CN114713187A - Liquid light hydrocarbon component adsorption dearsenic agent and preparation method thereof - Google Patents

Liquid light hydrocarbon component adsorption dearsenic agent and preparation method thereof Download PDF

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CN114713187A
CN114713187A CN202110015505.5A CN202110015505A CN114713187A CN 114713187 A CN114713187 A CN 114713187A CN 202110015505 A CN202110015505 A CN 202110015505A CN 114713187 A CN114713187 A CN 114713187A
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light hydrocarbon
liquid light
agent
activated carbon
adsorption
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冯琪
李阳
姜增琨
葛少辉
何盛宝
康宏敏
赵秦峰
袁晓亮
鞠雅娜
孙洪磊
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Petrochina Co Ltd
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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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention relates to a preparation method of a liquid light hydrocarbon component adsorption dearsenic agent, which comprises the following steps: (1) adding silica sol into a carrier precursor consisting of activated carbon and silicon dioxide to prepare a carrier, adding an active metal precursor solution, mixing, rolling, stirring, extruding and forming; (2) drying and carrying out high-temperature heat treatment on the water vapor to obtain the liquid light hydrocarbon component adsorption dearsenic agent. The adsorption dearsenization agent prepared by the method has high proportion of mesopores and macropores, high diffusion efficiency of liquid light hydrocarbon components in the catalyst, and the advantages of high dearsenization activity, large arsenic capacity, long service life, simple preparation process, low production cost, easy large-scale popularization and application and the like.

Description

Liquid light hydrocarbon component adsorption dearsenic agent and preparation method thereof
Technical Field
The invention relates to an adsorption dearsenifying agent for liquid light hydrocarbon components and a preparation method thereof, in particular to an adsorption dearsenifying agent with multi-stage pore structure distribution, which is suitable for dearsenifying naphtha and catalytic cracking gasoline.
Background
It is known that liquid light hydrocarbon components in petroleum contain various trace elements, such as: arsenic, lead, copper, iron, nickel, mercury, etc., wherein the content of arsenide is extremely low, but the arsenide has a great influence on subsequent processing, particularly on the catalytic hydrodesulfurization process, and can cause catalyst poisoning and even deactivation. Arsenides in petroleum hydrocarbons are mainly trivalent organic arsenic complexes, with R3As form, wherein R is hydrogen atom or alkyl group such As methyl, ethyl, propyl or phenyl, etc., and organic arsenic complexes with different boiling points are respectively introduced into each fraction after crude oil fractionation. Low boiling arsenides in liquid petroleum hydrocarbons include AsH3、 CH3AsH2Etc., high boiling arsenides include As (CH)3)3、As(C2H5)3And the like. The presence of these arsenides can cause some processes to be unable to run smoothly, thus seriously affecting the quality and economic benefits of the products.
The adsorption dearsenization technology is that at a lower temperature (100 ℃), an arsenide and an active metal of a dearsenization agent are combined together in a chemical adsorption mode, and arsenic and the active metal generate partial electron cloud transfer and are adsorbed on the surface of an active group of the metal, so that the purpose of dearsenization is achieved. 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, and can treat raw materials with complex components, wide range and high arsenic content. The main problems faced by the adsorption dearsenification technology are that the adsorption dearsenification catalyst serving as the technical core of the 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 waste residue is difficult to treat, and the environmental pollution is easily caused. Therefore, the low-temperature adsorption dearsenification catalyst which has the advantages of large arsenic capacity, high dearsenification efficiency, long service life and easy treatment of waste residue is always a research hotspot of the liquid hydrocarbon arsenide removal catalyst.
The dearsenization agent for adsorbing dearsenization mainly comprises two parts of a carrier and an active component, and also comprises other small amount of auxiliary agents. The common carrier is one or a mixture of more of alumina, silicon dioxide, manganese oxide, titanium dioxide, activated carbon, molecular sieve and silicon-aluminum oxide, the main active component is one or more of transition metals such as copper, zinc, manganese and the like or oxides thereof, and rare earth elements such as lanthanum, cerium, samarium and the like and noble metals such as gold, silver, rhodium, palladium and the like are added as auxiliary active components in some dearsenization agents.
Chinese patent CN 101590409C discloses a lead-based dearsenization agent of liquid hydrocarbon and gaseous hydrocarbon, which adopts one or more transition metal oxides and PbO as active components, has high lead content and good dearsenization effect, but because lead belongs to heavy metal, the lead-based dearsenization agent seriously pollutes the environment, and the dearsenization agent does not meet the requirement of environmental protection.
