CN114377667A - Liquid hydrocarbon adsorption dearsenifying catalyst and its preparation method - Google Patents
Liquid hydrocarbon adsorption dearsenifying catalyst and its preparation method Download PDFInfo
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- CN114377667A CN114377667A CN202011108577.6A CN202011108577A CN114377667A CN 114377667 A CN114377667 A CN 114377667A CN 202011108577 A CN202011108577 A CN 202011108577A CN 114377667 A CN114377667 A CN 114377667A
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- Prior art keywords
- catalyst
- roasting
- temperature
- dearsenification
- carrier
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The invention discloses a preparation method of a liquid hydrocarbon adsorption dearsenification catalyst with large specific surface area, multi-level pore distribution and high dearsenification performance and an aerobic roasting method thereof, wherein the method comprises the following steps: 1) mixing activated carbon and pseudo-boehmite according to a ratio, kneading, rolling, adding a pore-expanding agent and an acid solution, extruding strips, and roasting at a high temperature in a nitrogen atmosphere to obtain a carbon-alumina composite carrier; 2) adjusting the pH value of the main metal precursor solution to be higher than the isoelectric point of the used active metal oxide; 3) impregnating the composite carrier, and continuously roasting at low temperature-medium temperature-high temperature step by step in an aerobic environment to obtain the finished catalyst. Aerobic stepwise continuous roasting, which not only overcomes the defect of flammability of the active carbon, but also reduces the preparation cost of the catalyst. The low temperature ensures the deep drying of the catalyst, the medium temperature metal precursor is decomposed slowly, the high temperature roasting ensures the active metal precursor to be converted into oxidation state completely, and the dearsenifying activity is fully exerted.
Description
Technical Field
The invention relates to a preparation method of an adsorption dearsenification catalyst in the field of petrochemical industry, which is particularly suitable for the field of low-temperature adsorption and dearsenification of arsenide in liquid petroleum hydrocarbon.
Background
As petroleum resources become increasingly depleted and the composition of crude oil becomes more complex, the arsenic content of crude oil produced in certain oil fields increases year by year. The hydrogenation catalyst contains VIII group elements, and organic arsenic and inorganic arsenic in the oil product can be reduced into AsH under the condition of high temperature and hydrogen3Trivalent As has active reducibility and is easily combined with d orbital electrons of VIII group elements to form coordinate bonds to deactivate catalyst poisoning, and the poisoning is difficult to remove by an activation or regeneration method, so that a very small amount of arsenide in raw oil can permanently deactivate the catalyst poisoning. Therefore, in order to maintain the activity of the hydrogenation catalyst and prolong the service life, the removal of arsenide in liquid hydrocarbon has important practical value.
At present, two kinds of dearsenification methods for hydrocarbon compounds mainly comprise an adsorption dearsenification technology and a hydrodearsenication technology. The hydrodearsenization technology is that under certain reaction conditions (usually 1.5-3.0MPa, 180-2Addition reaction with alkyl arsenide or phenyl arsenide to produce AsH3，AsH3As is decomposed to be adsorbed on the active metal, and the reaction can enter the bulk phase of the active group due to the high temperature of the hydrodearsenic removal reaction, so that the active metal can fully play a role, the arsenic capacity is high, and the arsenic removal effect is good. The disadvantages of complex application process and inconvenient operation of the hydrodearsenization agent, and partial olefin saturation can be caused in the dearsenization process to cause octane number loss. The adsorption dearsenification technology refers to that at a lower temperature (<At 100 ℃), the arsenide and the active metal of the dearsenization agent are combined together in a chemical adsorption mode, and the arsenic and the active metal generate partial electron cloud transfer and are adsorbed on the surface of the active group of the metal, thereby achieving the purpose of dearsenization. The adsorption dearsenification technology has simple process, convenient operation and low reaction temperature, is not easy to influence the properties of oil products, can be used as a front dearsenification unit to be arranged in front of a set of hydrogenation equipment, treats raw materials with complex components, wide range and high arsenic content, and is mainly used for stoneRemoving arsenide in naphtha and gasoline. The main problems faced by the adsorption dearsenification technology are that the adsorption dearsenification agent as the technical core of the adsorption dearsenification technology has not been greatly broken through, the dearsenification efficiency is not high, the adsorption capacity is small, the service life is short, the waste residue amount is large, the treatment is difficult, the environmental pollution is easily caused, and the method is particularly obvious in the aspect of treating liquid hydrocarbon. Therefore, the low-temperature adsorption dearsenization agent which has large arsenic capacity, high dearsenization efficiency, long service life and easy treatment of waste residue is always a research hotspot of the liquid hydrocarbon arsenide removal catalyst.
Arsenides in petroleum hydrocarbons are mainly trivalent organic arsenic complexes, with R3As is, wherein R is a hydrogen atom or a hydrocarbon group such As methyl, ethyl, propyl, phenyl or the like, and organic arsine complexes having different boiling points are introduced into respective fractions after the crude oil is fractionated. Low boiling arsenides in liquid petroleum hydrocarbons include AsH3、CH3AsH2Etc., high boiling arsenides include As (CH)3)3、As(C2H5)3And the like. Higher boiling arsenides containing one or more hydrocarbyl groups have a lower affinity for the transition metal oxide and are difficult to remove by adsorption, and higher boiling points of arsenides or longer alkyl chain lengths are less likely to be removed and are more demanding on dearsenifying agents.
