorine in the liquid phase is significantly higher than that of organic chlorine and inorganic chlorine in the gas phase. Therefore, when removing organic chlorine and inorganic chlorine in the liquid phase, in addition to considering the active components, the dechlorinating agent also needs to consider parameters such as the specific surface area, pore size and distribution of the carrier. These parameters directly affect the dispersion of the active components in the dechlorinating agent, thereby affecting the contact efficiency between the dechlorination active components and organic chlorine and inorganic chlorine in the reformed oil, and ultimately determining the dechlorination effect of the dechlorinating agent. In addition, the crushing strength and abrasion rate of the dechlorinating agent are also crucial. If the crushing strength is too low, it is easy to cause an increase in the pressure drop in the dechlorination device, which not only has the risk of damaging the device but also seriously affects the dechlorination effect. At the same time, the pulverization of the dechlorinating agent is extremely likely to contaminate the materials in the device. The abrasion rate is mainly related to the attenuation of the dechlorination performance and the service life of the dechlorinating agent. If the abrasion rate is too high, it will lead to frequent replacement of the dechlorinating agent, increasing the operating cost of the dechlorination device.

[0005] Chinese Patent CN104437342A discloses a high-chlorine-capacity liquid-phase dechlorinating agent and its preparation method and application, which is suitable for removing inorganic chlorine in oil products, especially suitable for removing hydrogen chloride in reformed product oil. The carrier of this dechlorinating agent is carbon molecular sieve, the active components are oxides of alkali metals and alkaline earth metals, and the auxiliary components are copper oxide, iron oxide or zinc oxide. The dechlorinating agent prepared by this patent only has the function of removing inorganic chlorine in reformed oil and has no dechlorination effect on organic chlorine. The breakthrough chlorine capacity of inorganic chlorine only reaches 33% at most, and the carrier of this liquid-phase dechlorinating agent is carbon molecular sieve, and its compressive strength and wear resistance are limited, and the service life is difficult to guarantee.

[0006] Chinese Patent CN117504807A discloses a macroporous liquid-phase dechlorination agent and its preparation method and application. The macroporous liquid-phase dechlorination agent comprises the following components in parts by weight: 45-70 parts of dechlorination active substance M-modified silica micropowder; 15-25 parts of inorganic macroporous material; 15-25 parts of clay; the dechlorination active substance M is selected from one or more of Ca, Mg, and / or Zn, Fe, Cu elements; by highly dispersing the dechlorination active component in water glass and then rapidly reacting with dilute sulfuric acid, micron-sized modified silica micropowder is prepared, and then mixed and formed with the inorganic macroporous material and clay to prepare a high-activity, large-pore-diameter, large-pore-volume liquid-phase dechlorination agent. Due to the in-situ high dispersion of the dechlorination active component, the large pore diameter improves liquid-phase diffusion, and the large pore volume improves the dechlorination ability. The liquid-phase dechlorination agent prepared by this patent can only remove inorganic chlorine, and the breakthrough chlorine capacity of inorganic chlorine is relatively low. In addition, the support strength of the macroporous structure is relatively low, and the service life is relatively limited.

[0007] As can be seen above, the liquid-phase dechlorination agent for reforming oil dechlorination still has problems such as difficulty in simultaneously removing organic chlorine and inorganic chlorine, low breakthrough chlorine capacity of inorganic chlorine, poor crushing strength, and high abrasion rate. Therefore, developing a dechlorination agent with high strength and low abrasion rate for removing organic and inorganic chlorine from reforming oil has very practical application value. Summary of the Invention

[0008] In view of the deficiencies of the above-mentioned prior art, the present invention provides a dechlorination agent for removing organic and inorganic chlorine from reforming oil and its preparation method, and realizes the following invention purposes: preparing a liquid-phase dechlorination agent for removing organic and inorganic chlorine from reforming oil, which has good organic chlorine adsorption capacity and very high inorganic chlorine breakthrough chlorine capacity, and also has performance advantages such as high crushing strength and low abrasion rate.

[0009] To achieve the above invention purposes, the present invention adopts the following technical solutions:

[0010] A dechlorination agent for removing organic and inorganic chlorine from reforming oil and its preparation method. The dechlorination agent for removing organic and inorganic chlorine from reforming oil has an organic chlorine removal rate of 95.8-97.2%, an inorganic chlorine breakthrough chlorine capacity of 40.5-42.7%, a crushing strength of 164-173 N·cm -1 , and an abrasion rate of 0.9-1.2%;

[0011] The preparation method of the dechlorination agent for removing organic and inorganic chlorine from reforming oil includes five steps: preparing metal-organic framework material MOF-copper-nickel composite molecular sieve, preparing modified activated carbon, preparing slurry, extrusion molding, and curing and calcining.

[0012] The following is a further improvement of the above technical solution:

[0013] Step 1: Prepare metal-organic framework material MOF-copper nickel composite molecular sieve

[0014] Put sodium aluminate, sodium hydroxide, potassium hydroxide, deionized water, and sodium metasilicate aqueous solution into a reaction kettle. After mixing evenly, carry out constant-temperature aging. Then add the metal-organic framework material MOF-copper nickel composite solution, stir and mix evenly, age at room temperature, then heat up to the constant temperature, carry out constant-temperature crystallization, and then filter, wash, and dry to obtain the metal-organic framework material MOF-copper nickel composite molecular sieve;

[0015] The mass ratio of the sodium aluminate, sodium hydroxide, potassium hydroxide, deionized water, sodium metasilicate aqueous solution, and metal-organic framework material MOF-copper nickel composite solution is 10~45:2~7:1~2.5:30~90:25~60:8~15;

[0016] In the sodium metasilicate aqueous solution, the mass fraction of sodium metasilicate is 25~33wt%, and the modulus of sodium metasilicate is 1.5~3;

[0017] For the constant-temperature aging, the constant temperature is 50~70°C, and the aging time is 3~7 hours;

[0018] For the room-temperature aging, the aging time is 4~9 hours;

[0019] For the constant-temperature crystallization, the constant temperature is 95~100°C, and the crystallization time is 6~10 hours;

[0020] The preparation method of the metal-organic framework material MOF-copper nickel composite solution is as follows: Dissolve copper phosphate and nickel phosphate in ammonia water to form a solution, then add metal-organic framework material MOF powder to the solution, and under high-speed shear dispersion, disperse the metal-organic framework material MOF powder until the particle size of the agglomerated particles is less than 1 micron, thus obtaining the metal-organic framework material MOF-copper nickel composite solution;

[0021] The mass ratio of the copper phosphate, nickel phosphate, ammonia water, and metal-organic framework material MOF powder is 6~12:4~10:60~110:3~10;

[0022] In the ammonia water, the mass concentration of NH₃·H₂O is 6~13wt%;

[0023] The metal-organic framework material MOF powder is one of metal-organic framework material MOF-808 and metal-organic framework material MOF-818;

[0024] The particle size of the metal-organic framework material MOF powder is 100~600nm;

[0025] For the washing operation, wash the filtered solid with deionized water until the pH value of the wash liquor is 8.5~9;

[0026] For the drying, the drying temperature is 70 to 80 °C.