Chinese patent CN 1197052a discloses a method for removing arsenide from liquid hydrocarbon, the used catalyst is copper oxide or copper sulfide prepared by coprecipitation method, it is suitable for dearsenification process of liquid hydrocarbon under low temperature and low pressure hydrogen-free condition, but the preparation process is complex, and the catalyst needs to be sulfurized before use, so the preparation and operation cost is high.
Chinese patent CN 1294174A discloses a dearsenization agent for light oil and a preparation method thereof, the catalyst adopts alumina and aluminosilicate molecular sieves as main components, active metal components do not need to be impregnated, the catalyst is used for dearsenization only by physical adsorption, the arsenic capacity is small, the cost for producing catalyst powder is high, and the dearsenization effect is poor.
Chinese patent CN 1043151C discloses a dearsenification catalyst for liquid hydrocarbon and a preparation method thereof, the catalyst consists of an active component containing nickel and an alumina carrier, the catalyst is reduced by introducing mixed gas of at least 10% of hydrogen at 250-450 ℃, then hydrogen is introduced at 300 ℃ for activation, the activated catalyst is used for dearsenification of the arsenic-containing liquid hydrocarbon at 80-250 ℃, and the arsenic content of the liquid hydrocarbon can be reduced to below 5 ppb. Before the dearsenization catalyst is used, hydrogen is needed for reduction and activation, the reaction temperature is high, and the start-up is complex. And only alumina is used as a carrier, so that the specific surface area is small, the bulk ratio is large, and the cost is high.
Chinese patent CN 109251764A discloses a dearsenic agent suitable for gasoline, a preparation method and application thereof, wherein the dearsenic agent carrier is a mixture of activated carbon and alumina, and the active component is a Ni-Cu-Mo-Co system. The preparation process needs 4 times of dipping and roasting to obtain the finished product dearsenic agent, has complex process and high cost, and is not beneficial to large-scale industrial production.
Chinese patent CN 106000280B discloses a supported dearsenifying catalyst and a preparation method thereof, wherein the dearsenifying agent carrier is porous amorphous magnalium crystalloid, and the active component comprises NiMn2O4Spinel. The dearsenization agent can perform dearsenization treatment on coal synthesis gas under the conditions of high temperature, high pressure, high steam-gas ratio and high concentration CO. The porous amorphous magnalium crystallite is unstable in property and is easily influenced by the outside, so that the performance of the porous amorphous magnalium crystallite is changed, side reactions are increased, and the target product and the arsenic removal effect are influenced. In addition, the reaction conditions of the dearsenization agent are not suitable for dearsenization reaction of liquid-phase light hydrocarbon components in petroleum.
Chinese patent CN 105562008B discloses a normal temperature dearsenic agent and a preparation method thereof, the raw materials of the normal temperature dearsenic agent are copper oxide, zinc oxide, nickel oxide and/or lead oxide, attapulgite clay and waste catalyst, silica sol and/or methyl cellulose are added, and the finished product dearsenic agent is obtained by mixing, kneading, rolling, drying and roasting. The preparation method overcomes the problems of complex production process and low production capacity in the prior art, but the normal-temperature dearsenic agent is mainly used for removing arsenic element in ethylene and/or propylene, belongs to the technical field of gas purification, and is not described for liquid light hydrocarbon components in petroleum.
Chinese patent CN 105562000A discloses a normal temperature dearsenic agent and a preparation method thereof, and the normal temperature dearsenic agent comprises a carrier and a Cu-Ni active component loaded on the carrier. The carrier is one of active carbon, alumina, silica gel or titanium-aluminum composite oxide, and the Cu-Ni active component is NiO and CuO. The normal temperature dearsenization agent is mainly used for removing inorganic arsenic in catalytic cracking gasoline. The preparation method has the disadvantages that the first step of the catalyst preparation process adopts a rotary vacuum impregnation method to impregnate nickel salt, the second impregnation of copper salt is ultrasonic impregnation, two steps of nitrogen roasting are needed, the preparation process is very complicated, the preparation condition requirement is high, the production cost is high, and the large-scale industrial production is not facilitated.
Chinese patent CN 1197052a discloses an arsenic removing agent comprising as an active component at least one of copper oxide or copper sulfide deposited on alumina spheres, silica support, which achieves arsenic removal from liquid hydrocarbon feedstock at a temperature in the range of 0 ℃ to 100 ℃, at low pressure and in the complete absence of hydrogen. The preparation of the dearsenization agent still needs a vulcanization process, the dearsenization agent has small specific surface area, weaker adsorption capacity to high boiling point arsenide and low arsenic capacity.
