CN113522233A - Purifying agent, preparation method and application thereof, and purifying method - Google Patents

Purifying agent, preparation method and application thereof, and purifying method Download PDF

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CN113522233A
CN113522233A CN202010306546.5A CN202010306546A CN113522233A CN 113522233 A CN113522233 A CN 113522233A CN 202010306546 A CN202010306546 A CN 202010306546A CN 113522233 A CN113522233 A CN 113522233A
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water
weight
parts
zinc
copper
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CN113522233B (en
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贾银娟
高焕新
王灿
吴双
杨贺勤
高晓晨
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • 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
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28085—Pore diameter being more than 50 nm, i.e. macropores
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • C10L3/103—Sulfur containing contaminants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/306—Organic sulfur compounds, e.g. mercaptans
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton

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  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention relates to the field of purification, and discloses a purifying agent which comprises active carbon and an active component loaded on the active carbon, wherein the active component contains copper element and zinc element, and the specific surface area of the active carbon is more than or equal to 1000m2The mesopore rate is more than or equal to 40 percent; also discloses a preparation method of the purifying agent, which comprises the following steps: the specific surface area is more than or equal to 1000m2(ii) coconut shell carbon with a mesopore ratio of not less than 40%; in the presence of water, the coconut shell carbon, a water-soluble copper source, a water-soluble zinc source, a water-soluble aluminum source and a precipitator are contacted to obtain an insoluble reaction mixture; roasting the insoluble reaction mixture; the purifying agent of the invention can be used for purifying the impurity containing sulfur and arsenicPurifying the gas or liquid containing impurities and/or phosphorus impurities, wherein the contents of sulfur impurities, arsenic impurities and phosphorus impurities in the purified gas or liquid are all below 1ppm, and the utilization rate of active components in the purifying agent is above 85%.

Description

Purifying agent, preparation method and application thereof, and purifying method
Technical Field
The invention relates to the field of purification, and particularly relates to a purifying agent, and a preparation method, application and a purification method thereof.
Background
The impurities such as sulfur, arsenic, phosphorus and the like widely exist in raw materials such as natural gas, synthesis gas, coal gas, light gas, liquid hydrocarbon and the like, and the existence of the impurities can cause poisoning and inactivation of various catalysts, greatly shorten the service life of the catalysts and even cause abnormal catalytic reaction; in addition, during production, residual impurities can enter downstream synthetics as production progresses, thereby causing a series of problems in terms of environment, health and the like. Therefore, the efficient and accurate removal of impurities such as sulfur, arsenic, and phosphorus is very important for protecting the main catalyst of the downstream equipment and improving the quality of the downstream product.
In general, sulfur impurities in industrial feedstocks are predominantly H2S and COS (carbonyl sulfide) with arsenic impurities mainly in the form of AsH3In the form of phosphorus impurities mainly at pH3Exist in the form of (1). At present, the method for removing sulfur impurities, arsenic impurities and phosphorus impurities in gas is to use a desulfurizer, a dearsenization agent and a dephosphorizing agent for adsorption and removal.
At present, the development trend of the desulfurizing agent, the dearsenizing agent and the dephosphorizing agent is towards the development of low bulk density, low use temperature, high strength and high sulfur capacity and arsenic capacity.
CN201410575030.5 discloses a normal temperature desulfurization and dearsenization agent and a preparation method thereof, which comprises the following components in parts by weight: a) 1-10 parts of green copper zinc ore; b) 10-50 parts of copper oxide; c) 10-60 parts of zinc oxide; d) 0.01-3 parts of rare earth metal R. The addition of rare earth metal improves the charge distribution around Zn and Cu and improves the purification capacity of the Zn and Cu.
CN201410314482.8 discloses a sulfur-arsenic adsorbent and a preparation method thereof, wherein the sulfur-arsenic adsorbent comprises the following components in parts by weight: a) 1-10 parts of green copper zinc ore; b) 13-50 parts of copper oxide; c) 10-55 parts of zinc oxide; d) 0.1-5 parts of iron oxide; e) 0.1-5 parts of manganese oxide. The addition of ferric oxide and manganese oxide improves the sulfur capacity and arsenic capacity of the adsorbent.
CN201510678194.5 discloses a preparation method of an adsorbent for simultaneously purifying hydrogen sulfide, phosphine and arsine, which specifically comprises the following steps: (1) dissolving concentrated acid in distilled water according to the proportion of 1-5 mol/1000ml, and stirring until the concentrated acid is uniformly mixed; (2) adding P123 or F127 into the solution in the step (1) according to the proportion of 5-30 g/100ml, and stirring for 20-60 minutes at 30-50 ℃; (3) adding a pore-expanding agent into the solution obtained in the step (2) according to the proportion of 1-5 g/100ml, then adding tetraethoxysilane into a mixed solution of the solution obtained in the step (2) and tetraethoxysilane according to the volume ratio of 10: 1-30: 1, and stirring for 1-6 hours at the temperature of 30-50 ℃; (4) pouring the mixed solution obtained in the step (3) into a reaction kettle, crystallizing for 24-72 hours at 100-150 ℃, washing the obtained powder with distilled water, and filtering until the test paper does not change color; (5) drying the solid matter obtained in the step (4) at 100-150 ℃ for 12-60 hours, finally placing the obtained white powder in a roasting furnace, heating to 400-600 ℃ at a speed of 1-5 ℃/min, keeping the temperature for 2-6 hours, and naturally cooling to room temperature to obtain an adsorbent carrier; (6) adding the adsorbent carrier dried in the step (5) into a metal salt solution, carrying out ultrasonic impregnation for 30-60 minutes, drying the impregnated adsorbent at 100-150 ℃ for 3-7 hours, and roasting at 300-700 ℃ for 2-6 hours; (7) placing the macroporous adsorbent roasted in the step (6) into an acid solution for ultrasonic impregnation for 30-60 minutes, and drying the impregnated adsorbent at 100-150 ℃ for 3-7 hours to obtain the macroporous adsorbent capable of deeply purifying hydrogen sulfide, phosphine and arsine; the three gases are adsorbed simultaneously using a large pore adsorbent.
The scheme improves and enhances the adsorption capacity of the adsorbent. However, there is still a problem of low utilization of the active components of the scavenger.