[0027] Step 2: Prepare modified activated carbon

[0028] Add zirconium oxychloride aqueous solution, micron-sized activated carbon, and polyethylene glycol into a high-speed dispersion kettle. After dispersing evenly at the first dispersion speed, reduce the speed to the second dispersion speed and then dropwise add ammonia water until the pH of the solution reaches 9 to 10.5 to obtain a sol. Then, let it stand and age at room temperature to obtain a gel. After washing with deionized water, washing with absolute ethanol, air-drying at room temperature, drying, and grinding, powdery modified activated carbon is obtained;

[0029] The mass ratio of the zirconium oxychloride aqueous solution, micron-sized activated carbon, and polyethylene glycol is 100 to 200:15 to 45:0.1 to 0.4;

[0030] In the zirconium oxychloride aqueous solution, the mass fraction of zirconium oxychloride is 18 to 40 wt%;

[0031] The particle size of the micron-sized activated carbon is 4 to 45 μm, and the specific surface area is 1500 to 3000 m 2 / g;

[0032] The number-average molecular weight of the polyethylene glycol is 1800 to 4500 g / mol;

[0033] The first dispersion speed is 7000 to 9000 revolutions per minute;

[0034] The second dispersion speed is 600 to 900 revolutions per minute;

[0035] In the ammonia water, the mass concentration of NH₃·H₂O is 8 to 15 wt%;

[0036] For the dropwise addition of ammonia water, the dropping speed is 0.4 to 1.5 grams per minute;

[0037] For the standing and aging at room temperature, the aging time is 30 to 52 hours;

[0038] For the washing with deionized water, the number of washing times is 2 to 5 times, and the amount of deionized water used for each washing is 1.5 to 2 times the mass of the obtained gel;

[0039] For the washing with absolute ethanol, the number of washing times is 3 to 5 times, and the amount of absolute ethanol used for each washing is 1 to 1.5 times the mass of the obtained gel;

[0040] For the air-drying at room temperature, the air-drying time is 60 to 100 hours;

[0041] For the drying, the drying temperature is 85 to 100 °C, and the drying time is 12 to 18 hours;

[0042] The particle size of the powdered modified activated carbon is 400 - 800 mesh.

[0043] Step 3: Prepare the slurry

[0044] Add the pore former, deionized water, and high - modulus potassium silicate into a double - planetary mixer. After stirring and dissolving completely, then add the metal - organic framework material MOF - copper - nickel composite molecular sieve, modified activated carbon, pseudo - boehmite, and sodium - based bentonite. After strong stirring and uniform dispersion, a viscous slurry is obtained;

[0045] The pore former is one of alkyl polyglycoside and cyclodextrin;

[0046] The average degree of polymerization of the alkyl polyglycoside is 1.2 - 1.8, and the HLB value is 10 - 16;

[0047] The number - average molecular weight of the cyclodextrin is 973 - 1300 g / mol;

[0048] The pore volume of the pseudo - boehmite is 0.38 - 1.2 mL / g, and the specific surface area is 240 - 320 m 2 / g;

[0049] The blue - adsorption amount of the sodium - based bentonite is 28 - 50 g / 100 g, the water - absorption multiple is 16 - 33 times, the swelling capacity is 60 - 90 mL / 15 g, the colloidal value is 500 - 820 mL / 15 g, and the particle size is 500 - 1000 mesh;

[0050] The modulus of the high - modulus potassium silicate is 2 - 3.5;

[0051] The mass ratio of the pore former, deionized water, high - modulus potassium silicate, metal - organic framework material MOF - copper - nickel composite molecular sieve, modified activated carbon, pseudo - boehmite, and sodium - based bentonite is 1 - 4:40 - 90:8 - 20:10 - 25:9 - 20:3 - 7:5 - 9;

[0052] For the strong stirring and dispersion, the stirring speed is 90 - 140 revolutions per minute, and the dispersion speed is 8000 - 11000 revolutions per minute.

[0053] Step 4: Extrusion molding

[0054] Inject the slurry into the extruder, adjust the screw speed and the diameter of the die orifice at the head, so that the diameter of the extruded nearly circular particles is 9 - 15 mm, and the original particles of the dechlorination agent are obtained.

[0055] Step 5: Curing and calcination

[0056] The original particles of the dechlorination agent are vacuum - dried, aged at room temperature, cured at a constant temperature, and calcined at a constant temperature to obtain the dechlorination agent for removing organic chlorine and inorganic chlorine from reformed oil;

[0057] For the vacuum drying, the drying temperature is 40 - 65 °C and the drying time is 7 - 11 hours;

[0058] For the room temperature static aging, the relative air humidity of the static environment is 40 - 55% and the aging time is 14 - 24 hours;

[0059] For the isothermal curing, the operation is as follows: put the original dechlorination agent particles after aging into a muffle furnace, and increase the temperature from room temperature to 100 - 130 °C at a heating rate of 0.5 - 1.5 °C / min, and isothermally cure for 6 - 10 hours;

[0060] For the isothermal roasting, the operation is as follows: increase the temperature from the temperature of isothermal curing to 400 - 500 °C at a heating rate of 1 - 3 °C / min, isothermally roast for 12 - 19 hours, and then naturally cool to room temperature.