Chinese patent CN 102553517B discloses a light oil adsorption dearsenization catalyst, which utilizes waste silicon-aluminum catalyst to obtain waste catalyst powder through carbon burning, grinding and screening; mixing and kneading waste catalyst powder, alumina, extrusion aid and nitric acid solution, extruding into strips, drying and roasting to obtain a carrier; loading the oxide of the active component copper and zinc on a carrier, drying and roasting to obtain the dearsenic agent; or mixing the active metal component with nitric acid and adding the mixture in the extrusion molding process. The method fully utilizes the waste silicon-aluminum catalyst, achieves the aim of reducing the cost, but has small specific surface area, single pore structure and poor effect of treating liquid light hydrocarbon components in petroleum due to only using alumina and waste catalyst powder as adsorption carriers.
Chinese patent CN 1978594A discloses a liquid petroleum hydrocarbon dearsenic agent with double mesopore structure distribution and a preparation method thereof, wherein the dearsenic agent carrier is a silicon dioxide/silicon aluminum double mesopore molecular sieve, the active component is one or more of nitrate or chloride or sulfate or sulfide or oxalate of five elements of copper, iron, manganese, nickel and silver, and the dearsenic agent is obtained by heat treatment at 200-700 ℃. The method relates to the preparation of the molecular sieve, has complex process and higher cost, and is not beneficial to large-scale production.
In summary, the above patent technologies have some common problems, such as high cost, complex process, and being not suitable for large-scale popularization and application, or although the process is improved, the dearsenification effect in the liquid light hydrocarbon component in petroleum is not good.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention aims to provide a preparation method of an adsorption dearsenic agent for liquid light hydrocarbon components, which takes activated carbon and silicon dioxide as a composite carrier, directly adds silica sol without adding acid, loads active metal, and completes physical modification of the activated carbon and phase state conversion of the active metal in situ by one step through steam high-temperature heat treatment. In addition, the adsorption dearsenization agent has the advantages of high dearsenization activity, large arsenic capacity, long service life, simple preparation process, low production cost, easy large-scale popularization and application and the like.
Therefore, the invention provides a preparation method of a liquid light hydrocarbon component adsorption dearsenic agent, which comprises the following steps:
(1) adding silica sol into a carrier precursor consisting of activated carbon and silicon dioxide to prepare a carrier, adding an active metal precursor solution, mixing, rolling, stirring, extruding and forming;
(2) drying and carrying out high-temperature heat treatment on the water vapor to obtain the liquid light hydrocarbon component adsorption dearsenic agent.
Specifically, the pore channels of the activated carbon and the silicon dioxide are single, and the carrier prepared by using the activated carbon and the silicon dioxide alone cannot obtain a good arsenic removal effect. In the invention, the active carbon and the silicon dioxide are compounded for use, the carrier structure is optimized, the pore volume and the specific surface area of the carrier are improved, the dispersion of pore channels and pore diameters is more uniform, multistage and ordered, and the active carbon-silicon dioxide composite carrier with proper specific surface area and multistage pore channel distribution can be prepared by regulating and controlling the addition proportion of the active carbon, thereby being beneficial to the diffusion, reaction and escape of reactant molecules in the pore channels.
Specifically, the silica sol can play a role of a binder in the strip extrusion process, and other organic acid and inorganic acid are not required to be additionally added, so that the damage of a strong acid solution to a carrier pore channel structure is avoided, and the production cost is reduced.
Specifically, the invention adopts a steam high-temperature treatment mode, and the physical modification of the active carbon and the phase state conversion of the active metal can be completed in situ in one step in the steam high-temperature heat treatment process.
The preparation method of the liquid light hydrocarbon component adsorption dearsenic agent of the invention preferably comprises the following steps: the drying conditions are as follows: the temperature is 80-140 ℃, the temperature is further preferably 100-130 ℃, and the time is 2-6h, further preferably 3-5 h; the conditions of the high-temperature steam heat treatment are as follows: the temperature is 400-900 ℃, the further optimization is 600-900 ℃, the time is 1-6h, the further optimization is 1-4h, and the space velocity of the steam is 500--1。
The preparation method of the liquid light hydrocarbon component adsorption dearsenic agent of the invention preferably comprises the following steps: the activated carbon is one or more of wood activated carbon, coal activated carbon, shell activated carbon and coconut shell activated carbon, and the wood activated carbon and/or coconut shell activated carbon are further preferred.
The preparation method of the liquid light hydrocarbon component adsorption dearsenic agent of the invention preferably comprises the following steps: the silicon dioxide is one or more of precipitated silicon dioxide, fumed silicon dioxide and colloidal silicon dioxide.
The preparation method of the liquid light hydrocarbon component adsorption dearsenic agent of the invention preferably comprises the following steps: the mass ratio of the activated carbon to the silicon dioxide is 0.2-5: 1.
the preparation method of the liquid light hydrocarbon component adsorption dearsenic agent of the invention preferably comprises the following steps: the adding amount of the silica sol accounts for 1-10% of the mass of the carrier precursor.