The adsorption dearsenification generally achieves the purpose of dearsenification by utilizing the combined action of physical adsorption and chemical adsorption at normal temperature and pressure. The dearsenization agent for adsorbing dearsenization mainly consists of two parts of carrier and active component, and also includes other small quantity of adjuvant. The carrier is used as carrier for adsorbing dearsenization agent, and is one or several of alumina, silica, manganese oxide, titania, active carbon, molecular sieve and silica-alumina oxide, and its main active component is selected from one or several of transition metals of copper, zinc, manganese, etc. and their oxides, and some dearsenization agents also have added rare earth elements of lanthanum, cerium, samarium, etc. and noble metals of gold, silver, rhodium, palladium, etc. as auxiliary active components. The summary of the liquid adsorption dearsenization agent under normal temperature and pressure in the literature shows that: the common adsorption dearsenization agents which are researched more comprise two types, one type is the dearsenization agent which takes silicon-aluminum oxide as a carrier and loads metals such as copper, zinc and the like and metal oxides thereof as active components; the other type is that active carbon is used as a carrier, and active metal oxide thereof are loaded as a dearsenization agent.
For the adsorption dearsenization agent, the specific surface area, the effective pore volume and the pore structure of the formed carrier have direct influence on the performance of the dearsenization agent, especially for the adsorption dearsenization of liquid petroleum hydrocarbon at normal temperature and normal pressure, the increase of the proportion of mesopores or macropores is beneficial to the transmission of the liquid petroleum hydrocarbon, and the higher specific surface area ensures that more dearsenization active points exist. The pore structure of the dearsenization agent carrier prepared by taking silicon-aluminum oxide or alumina as the carrier has uncontrollable property and smaller specific surface. The activated carbon has the excellent performances of developed pore channel structure, high specific surface area, high surface activity and diversity of surface chemical properties, and is used as a carrier of the dearsenization agent to obtain the dearsenization agent of the oil product with excellent performance, and the pore structure of the activated carbon can be adjusted to adapt to the change of dearsenization conditions. The small molecular arsenide has strong reducibility, is easy to generate oxidation-reduction reaction with active metals such as copper oxide, nickel oxide, zinc oxide and the like to generate corresponding metal arsenide, and the reaction equation is as follows:
3CuO+2R3As→Cu3As+As+3R2O
3CuO+2R3As→3Cu+As+3R2O
therefore, the dearsenization catalyst is prepared by taking the active carbon as a carrier, and the adsorption dearsenization activity of the catalyst is higher when the active metal is in an oxidation state. In the existing dearsenification catalyst patents, in order to ensure that an adsorption dearsenification catalyst taking active carbon as a carrier can be successfully prepared, an oxygen-free roasting mode is usually adopted, the mode is firstly complex in process, harsh in conditions and high in cost, and the oxygen-free environment is difficult to ensure that the active metal of the catalyst is converted into an oxidation state, so that the dearsenification activity of the active metal cannot be fully exerted. The aerobic method for preparing the activated carbon-based adsorption dearsenification catalyst has few patents, and other related patents show a definite aerobic roasting process method.
More excellent dearsenifying effect can be obtained by loading a certain active component on the formed carrier. Patent CN101591556B describes a dearsenization agent suitable for deep removal of arsenide in various oils, which is prepared by using one or more oxides of metals in copper oxide, zinc oxide, and group viii as active components, and using alumina as a carrier. The invention reduces the consumption of metal copper with higher price, correspondingly improves the content of other high-activity metals with lower price, further reduces the cost of the dearsenization agent, simultaneously leads the dearsenization rate to reach more than 99.0 percent, and ensures the dearsenization efficiency. However, the present invention does not evaluate the arsenic content of the dearsenization agent and cannot evaluate the dearsenization performance from the perspective of a long cycle.
The dearsenization agent introduced in patent CN102553517A uses copper oxide and zinc oxide as active components, but uses silicon-aluminum oxide as a carrier, and can be applied to the adsorption dearsenization agent of light oil. The method comprises the steps of carrying out carbon burning, grinding and screening on waste silicon-aluminum catalysts which have no recycling value in a fluidized catalytic cracking device to obtain waste catalyst powder, carrying out mixing kneading, strip extruding, drying and roasting on the powder and alumina to obtain a carrier, and then loading active components containing copper oxide and zinc oxide in an impregnation mode to finally obtain the dearsenicating agent. The dearsenization agent is used at 60 ℃ and the space velocity of 2h-1Under the condition, the arsenic removal rate reaches more than 94 percent, the arsenic capacity can reach 0.12 percent, and is improved by 1.3 times compared with the arsenic capacity of 0.09 percent of an industrial contrast agent. The dearsenization agent has good dearsenization performance, and simultaneously, the waste silicon-aluminum catalyst is simply treated, so that waste materials are changed into valuable materials, the pollution to the environment is reduced, and the production cost of the dearsenization agent is reduced. But the arsenic content of the catalyst is 0.12 percent, and the catalyst is lower, so that the requirement of the catalyst on long-period operation cannot be met.
Patent CN101591556A describes a dearsenization agent suitable for deep removal of arsenide in various oils, which is prepared by using one or more oxides of metals in copper oxide, zinc oxide, and group viii as active components, and using alumina as a carrier. The invention reduces the consumption of metal copper with higher price, correspondingly improves the content of other high-activity metals with lower price, further reduces the cost of the dearsenization agent, simultaneously leads the dearsenization rate to reach more than 99.0 percent, and ensures the dearsenization efficiency. However, the same examination of the use of a high concentration of arsine gas and the supplementation of a constant amount of nitrogen gas to determine the dearsenification effect of the gas containing arsine does not represent the dearsenification effect in the oil, and the invention does not evaluate the arsenic content of the dearsenification agent and cannot evaluate the dearsenification performance in terms of a long cycle.
Patent CN201310342825.7 relates to a supported dearsenic agent, the carrier is active carbon, and the active component is metal oxide. When the supported dearsenic agent is prepared, firstly, the activated carbon carrier is pretreated, secondly, a semi-finished product of the supported dearsenic agent impregnated with the active component is prepared, and then the semi-finished product is subjected to alkali treatment, so that the active metal salt component loaded on the activated carbon carrier can be decomposed at a lower temperature to generate an active oxide component. The preparation method is complex in process and difficult to popularize and apply on a large scale.