[0061] Compared with the prior art, the present invention has the following beneficial effects:

[0062] 1. In the process of preparing molecular sieve by sol - gel method, the present invention adds a metal - organic framework material MOF capable of adsorbing copper and nickel elements. The sources of copper and nickel elements are copper phosphate and nickel phosphate, which can dissolve in ammonia water solution. Combining with the high - speed dispersion process, MOF can be dispersed into the ammonia water solution of copper phosphate and nickel phosphate at the sub - micron particle scale. In this way, it can not only ensure the effective adsorption of MOF on copper and nickel ions, but also ensure that MOF particles can be evenly dispersed into the molecular sieve during the formation of the molecular sieve, and then form a uniform and stable metal - organic framework material MOF - copper - nickel composite molecular sieve. Finally, the obtained composite molecular sieve, after subsequent curing and sintering, enables the dechlorination agent to simultaneously have four active adsorption substances, namely molecular sieve, MOF, and copper oxide and nickel oxide formed by the oxidation of the loaded copper and nickel. The composite effect of molecular sieve, MOF, copper oxide and nickel oxide endows the dechlorination agent with very excellent adsorption and removal performance for organic chlorine and inorganic chlorine;

[0063] 2. The main purpose of the activated carbon added in the present invention is to increase the organic chlorine adsorption performance of the dechlorination agent. However, the activated carbon has low crushing strength and poor abrasion resistance, and it is difficult to firmly sinter with non - carbon inorganic substances such as molecular sieve, pseudo - boehmite, and sodium - based bentonite. Therefore, in the present invention, a layer of zirconia gel is coated on the surface of micron - sized activated carbon by sol - gel method. This layer of zirconia gel can undergo an inorganic ceramization sintering effect with high - modulus potassium silicate, pseudo - boehmite, sodium - based bentonite, etc. during curing and sintering, thus forming a sintered body with high crushing strength and good abrasion resistance. Moreover, during the sintering process, pores are generated on the surface of the micron - sized activated carbon coated with zirconia due to thermal expansion and ceramization reaction. In this way, the coating of zirconia is not a very dense and tight coating, and the adsorption performance of the activated carbon will not decrease due to the coating of zirconia;

[0064] 3. The alkyl glycoside or cyclodextrin added in the present invention acts as a pore-forming agent. Its decomposition temperature is relatively low. During the curing and roasting process, it can form uniform and dense micropores inside the dechlorinating agent, so that the adsorption active substances inside the dechlorinating agent can effectively contact the reformed oil. In addition, this microporous structure will not cause substantial damage to the crushing strength and wear resistance of the dechlorinating agent. Therefore, the dechlorinating agent obtained in the present invention has a very high crushing strength and excellent wear resistance;

[0065] 4. For the dechlorinating agent obtained in the present invention for removing organic chlorine and inorganic chlorine from reformed oil, the organic chlorine removal rate is 95.8 - 97.2%. In the reformed oil with a chlorine content of about 4 μg / L and a water content of about 25 μg / L, under the conditions of controlling at 70 °C, 1 MPa, and a liquid mass space velocity of about 5 h -1 −1, the measured breakthrough chlorine capacity of inorganic chlorine is 40.5 - 42.7%, and the crushing strength is 164 - 173 N·cm -1 , and the attrition rate is 0.9 - 1.2%. Description of the Drawings

[0066] Figure 1 It is a scanning electron microscope photograph of the dechlorinating agent obtained in Example 1 for removing organic chlorine and inorganic chlorine from reformed oil, with its cross-section magnified 10,000 times;

[0067] Figure 2 It is a scanning electron microscope photograph of the dechlorinating agent obtained in Comparative Example 3 for removing organic chlorine and inorganic chlorine from reformed oil, with its cross-section magnified 10,000 times. Detailed Embodiments

[0068] The following are the preferred embodiments of the present invention. It should be understood that the preferred embodiments described herein are only for illustrating and explaining the present invention, and are not used to limit the present invention.

[0069] Example 1: A preparation method of a dechlorinating agent for removing organic chlorine and inorganic chlorine from reformed oil

[0070] Step 1. Prepare a metal-organic framework material MOF - copper-nickel composite molecular sieve

[0071] Put sodium aluminate, sodium hydroxide, potassium hydroxide, deionized water, and an aqueous solution of sodium metasilicate into a reaction kettle. After mixing evenly, carry out constant-temperature aging. Then add a metal-organic framework material MOF - copper-nickel composite solution. After stirring and mixing evenly, carry out room-temperature aging. Then raise the temperature to the constant-temperature temperature and carry out constant-temperature crystallization. Then, after filtration, washing, and drying, obtain the metal-organic framework material MOF - copper-nickel composite molecular sieve;

[0072] The mass ratio of the sodium aluminate, sodium hydroxide, potassium hydroxide, deionized water, sodium metasilicate aqueous solution, and metal organic framework material MOF-copper nickel composite solution is 40:5:2:70:50:11;

[0073] In the sodium metasilicate aqueous solution, the mass fraction of sodium metasilicate is 30wt%, and the modulus of sodium metasilicate is 2;

[0074] The constant temperature aging is 65°C and the aging time is 6 hours;

[0075] The room temperature aging time is 8 hours;

[0076] The constant temperature crystallization is performed at 98°C and the crystallization time is 7 hours;

[0077] The preparation method of the metal organic framework material MOF-copper nickel composite liquid is as follows: after copper phosphate and nickel phosphate are dissolved in ammonia water to prepare a solution, metal organic framework material MOF powder is added to the solution, and the metal organic framework material MOF powder is dispersed under high-speed shear dispersion until the particle size of the agglomerated particles is less than 1 micron, so as to obtain the metal organic framework material MOF-copper nickel composite liquid;

[0078] The mass ratio of the copper phosphate, nickel phosphate, ammonia water, and metal organic framework material MOF powder is 10:8:90:8;

[0079] In the ammonia water, the mass concentration of NH3·H2O is 11wt%;

[0080] The metal organic framework material MOF powder is a metal organic framework material MOF-808;

[0081] The particle size of the metal organic framework material MOF powder is 300nm;

[0082] The washing comprises washing the filtered solid with deionized water until the pH value of the washing solution is 8.8;

[0083] The drying temperature is 78°C.