The preparation method of the liquid light hydrocarbon component adsorption dearsenic agent of the invention preferably comprises the following steps: the extrusion molding condition is that the rolling is 30-60min and the kneading is 40-80 min.
The preparation method of the liquid light hydrocarbon component adsorption dearsenic agent of the invention preferably comprises the following steps: the using amount of the active metal precursor accounts for 5-25% of the total mass of the adsorption dearsenization agent by the mass of the corresponding metal oxide, and is further preferably 18-23%; more preferably, the active metal precursor includes a copper salt and a nickel salt, and the mass ratio of the copper salt to the nickel salt is 5-15: 1.
the preparation method of the liquid light hydrocarbon component adsorption dearsenic agent of the invention preferably comprises the following steps: the copper salt is one or more of copper acetate, copper sulfate and copper nitrate; the nickel salt is one or more of nickel acetate, nickel sulfate and nickel nitrate.
Therefore, the invention also provides a liquid light hydrocarbon component adsorption dearsenic agent prepared by the method, and the specific surface area of the adsorption dearsenic agent is 420-650 m2Per g, pore volume of 0.50-0.85 ml/g, bulk density of 0.45-0.55 g/cm3The most probable aperture is 6-12 nm; more preferably, the specific surface area of the adsorption dearsenization agent is 450-550 m2(iv) per gram, pore volume of 0.65-0.75 mL/g, bulk density of 0.48-0.52 g/cm3The most probable pore diameter is 8-10 nm.
The liquid light hydrocarbon component of the invention adsorbs dearsenization agent, wherein the preferable is: the shape of the adsorption dearsenic agent is one or more of clover shape, sphere shape and dentate sphere shape.
The preparation method of the adsorption dearsenic agent provided by the invention specifically comprises the following steps:
(1) mixing activated carbon and silicon dioxide according to a mass ratio of 0.2-5: 1, mixing, adding silica sol accounting for 1-10% of the mass of a carrier precursor, and fully and uniformly mixing;
(2) mixing one or more of copper acetate, copper sulfate or copper nitrate with one or more of nickel acetate, nickel sulfate or nickel nitrate to obtain mixed metal salt, dissolving the mixed metal salt in deionized water, and stirring until the metal salt is completely dissolved, wherein the content of active components copper oxide and nickel oxide accounts for 18-23% of the weight of the adsorption dearsenification catalyst;
(3) fully mixing the activated carbon, the silicon dioxide, the silica sol and the active metal precursor solution, rolling for 30-60min, kneading for 40-80min, and extruding to form strips;
(4) standing for 5-10 h;
(5) placing the catalyst after standing in an oven, and drying for 3-5h at 100-130 ℃;
(6) and (3) carrying out high-temperature heat treatment on the dried catalyst by using steam, wherein the treatment temperature is 600-800 ℃, and the treatment time is 1-4h, thus obtaining the adsorption dearsenification catalyst suitable for the liquid light hydrocarbon component in the petroleum.
The research of the invention finds that the specific surface area, the effective pore volume and the pore structure of the carrier for adsorbing the dearsenization agent by the liquid light hydrocarbon in the petroleum directly influence the performance of the dearsenization agent. The higher specific surface area ensures more dearsenifying active sites, and the increase of the proportion of medium pores or large pores is beneficial to the transmission of liquid light hydrocarbon components in petroleum. The dearsenization agent carrier prepared by taking alumina or silicon-aluminum oxide as a carrier has small specific surface area and single pore structure. The activated carbon has a developed pore channel structure, a high specific surface area and high surface activity, can be used as a carrier of the dearsenization agent, and can obtain an oil dearsenization agent with excellent performance by adjusting the pore channel structure, and has low cost and good raw material adaptability. Active carbon and silicon dioxide are used as carriers, silica sol and active metal precursor solution are added, other acid solution, pore-expanding agent and auxiliary agent do not need to be additionally added, and the catalyst is formed by one-step extrusion. The active carbon pore channel structure modulation and the metal phase state transformation process can be simultaneously completed through high-temperature hydrothermal treatment. The high-activity liquid light hydrocarbon adsorption dearsenification catalyst is prepared by a simple process with low cost and a pollution-free preparation process, and has great innovation and industrial application value.
In conclusion, the beneficial effects of the invention are as follows:
(1) according to the invention, the active carbon and silicon dioxide composite carrier with a proper specific surface area and hierarchical pore channel distribution can be prepared by regulating and controlling the adding proportion of the active carbon and the silicon dioxide, so that the diffusion, the reaction and the escape of reactant molecules in the pore channels are facilitated, and the arsenic removal efficiency and the raw material adaptability are improved.