Patent CN201310279739.6 relates to a liquid hydrocarbon dearsenization agent and a preparation method thereof. The dearsenization agent is prepared by carrying out primary carrier pretreatment and three times of impregnation, and comprises an active component CuO and a transition metal La2O3With CeO2And the noble metal PdO, the AgO auxiliary agent and the active carbon carrier. The preparation process is complicated and is not beneficial to large-scale industrial production.
The patent CN201811162149.4 adopts activated carbon and alumina in a certain proportion as carriers, nickel, copper, molybdenum and cobalt active metal precursors are respectively prepared into solutions, and the solutions are immersed on the carriers step by step and roasted to prepare the Ni-Cu-Mo-Co system adsorption dearsenification catalyst for adsorption dearsenification of gasoline. The preparation process of the method is complicated, and a roasting method for obtaining the oxidation state active metal is not mentioned.
Patent CN201511020498.9 adopts a one-step preparation method, and the precursor for preparing the carrier, the extrusion aid, the nitric acid solution and the prepared active component precursor solution are mixed, wet mixing, strip extrusion and molding are carried out in one step, and the FCC gasoline adsorption dearsenification catalyst is obtained by roasting in a nitrogen atmosphere. The roasting mode of the catalyst is oxygen-free roasting.
Patent CN201310342825.7 relates to a supported dearsenification catalyst, the carrier is activated carbon. The preparation process needs to firstly carry out pretreatment on the activated carbon carrier, and then carry out alkali treatment on the catalyst loaded with metal, so as to ensure that the active metal salt component is decomposed to generate an oxide component under the aerobic condition at a lower temperature, but the preparation process is complex, and a large amount of sodium or potassium ions are enriched on the catalyst by the alkali treatment, so that the activity of the dearsenification catalyst is influenced.
In summary, some of the technologies reported in the patent or literature are limited to written reports and theoretical discussions but are not practically applied, and some technologies, although already applied in industry, have relatively complicated processes and high preparation cost, and are not beneficial to large-scale industrial production and popularization. Meanwhile, the roasting mode of the catalyst containing the activated carbon mostly adopts oxygen-free roasting, and the mode has the advantages of safety and nonflammability, and simultaneously has the defect that some active metals on the catalyst cannot be completely converted into oxidation state metals. After the activated carbon-alumina-based carrier is prepared, the pH value of the metal precursor solution is improved to be higher than the isoelectric point of metal oxide or hydroxide in the impregnation process, the dispersity of metal loaded on the metal precursor solution can be improved, and metal agglomeration is avoided. Meanwhile, the catalyst is continuously calcined step by step at low temperature-medium temperature-high temperature in aerobic environment, so that the preparation cost of the catalyst is reduced, the defect of flammability of activated carbon is overcome, and the active metal precursor is completely converted into an oxidation state, thereby fully exerting the dearsenification activity.
Disclosure of Invention
The invention mainly aims to provide a liquid hydrocarbon adsorption dearsenification catalyst and a preparation method thereof, which overcome the defects of complex process operation, low dearsenification efficiency of the prepared catalyst, small adsorption capacity and short service life in the existing preparation method.
The preparation method of the adsorption dearsenification catalyst is characterized by comprising the following steps of: adding auxiliary agent and acid solution into powder containing activated carbon and pseudo-boehmite, extruding strips, drying and baking under oxygen-free condition to obtain a composite carrier mainly composed of carbon-alumina; adjusting the pH value of the active metal precursor solution to be higher than the isoelectric point of the active metal oxide to prepare an impregnation solution, impregnating the composite carrier by adopting an isovolumetric saturation impregnation method, and then drying and continuously roasting at low temperature-medium temperature-high temperature step by step under aerobic condition to prepare the formed catalyst.
The active carbon of the invention can be one or a mixture of more of wood active carbon, coal active carbon or coconut shell active carbon and the like.
The alumina in the composite carrier prepared by roasting in the invention can be gamma-Al2O3And gamma-Al containing B2O3gamma-Al containing F2O3And gamma-Al containing Si2O3P-containing gamma-Al2O3One or a mixture of several of them.
The auxiliary agent can be an extrusion aid, a pore-expanding agent and the like, and the preferable addition amount accounts for 1-10% of the weight of the carrier; the preferable auxiliary agent is one or a mixture of sesbania powder, methyl cellulose and ethyl cellulose.
In the invention, the powder containing the activated carbon and the pseudo-boehmite is mixed, preferably by rolling and fully stirring, the activated carbon usually has larger pore diameter, the granularity of about 3-6 mm and higher specific surface area, and the specific surface area is usually more than or equal to 500m2And/g, the pseudo-boehmite is fully mixed and preferably rolled, the rolling time is preferably 10-60min, and the stirring time is preferably 10-80 min.
In the invention, the acidic solution is organic acid and/or inorganic acid, preferably one or a mixture of nitric acid, citric acid, phosphoric acid, ethylene diamine tetraacetic acid and oxalic acid.
In the invention, the drying temperature of the carrier is 80-150 ℃, the drying time is 2-6h, the baking temperature in the oxygen-free atmosphere is 400-; the low-temperature roasting temperature of the catalyst is 80-170 ℃, the roasting time is 2-6h, the more preferable roasting temperature is 130-170 ℃, and the roasting time is 2-4 h; the medium-temperature roasting temperature is the decomposition temperature of the active metal precursor +/-40 ℃, the roasting time is 1-6h, and the more preferable first-step aerobic roasting temperature is the decomposition temperature of the active metal precursor +/-20 ℃, and the roasting time is 2-4 h; the high-temperature roasting temperature is 300-500 ℃, the roasting time is 1-6h, the more preferable high-temperature roasting temperature is 350-450 ℃, and the roasting time is 2-4 h.