[0084] Step 2: Preparation of modified activated carbon

[0085] Add zirconium oxychloride aqueous solution, micron-sized activated carbon and polyethylene glycol into a high-speed dispersing kettle, disperse uniformly at a first dispersing speed, then reduce the speed to a second dispersing speed and drop ammonia water until the pH of the solution reaches 10 to obtain a sol, then stand and age at room temperature to obtain a gel, and then wash with deionized water, wash with anhydrous ethanol, stand at room temperature, dry and grind to obtain a powdered modified activated carbon;

[0086] The mass ratio of the zirconium oxychloride aqueous solution, micro-scale activated carbon, and polyethylene glycol is 130:30:0.2;

[0087] In the zirconium oxychloride aqueous solution, the mass fraction of zirconium oxychloride is 30 wt%;

[0088] The particle size of the micro-scale activated carbon is 6 μm, and the specific surface area is 2000 m 2 / g;

[0089] The number-average molecular weight of the polyethylene glycol is 3500 g / mol;

[0090] The first dispersion speed is 8500 revolutions per minute;

[0091] The second dispersion speed is 800 revolutions per minute;

[0092] In the ammonia water, the mass concentration of NH₃·H₂O is 11 wt%;

[0093] When adding the ammonia water dropwise, the dropping speed is 1 gram per minute;

[0094] For the room-temperature static aging, the aging time is 44 hours;

[0095] For the deionized water washing, the number of washing times is 4 times, and the amount of deionized water used each time is 1.8 times the mass of the obtained gel;

[0096] For the anhydrous ethanol washing, the number of washing times is 4 times, and the amount of anhydrous ethanol used each time is 1.3 times the mass of the obtained gel;

[0097] For the room-temperature air drying, the drying time is 90 hours;

[0098] For the drying, the drying temperature is 95 °C, and the drying time is 17 hours;

[0099] The particle size of the powdered modified activated carbon is 700 mesh.

[0100] Step 3: Prepare the slurry

[0101] Add the pore-forming agent, deionized water, and high-modulus potassium silicate into a double planetary mixer. After stirring and dissolving completely, then add the metal-organic framework material MOF-copper-nickel composite molecular sieve, modified activated carbon, pseudo-boehmite, and sodium-based bentonite, and strongly stir and disperse evenly to obtain a viscous slurry;

[0102] The pore-forming agent is alkyl polyglycoside;

[0103] The average degree of polymerization of the alkyl polyglycoside is 1.6, and the HLB value is 13;

[0104] The pore volume of the pseudo-boehmite is 0.9 mL / g, and the specific surface area is 280 m 2 / g;

[0105] The blue adsorption amount of the sodium-based bentonite is 40 g / 100 g, the water absorption multiple is 26 times, the swelling capacity is 80 mL / 15 g, the colloidal value is 700 mL / 15 g, and the particle size is 800 mesh;

[0106] The modulus of the high-modulus potassium silicate is 3;

[0107] The mass ratio of the pore-forming agent, deionized water, high-modulus potassium silicate, metal-organic framework material MOF-copper nickel composite molecular sieve, modified activated carbon, pseudo-boehmite, and sodium-based bentonite is 3:7:15:20:13:6:8;

[0108] For the strong stirring and dispersion, the stirring rate is 110 revolutions per minute, and the dispersion rate is 9000 revolutions per minute.

[0109] Step 4, extrusion molding

[0110] Inject the slurry into the extruder, adjust the screw speed and the diameter of the die orifice at the head, so that the diameter of the extruded nearly circular particles is 11 mm, and the original particles of the dechlorination agent are obtained.

[0111] Step 5, curing and roasting

[0112] The original particles of the dechlorination agent are vacuum-dried, aged at room temperature, cured at a constant temperature, and roasted at a constant temperature to obtain a dechlorination agent for removing organic chlorine and inorganic chlorine from reforming oil;

[0113] For the vacuum drying, the drying temperature is 50 °C, and the drying time is 10 hours;

[0114] For the aging at room temperature and standing still, the relative air humidity of the standing environment is 50%, and the aging time is 19 hours;

[0115] For the constant-temperature curing, the operation is as follows: put the original particles of the dechlorination agent after aging into a muffle furnace, and increase the temperature from room temperature to 120 °C at a heating rate of 1 °C / min, and cure at a constant temperature for 7 hours;

[0116] For the constant-temperature roasting, the operation is as follows: increase the temperature from the constant-temperature curing temperature to 480 °C at a heating rate of 2 °C / min, roast at a constant temperature for 16 hours, and then naturally cool to room temperature.

[0117] Example 2: A preparation method of a dechlorination agent for removing organic chlorine and inorganic chlorine from reforming oil

[0118] Step 1, prepare the metal-organic framework material MOF-copper nickel composite molecular sieve

[0119] Put sodium aluminate, sodium hydroxide, potassium hydroxide, deionized water, and an aqueous solution of sodium metasilicate into a reaction kettle. After mixing evenly, carry out aging at a constant temperature, then add a metal-organic framework material MOF-copper nickel composite solution, stir and mix evenly, age at room temperature, then raise the temperature to the constant temperature, carry out crystallization at a constant temperature, and then filter, wash, and dry to obtain a metal-organic framework material MOF-copper nickel composite molecular sieve;

[0120] The mass ratio of the sodium aluminate, sodium hydroxide, potassium hydroxide, deionized water, aqueous solution of sodium metasilicate, and metal-organic framework material MOF-copper nickel composite solution is 10:2:1:30:25:8;

[0121] In the aqueous solution of sodium metasilicate, the mass fraction of sodium metasilicate is 25 wt%, and the modulus of sodium metasilicate is 1.5;

[0122] For the aging at a constant temperature, the constant temperature is 50 °C, and the aging time is 3 hours;

[0123] For the aging at room temperature, the aging time is 4 hours;

[0124] For the crystallization at a constant temperature, the constant temperature is 95 °C, and the crystallization time is 6 hours;

[0125] The preparation method of the metal-organic framework material MOF-copper nickel composite solution is as follows: Dissolve copper phosphate and nickel phosphate in ammonia water to form a solution, then add metal-organic framework material MOF powder to the solution, and under high-speed shear dispersion, disperse the metal-organic framework material MOF powder until the particle size of the agglomerated particles is below 1 micron, thus obtaining the metal-organic framework material MOF-copper nickel composite solution;

[0126] The mass ratio of the copper phosphate, nickel phosphate, ammonia water, and metal-organic framework material MOF powder is 6:4:60:3;

[0127] In the ammonia water, the mass concentration of NH₃·H₂O is 6 wt%;

[0128] The metal-organic framework material MOF powder is metal-organic framework material MOF-818;

[0129] The particle size of the metal-organic framework material MOF powder is 100 nm;

[0130] For the washing, the operation is to wash the filtered solid with deionized water until the pH value of the washing liquid is 8.5;

[0131] For the drying, the drying temperature is 70 °C.