(2) According to the invention, other organic acid or inorganic acid, extrusion aid, pore-expanding agent and the like are not required to be additionally added in the preparation process, the preparation process can be completed at a lower cost, and the damage of strong acid solution to the pore structure of the carrier is avoided.
(3) The invention can complete the physical modification of the active carbon and the phase state conversion of the active metal in situ by one step through the steam high-temperature heat treatment process, and has simple preparation method and low preparation cost.
(4) The dearsenization agent is mainly used for dearsenization of liquid light hydrocarbon components in petroleum, the arsenic capacity can reach more than 1.0 percent, the dearsenization efficiency is high, the service life is long, a multistage pore channel structure formed by compounding activated carbon and silicon dioxide is beneficial to transmission of the liquid light hydrocarbon components in the petroleum in a pore channel, the preparation process is simple, the cost is low, and the dearsenization agent is suitable for industrial large-scale production and application.
Drawings
FIG. 1 is a graph comparing the arsenic removal effect of the adsorbent dearsenization agent prepared in example 13 of the present invention and the comparative example 2.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme 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 experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
Example 1
Weighing 500g of activated carbon, 1000g of silicon dioxide and 50g of silica sol, fully and uniformly mixing, then weighing 250g of copper nitrate and 50g of nickel nitrate, adding into deionized water for fully dissolving, and then adding the dissolved metal salt solution into the mixture of the activated carbon, the silicon dioxide and the silica sol. Rolling for 40min, kneading for 50min, extruding, standing for 8 hr, drying at 120 deg.C for 4 hr,performing high-temperature hydrothermal treatment at 700 ℃ for 2h, wherein the space velocity of water vapor is 1500h-1Thus, a dearsenicating agent sample C1 was prepared.
Example 2
Weighing 500g of activated carbon, 500g of silicon dioxide and 50g of silica sol, fully and uniformly mixing, then weighing 180g of copper nitrate and 20g of nickel nitrate, adding the copper nitrate and the nickel nitrate into deionized water to be fully dissolved, and then adding the dissolved metal salt solution into the mixture of the activated carbon, the silicon dioxide and the silica sol. Rolling for 50min, kneading for 70min, extruding, standing for 8 hr, drying at 110 deg.C for 5 hr, hydrothermal treating at 700 deg.C for 2 hr, wherein the space velocity of water vapor is 1000 hr-1Thus, a dearsenicating agent sample C2 was prepared.
Example 3
Weighing 1000g of activated carbon, 500g of silicon dioxide and 50g of silica sol, fully and uniformly mixing, then weighing 300g of copper nitrate and 40g of nickel nitrate, adding into deionized water for fully dissolving, and then adding the dissolved metal salt solution into the mixture of the activated carbon, the silicon dioxide and the silica sol. Rolling for 40min, kneading for 80min, extruding, standing for 8 hr, drying at 130 deg.C for 4 hr, hydrothermal treating at 700 deg.C for 2 hr with vapor space velocity of 1500 hr-1Thus, a dearsenicating agent sample C3 was prepared.
Example 4
Weighing 500g of activated carbon, 500g of silicon dioxide and 75g of silica sol, fully and uniformly mixing, then weighing 200g of copper nitrate and 15g of nickel nitrate, adding the copper nitrate and the nickel nitrate into deionized water for fully dissolving, and then adding the dissolved metal salt solution into the mixture of the activated carbon, the silicon dioxide and the silica sol. Rolling for 40min, kneading for 40min, extruding, standing for 8 hr, drying at 130 deg.C for 3 hr, hydrothermal treating at 700 deg.C for 1 hr with water vapor space velocity of 1000 hr-1Thus, a dearsenicating agent sample C4 was prepared.
Example 5
Weighing 500g of activated carbon, 500g of silicon dioxide and 100g of silica sol, fully and uniformly mixing, then weighing 200g of copper nitrate and 20g of nickel nitrate, adding the copper nitrate and the nickel nitrate into deionized water for fully dissolving, and then adding the dissolved metal salt solution into the mixture of the activated carbon, the silicon dioxide and the silica sol. Rolling for 50minKneading for 50min, extruding, standing for 8 hr, drying at 120 deg.C for 4 hr, hydrothermal treating at 700 deg.C for 1 hr, wherein the space velocity of steam is 1000 hr-1Thus, a dearsenicating agent sample C5 was prepared.