Disclosure of Invention
The invention aims to overcome the problem of low utilization rate of active components of a purifying agent in the prior art, and provides the purifying agent, a preparation method, application and a purifying method thereof, so as to achieve the purpose of improving the utilization rate of the active components of the purifying agent.
In order to achieve the above object, the present invention provides a purifying agent, wherein the purifying agent comprises activated carbon and an active component loaded on the activated carbon, wherein the active component comprises copper element and zinc element, and the specific surface area of the activated carbon is more than or equal to 1000m2The mesopore rate is more than or equal to 40 percent.
The second aspect of the invention provides a preparation method of a purifying agent, wherein the method comprises the following steps:
(1) in the inert gas atmosphere, the coconut shell carbon powder as the raw material is heated to 700-1000 ℃, then is activated for 300 minutes at 700-1000 ℃ in the carbon dioxide atmosphere, and is cooled in the inert gas atmosphere to obtain the coconut shell carbon powder with the specific surface area of more than or equal to 1000m2(ii) coconut shell carbon with a mesopore ratio of not less than 40%;
(2) in the presence of water, the coconut shell carbon, a water-soluble copper source, a water-soluble zinc source, a water-soluble aluminum source and a precipitator are contacted to obtain an insoluble reaction mixture;
(3) the insoluble reaction mixture is calcined.
In a third aspect, the present invention provides a purifying agent obtained by the above method.
In a fourth aspect, the invention provides a use of the above-described purification agent for purification of a gas or liquid.
A fifth aspect of the invention provides a purification method, wherein the method comprises contacting the gas or liquid to be purified with the above-mentioned purifying agent.
The purifying agent has a good purifying effect and a high utilization rate of active components, and can be used for purifying gas or liquid containing at least one of sulfur impurities, arsenic impurities and phosphorus impurities, the content of the sulfur impurities, the content of the arsenic impurities and the content of the phosphorus impurities in the purified gas or liquid are all below 1ppm, and the utilization rate of the active components is up to more than 85%.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, the adsorption capacity means the amount of adsorbate adsorbed per unit adsorbent, and the unit is mg/g.
In order to achieve the above object, the present invention provides a purifying agent, wherein the purifying agent comprises activated carbon and an active component loaded on the activated carbon, wherein the active component comprises copper element and zinc element, and the specific surface area of the activated carbon is more than or equal to 1000m2The mesopore rate is more than or equal to 40 percent.
In the present invention, the mesoporosity means a percentage of the pore volume of pores having a pore diameter of 2nm or more in the total pore volume. Namely, the medium porosity is medium pore volume/total pore volume; and (3) measuring the pore structure of the coconut shell carbon by adopting an American ASAP2600 type surface analyzer, calculating the pore volume of the micropores by using a t-plot method, and calculating the total pore volume by using a single-point method.
In the present invention, the specific surface area is measured by the BET method.
In the invention, the content of sulfur impurities is calculated by sulfur, the content of arsenic impurities is calculated by arsenic, and the content of phosphorus impurities is calculated by phosphorus.
In the present invention, in order to improve the purification effect of the purifying agent and the utilization rate of the active components of the purifying agent, the content of the activated carbon in the purifying agent is preferably 50 to 90 parts by weight, more preferably 60 to 80 parts by weight; the content of the copper element is 1 to 10 parts by weight, and more preferably 1 to 8 parts by weight, calculated by oxide; the content of the zinc element is 1 to 10 parts by weight, more preferably 1 to 8 parts by weight, in terms of oxide.
In the present invention, the existence form of copper element and zinc element in the depurative is not particularly limited, and in order to improve the purifying effect of the depurative and the utilization rate of the active component of the depurative, it is preferable that the copper element exists in the form of copper oxide or in the form of copper oxide and aurichalcite, and the zinc element exists in the form of zinc oxide or in the form of zinc oxide and aurichalcite.
In the present invention, in order to further improve the purification effect of the purification agent and the utilization rate of the active component of the purification agent, it is preferable that the copper element is present in the form of copper oxide and the zinc element is present in the form of zinc oxide.
In the invention, in order to improve the diffusion performance of the purifying agent and the utilization rate of the active components and increase the residence time of the purified material flow in the purifying agent, the mesopore ratio of the active carbon is preferably 40-50%, and the specific surface area of the active carbon is 1000-1500m2(ii) in terms of/g. As will be understood by those skilled in the art, the diffusion properties refer to the ability of the decontaminant to allow diffusion of the decontaminant in the decontaminant.
In the invention, in order to further improve the diffusion performance and the utilization rate of active components of the purifying agent and increase the residence time of the purified material flow in the purifying agent, the activated carbon is preferably wood activated carbon, and more preferably coconut shell carbon.
The inventor of the invention finds that the specific surface area is more than or equal to 1000m2The activated carbon with the mesopore rate of more than or equal to 40 percent and the activated component loaded on the activated carbon and containing the copper element and the zinc element can generate obvious synergistic purification effect under a specific weight proportion, and the utilization rate of the activated component is effectively improved, particularly under the condition that the activated carbon is coconut shell carbon and the activated components are copper oxide and zinc oxide, the activated carbon has better synergistic purification effect and higher utilization rate of the activated component.
In the present invention, the preparation method of the coconut shell carbon is not particularly limited, and in order to further improve the diffusion performance of the purifying agent and the utilization rate of active components in the purifying agent, and increase the retention time of the purified material flow in the purifying agent, preferably, the preparation method of the coconut shell carbon comprises the steps of heating the raw material coconut shell carbon powder to 700-1000 ℃ in an inert gas atmosphere, then performing activation treatment at 700-1000 ℃ for 300 minutes in a carbon dioxide atmosphere, and then cooling in the inert gas atmosphere.
In the present invention, the source of the inert gas is not particularly limited as long as it does not react with the coconut shell charcoal powder as the raw material, and may be, for example, one or more of nitrogen and a group 0 element gas in the periodic table.
In the present invention, the amount of carbon dioxide is not particularly limited, but it is preferably 1 to 15 parts by weight per minute per 100 parts by weight of the raw coconut shell charcoal powder in order to enhance the activation effect of the raw coconut shell charcoal powder.
In the present invention, the scavenger may further contain an aluminum-containing compound, preferably, the aluminum-containing compound is alumina, and the alumina is contained in an amount of 1 to 6 parts by weight relative to 50 to 90 parts by weight of the activated carbon.