In the present invention, it is not particularly limited which active metal is used, and metals generally used in the prior art for arsenic removal may be used, such as one or more of group VIII elements in the periodic Table, one or more of transition metal elements, one or more of alkali metal or alkaline earth metal elements, and the like. The invention also particularly recommends that a metal with a partially filled d track is selected as an active metal, so that the active acting force between the arsenide and the metal can be improved, a strong metal-arsenic chemical bond is formed, and the arsenide is efficiently and deeply removed. The active metal is preferably one or more of Ni, Cu, Co, Zn, Mo, Fe, Pb, V, Ag and Mn; the active metal precursor is one or more of corresponding nitrate, acetate, sulfate and alkali carbonate.
The isoelectric point refers to the pH value of a molecule or a surface without charges. In the invention, the pH value of the metal precursor solution is required to be increased to be higher than the isoelectric point of the oxide or hydroxide of the main agent metal element, so that the acting force between the main agent metal and the carrier can be weakened, the dispersion degree of the metal loaded on the main agent metal is improved, and the higher dearsenization efficiency is realized. Table 1 shows the isoelectric point data of the metals used.
TABLE 1 isoelectric points of oxides or hydroxides of common metal elements
The catalyst is prepared by adopting an impregnation loading mode, and particularly, the catalyst is prepared by adopting an isometric saturation impregnation mode, which is greatly different from the preparation by a coprecipitation method. Activated carbon and pseudo-boehmite powder and an active metal precursor solution are subjected to coprecipitation, forming, drying and roasting, the roasting temperature is too high to be beneficial to dispersion of active metals, the roasting temperature is too low to influence the form of alumina, and most metal components are not distributed on pore channels and outer surfaces of a carrier in high dispersion degree due to the dearsenization catalyst obtained in the coprecipitation process, so that the metal utilization rate is low; meanwhile, the prepared active component precursor solution is mixed with alumina/activated carbon to extrude strips in an acidic environment, the acting force between the carrier and metal is strong under the strong acid condition, and the metal is more easily agglomerated, so that the utilization efficiency is further reduced. The catalyst obtained by the method cannot meet the requirement of long-period dearsenification of the liquid hydrocarbon with high arsenic content.
The carrier prepared by using the activated carbon or the pseudo-boehmite alone cannot obtain good arsenic removal effect. According to the invention, the activated carbon and the pseudo-boehmite are compounded for use, the structural characteristics of the carrier are optimized, the pore volume and the specific surface area of the composite carrier are improved, the dispersion of pore channels and pore diameters is more uniform, multistage and ordered, the carbon-alumina composite carrier with appropriate specific surface area and multistage pore channel distribution can be prepared by regulating and controlling the addition proportion of the activated carbon, and the diffusion, reaction and escape of reactant molecules in the pore channels are facilitated.
The invention also provides the adsorption dearsenification catalyst obtained by the preparation method, preferably, in the composite carrier, the weight ratio of activated carbon: alumina is 0.5-2: 1. the preferred adsorption dearsenification catalyst accounts for 15-25% by mass of the catalyst based on 100% by mass of the active metal oxide.
The invention also provides a more specific adsorption dearsenification catalyst, which takes the catalyst as 100 mass percent as a reference, and is calculated by the oxides of respective metals, wherein the content of Cu or Mo is 5-30 mass percent, the content of Co or Ni is 1-11 mass percent, the content of Zn or Mn is 0-10 mass percent, and the total loading of Zn, Fe, Pb, V and Ag is 1-5 mass percent.
The specific surface area of the catalyst recommended by the invention is 350-550 m2The pore volume is 0.55-0.75 mL/g, and the bulk density is 0.48-0.58 g/cm3The most probable pore diameter is 7-11 nm; more preferably, the specific surface area is 400 to 500m2(ii) a pore volume of 0.60 to 0.70mL/g and a bulk density of 0.50 to 0.55g/cm3The most probable pore diameter is 8-9 nm.
The invention particularly provides a more preferable preparation method of an adsorption dearsenification catalyst, which mainly comprises the following specific preparation steps:
(1) and mixing the activated carbon and the pseudo-boehmite according to the mass ratio of 0.5-2: 1, adding an auxiliary agent accounting for 1-10% of the mass of the carrier, such as one or a mixture of sesbania powder, methylcellulose and ethylcellulose, adding an acid, such as one or a mixture of nitric acid, citric acid, phosphoric acid, ethylene diamine tetraacetic acid and oxalic acid, grinding for 10-60min, stirring for 10-60min, and forming, such as a phi 3.0 clover shape, at 80-150 ℃, and drying for 2-6 h. The roasting temperature in the oxygen-free atmosphere is 400-750 ℃, and the roasting time is 1-6 h. Obtaining the composite carrier.
(2) Putting mixed metal salt containing one or more of Cu, Zn and Co into a solution containing water or ammonia water, adjusting the pH value of the solution to be higher than the isoelectric point of the used metal, and then heating and stirring until the metal salt is dissolved;
(3) adding one or more mixed salts containing Ni, Fe, Mo, Pb, V, Ag or Mn into the solution containing the step (2), and continuously adjusting the pH value of the solution to be higher than the isoelectric point of the metal precursor salt so as to completely dissolve the metal salt;
(4) loading the impregnation liquid prepared in the step (3) on the composite carrier prepared in the step (1) by adopting an isometric saturated impregnation method, and standing for 12-24 hours to prepare a catalyst;
(5) the low-temperature roasting temperature is 130-; the medium-temperature roasting temperature is the decomposition temperature of the active metal precursor +/-20 ℃, and the roasting time is 2-4 h; the high-temperature roasting temperature is 350-450 ℃, and the roasting time is 2-4 h.
The invention has the advantages that:
(1) the preparation method firstly prepares the carrier with the composite pore structure distribution, which is beneficial to the high dispersion of metal components on the carrier, improves the utilization rate of metal, and simultaneously can improve the diffusion, reaction and escape of reactant molecules in the pore and improve the reaction efficiency;
(2) the metal with a partially filled d track is selected as the active metal, so that the active acting force between the arsenide and the metal can be improved, a strong metal-arsenic chemical bond is formed, and the arsenide is efficiently and deeply removed;
(3) the pH value of the metal precursor solution is increased to be higher than the isoelectric point of metal oxide or hydroxide, so that the acting force between metal and a carrier can be weakened, the dispersion degree of metal loaded on the metal can be improved, the metal agglomeration condition is avoided, and the dearsenification efficiency of the catalyst is finally improved.