[0132] Step 2: Prepare modified activated carbon

[0133] Add zirconium oxychloride aqueous solution, micron-sized activated carbon, and polyethylene glycol into a high-speed dispersion kettle. After dispersing evenly at the first dispersion speed, reduce the speed to the second dispersion speed and then dropwise add ammonia water until the pH of the solution reaches 9 to obtain a sol. Then, let it stand and age at room temperature to obtain a gel. After washing with deionized water, washing with absolute ethanol, air-drying at room temperature, drying, and grinding, powdery modified activated carbon is obtained.

[0134] The mass ratio of the zirconium oxychloride aqueous solution, micron-sized activated carbon, and polyethylene glycol is 100:15:0.1.

[0135] In the zirconium oxychloride aqueous solution, the mass fraction of zirconium oxychloride is 18 wt%.

[0136] The particle size of the micron-sized activated carbon is 4 μm, and the specific surface area is 1500 m 2 / g.

[0137] The number-average molecular weight of the polyethylene glycol is 1800 g / mol.

[0138] The first dispersion speed is 7000 revolutions per minute.

[0139] The second dispersion speed is 600 revolutions per minute.

[0140] In the ammonia water, the mass concentration of NH3·H2O is 8 wt%.

[0141] When dropping the ammonia water, the dropping speed is 0.4 grams per minute.

[0142] When standing and aging at room temperature, the aging time is 30 hours.

[0143] When washing with deionized water, the number of washing times is 2 times, and the amount of deionized water used each time is 1.5 times the mass of the obtained gel.

[0144] When washing with absolute ethanol, the number of washing times is 3 times, and the amount of absolute ethanol used each time is 1 times the mass of the obtained gel.

[0145] When air-drying at room temperature, the air-drying time is 60 hours.

[0146] When drying, the drying temperature is 85 °C and the drying time is 12 hours.

[0147] The particle size of the powdery modified activated carbon is 400 mesh.

[0148] Step 3: Prepare the slurry

[0149] Add the pore former, deionized water, and high-modulus potassium silicate into a double planetary mixer. After stirring and dissolving completely, add the metal-organic framework material MOF-copper nickel composite molecular sieve, modified activated carbon, pseudoboehmite, and sodium-based bentonite. After strong stirring and uniform dispersion, a viscous slurry is obtained;

[0150] The pore former is cyclodextrin;

[0151] The number-average molecular weight of the cyclodextrin is 973 g / mol;

[0152] The pore volume of the pseudoboehmite is 0.38 mL / g, and the specific surface area is 240 m 2 / g;

[0153] The blue adsorption amount of the sodium-based bentonite is 28 g / 100 g, the water absorption multiple is 16 times, the swelling capacity is 60 mL / 15 g, the colloidal value is 500 mL / 15 g, and the particle size is 500 mesh;

[0154] The modulus of the high-modulus potassium silicate is 2;

[0155] The mass ratio of the pore former, deionized water, high-modulus potassium silicate, metal-organic framework material MOF-copper nickel composite molecular sieve, modified activated carbon, pseudoboehmite, and sodium-based bentonite is 1:40:8:10:9:3:5;

[0156] For the strong stirring and dispersion, the stirring speed is 90 revolutions per minute, and the dispersion speed is 8000 revolutions per minute.

[0157] Step 4, extrusion molding

[0158] Inject the slurry into the extruder, adjust the screw speed and the diameter of the die orifice at the head to make the diameter of the extruded near-circular particles 9 mm, and obtain the original particles of the dechlorination agent.

[0159] Step 5, curing and roasting

[0160] The original particles of the dechlorination agent are vacuum dried, aged at room temperature and static, cured at a constant temperature, and roasted at a constant temperature to obtain a dechlorination agent for removing organic chlorine and inorganic chlorine from reforming oil;

[0161] For the vacuum drying, the drying temperature is 40 °C, and the drying time is 7 hours;

[0162] For the aging at room temperature and static, the relative air humidity of the static environment is 40%, and the aging time is 14 hours;

[0163] For the constant-temperature curing, the operation is as follows: put the original particles of the dechlorination agent after aging into a muffle furnace, and increase the temperature from room temperature to 100 °C at a heating rate of 0.5 °C / min, and cure at a constant temperature for 6 hours;

[0164] For the constant-temperature roasting, the operation is as follows: at a heating rate of 1 °C / min, heat from the constant-temperature curing temperature to 400 °C, perform constant-temperature roasting for 12 hours, and then naturally cool to room temperature.

[0165] Example 3: A preparation method of a dechlorinating agent for removing organic chlorine and inorganic chlorine from reformed oil

[0166] Step 1: Prepare a metal-organic framework material MOF - copper-nickel composite molecular sieve

[0167] Put sodium aluminate, sodium hydroxide, potassium hydroxide, deionized water, and an aqueous sodium metasilicate solution into a reaction kettle. After mixing evenly, perform constant-temperature aging, then add a metal-organic framework material MOF - copper-nickel composite solution. After stirring and mixing evenly, age at room temperature, then raise the temperature to the constant-temperature, perform constant-temperature crystallization, and then filter, wash, and dry to obtain the metal-organic framework material MOF - copper-nickel composite molecular sieve;

[0168] The mass ratio of the sodium aluminate, sodium hydroxide, potassium hydroxide, deionized water, aqueous sodium metasilicate solution, and metal-organic framework material MOF - copper-nickel composite solution is 45:7:2.5:90:60:15;

[0169] In the aqueous sodium metasilicate solution, the mass fraction of sodium metasilicate is 33 wt%, and the modulus of sodium metasilicate is 3;

[0170] For the constant-temperature aging, the constant-temperature is 70 °C, and the aging time is 7 hours;

[0171] For the room-temperature aging, the aging time is 9 hours;

[0172] For the constant-temperature crystallization, the constant-temperature is 100 °C, and the crystallization time is 10 hours;

[0173] For the metal-organic framework material MOF - copper-nickel composite solution, its preparation method is as follows: dissolve copper phosphate and nickel phosphate in ammonia water to form a solution, then add metal-organic framework material MOF powder to the solution. Under high-speed shear dispersion, disperse the metal-organic framework material MOF powder until the particle size of the agglomerates is below 1 micron, and then the metal-organic framework material MOF - copper-nickel composite solution is obtained;

[0174] The mass ratio of the copper phosphate, nickel phosphate, ammonia water, and metal-organic framework material MOF powder is 12:10:110:10;

[0175] In the ammonia water, the mass concentration of NH₃·H₂O is 13 wt%;

[0176] The metal-organic framework material MOF powder is metal-organic framework material MOF - 808;

[0177] The particle size of the metal-organic framework material MOF powder is 600 nm;

[0178] For the washing operation, the solid filtered out is washed with deionized water until the pH value of the washing liquid is 9;

[0179] For the drying, the drying temperature is 80 °C.