In the present invention, when the depurative is a molded body, the depurative further contains a binder. The source of the binder is not particularly limited as long as it does not adversely affect the purifying effect of the purifying agent, and for example, the binder is one or more of alumina, and kaolin, and preferably alumina.
In the present invention, the amount of the binder is not particularly limited, and preferably, the binder is contained in an amount of 1 to 5 parts by weight relative to 50 to 90 parts by weight of the activated carbon in order to enhance the binding effect.
The second aspect of the invention provides a preparation method of a purifying agent, wherein the method comprises the following steps:
(1) in the inert gas atmosphere, the coconut shell charcoal powder as the raw material is heated to 700-1000 ℃, and then is activated at 700-1000 ℃ in the carbon dioxide atmosphere to 160-300 min, cooling in inert gas atmosphere to obtain specific surface area not less than 1000m2(ii) coconut shell carbon with a mesopore ratio of not less than 40%;
(2) in the presence of water, the coconut shell carbon, a water-soluble copper source, a water-soluble zinc source, a water-soluble aluminum source and a precipitator are contacted to obtain an insoluble reaction mixture;
(3) the insoluble reaction mixture is calcined.
The inventors of the present invention found that the specific surface area and the porosity of coconut charcoal can be increased by subjecting conventional, commercially available coconut charcoal powder to an activation treatment at 700 ℃ to 1000 ℃ for 300 minutes in a carbon dioxide atmosphere.
In the present invention, for the sake of distinction, the coconut shell charcoal before treatment is referred to as raw coconut shell charcoal powder (conventional, commercially available coconut shell charcoal powder), and the coconut shell charcoal after treatment, which can be used as the activated charcoal of the present invention, is referred to as coconut shell charcoal.
The temperature rise rate in step (1) is preferably 1 ℃ to 10 ℃ per minute.
The cooling rate of step (1) is preferably 5 ℃ to 20 ℃/min.
In the invention, the coconut shell charcoal powder is heated to 700-1000 ℃ and then activated in the carbon dioxide atmosphere, wherein the temperature of the activation treatment can be the end temperature after heating, and can be slightly different as long as the temperature is 700-1000 ℃, preferably 850-980 ℃.
In the present invention, in order to further enhance the activation effect of the raw coconut shell charcoal powder, the raw coconut shell charcoal powder is preferably subjected to an activation treatment at 700 ℃ to 1000 ℃ for 200-280 minutes in a carbon dioxide atmosphere.
In the present invention, the amount of the carbon dioxide is not particularly limited, but it is preferably 1 to 15 parts by weight per minute per 100 parts by weight of the coconut charcoal powder in order to further enhance the activation effect of the coconut charcoal powder as the raw material.
In the present invention, the activating treatment may be carried out by placing the coconut shell charcoal powder as the raw material in a reaction furnace, heating in an inert gas atmosphere, introducing carbon dioxide to replace the inert gas atmosphere in the reaction furnace, continuously introducing carbon dioxide into the reaction furnace, and heating at 700-1000 deg.C, preferably 850-980 deg.C for 160-280 min, preferably 200-280 min.
In the present invention, it is preferable that the inert gas atmosphere in the reaction furnace is replaced by introducing carbon dioxide gas at a rate of 160-300ml/min with respect to the reaction furnace having a volume of 1000 ml.
In the invention, after the activation treatment of the raw material coconut shell carbon powder is finished, inert gas is introduced into the reaction furnace to replace the gas in the reaction furnace, and then the coconut shell carbon is cooled in the inert gas atmosphere. Preferably, the coconut shell charcoal is cooled to 15 ℃ to 30 ℃.
In the present invention, after the activation of the coconut charcoal as the raw material is completed, the rate of introducing the inert gas is not particularly limited, and for example, the inert gas may be introduced at a rate of 200-300ml/min with respect to a reaction furnace having a volume of 1000ml to form an inert gas atmosphere.
In the present invention, the inert gas may be one or more of nitrogen and a gas of an element of group 0 of the periodic table. The inert gas in the temperature raising process and the inert gas in the temperature lowering process of the reaction furnace can be the same or different, and the same inert gas is preferred.
In the present invention, the manner of contacting the coconut shell carbon, the water-soluble copper source, the water-soluble zinc source, the water-soluble aluminum source and the precipitant is not particularly limited, and in order to uniformly support the active component in the scavenger on the activated carbon, a preferable contacting manner includes: (1) mixing a precipitator and water to obtain a solution I;
(2) mixing the activated carbon with the solution I to obtain a suspension II;
(3) mixing a water-soluble copper source, a water-soluble zinc source, a water-soluble aluminum source and water to obtain a solution III;
(4) mixing a precipitator and water to obtain a solution IV, wherein the concentration of the precipitator in the solution IV is greater than that of the precipitator in the solution I;
(5) mixing the suspension II, the solution III and the solution IV.
In the invention, the precipitator is used for precipitating copper elements, zinc elements and aluminum elements in a water-soluble copper source, a water-soluble zinc source and a water-soluble aluminum source, attaching the precipitates to the surface of activated carbon, and roasting to obtain oxides of the metal elements.
In the invention, the precipitant in the step (4) and the precipitant in the step (1) can be used together to prepare the solution I, so that the preparation of the solution IV in the step (4) is omitted; or preparing the solution IV by the precipitant in the step (4) and the precipitant in the step (1) together, and omitting the preparation of the solution I in the step (4); in order to uniformly load the active components on the activated carbon, improve the adsorption capacity of the purifying agent and improve the utilization rate of the active components, preferably, the precipitating agents are respectively prepared into a solution I and a solution IV.
In the present invention, there is no particular limitation on the source of the water-soluble copper source, which may be selected from one or more of copper nitrate, copper sulfate, and copper chloride, and it is preferable that the water-soluble copper source is copper nitrate in order to improve the purification effect of the purification agent and the utilization rate of the active component.
In the present invention, there is no particular limitation on the source of the water-soluble copper source, which may be selected from one or more of zinc nitrate, zinc sulfate, and zinc chloride, and it is preferable that the water-soluble zinc source is zinc nitrate in order to improve the purification effect of the purification agent and to improve the utilization rate of the active components.
In the present invention, the source of the water-soluble aluminum source is not particularly limited, and the water-soluble aluminum source may be one or more selected from aluminum nitrate, aluminum sulfate, and aluminum chloride, and in order to improve the purification effect of the purification agent and to improve the utilization rate of the active component, the water-soluble aluminum source is preferably aluminum nitrate.