(4) The roasting temperature and the roasting step of the catalyst are adjusted in an aerobic environment, and a low-temperature-medium-high-temperature step-by-step continuous roasting method is adopted, so that the preparation cost of the catalyst is reduced, the defect of flammability of activated carbon is overcome, and the active metal precursor is completely converted into an oxidation state, thereby fully exerting the dearsenification activity. The catalyst prepared by the method shows excellent arsenic removal performance, high arsenic capacity and high arsenic removal stability.
Drawings
FIG. 1 is an XRD characterization spectrum of the adsorption dearsenification catalysts of example 2, example 7, comparative example 1 and comparative example 2.
Detailed Description
The following examples are intended to further illustrate the process of the present invention but should not be construed as limiting thereof.
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical solution of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the following examples do not indicate process parameters of specific conditions, and generally follow conventional conditions.
Example 1
Mixing 500g of activated carbon, 1000g of pseudo-boehmite, 30g of sesbania powder and 20g of methyl cellulose for 5min, adding 1600g of aqueous solution containing 5% of nitric acid, rolling for 30min, kneading for 30min, extruding strips by a phi 3.0 pore plate, drying for 2h at 120 ℃, and roasting for 4h at 450 ℃ in an oxygen-free atmosphere to obtain the carrier Z-1. Taking 10g of carrier, dissolving 5.5g of cupric nitrate in deionized water, and loading the impregnation liquid to the carrier Z by adopting an isometric saturated impregnation method-1, standing and airing for 12h, carrying out aerobic roasting at 130 ℃ for 4h, and then carrying out roasting at a volume space velocity of 200m3.h-1And after nitrogen with the oxygen content of 2% is blown for 30min, roasting for 4h at 240 ℃, and carrying out aerobic roasting for 2h at 350 ℃ to obtain the catalyst C1.
Example 2
Mixing 500g of activated carbon, 500g of pseudo-boehmite, 50g of sesbania powder and 50g of methyl cellulose for 5min, adding 1000g of aqueous solution containing 5% nitric acid, rolling for 30min, kneading for 30min, extruding strips by a phi 3.0 pore plate, drying for 2h at 120 ℃, and roasting for 4h at 450 ℃ in an oxygen-free atmosphere to obtain the carrier Z-2. Taking 10g of carrier, dissolving 7.2g of copper nitrate in deionized water, loading the impregnation liquid on the carrier Z-2 by adopting an isometric saturation impregnation method, standing and airing for 12h, then carrying out aerobic roasting for 4h at 130 ℃, and then carrying out roasting at a volume space velocity of 200m3.h-1And after nitrogen with the oxygen content of 2% is blown for 30min, roasting for 4h at 240 ℃, and carrying out aerobic roasting for 2h at 350 ℃ to obtain the catalyst C2.
Example 3
Mixing 1000g of activated carbon, 500g of pseudo-boehmite, 80g of sesbania powder and 80g of ethyl cellulose for 5min, adding 1600g of aqueous solution containing 5% of nitric acid, rolling for 30min, kneading for 30min, extruding strips by a phi 3.0 pore plate, drying for 2h at 120 ℃, and roasting for 4h at 450 ℃ in an oxygen-free atmosphere to obtain the carrier Z-3. Taking 10g of carrier, dissolving 9.5g of copper nitrate in deionized water, loading the impregnation liquid to the carrier Z-3 by adopting an isometric saturated impregnation method, standing and airing for 12h, carrying out aerobic roasting at 150 ℃ for 3h, and then carrying out aerobic roasting at a volume space velocity of 300m3.h-1And after nitrogen with the oxygen content of 2% is blown for 30min, roasting for 4h at 260 ℃, and carrying out aerobic roasting for 2h at 400 ℃ to obtain the catalyst C3.
Example 4
Taking 10g of carrier Z-1, dissolving 6.0g of copper nitrate and 1.0g of nickel nitrate in deionized water, loading the impregnation liquid on the carrier by adopting an isometric saturation impregnation method, standing and airing for 12h, then drying for 2h at 120 ℃, carrying out aerobic roasting for 4h at 130 ℃, and then carrying out aerobic roasting at a volume space velocity of 300m3.h-1And after nitrogen with the oxygen content of 2% is blown for 50min, roasting for 4h at 260 ℃ and carrying out aerobic roasting for 2h at 400 ℃ to finally obtain the catalyst C4.
Example 5
Taking 10g of carrier Z-1, dissolving 6.0g of copper nitrate and 1.0g of nickel nitrate in deionized water, adjusting the pH value of the solution to 11.0 by using ammonia water, loading the impregnation solution to the carrier Z-1 by adopting an isovolumetric saturated impregnation method, standing and airing for 12h, carrying out aerobic roasting at 170 ℃ for 2h, and then carrying out aerobic roasting at a volume space velocity of 300m3.h-1And roasting the mixture for 4 hours at 260 ℃ in a nitrogen atmosphere with the oxygen content of 2 percent, and roasting the mixture for 2 hours at 350 ℃ in an aerobic manner to finally obtain the catalyst C5.
Example 6
Taking 10g of carrier Z-2, dissolving 6.0g of copper nitrate and 1.0g of nickel nitrate in deionized water, adjusting the pH value of the solution to 12.0 by using ammonia water, loading the impregnation liquid to the carrier Z-2 by adopting an equal-volume saturated impregnation method, standing and airing for 12h, carrying out aerobic roasting at 170 ℃ for 2h, and then carrying out aerobic roasting at a volume space velocity of 300m3.h-1And roasting the mixture for 4 hours at 260 ℃ in a nitrogen atmosphere with the oxygen content of 2 percent, and roasting the mixture for 2 hours at 350 ℃ in an aerobic manner to finally obtain the catalyst C6.