[0180] Step 2: Prepare the modified activated carbon

[0181] Add zirconium oxychloride aqueous solution, micron-sized activated carbon, and polyethylene glycol into a high-speed dispersion kettle. After dispersing evenly at the first dispersion speed, lower the speed to the second dispersion speed and then dropwise add ammonia water until the pH of the solution reaches 10.5 to obtain a sol. Then let it stand and age at room temperature to obtain a gel. After washing with deionized water, washing with absolute ethanol, air-drying at room temperature, drying, and grinding, the powdered modified activated carbon is obtained;

[0182] The mass ratio of the zirconium oxychloride aqueous solution, micron-sized activated carbon, and polyethylene glycol is 200:45:0.4;

[0183] In the zirconium oxychloride aqueous solution, the mass fraction of zirconium oxychloride is 40 wt%;

[0184] The particle size of the micron-sized activated carbon is 45 μm, and the specific surface area is 3000 m 2 / g;

[0185] The number-average molecular weight of the polyethylene glycol is 4500 g / mol;

[0186] The first dispersion speed is 9000 revolutions per minute;

[0187] The second dispersion speed is 900 revolutions per minute;

[0188] In the ammonia water, the mass concentration of NH₃·H₂O is 15 wt%;

[0189] For the dropwise addition of ammonia water, the dropping speed is 1.5 grams per minute;

[0190] For the standing and aging at room temperature, the aging time is 52 hours;

[0191] For the washing with deionized water, the number of washing times is 5 times, and the amount of deionized water used for each washing is 2 times the mass of the obtained gel;

[0192] For the washing with absolute ethanol, the number of washing times is 5 times, and the amount of absolute ethanol used for each washing is 1.5 times the mass of the obtained gel;

[0193] For the air-drying at room temperature, the air-drying time is 100 hours;

[0194] For the drying process, the drying temperature is 100 °C and the drying time is 18 hours;

[0195] The powdered modified activated carbon has a particle size of 800 mesh.

[0196] Step 3: Prepare the slurry

[0197] Add the pore-forming agent, deionized water, and high-modulus potassium silicate to a double planetary mixer. After complete stirring and dissolution, add the metal-organic framework material MOF-copper-nickel composite molecular sieve, modified activated carbon, pseudo-boehmite, and sodium-based bentonite, and vigorously stir and disperse evenly to obtain a viscous slurry;

[0198] The pore-forming agent is alkyl polyglycoside;

[0199] The average degree of polymerization of the alkyl polyglycoside is 1.8, and the HLB value is 16;

[0200] The pore volume of the pseudo-boehmite is 1.2 mL / g, and the specific surface area is 320 m 2 / g;

[0201] The sodium-based bentonite has a blue adsorption capacity of 50 g / 100 g, a water absorption multiple of 33 times, a swelling capacity of 90 mL / 15 g, a colloidal value of 820 mL / 15 g, and a particle size of 1000 mesh;

[0202] The modulus of the high-modulus potassium silicate is 3.5;

[0203] The mass ratio of the pore-forming agent, deionized water, high-modulus potassium silicate, metal-organic framework material MOF-copper-nickel composite molecular sieve, modified activated carbon, pseudo-boehmite, and sodium-based bentonite is 4:90:20:25:20:7:9;

[0204] For the vigorous stirring and dispersion, the stirring rate is 140 revolutions per minute, and the dispersion rate is 11,000 revolutions per minute.

[0205] Step 4: Extrusion molding

[0206] Inject the slurry into the extruder, adjust the screw speed and the diameter of the die orifice at the head to make the diameter of the extruded nearly circular particles 15 mm, and obtain the original particles of the dechlorination agent.

[0207] Step 5: Curing and roasting

[0208] The original particles of the dechlorination agent are vacuum dried, aged at room temperature, cured at a constant temperature, and roasted at a constant temperature to obtain a dechlorination agent for removing organic chlorine and inorganic chlorine from reforming oil;

[0209] For the vacuum drying, the drying temperature is 65 °C and the drying time is 11 hours;

[0210] For the room-temperature static aging, the relative air humidity of the static environment is 55%, and the aging time is 24 hours;

[0211] For the constant-temperature curing, the operation is as follows: put the aged dechlorination agent raw particles into a muffle furnace, and increase the temperature from room temperature to 130 °C at a heating rate of 1.5 °C / min, and cure at a constant temperature for 10 hours;

[0212] For the constant-temperature roasting, the operation is as follows: increase the temperature from the constant-temperature curing temperature to 500 °C at a heating rate of 3 °C / min, roast at a constant temperature for 19 hours, and then cool naturally to room temperature.

[0213] Comparative Example 1: On the basis of Example 1, in Step 1 of preparing the metal-organic framework material MOF-copper-nickel composite molecular sieve, do not add the metal-organic framework material MOF-copper-nickel composite liquid, only prepare the ordinary molecular sieve, and replace 11 parts of the metal-organic framework material MOF-copper-nickel composite liquid with 11 parts of sodium metasilicate aqueous solution in equal amount. In Step 3 of preparing the slurry, replace 20 parts of the metal-organic framework material MOF-copper-nickel composite molecular sieve with 20 parts of the ordinary molecular sieve. The specific operation is as follows:

[0214] Step 1. Prepare the ordinary molecular sieve

[0215] On the basis of Example 1, replace 11 parts of the metal-organic framework material MOF-copper-nickel composite liquid with 11 parts of sodium metasilicate aqueous solution in equal amount, and other operations are the same as those in Example 1 to obtain the ordinary molecular sieve;

[0216] The operation in Step 2 is the same as that in Example 1;

[0217] Step 3. Prepare the slurry

[0218] Replace 20 parts of the metal-organic framework material MOF-copper-nickel composite molecular sieve with 20 parts of the ordinary molecular sieve in equal amount, and other operations are the same as those in Example 1;

[0219] The operations in Steps 4 and 5 are the same as those in Example 1.