In the present invention, in order to improve the purification effect of the purification agent and improve the utilization rate of the active component, the precipitant is preferably a water-soluble carbonate, and more preferably one or more selected from sodium carbonate, potassium carbonate, and ammonium carbonate.
In the present invention, the content of the precipitant in the solution i is not particularly limited as long as the precipitant can be completely dissolved in water, and in order to improve the purification effect of the purifying agent and to improve the utilization rate of the active component, it is preferable that the molar content of the precipitant in the solution i is 0.1% to 0.3%.
In the present invention, there is no particular limitation on the weight ratio of the precipitant in the solution i to the precipitant in the solution iv, and in order to improve the purification effect of the purification agent and improve the utilization rate of the active component, it is preferable that the weight ratio of the precipitant in the solution i to the precipitant in the solution iv is 1: 0.5-10.
In the present invention, the molar ratio of the precipitant to the total amount of the water-soluble copper source, the water-soluble zinc source, and the water-soluble aluminum source is not particularly limited, and in order to improve the purification effect of the purification agent and to improve the utilization rate of the active component, it is preferable that the molar ratio of the precipitant to the total amount of the water-soluble copper source, the water-soluble zinc source, and the water-soluble aluminum source is 1: 0.8-2.
In the present invention, the amounts of coconut shell carbon, water-soluble copper source, water-soluble zinc source and water-soluble aluminum source are not particularly limited, but preferably such that the activated carbon is contained in the resulting depurative in an amount of 50 to 90 parts by weight, preferably 60 to 80 parts by weight; the content of the copper element is 1-10 parts by weight, preferably 1-8 parts by weight calculated on oxide; the content of the zinc element is 1 to 10 parts by weight, preferably 1 to 8 parts by weight calculated on oxide; the content of the alumina is 1-6 parts by weight.
In the present invention, the conditions for the contact are not particularly limited as long as the reaction proceeds normally, and in order to uniformly support the reactants on the activated carbon and improve the purification effect of the purification agent and the utilization rate of the active component, it is preferable that the conditions for the contact include: the temperature is 40-90 ℃ and the time is 0.5-3 h.
In the present invention, the calcination conditions are not particularly limited, and in order to further improve the adsorption capacity of the scavenger and to improve the utilization rate of the active component, it is preferable that the calcination conditions include: the roasting temperature is 250-500 ℃, preferably 350-500 ℃, and the roasting time is 1-5 h.
In the present invention, in order to improve the purifying effect of the purifying agent, the method further comprises kneading and molding after washing the insoluble reaction mixture to an electric conductivity of 100. mu.S/cm or less before calcination.
In the present invention, the kneading and molding method is not particularly limited, and for example, kneading and molding is performed after mixing the washed insoluble reaction mixture with a binder and an acid in the presence of water.
In the present invention, in order to increase the kneading molding rate and to increase the purifying effect of the purifying agent, the binder is preferably one or more of alumina, and kaolin, and is preferably alumina. The acid is one or more of nitric acid, sulfuric acid and hydrochloric acid, and preferably, the acid is nitric acid in order to improve the kneading molding rate and improve the purification effect of the purification agent.
In the present invention, the amount of the binder is not particularly limited, and in order to improve the binding effect, it is preferable that the content of the binder is 1 to 5 parts by weight with respect to 50 to 90 parts by weight of the content of the activated carbon.
In the present invention, the amount of the acid to be used is not particularly limited and may be a conventional amount, and in order to enhance the binding effect, it is preferable that the weight ratio of the total amount of the insoluble reaction mixture and the binder to the amount of the acid to be used is 1 to 3: 1.
In the present invention, the use of water is further included in the kneading molding process, and the amount of water is not particularly limited, and for the purpose of enhancing the binding effect, it is preferable that the amount of water is 10 to 50% by weight relative to the total weight of the insoluble reaction mixture, the binder and the acid.
In a third aspect, the present invention provides a purifying agent obtained by the above method.
In a fourth aspect, the invention provides a use of the above-described purification agent for purification of a gas or liquid.
The purifying agent is especially suitable for purifying gas or liquid containing one or more of sulfur impurities, arsenic impurities and phosphorus impurities.
In the present invention, the source of the gas is not particularly limited as long as the components of the gas other than the sulfur impurities, arsenic impurities and phosphorus impurities do not adversely affect the scavenger, and for example, the gas may be one or more of nitrogen, carbon dioxide, natural gas, synthesis gas, coal gas, natural gas, oil field gas, refinery gas.
In the present invention, the source of the liquid is not particularly limited as long as the components other than the sulfur impurity, the arsenic impurity and the phosphorus impurity in the liquid do not adversely affect the purification agent, and for example, the liquid may be a liquid hydrocarbon, preferably, the liquid may be a liquid formed by cooling and/or pressurizing a hydrocarbon which is gaseous at normal temperature and normal pressure, more preferably, the liquid is a liquid formed by pressurizing a hydrocarbon which is gaseous at normal temperature and normal pressure, and further, the liquid is liquid propylene.
In the present invention, the type of the sulfur impurities is not particularly limited, and for example, the sulfur impurities are one or more of hydrogen sulfide, sulfur dioxide, carbonyl sulfide.
In the present invention, the type of the arsenic impurity is not particularly limited, and for example, the arsenic impurity is arsine.
In the present invention, the type of the phosphorus impurity is not particularly limited, and for example, the phosphorus impurity is phosphine.
In the present invention, the total content of sulfur impurities, arsenic impurities and phosphorus impurities in the gas or liquid is not particularly limited, and in order to improve the purification effect of the purification agent, it is preferable that the total content of sulfur impurities, arsenic impurities and phosphorus impurities in the gas or liquid is 5 to 50000 ppm.
A fifth aspect of the invention provides a method of decontamination, wherein the method comprises contacting the gas or liquid to be decontaminated with the decontaminant.
The purifying agent is especially suitable for purifying gas or liquid containing one or more of sulfur impurities, arsenic impurities and phosphorus impurities.
In the present invention, the source of the gas to be purified is not particularly limited as long as the components of the gas to be purified other than the sulfur impurity, the arsenic impurity and the phosphorus impurity do not adversely affect the purifying agent, and for example, the gas to be purified may be one or more of nitrogen, carbon dioxide, natural gas, synthesis gas, coal gas, natural gas, oil field gas and refinery gas.