Example 7
Taking 10g of carrier Z-3, dissolving 8.0g of copper nitrate, 0.6g of nickel nitrate and 1.2g of zinc nitrate in deionized water, adjusting the pH value of the solution to 11.0 by using ammonia water, loading the impregnation liquid to the carrier Z-3 by adopting an isovolumetric saturated impregnation method, standing, airing for 12h, carrying out aerobic roasting for 3h at 150 ℃, and then carrying out aerobic roasting at a volume airspeed of 300m3.h-1And roasting at 280 ℃ for 4h in a nitrogen atmosphere with the oxygen content of 2%, and roasting at 400 ℃ for 2h in an aerobic manner to finally obtain the catalyst C7.
Example 8
Taking 10g of carrier Z-3, dissolving 10.0g of copper nitrate, 1.2g of nickel nitrate and 1.0g of ferric nitrate in deionized water, adjusting the pH value of the solution to 11.0 by using ammonia water, loading the impregnation liquid to the carrier Z-3 by adopting an isovolumetric saturated impregnation method, standing, airing for 12h, carrying out aerobic roasting for 3h at 150 ℃, and then carrying out aerobic roasting at a volume airspeed of 300m3.h-1And roasting at 280 ℃ for 4h in a nitrogen atmosphere with the oxygen content of 2%, and roasting at 400 ℃ for 2h in an aerobic manner to finally obtain the catalyst C8.
Example 9
Taking 10g of carrier Z-3, dissolving metal salts of copper nitrate 8.0g, nickel nitrate 2.5g and cobalt nitrate 1.0g in deionized water, adjusting the pH value of the solution to 13.0 by using ammonia water, and adopting the methodLoading the impregnation liquid on a carrier Z-3, standing and airing for 12h, carrying out aerobic roasting at 130 ℃ for 4h, and then carrying out volume space velocity of 300m3.h-1And after nitrogen with the oxygen content of 2% is blown for 40min, roasting for 4h at 260 ℃ and roasting for 2h with oxygen at 450 ℃ to finally obtain the catalyst C9.
Example 10
Taking 10g of carrier Z-3, dissolving 12.0g of copper nitrate, 3.0g of nickel nitrate and 4.5g of ammonium molybdate in deionized water, adjusting the pH value of the solution to be 11.0 by using ammonia water, loading the impregnation liquid to the carrier Z-3 by adopting an isometric saturated impregnation method, standing, airing for 12h, carrying out aerobic roasting at 130 ℃ for 4h, and then carrying out aerobic roasting at a volume airspeed of 300m3.h-1And after nitrogen with the oxygen content of 2% is blown for 40min, roasting for 4h at 260 ℃ and roasting for 2h with oxygen at 450 ℃ to finally obtain the catalyst C10.
Example 11
Taking 10g of carrier Z-3, dissolving 5.0g of copper nitrate, 3.0g of nickel nitrate and 8.0g of lead nitrate in deionized water, adjusting the pH value of the solution to 12.0 by using ammonia water, loading the impregnation liquid to the carrier Z-3 by adopting an isometric saturated impregnation method, standing, airing for 12h, carrying out aerobic roasting at 170 ℃ for 2h, and then carrying out aerobic roasting at a volume airspeed of 300m3.h-1And after nitrogen with the oxygen content of 2% is blown for 20min, roasting at 260 ℃ for 4h, and carrying out aerobic roasting at 350 ℃ for 2h to finally obtain the catalyst C11.
Example 12
Taking 10g of carrier Z-3, dissolving 8.0g of copper nitrate, 1.5g of nickel nitrate and 6.0g of ammonium metavanadate in deionized water, adjusting the pH value of the solution to 10.0 by using ammonia water, loading the impregnation liquid to the carrier Z-3 by adopting an isovolumetric saturated impregnation method, standing, airing for 12h, carrying out aerobic roasting at 170 ℃ for 2h, and then carrying out aerobic roasting at a volume airspeed of 300m3.h-1And after nitrogen with the oxygen content of 2% is blown for 20min, roasting at 260 ℃ for 4h, and carrying out aerobic roasting at 350 ℃ for 2h to finally obtain the catalyst C12.
Example 13
Taking 10g of carrier Z-3, dissolving 9.0g of copper nitrate, 1.5g of nickel nitrate and 2.5g of silver nitrate in deionized water, adjusting the pH value of the solution to 12.0 by using ammonia water, loading the impregnation liquid to the carrier Z-3 by adopting an equal-volume saturated impregnation method, standing and airing for 12h at 130 DEG COxygen roasting for 4h, and then at a volume space velocity of 400m3.h-1And after nitrogen with the oxygen content of 2% is blown for 40min, roasting for 4h at 240 ℃, and carrying out aerobic roasting for 2h at 350 ℃ to finally obtain the catalyst C13.
Example 14
Taking 10g of carrier Z-3, dissolving 5.0g of copper acetate, 1.0g of nickel acetate and 4.0g of ferric nitrate in deionized water, adjusting the pH value of the solution to 12.0 by using ammonia water, loading the impregnation liquid to the carrier Z-3 by adopting an isometric saturated impregnation method, standing, airing for 12h, carrying out aerobic roasting at 130 ℃ for 4h, and then carrying out aerobic roasting at a volume airspeed of 400m3.h-1And after nitrogen with the oxygen content of 2% is blown for 40min, roasting for 4h at 240 ℃, and carrying out aerobic roasting for 2h at 350 ℃ to finally obtain the catalyst C14.
Example 15
Taking 10g of carrier Z-3, dissolving 3.0g of copper acetate, 5.0g of nickel acetate and 6.0g of silver nitrate in deionized water, adjusting the pH value of the solution to 11.0 by using ammonia water, loading the impregnation liquid to the carrier Z-3 by adopting an isovolumetric saturated impregnation method, standing, airing for 12h, carrying out aerobic roasting for 3h at 150 ℃, and then carrying out aerobic roasting at a volume airspeed of 400m3.h-1And after nitrogen with the oxygen content of 2% is blown for 20min, roasting for 4h at 240 ℃, and roasting for 2h with oxygen at 450 ℃ to finally obtain the catalyst C15.