[0220] Comparative Example 2: On the basis of Example 1, do not perform Step 2 of preparing the modified activated carbon. In Step 3 of preparing the slurry, replace 13 parts of the modified activated carbon with 13 parts of micron-sized activated carbon. The specific operation is as follows:

[0221] Step 1. The operation is the same as that in Example 1;

[0222] Do not perform Step 2 of preparing the modified activated carbon;

[0223] Step 3. Prepare the slurry

[0224] Replace 13 parts of the modified activated carbon with 13 parts of micron-sized activated carbon in equal amount, and other operations are the same as those in Example 1;

[0225] The particle size of the micron-sized activated carbon is 6 μm, and the specific surface area is 2000 m 2 / g;

[0226] The operations in Steps 4 and 5 are the same as those in Example 1.

[0227] Comparative Example 3: On the basis of Example 1, in Step 3 of preparing the slurry, no pore-forming agent is added, and 3 parts of the pore-forming agent are replaced with 3 parts of deionized water in equal amounts. The specific operations are as follows:

[0228] The operations in Steps 1 and 2 are the same as those in Example 1;

[0229] Step 3: Preparing the slurry

[0230] Replace 3 parts of the pore-forming agent with 3 parts of deionized water in equal amounts, and other operations are the same as those in Example 1;

[0231] The operations in Steps 4 and 5 are the same as those in Example 1.

[0232] Performance test:

[0233] For the dechlorinating agents obtained in Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3 for removing organic chlorine and inorganic chlorine from reformed oil, the following indicators are tested:

[0234] 1. Inorganic chlorine breakthrough chlorine capacity. The test method is as follows: Feed the reformed product oil with a chlorine content of about 4 μg / L and a water content of about 25 μg / L into the dechlorinating agent for a liquid-phase dynamic dechlorination experiment at 70 °C, 1 MPa, and a liquid mass space velocity of 5 h -1 . Measure the chlorine content in the reformed product oil flowing out of the dechlorination tank. When the chlorine content in the effluent is greater than 0.5 μg / L, it can be regarded as breakthrough. According to the formula: breakthrough chlorine capacity = (mass content of chlorine in the dechlorinating agent after breakthrough) / (total mass of the dechlorinating agent after breakthrough) × 100%, the breakthrough chlorine capacity of the dechlorinating agent is obtained;

[0235] 2. Organic chlorine removal efficiency. The test method is as follows: In reformed oil with a content of 0 for both organic chlorine and inorganic chlorine, add dichloromethane, chloroform, carbon tetrachloride, and 1,2-dichloroethane. The volume ratio of the four chlorides is 1:1:1:1. After mixing evenly, the reformed oil containing organic chlorine is obtained. Measure the content of organic chlorides. Weigh a certain mass of the reformed oil containing organic chlorine and add it to a 250 mL round-bottom flask, and then place it in a constant-temperature water bath and keep it at a constant temperature of 70 °C. The volume ratio of the dechlorinating agent to the reformed oil containing organic chlorine is 1:1. Add the dechlorinating agent to the reformed oil containing organic chlorine, control the stirring rate at 150 revolutions per minute, adsorb for 3 hours, let it stand for sedimentation, and then take the supernatant. Measure the content of organic chlorides in the reformed oil after adsorption to obtain the organic chlorine removal rate of the dechlorinating agent;

[0236] 3. Crushing strength: Refer to "HG / T 2782-2011 Determination of Crushing Strength of Granular Fertilizer Catalysts" to test the crushing strength;

[0237] 4. Abrasion rate: Refer to "HG / T 2976-2011 Determination of Abrasion Rate of Fertilizer Catalysts" to test the abrasion rate;

[0238] The specific test results are shown in Table 1:

[0239] Table 1

[0240]

[0241] From the data in Table 1, it can be seen that the inorganic chlorine breakthrough chlorine capacity of Examples 1-3 is above 40%, the organic chlorine removal rate is above 95%, the crushing strength is greater than 160 N·cm -1 , and the abrasion rate is less than 1.2%. This shows that the dechlorination agent obtained by the present invention has good organic chlorine adsorption capacity and very high inorganic chlorine breakthrough chlorine capacity, and at the same time has performance advantages such as high crushing strength and low abrasion rate; in Comparative Example 1, it is a common molecular sieve and is not compounded with the metal-organic framework material MOF-copper nickel. The crushing strength and abrasion rate of Comparative Example 1 have no difference from those of the 3 examples, but the inorganic chlorine breakthrough chlorine capacity and organic chlorine removal rate of Comparative Example 1 have decreased significantly. This shows that the metal-organic framework material MOF-copper nickel composite molecular sieve has no effect on the mechanical strength and wear resistance of the dechlorination agent, and can improve the dechlorination ability of both inorganic chlorine and organic chlorine of the dechlorination agent; in Comparative Example 2, the micron-sized activated carbon is not modified and directly added. The inorganic chlorine breakthrough chlorine capacity and organic chlorine removal rate of Comparative Example 2 have not changed significantly, but the crushing strength and abrasion rate of Comparative Example 2 have decreased very sharply. This shows that after the activated carbon is modified, it does not have an obvious impact on its adsorption performance, but improves the binding force between the activated carbon and other components in the dechlorination agent, thereby improving the overall mechanical properties and wear resistance of the dechlorination agent; in Comparative Example 3, no pore-forming agent is added. The inorganic chlorine breakthrough chlorine capacity and organic chlorine removal rate of Comparative Example 3 have dropped to the lowest values among all examples and comparative examples, while the crushing strength and abrasion rate of Comparative Example 3 are much better than those of the 3 examples and the other 2 comparative examples. This shows that the pore-forming agent can form many micropores inside the dechlorination agent, enabling the molecular sieve and activated carbon with adsorption active properties inside the dechlorination agent to effectively contact the reforming oil, thereby ensuring the dechlorination ability of the organic chlorine and inorganic chlorine of the dechlorination agent. In addition, the micropores formed by the pore-forming agent have a very large damage to the crushing strength and wear resistance of the dechlorination agent, but the microporous structure formed by the present invention is relatively uniform and dense, and does not cause particularly serious damage to the crushing resistance and wear resistance of the dechlorination agent.