In the present invention, the source of the liquid to be purified is not particularly limited as long as the components of the liquid to be purified other than the sulfur impurity, the arsenic impurity and the phosphorus impurity do not adversely affect the purifying agent, and for example, the liquid to be purified may be liquid hydrocarbon, preferably, the liquid to be purified may be liquid formed by cooling and/or pressurizing hydrocarbon which is gaseous at normal temperature and normal pressure, more preferably, the liquid to be purified is liquid formed by pressurizing hydrocarbon which is gaseous at normal temperature and normal pressure, and further, the liquid to be purified is liquid propylene.
In the present invention, the type of the sulfur impurities is not particularly limited, and for example, the sulfur impurities are one or more of hydrogen sulfide, sulfur dioxide, carbonyl sulfide.
In the present invention, the type of the arsenic impurity is not particularly limited, and for example, the arsenic impurity is arsine.
In the present invention, the type of the phosphorus impurity is not particularly limited, and for example, the phosphorus impurity is phosphine.
In the present invention, the total content of sulfur impurities, arsenic impurities and phosphorus impurities in the gas or liquid to be purified is not particularly limited, and in order to improve the purification effect of the purification agent, the total content of sulfur impurities, arsenic impurities and phosphorus impurities in the gas or liquid to be purified is preferably 5 to 50000 ppm.
In the present invention, the contacting conditions are not particularly limited, and in order to improve the purifying effect of the purifying agent and to improve the utilization rate of the active component, it is preferable that the contacting conditions include a temperature of 20 ℃ to 100 ℃, a pressure of 0.1 to 5MPa, and a volume space velocity of the gas to be purified of 10 to 10000h-1Or the mass space velocity of the liquid to be purified is 0.1-10h-1. The pressure in the present invention is absolute pressure.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
when the material flow to be purified is gas, the method for calculating the adsorption capacity comprises the following steps:
S＝V×t×(Cin-Cout)÷22.4÷1000×M÷mad×10-6；
when the material flow to be purified is liquid, the method for calculating the adsorption capacity comprises the following steps:
s is t x mass space velocity (C)in-Cout)×10-6；
V: flow rate of gas to be purified (mL/min);
t: contact time (min);
mad: adsorbent loading (g);
m: is the molar mass (L/mol) of sulfur, arsenic or phosphorus;
mass airspeed: mass space velocity (h) of the stream to be purified-1)；
Cin: inlet to-be-purified gas or liquid contains sulfur impurity, arsenic impurity and/or phosphorus impurity content (ppm);
Cout: the content (ppm) of sulfur impurities, arsenic impurities and/or phosphorus impurities in the gas or liquid after outlet purification;
the method for calculating the theoretical value of the adsorption capacity comprises the following steps: ideally, 1mol of copper element is combined with 1mol of sulfur element, 1mol of copper element is combined with 2/3mol of arsenic element and/or phosphorus element, 1mol of zinc element is combined with 1mol of sulfur element, and the total amount of copper element and zinc element in the purifying agent is calculated, so that the total amount of adsorbed sulfur impurity, arsenic impurity and phosphorus impurity can be obtained, and the theoretical value of the adsorption capacity of the purifying agent can be obtained;
the method for measuring the utilization rate of the active components comprises the following steps: active ingredient utilization rate ═ adsorption capacity measured value ÷ adsorption capacity theoretical value × 100%;
the method for measuring the mesoporosity comprises the following steps: the mesoporosity is the ratio of the pore volume of pores with the pore diameter of more than 2nm to the total pore volume, namely the mesoporosity is the mesoporosity divided by the total pore volume; measuring the pore structure of the coconut shell carbon by adopting an American ASAP2600 type surface analyzer, calculating the pore volume of the micropores by using a t-plot method, and calculating the total pore volume by using a single-point method;
the specific surface area was determined by the following method: measuring the adsorption curve of the coconut shell carbon by adopting an American ASAP2600 type surface analyzer, and calculating the specific surface area of the coconut shell carbon by adopting a BET method according to the adsorption curve;
the activated carbon content, the copper oxide content and the zinc oxide phase in the purifying agent are characterized by XRD (X-ray diffraction);
the content of active carbon, the content of copper oxide and the content of zinc oxide in the purifying agent are measured by XRF (X-ray fluorescence spectroscopy);
detecting the content of sulfur impurities in gas or liquid by adopting Agilent GC7890 gas chromatography, wherein a detector is SCD;
detecting the contents of arsenic impurities and phosphorus impurities in gas or liquid by adopting Agilent GC7890 gas chromatography, wherein a detector is PDHID;
raw material coconut shell charcoal powder: the specific surface area is 800m2The mesopore ratio was 20% in g.
Preparation example 1
100g of raw coconut shell charcoal powder is put into a reaction furnace with the volume of 5000ml, the temperature is raised from room temperature to 900 ℃ at the speed of 5 ℃/min in nitrogen atmosphere, carbon dioxide is introduced at the speed of 1000ml per minute to replace the inert gas atmosphere in the reaction furnace, then carbon dioxide is continuously introduced at the speed of 1000ml per minute to activate the coconut shell charcoal powder in the carbon dioxide atmosphere for 200 minutes, then nitrogen is introduced at the speed of 1200ml per minute to form the nitrogen atmosphere, and the coconut shell charcoal powder is cooled to 20 ℃ at the speed of 10 ℃/min in the nitrogen atmosphere. The specific surface area of the prepared coconut shell carbon is measured to be 1245m2The mesopore ratio was 45%/g.
Preparation example 2
100g of raw coconut shell charcoal powder is put into a reaction furnace with the volume of 5000ml, the temperature is raised from room temperature to 980 ℃ at the speed of 5 ℃/min in a nitrogen atmosphere, carbon dioxide is introduced at the speed of 1000ml per minute to replace the inert gas atmosphere in the reaction furnace, then carbon dioxide is continuously introduced at the speed of 1000ml per minute to activate the coconut shell charcoal powder in the carbon dioxide atmosphere for 300 minutes, then nitrogen is introduced at the speed of 1200ml per minute to form the nitrogen atmosphere, and the coconut shell charcoal powder is cooled to 20 ℃ at the speed of 10 ℃/min in the nitrogen atmosphere. The specific surface area of the prepared coconut shell carbon is determined to be 1500m2The mesopore ratio was 50% in g.