Example 6
Weighing 500g of activated carbon, 500g of silicon dioxide and 75g of silica sol, fully and uniformly mixing, then weighing 180g of copper acetate and 30g of nickel acetate, adding the copper acetate and the nickel acetate into deionized water for fully dissolving, and then adding the dissolved metal salt solution into the mixture of the activated carbon, the silicon dioxide and the silica sol. Rolling for 40min, kneading for 60min, extruding, standing for 8 hr, drying at 110 deg.C for 5 hr, hydrothermal treating at 700 deg.C for 3 hr, wherein the space velocity of water vapor is 1000 hr-1Thus, sample C6 was prepared as a dearsenifying agent.
Example 7
Weighing 1000g of activated carbon, 500g of silicon dioxide and 100g of silica sol, fully and uniformly mixing, then weighing 275g of copper acetate and 25g of nickel acetate, adding the copper acetate and the nickel acetate into deionized water for fully dissolving, and then adding the dissolved metal salt solution into the mixture of the activated carbon, the silicon dioxide and the silica sol. Rolling for 40min, kneading for 50min, extruding, standing for 8 hr, drying at 120 deg.C for 4 hr, hydrothermal treating at 700 deg.C for 3 hr with vapor space velocity of 1500 hr-1Thus, a dearsenicating agent sample C7 was prepared.
Example 8
Weighing 500g of activated carbon, 1000g of silicon dioxide and 100g of silica sol, fully and uniformly mixing, then weighing 300g of copper acetate and 40g of nickel acetate, adding the copper acetate and the nickel acetate into deionized water for full dissolution, and then adding the dissolved metal salt solution into the mixture of the activated carbon, the silicon dioxide and the silica sol. Rolling for 60min, kneading for 60min, extruding, standing for 8 hr, drying at 130 deg.C for 4 hr, hydrothermal treating at 700 deg.C for 2 hr with vapor space velocity of 1500 hr-1Thus, a dearsenicating agent sample C8 was prepared.
Example 9
Weighing 500g of activated carbon, 500g of silicon dioxide and 75g of silica sol, fully and uniformly mixing, then weighing 180g of copper acetate and 15g of nickel acetate, adding the copper acetate and the nickel acetate into deionized water for full dissolution, and then dissolving the dissolved metal saltThe solution is added into a mixture of activated carbon, silica and silica sol. Rolling for 40min, kneading for 50min, extruding, standing for 8 hr, drying at 120 deg.C for 4 hr, hydrothermal treating at 600 deg.C for 4 hr with vapor space velocity of 800 hr-1Thus, a dearsenicating agent sample C9 was prepared.
Example 10
Weighing 1000g of activated carbon, 500g of silicon dioxide and 100g of silica sol, fully and uniformly mixing, then weighing 260g of copper sulfate and 40g of nickel sulfate, adding the weighed materials into deionized water for fully dissolving, and then adding the dissolved metal salt solution into the mixture of the activated carbon, the silicon dioxide and the silica sol. Rolling for 60min, kneading for 60min, extruding, standing for 8 hr, drying at 110 deg.C for 4 hr, hydrothermal treating at 700 deg.C for 3 hr with water vapor space velocity of 1000 hr-1Thus, a dearsenicating agent sample C10 was prepared.
Example 11
Weighing 500g of activated carbon, 1000g of silicon dioxide and 100g of silica sol, fully and uniformly mixing, then weighing 300g of copper sulfate and 20g of nickel sulfate, adding into deionized water for full dissolution, and then adding the dissolved metal salt solution into the mixture of the activated carbon, the silicon dioxide and the silica sol. Rolling for 50min, kneading for 60min, extruding to form strips, standing for 8h, drying the catalyst at 130 ℃ for 5h, and carrying out hydrothermal treatment at 700 ℃ for 2h, wherein the airspeed of water vapor is 2000h-1Thus, a dearsenicating agent sample C11 was prepared.
Example 12
Weighing 500g of activated carbon, 500g of silicon dioxide and 75g of silica sol, fully and uniformly mixing, then weighing 160g of copper acetate and 20g of nickel acetate, adding the copper acetate and the nickel acetate into deionized water for fully dissolving, and then adding the dissolved metal salt solution into the mixture of the activated carbon, the silicon dioxide and the silica sol. Rolling for 30min, kneading for 40min, extruding, standing for 8 hr, drying at 120 deg.C for 4 hr, hydrothermal treating at 700 deg.C for 3 hr with vapor space velocity of 2000 hr-1Thus, a dearsenicating agent sample C12 was prepared.
Example 13
Weighing 500g of active carbon, 500g of silicon dioxide and 75g of silica sol, fully and uniformly mixing, and then weighing 185g of copper acetate and 185g of ethyl acetateAnd 35g of nickel acid is added into deionized water to be fully dissolved, and then the dissolved metal salt solution is added into the mixture of activated carbon, silicon dioxide and silica sol. Rolling for 40min, kneading for 40min, extruding, standing for 8 hr, drying at 120 deg.C for 4 hr, hydrothermal treating at 800 deg.C for 3 hr with vapor space velocity of 2000 hr-1Thus, sample C13 was prepared as a dearsenifying agent.