[0242] Appendix Figure 1It is the dechlorination agent obtained in Example 1 for removing organic chlorine and inorganic chlorine from reformed oil. The electron microscope photograph of its cross-section magnified 10,000 times shows that molecular sieves and activated carbon particles inside the dechlorination agent are sintered together, and there are micron-sized pores formed after the decomposition of the pore-forming agent between the particles. This pore structure not only ensures the effective contact between the internal adsorption active substances and the reformed oil but also enables the dechlorination agent to maintain a certain crushing strength and wear resistance; Attachment Figure 2 It is the dechlorination agent obtained in Comparative Example 3 for removing organic chlorine and inorganic chlorine from reformed oil. The scanning electron microscope photograph of its cross-section magnified 10,000 times, compared with Attachment Figure 1 shows that Figure 2 the porosity in it is very low. It can be seen that in Comparative Example 3 without the pore-forming agent, its interior is very dense, which also indicates that the pore-forming agent can effectively form a microporous structure.

[0243] As mentioned above, it is only the preferred specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, makes equivalent substitutions or changes, and should be covered within the protection scope of the present invention.

Claims

1. A method for preparing a dechlorinating agent for removing organic and inorganic chlorine from reformed oil, wherein Features include: The preparation method of the dechlorinating agent for removing organic and inorganic chlorine from reformed oil comprises five steps: preparing a metal organic framework material MOF-copper-nickel composite molecular sieve, preparing modified activated carbon, preparing slurry, extrusion molding, and curing and roasting; The method for preparing the metal organic framework material MOF-copper nickel composite molecular sieve comprises putting sodium aluminate, sodium hydroxide, potassium hydroxide, deionized water, and sodium metasilicate aqueous solution into a reaction kettle, mixing them evenly, aging them at a constant temperature, then adding the metal organic framework material MOF-copper nickel composite liquid, stirring and mixing them evenly, aging them at room temperature, then heating them to a constant temperature, crystallizing them at a constant temperature, and then filtering, washing, and drying them to obtain the metal organic framework material MOF-copper nickel composite molecular sieve; The preparation method of the metal organic framework material MOF-copper nickel composite liquid is as follows: after copper phosphate and nickel phosphate are dissolved in ammonia water to prepare a solution, metal organic framework material MOF powder is added to the solution, and the metal organic framework material MOF powder is dispersed under high-speed shear dispersion until the particle size of the agglomerated particles is less than 1 micron, so as to obtain the metal organic framework material MOF-copper nickel composite liquid; The modified activated carbon is prepared by adding a zirconium oxychloride aqueous solution, micron-sized activated carbon, and polyethylene glycol into a high-speed dispersing kettle, dispersing them uniformly at a first dispersing speed, then dropping ammonia water to a second dispersing speed until the pH of the solution reaches 9 to 10.5 to obtain a sol, then standing and aging at room temperature to obtain a gel, and then washing with deionized water, washing with anhydrous ethanol, standing at room temperature, drying, and grinding to obtain a powdered modified activated carbon; The slurry is prepared by adding a pore-forming agent, deionized water, and high modulus potassium silicate into a double planetary mixer, stirring and dissolving completely, and then adding a metal organic framework material MOF-copper nickel composite molecular sieve, modified activated carbon, pseudo-boehmite, and sodium bentonite, and vigorously stirring and dispersing them evenly to obtain a viscous slurry; The modulus of the high modulus potassium silicate is 2 to 3.5; The pore-forming agent is one of alkyl glycoside and cyclodextrin; In the preparation of the metal organic framework material MOF-copper nickel composite solution, the mass ratio of copper phosphate, nickel phosphate, ammonia water, and metal organic framework material MOF powder is 6-12:4-10:60-110:3-10; In the preparation of the metal organic framework material MOF-copper nickel composite solution, the mass concentration of NH3·H2O in ammonia water is 6-13wt%; The metal organic framework material MOF powder is one of metal organic framework material MOF-808 and metal organic framework material MOF-818; The particle size of the metal organic framework material MOF powder is 100-600nm.

2. The method for preparing a dechlorinating agent for removing organic and inorganic chlorine from reformed oil according to claim 1, characterized in that: The mass ratio of the sodium aluminate, sodium hydroxide, potassium hydroxide, deionized water, sodium metasilicate aqueous solution, and metal organic framework material MOF-copper nickel composite liquid is 10-45:2-7:1-2.5:30-90:25-60:8-15; In the sodium metasilicate aqueous solution, the mass fraction of sodium metasilicate is 25-33wt%, and the modulus of sodium metasilicate is 1.5-3.

3. The method for preparing a dechlorinating agent for removing organic and inorganic chlorine from reformed oil according to claim 1, characterized in that: The mass ratio of the zirconium oxychloride aqueous solution, micron-sized activated carbon, and polyethylene glycol is 100-200:15-45:0.1-0.4; The particle size of the micron-sized activated carbon is 4-45 μm, and the specific surface area is 1500-3000 m 2 / g; In the preparation of modified activated carbon, the mass concentration of NH3·H2O in ammonia water is 8-15wt%; In the preparation of the modified activated carbon, aqueous ammonia is added dropwise at a rate of 0.4 to 1.5 g / min.

4. The method for preparing a dechlorinating agent for removing organic and inorganic chlorine from reformed oil according to claim 1, characterized in that: The mass ratio of the pore former, deionized water, high modulus potassium silicate, metal organic framework material MOF-copper nickel composite molecular sieve, modified activated carbon, pseudo-boehmite and sodium bentonite is 1-4:40-90:8-20:10-25:9-20:3-7:5-9.

5. The method for preparing a dechlorinating agent for removing organic and inorganic chlorine from reformed oil according to claim 1, characterized in that: In the extrusion molding, the slurry is injected into the extruder, and the screw speed and the diameter of the die of the die head are adjusted to make the diameter of the extruded nearly round particles 9-15 mm to obtain the original particles of the dechlorinating agent.

6. The method for preparing a dechlorinating agent for removing organic and inorganic chlorine from reformed oil according to claim 5, characterized in that: The solidification and calcination process is performed by vacuum drying, room temperature static aging, constant temperature solidification and constant temperature calcination to obtain a dechlorinating agent for removing organic and inorganic chlorine from reformed oil.

7. A dechlorinating agent for removing organic and inorganic chlorine from reformed oil obtained by the preparation method according to any one of claims 1 to 6, characterized in that: The dechlorinating agent for removing organic and inorganic chlorine from reformed oil has an organic chlorine removal rate of 95.8-97.2%, an inorganic chlorine penetration capacity of 40.5-42.7%, and a crushing strength of 164-173 N·cm -1 The wear rate is 0.9~1.2%.

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