Preparation example 3
100g of raw coconut shell charcoal powder is put into a reaction furnace with the volume of 5000ml, the temperature is raised from room temperature to 850 ℃ at the speed of 5 ℃/min in a nitrogen atmosphere, carbon dioxide is introduced at the speed of 1000ml per minute to replace the inert gas atmosphere in the reaction furnace, then carbon dioxide is continuously introduced at the speed of 1000ml per minute to activate the coconut shell charcoal powder in the carbon dioxide atmosphere for 160 minutes, then nitrogen is introduced at the speed of 1200ml per minute to form the nitrogen atmosphere, and the coconut shell charcoal powder is cooled to 20 ℃ at the speed of 10 ℃/min in the nitrogen atmosphere. The specific surface area of the prepared coconut shell carbon is measured to be 1005m2The mesopore ratio was 41% in g.
Preparation example 4
100g of raw coconut shell charcoal powder is put into a reaction furnace with the volume of 5000ml, the temperature is raised from room temperature to 800 ℃ at the speed of 5 ℃/min in a nitrogen atmosphere, carbon dioxide is introduced at the speed of 1000ml per minute to replace the inert gas atmosphere in the reaction furnace, then carbon dioxide is continuously introduced at the speed of 1000ml per minute to activate the coconut shell charcoal powder in the carbon dioxide atmosphere for 200 minutes, then nitrogen is introduced at the speed of 1200ml per minute to form the nitrogen atmosphere, and the coconut shell charcoal powder is cooled to 20 ℃ at the speed of 10 ℃/min in the nitrogen atmosphere. The specific surface area of the prepared coconut shell carbon is determined to be 950m2The mesopore ratio was 35% by weight.
Preparation example 5
100g of raw coconut shell charcoal powder is put into a reaction furnace with the volume of 5000ml, the temperature is raised from room temperature to 900 ℃ at the speed of 5 ℃/min in a nitrogen atmosphere, carbon dioxide is introduced at the speed of 1000ml per minute to replace the inert gas atmosphere in the reaction furnace, then carbon dioxide is continuously introduced at the speed of 1000ml per minute to activate the coconut shell charcoal powder in the carbon dioxide atmosphere for 150 minutes, then nitrogen is introduced at the speed of 1200ml per minute to form the nitrogen atmosphere, and the coconut shell charcoal powder is cooled to 20 ℃ at the speed of 10 ℃/min in the nitrogen atmosphere. The specific surface area of the prepared coconut shell carbon is determined to be 907m2The mesopore ratio was 30% by weight.
Example 1
1) Mixing 10 kg of sodium carbonate and 700 kg of water uniformly, adding 90 kg of coconut charcoal of preparation example 1, and stirring at 70 ℃ for 2h to obtain a suspension;
mixing and stirring 30 kg of copper nitrate trihydrate, 40 kg of zinc nitrate hexahydrate, 10 kg of aluminum nitrate nonahydrate and 500 kg of water uniformly to obtain a metal salt solution;
20 kg of sodium carbonate and 500 kg of water are mixed homogeneously to obtain a sodium carbonate solution.
2) A sodium carbonate solution and a metal salt solution were simultaneously added to the above suspension, and reacted at 70 ℃ for 1 hour to obtain an insoluble reaction mixture.
3) Filtering the insoluble reaction mixture from the solution, washing until the conductivity of the washing liquid is less than 100 mus/cm to obtain insoluble substances, drying the insoluble substances, adding 20 kg of alumina, adding 33 wt% of nitric acid with concentration of 2.5 wt% relative to the total weight of the insoluble substances and the added alumina, kneading, extruding to form
Figure BDA0002455976140000161
Millimeter strips were dried at 120 ℃ and baked at 360 ℃ for 3 hours to obtain samples having the compositions shown in Table 1.
Example 2
1) Mixing 10 kg of sodium carbonate and 700 kg of water uniformly, adding 70 kg of coconut charcoal of preparation example 1, and stirring at 70 ℃ for 2h to obtain a suspension;
mixing 60 kg of copper nitrate trihydrate, 80 kg of zinc nitrate hexahydrate, 20 kg of aluminum nitrate nonahydrate and 500 kg of water, and uniformly stirring to obtain a metal salt solution;
uniformly mixing 40 kg of sodium carbonate and 500 kg of water to obtain a sodium carbonate solution;
2) adding a sodium carbonate solution and a metal salt solution into the suspension at the same time, and reacting at 70 ℃ for 1 hour to obtain an insoluble reaction mixture;
3) filtering the insoluble reaction mixture from the solution and washing until the conductivity of the washing solution is less than 100 mus/cm to obtain insoluble substances, drying the insoluble substances, adding 20 kg of alumina, and concentrating the insoluble substances and the added aluminaNitric acid with a degree of 2.5 wt% was added in an amount of 33 wt%, kneaded, extruded and formed into
Figure BDA0002455976140000162
Millimeter strips were dried at 120 ℃ and baked at 360 ℃ for 5 hours to obtain samples having the compositions shown in Table 1.
Example 3
1) Mixing 10 kg of sodium carbonate and 700 kg of water uniformly, adding 100 kg of coconut charcoal of preparation example 1, and stirring at 70 ℃ for 2h to obtain a suspension;
mixing 6 kg of copper nitrate trihydrate, 8 kg of zinc nitrate hexahydrate, 2 kg of aluminum nitrate nonahydrate and 500 kg of water, and uniformly stirring to obtain a metal salt solution;
8 kg of sodium carbonate and 500 kg of water are mixed uniformly to obtain a sodium carbonate solution.
2) A sodium carbonate solution and a metal salt solution were simultaneously added to the above suspension, and reacted at 70 ℃ for 1 hour to obtain an insoluble reaction mixture.
3) Filtering the insoluble reaction mixture from the solution, washing until the conductivity of the washing liquid is less than 100 mus/cm to obtain insoluble substances, drying the insoluble substances, adding 20 kg of alumina, adding 33 wt% of nitric acid with concentration of 2.5 wt% relative to the total weight of the insoluble substances and the added alumina, kneading, extruding to form
Figure BDA0002455976140000171
Millimeter strips were dried at 120 ℃ and calcined at 380 ℃ for 1 hour to obtain samples having the compositions shown in Table 1.