Example 14
Weighing 500g of activated carbon, 500g of silicon dioxide and 75g of silica sol, fully and uniformly mixing, then weighing 180g of copper nitrate and 25g of nickel nitrate, adding the copper nitrate and the nickel nitrate into deionized water, fully dissolving, and then adding the dissolved metal salt solution into the mixture of the activated carbon, the silicon dioxide and the silica sol. Rolling for 30min, kneading for 40min, extruding, standing for 8 hr, drying at 120 deg.C for 4 hr, hydrothermal treating at 600 deg.C for 4 hr with vapor space velocity of 1500 hr-1Thus, a dearsenicating agent sample C14 was prepared.
Example 15
Weighing 500g of activated carbon, 500g of silicon dioxide and 75g of silica sol, fully and uniformly mixing, then weighing 180g of copper nitrate and 25g of nickel nitrate, adding the copper nitrate and the nickel nitrate into deionized water, fully dissolving, and then adding the dissolved metal salt solution into the mixture of the activated carbon, the silicon dioxide and the silica sol. Rolling for 40min, kneading for 40min, extruding, standing for 8 hr, drying at 120 deg.C for 4 hr, hydrothermal treating at 800 deg.C for 2 hr with vapor space velocity of 1500 hr-1Thus, a dearsenicating agent sample C15 was prepared.
Example 16
Weighing 500g of activated carbon, 500g of silicon dioxide and 75g of silica sol, fully and uniformly mixing, then weighing 180g of copper sulfate and 25g of nickel sulfate, adding the copper sulfate and the nickel sulfate into deionized water for fully dissolving, and then adding the dissolved metal salt solution into the mixture of the activated carbon, the silicon dioxide and the silica sol. Rolling for 40min, kneading for 40min, extruding, standing for 8 hr, drying at 120 deg.C for 4 hr, hydrothermal treating at 900 deg.C for 1 hr with vapor space velocity of 2000 hr-1Thus, a dearsenicating agent sample C16 was prepared.
Example 17
500g of active carbon,500g of silicon dioxide and 75g of silica sol are fully and uniformly mixed, 180g of copper sulfate and 25g of nickel sulfate are weighed and added into deionized water to be fully dissolved, and then the dissolved metal salt solution is added into the mixture of the activated carbon, the silicon dioxide and the silica sol. Rolling for 50min, kneading for 50min, extruding, standing for 8 hr, drying at 120 deg.C for 4 hr, hydrothermal treating at 900 deg.C for 2 hr with vapor space velocity of 2000 hr-1Thus, a dearsenicating agent sample C17 was prepared.
Comparative example 1
Weighing 500g of activated carbon, 500g of pseudo-boehmite and 50g of methylcellulose, fully and uniformly mixing, then weighing 160g of copper nitrate and 30g of nickel nitrate, adding the copper nitrate and the nickel nitrate into deionized water for fully dissolving, and then adding the dissolved metal salt solution into the mixture of the activated carbon, the pseudo-boehmite and the methylcellulose. And rolling for 30min, kneading for 40min, extruding into strips, standing for 8h, drying the catalyst for 4h at 110 ℃, and roasting in the absence of oxygen to obtain a dearsenic agent sample D1.
Comparative example 2
Weighing 500g of pseudo-boehmite and 20g of methylcellulose, fully and uniformly mixing, then weighing 80g of copper acetate and 18g of nickel nitrate, adding into deionized water for full dissolution, and then adding the dissolved metal salt solution into the mixture of activated carbon, pseudo-boehmite and methylcellulose. Rolling for 40min, kneading for 50min, extruding to form, standing for 8h, drying the catalyst at 110 deg.C for 4h, and aerobic roasting at 300 deg.C to obtain dearsenic agent sample D2.
Test example 1
Evaluation of catalytic Performance:
in this test example, the arsenic removal activities of the adsorptive dearsenification catalysts prepared in examples and the adsorptive dearsenification catalysts provided in comparative examples were evaluated in accordance with the following methods, and the results are 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: weight hourly space velocity of 1.5h-1At 25 ℃ and under a pressure of 0.5 MPa. Taking a sample after the reaction is stable for 24 hours, and using a graphite furnace for the arsenic content of the sampleThe results of the atomic absorption spectrometry are shown in Table 1. The arsenic content determination adopts a mode of adding triethyl arsenic into a liquid light hydrocarbon component of petroleum to prepare standard sample gasoline A containing arsenic with the arsenic content of 1000ppm, 10g of catalyst is put into 100g of standard sample gasoline containing arsenic, after oscillation is carried out for 24 hours, 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 the arsenic content is shown in Table 2.