Example 16
Taking 10g of carrier Z-3, dissolving 3.0g of copper sulfate, 8.0g of nickel acetate and 6.0g of silver nitrate in deionized water, adjusting the pH value of the solution to 12.0 by using ammonia water, loading the impregnation solution to the carrier Z-3 by adopting an isovolumetric saturated impregnation method, standing, airing for 12h, carrying out aerobic roasting for 3h at 150 ℃, and then carrying out aerobic roasting at a volume airspeed of 400m3.h-1And after nitrogen with the oxygen content of 2% is blown for 20min, roasting for 4h at 240 ℃, and roasting for 2h with oxygen at 450 ℃ to finally obtain the catalyst C16.
Comparative example 1
Adding 50g of activated carbon molding composite binder into 300g of activated carbon, and extruding a phi 3.0 pure carbon carrier strip AC 1. 10gAC1 is taken, 10.0g of copper nitrate, 1.0g of nickel nitrate and 2.0g of zinc nitrate are dissolved in deionized water, the impregnation liquid is loaded on a carrier by an isometric saturation impregnation method, the carrier is kept stand and dried for 12h, the carrier is dried for 2h at 120 ℃, and the carrier is roasted for 4h without oxygen at 500 ℃, so that the catalyst D1 is finally obtained.
Comparative example 2
Adding 10g of sesbania powder into 300g of pseudo-boehmite, uniformly mixing, adding 200g of aqueous solution containing 3% of nitric acid solution, rolling, stirring, extruding phi 3.0 strips, drying at 120 ℃ for 2h, and roasting at 550 ℃ for 4h to obtain the alumina carrier strip. Taking 10g of alumina carrier strip, dissolving 5.0g of copper nitrate, 2.0g of nickel nitrate and 6.0g of zinc nitrate in deionized water, loading the impregnation liquid on the alumina carrier by an isometric saturated impregnation method, standing and airing for 12h, then drying for 2h at 120 ℃, and carrying out anaerobic roasting for 4h at 500 ℃ to finally obtain the catalyst D2.
Comparative example 3
Adding 10g of sesbania powder into 300g of pseudo-boehmite, uniformly mixing, adding 200g of aqueous solution containing 3% of nitric acid solution, rolling, stirring, extruding phi 3.0 strips, drying at 120 ℃ for 2h, and roasting at 550 ℃ for 4h to obtain the alumina carrier strip. Taking 10g of alumina carrier strip, dissolving 7.0g of copper nitrate, 3.0g of nickel nitrate and 3.0g of zinc nitrate in deionized water, loading the impregnation liquid on the alumina carrier by an isometric saturated impregnation method, standing and airing for 12h, and carrying out aerobic roasting at 350 ℃ for 3h to obtain the catalyst D3. Since there is no fractional calcination, part of the catalyst is oxidized by oxygen and the surface is grayed.
Evaluation of catalytic performance:
in this test example, the arsenic removal activities of the adsorption-dearsenification catalyst prepared by the method of the present invention and the adsorption-dearsenification catalyst provided in the comparative example were evaluated in accordance with the following methods, and the results were shown.
Adsorption dearsenification: full-fraction FCC gasoline with the arsenic content of 125ppb is used as a raw material, and the adsorption and dearsenification activity of the catalyst is evaluated on a continuous high-pressure reaction device. The raw oil is fed in and discharged out from the bottom. The reaction conditions are as follows: the weight hourly space velocity is 3.0h-1, the temperature is 20 ℃, and the pressure is 0.5 MPa. After the reaction is stable for 24 hours, a sample is taken, the arsenic content of the sample is analyzed by graphite furnace atomic absorption spectrometry, and the result is shown in table 1. The arsenic content determination adopts a mode of adding triphenylarsenic into FCC gasoline to prepare standard sample gasoline A containing arsenic with the arsenic content of 2000ppm, 10g of catalyst is taken and placed into 100g of standard sample gasoline containing arsenic, after oscillation for 24h, standard sample gasoline B after arsenic removal is obtained, after the arsenic content in the gasoline B is determined, the arsenic content of the catalyst is obtained by calculation and is shown in Table 2.
The dearsenification rate is calculated according to formula 1:
the arsenic content is calculated according to equation 2:
TABLE 2 evaluation results of adsorption dearsenification activity of catalyst
The results in table 1 show that the adsorption dearsenification catalyst with high dearsenification efficiency and high arsenic content is successfully prepared by a method for preparing the carrier composition and loading the active metal component, and shows more excellent adsorption dearsenification activity compared with a contrast agent prepared from pure active carbon and alumina.
Catalyst structural characterization
This test example compares the XRD characterization results of catalysts C2, C7, D-1 and D-2 provided by the present invention. From fig. 1, it can be seen that under the condition of equivalent metal loading, the D1 and D2 catalysts prepared by using the conventional activated carbon and alumina as the supports have obvious characteristic diffraction peaks attributed to crystalline CuO, which indicates that the dispersion degree of CuO on the catalyst is poor. On the C2 catalyst prepared by mixing the activated carbon and the alumina in the mass ratio of 1:1, the characteristic diffraction peak intensity ratio D1 and D2 of CuO is greatly reduced, which shows that the addition of the activated carbon greatly improves the dispersion degree of metals on the catalyst. The active carbon in the C7 catalyst is greatly added, the specific surface area and the pore structure of the catalyst are greatly improved, the pH value of the solution is adjusted to be 11 and is higher than the isoelectric point of CuNiZn three metal oxides, at the moment, the metal components can be better dispersed without agglomeration, and the metal dispersion degree is greatly improved. This is a good indication that the preparation techniques provided by the present invention are advantageous in achieving high loadings of active ingredient while maintaining a high degree of dispersion of the active ingredient.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (13)
1. The preparation method of the liquid hydrocarbon adsorption dearsenification catalyst is characterized by comprising the following steps:
step 1: mixing activated carbon and pseudo-boehmite powder, adding an auxiliary agent and an acidic solution, extruding and forming to obtain a formed carrier;
step 2: drying the formed carrier, and roasting under an oxygen-free condition to obtain a composite carrier with a main component of carbon-alumina;
and step 3: adjusting the pH value of the active metal precursor solution to be higher than the isoelectric point of the active metal oxide to prepare impregnation liquid;
and 4, step 4: impregnating the composite carrier by adopting an isometric saturated impregnation method, and then drying to obtain a dried catalyst;
and 5: continuously roasting the dried catalyst step by step at low temperature-medium temperature-high temperature under aerobic condition to obtain a finished product catalyst;
the isoelectric point refers to the pH value of a molecule or a surface without electric charge.