Example 4
1) Mixing 10 kg of sodium carbonate and 700 kg of water uniformly, adding 120 kg of coconut charcoal of preparation example 1, and stirring at 70 ℃ for 2h to obtain a suspension;
mixing and stirring 30 kg of copper nitrate trihydrate, 40 kg of zinc nitrate hexahydrate, 10 kg of aluminum nitrate nonahydrate and 500 kg of water uniformly to obtain a metal salt solution;
20 kg of sodium carbonate and 500 kg of water are mixed homogeneously to obtain a sodium carbonate solution.
2) A sodium carbonate solution and a metal salt solution were simultaneously added to the above suspension, and reacted at 70 ℃ for 1 hour to obtain an insoluble reaction mixture.
3) Filtering the insoluble reaction mixture from the solution, washing until the conductivity of the washing liquid is less than 100 mus/cm to obtain insoluble substances, drying the insoluble substances, adding 20 kg of alumina, adding 33 wt% of nitric acid with concentration of 2.5 wt% relative to the total weight of the insoluble substances and the added alumina, kneading, extruding to form
Figure BDA0002455976140000172
Millimeter strips were dried at 120 ℃ and baked at 360 ℃ for 5 hours to obtain samples having the compositions shown in Table 1.
Example 5
1)10 kg of sodium carbonate and 700 kg of water were mixed uniformly, 140 kg of the coconut charcoal of preparation example 1 was added, and stirred at 70 ℃ for 2 hours to obtain a suspension;
mixing and stirring 30 kg of copper nitrate trihydrate, 40 kg of zinc nitrate hexahydrate, 10 kg of aluminum nitrate nonahydrate and 500 kg of water uniformly to obtain a metal salt solution;
20 kg of sodium carbonate and 500 kg of water are mixed homogeneously to obtain a sodium carbonate solution.
2) A sodium carbonate solution and a metal salt solution were simultaneously added to the above suspension, and reacted at 70 ℃ for 1 hour to obtain an insoluble reaction mixture.
3) Filtering the insoluble reaction mixture from the solution, washing until the conductivity of the washing liquid is less than 100 mus/cm to obtain insoluble substances, drying the insoluble substances, adding 20 kg of alumina, adding 33 wt% of nitric acid with concentration of 2.5 wt% relative to the total weight of the insoluble substances and the added alumina, kneading, extruding to form
Figure BDA0002455976140000181
Millimeter strips were dried at 120 ℃ and calcined at 400 ℃ for 3 hours to obtain samples having the compositions shown in Table 1.
Example 6
1) Mixing 10 kg of sodium carbonate and 700 kg of water uniformly, adding 60 kg of coconut charcoal of preparation example 1, and stirring at 70 ℃ for 2h to obtain a suspension;
mixing and stirring 30 kg of copper nitrate trihydrate, 40 kg of zinc nitrate hexahydrate, 10 kg of aluminum nitrate nonahydrate and 500 kg of water uniformly to obtain a metal salt solution;
20 kg of sodium carbonate and 500 kg of water are mixed homogeneously to obtain a sodium carbonate solution.
2) A sodium carbonate solution and a metal salt solution were simultaneously added to the above suspension, and reacted at 70 ℃ for 1 hour to obtain an insoluble reaction mixture.
3) Filtering the insoluble reaction mixture from the solution, washing until the conductivity of the washing liquid is less than 100 mus/cm to obtain insoluble substances, drying the insoluble substances, adding 20 kg of alumina, adding 33 wt% of nitric acid with concentration of 2.5 wt% relative to the total weight of the insoluble substances and the added alumina, kneading, extruding to form
Figure BDA0002455976140000191
Millimeter strips were dried at 120 ℃ and baked at 360 ℃ for 5 hours to obtain samples having the compositions shown in Table 1.
Example 7
1) Mixing 10 kg of sodium carbonate and 700 kg of water, adding 40 kg of coconut charcoal of preparation example 1, and stirring at 70 ℃ for 2h to obtain a suspension;
mixing and stirring 30 kg of copper nitrate trihydrate, 40 kg of zinc nitrate hexahydrate, 10 kg of aluminum nitrate nonahydrate and 500 kg of water uniformly to obtain a metal salt solution;
20 kg of sodium carbonate and 500 kg of water are mixed homogeneously to obtain a sodium carbonate solution.
2) A sodium carbonate solution and a metal salt solution were simultaneously added to the above suspension, and reacted at 70 ℃ for 1 hour to obtain an insoluble reaction mixture.
3) Filtering the insoluble reaction mixture from the solution and washing until the conductivity of the washing solution is less than 100 mus/cm to obtain insoluble substances, drying the insoluble substances, adding 20 kg of alumina, and adding the insoluble substances and the aluminaThe total weight of the added alumina, the addition of nitric acid with the concentration of 2.5 weight percent is 33 weight percent, and the mixture is kneaded and extruded into strips
Figure BDA0002455976140000192
Millimeter strips were dried at 120 ℃ and baked at 360 ℃ for 5 hours to obtain samples having the compositions shown in Table 1.
Example 8
1) Mixing 5 kg of sodium carbonate and 500 kg of water uniformly, adding 80 kg of coconut charcoal of preparation example 1, and stirring at 70 ℃ for 2h to obtain a suspension;
mixing 6 kg of copper nitrate trihydrate, 8 kg of zinc nitrate hexahydrate, 2 kg of aluminum nitrate nonahydrate and 500 kg of water, and uniformly stirring to obtain a metal salt solution;
4 kg of sodium carbonate and 500 kg of water are mixed homogeneously to obtain a sodium carbonate solution.
2) A sodium carbonate solution and a metal salt solution were simultaneously added to the above suspension, and reacted at 70 ℃ for 1 hour to obtain an insoluble reaction mixture.
3) Filtering the insoluble reaction mixture from the solution, washing until the conductivity of the washing liquid is less than 100 mus/cm to obtain insoluble substances, drying the insoluble substances, adding 10 kg of alumina, adding 33 wt% of nitric acid with concentration of 2.5 wt% relative to the total weight of the insoluble substances and the added alumina, kneading, extruding to form
Figure BDA0002455976140000201
Millimeter strips were dried at 120 ℃ and baked at 360 ℃ for 5 hours to obtain samples having the compositions shown in Table 1.