The arsenic removal rate is calculated according to the following formula 1:
Figure BDA0002885449450000151
the arsenic content is calculated as follows in equation 2:
Figure 2
TABLE 1 evaluation results of adsorption dearsenification activity between examples 1 to 20 and industrial agents
Figure BDA0002885449450000153
Figure BDA0002885449450000161
As can be seen from the results in Table 1, the CuNi/C-SiO with high arsenic removal efficiency and high arsenic content can be successfully prepared by blending the carrier composition and the active metal components, changing the conventional aerobic and anaerobic roasting mode into high-temperature hydrothermal treatment, and adjusting the treatment temperature and time and the flow of water vapor to completely decompose the metal salt into the metal active phase as much as possible2A catalyst.
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 (11)

1. A preparation method of a liquid light hydrocarbon component adsorption dearsenic agent is characterized by comprising the following steps:
(1) adding silica sol into a carrier precursor consisting of activated carbon and silicon dioxide to prepare a carrier, adding an active metal precursor solution, mixing, rolling, stirring, extruding and forming;
(2) drying and carrying out high-temperature heat treatment on the water vapor to obtain the liquid light hydrocarbon component adsorption dearsenic agent.
2. The method for preparing the liquid light hydrocarbon component adsorption dearsenifying agent according to claim 1, wherein the method comprises the following steps: the drying conditions are as follows: the temperature is 80-140 ℃, preferably 100-130 ℃, and the time is 2-6 hours, preferably 3-5 hours; the conditions of the high-temperature steam heat treatment are as follows: the temperature is 400-900 ℃, preferably 600-900 ℃, the time is 1-6h, preferably 1-4h, and the space velocity of the steam is 500--1。
3. The method for preparing the liquid light hydrocarbon component adsorption dearsenifying agent according to claim 1, wherein the method comprises the following steps: the activated carbon is one or more of wood activated carbon, coal activated carbon, shell activated carbon and coconut shell activated carbon, and the wood activated carbon and/or the coconut shell activated carbon are/is preferred.
4. The preparation method of the liquid light hydrocarbon component adsorption dearsenic agent according to claim 1, which is characterized in that: the silicon dioxide is one or more of precipitated silicon dioxide, fumed silicon dioxide and colloidal silicon dioxide.
5. The preparation method of the liquid light hydrocarbon component adsorption dearsenic agent according to claim 1, which is characterized in that: the mass ratio of the activated carbon to the silicon dioxide is 0.2-5: 1.
6. the method for preparing the liquid light hydrocarbon component adsorption dearsenifying agent according to claim 1, wherein the method comprises the following steps: the adding amount of the silica sol accounts for 1-10% of the mass of the carrier precursor.
7. The method for preparing the liquid light hydrocarbon component adsorption dearsenifying agent according to claim 1, wherein the method comprises the following steps: the extrusion molding condition is that the rolling is 30-60min and the kneading is 40-80 min.
8. The method for preparing the liquid light hydrocarbon component adsorption dearsenifying agent according to claim 1, wherein the method comprises the following steps: the using amount of the active metal precursor accounts for 5-25% of the total mass of the adsorption dearsenic agent by the mass of the corresponding metal oxide, and preferably 18-23%; more preferably, the active metal precursor comprises a copper salt and a nickel salt, and the mass ratio of the copper salt to the nickel salt is 5-15: 1.
9. the method for preparing the liquid light hydrocarbon component adsorption dearsenifying agent according to claim 1, wherein the method comprises the following steps: the copper salt is one or more of copper acetate, copper sulfate and copper nitrate; the nickel salt is one or more of nickel acetate, nickel sulfate and nickel nitrate.
10. A liquid light hydrocarbon component adsorption dearsenifying agent prepared by the process of claim 1, wherein: the specific surface area of the adsorption dearsenization agent is 420-650 m2Per g, pore volume of 0.50-0.85 ml/g, bulk density of 0.45-0.55 g/cm3The most probable aperture is 6-12 nm; more preferably, the specific surface area of the adsorption dearsenization agent is 450-550 m2(iv) per gram, pore volume of 0.65-0.75 mL/g, bulk density of 0.48-0.52 g/cm3The most probable pore diameter is 8-10 nm.
11. The liquid light hydrocarbon component adsorption dearsenicating agent as claimed in claim 10, wherein: the shape of the adsorption dearsenic agent is one or more of clover shape, sphere shape and dentate sphere shape.
CN202110015505.5A 2021-01-06 2021-01-06 Liquid light hydrocarbon component adsorption dearsenic agent and preparation method thereof Pending CN114713187A (en)

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