2. The method for preparing a liquid hydrocarbon adsorbing and dearsenifying catalyst as claimed in claim 1, wherein the activated carbon is at least one selected from the group consisting of wood activated carbon, coal activated carbon and coconut shell activated carbon.
3. The liquid according to claim 1The preparation method of the catalyst for adsorbing and dearsenifying the hydrocarbon is characterized in that the pseudo-boehmite is gamma-Al in the step 12O3And gamma-Al containing B2O3gamma-Al containing F2O3And gamma-Al containing Si2O3And gamma-Al containing P2O3At least one of (1).
4. The method for preparing a liquid hydrocarbon adsorption dearsenification catalyst according to claim 1, wherein the auxiliary agent is at least one of sesbania powder, methyl cellulose and ethyl cellulose, and the addition amount of the auxiliary agent is 1-10% of the total weight of the composite carrier.
5. The method for preparing a liquid hydrocarbon adsorption dearsenification catalyst according to claim 1, wherein the acidic solution is an organic acid and/or an inorganic acid.
6. The method for preparing a liquid hydrocarbon adsorption dearsenification catalyst according to claim 5, wherein the acidic solution is at least one of nitric acid, citric acid, phosphoric acid, ethylene diamine tetraacetic acid and oxalic acid.
7. The method for preparing a liquid hydrocarbon adsorption arsenic-removal catalyst as claimed in claim 1, wherein in the step 2, the drying temperature is 80-150 ℃, the drying time is 2-6h, the calcination temperature under oxygen-free condition is 750 ℃.,. the calcination time is 1-6h, the oxygen-free condition is inert gas or nitrogen atmosphere, more preferably the drying temperature is 100-; in the step 5, the low-temperature roasting temperature is 80-170 ℃, the roasting time is 2-6h, the more preferable roasting temperature is 130-; the medium-temperature roasting temperature is the decomposition temperature of the active metal precursor +/-40 ℃, the roasting time is 1-6h, and the more preferable medium-temperature roasting temperature is the decomposition temperature of the active metal precursor +/-20 ℃, and the roasting time is 2-4 h; the high-temperature roasting temperature is 300-500 ℃, the roasting time is 1-6h, the more preferable high-temperature roasting temperature is 350-450 ℃, and the roasting time is 2-4 h.
8. The method for preparing a liquid hydrocarbon adsorbing and dearsenifying catalyst as claimed in claim 1, wherein the active metal is at least one selected from the group VIII elements, transition metal elements, alkali metals or alkaline earth metal elements.
9. The method for preparing a liquid hydrocarbon adsorption dearsenification catalyst according to claim 8, wherein the active metal is at least one selected from the group consisting of Ni, Cu, Co, Zn, Mo, Fe, Pb, V, Ag, and Mn; the active metal precursor is at least one of nitrate, acetate, sulfate and basic carbonate corresponding to the active metal.
10. The method for preparing the liquid hydrocarbon adsorption dearsenification catalyst according to claim 9, wherein the mass ratio of the activated carbon to the pseudo-boehmite is 0.5-2: 1; the molding condition is rolling for 10-60min, and stirring for 10-80 min; the molded shape is at least one of clover, sphere and dentate sphere.
11. A liquid hydrocarbon adsorption dearsenification catalyst obtained by the preparation method according to any one of claims 1 to 10, wherein the active metal is 15 to 25 wt% in terms of oxide.
12. The liquid hydrocarbon adsorption dearsenification catalyst as claimed in claim 11, wherein the active metal has a Cu or Mo content of 5 to 30 wt%, a Co or Ni content of 1 to 11 wt%, a Zn or Mn content of 0 to 10 wt%, and a total loading of Zn, Fe, Pb, V, Ag of 0 to 5 wt%, based on 100 mass% of the catalyst, in terms of the oxide of each metal.
13. The liquid hydrocarbon adsorption dearsenification catalyst as claimed in claim 11, wherein the adsorption dearsenification catalyst has a specific surface area of 350-550 m2(ii) a pore volume of 0.55 to 0.75mL/g and a bulk density of 0.48 to 0.58g/cm3The most probable pore diameter is 7-11 nm; more preferably, the specific surface area is 400 to 500m2(iv) per gram, pore volume of 0.60 to 0.70mL/g, bulk density of 0.50 to 0.55g/cm3The most probable pore diameter is 8-9 nm.
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| CN115254131A (en) * | 2022-08-09 | 2022-11-01 | 南京工业大学 | Thermal desorption catalyst for solid heat carrier organic matter contaminated soil and preparation method thereof |
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| CN115254131A (en) * | 2022-08-09 | 2022-11-01 | 南京工业大学 | Thermal desorption catalyst for solid heat carrier organic matter contaminated soil and preparation method thereof |
| CN115254131B (en) * | 2022-08-09 | 2023-04-25 | 南京工业大学 | Thermal desorption catalyst for solid heat carrier organic matter contaminated soil and preparation method thereof |
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