Example 9
1) Mixing 5 kg of sodium carbonate and 500 kg of water uniformly, adding 80 kg of coconut charcoal of preparation example 1, and stirring at 70 ℃ for 2h to obtain a suspension;
mixing 45 kg of copper nitrate trihydrate, 60 kg of zinc nitrate hexahydrate, 15 kg of aluminum nitrate nonahydrate and 500 kg of water, and uniformly stirring to obtain a metal salt solution;
30 kg of sodium carbonate and 500 kg of water are mixed uniformly to obtain a sodium carbonate solution.
2) A sodium carbonate solution and a metal salt solution were simultaneously added to the above suspension, and reacted at 70 ℃ for 1 hour to obtain an insoluble reaction mixture.
3) Filtering the insoluble reaction mixture from the solution, washing until the conductivity of the washing liquid is less than 100 mus/cm to obtain insoluble substances, drying the insoluble substances, adding 12 kg of alumina, adding 33 wt% of nitric acid with concentration of 2.5 wt% relative to the total weight of the insoluble substances and the added alumina, kneading, extruding to form
Figure BDA0002455976140000202
Millimeter strips were dried at 120 ℃ and baked at 360 ℃ for 5 hours to obtain samples having the compositions shown in Table 1.
Example 10
1) Mixing 5 kg of sodium carbonate and 500 kg of water uniformly, adding 80 kg of coconut charcoal of preparation example 1, and stirring at 70 ℃ for 2h to obtain a suspension;
20 kg of copper nitrate trihydrate, 60 kg of zinc nitrate hexahydrate, 10 kg of aluminum nitrate nonahydrate and 500 kg of water are mixed and stirred uniformly to obtain a metal salt solution;
20 kg of sodium carbonate and 500 kg of water are mixed homogeneously to obtain a sodium carbonate solution.
2) A sodium carbonate solution and a metal salt solution were simultaneously added to the above suspension, and reacted at 70 ℃ for 1 hour to obtain an insoluble reaction mixture.
3) Filtering the insoluble reaction mixture from the solution, washing until the conductivity of the washing liquid is less than 100 mus/cm to obtain insoluble substances, drying the insoluble substances, adding 12 kg of alumina, adding 33 wt% of nitric acid with concentration of 2.5 wt% relative to the total weight of the insoluble substances and the added alumina, kneading, extruding to form
Figure BDA0002455976140000211
Millimeter strips were dried at 120 ℃ and baked at 360 ℃ for 5 hours to obtain samples having the compositions shown in Table 1.
Example 11
1) Mixing 7 kg of sodium carbonate and 500 kg of water uniformly, adding 80 kg of coconut charcoal of preparation example 1, and stirring at 70 ℃ for 2h to obtain a suspension;
mixing 50 kg of copper nitrate trihydrate, 30 kg of zinc nitrate hexahydrate, 10 kg of aluminum nitrate nonahydrate and 500 kg of water, and uniformly stirring to obtain a metal salt solution;
20 kg of sodium carbonate and 500 kg of water are mixed homogeneously to obtain a sodium carbonate solution.
2) A sodium carbonate solution and a metal salt solution were simultaneously added to the above suspension, and reacted at 70 ℃ for 1 hour to obtain an insoluble reaction mixture.
3) Filtering the insoluble reaction mixture from the solution, washing until the conductivity of the washing solution is less than 100 mus/cm to obtain insoluble substance, drying the insoluble substance, adding 10 kg of alumina, adding 33 wt% of nitric acid with concentration of 2.5 wt% relative to the total weight of the insoluble substance and the added alumina, kneading, extruding to obtain the final product
Figure BDA0002455976140000212
Millimeter strips were oven dried at 120 ℃ and baked at 355 ℃ for 5 hours to give samples having the compositions shown in Table 1.
Example 12
1) Uniformly mixing 3 kg of sodium carbonate and 500 kg of water, adding 80 kg of coconut shell charcoal of preparation example 1, and stirring at 70 ℃ for 2h to obtain a suspension;
mixing 40 kg of copper nitrate trihydrate, 50 kg of zinc nitrate hexahydrate, 10 kg of aluminum nitrate nonahydrate and 500 kg of water, and uniformly stirring to obtain a metal salt solution;
30 kg of sodium carbonate and 500 kg of water are mixed uniformly to obtain a sodium carbonate solution.
2) A sodium carbonate solution and a metal salt solution were simultaneously added to the above suspension, and reacted at 70 ℃ for 1 hour to obtain an insoluble reaction mixture.
3) Filtering the insoluble reaction mixture from the solution and washing until the conductivity of the washing solution is less than 100 mus/cm to obtain insoluble substance, drying the insoluble substance, and adding 40 kgAlumina, 33 wt% of nitric acid having a concentration of 2.5 wt% based on the total weight of the insoluble matter and the added alumina, kneaded and extruded to form
Figure BDA0002455976140000222
Millimeter strips were oven dried at 120 ℃ and baked at 355 ℃ for 5 hours to give samples having the compositions shown in Table 1.
Example 13
1) Mixing 10 kg of sodium carbonate and 500 kg of water uniformly, adding 80 kg of coconut charcoal of preparation example 1, and stirring at 70 ℃ for 2h to obtain a suspension;
mixing and stirring 15 kg of copper nitrate trihydrate, 20 kg of zinc nitrate hexahydrate, 10 kg of aluminum nitrate nonahydrate and 500 kg of water uniformly to obtain a metal salt solution;
10 kg of sodium carbonate and 500 kg of water are mixed homogeneously to obtain a sodium carbonate solution.
2) A sodium carbonate solution and a metal salt solution were simultaneously added to the above suspension, and reacted at 70 ℃ for 1 hour to obtain an insoluble reaction mixture.
3) Filtering the insoluble reaction mixture from the solution, washing until the conductivity of the washing solution is less than 100 mus/cm to obtain insoluble matter, drying the insoluble matter, adding 8 kg of alumina, adding 33 wt% of nitric acid with concentration of 2.5 wt% relative to the total weight of the insoluble matter and the added alumina, kneading, extruding to obtain the final product
Figure BDA0002455976140000221
Millimeter strips were dried at 120 ℃ and baked at 360 ℃ for 5 hours to obtain samples having the compositions shown in Table 1.
Example 14
A cleaning agent was prepared by following the procedure of example 2, except that the coconut shell charcoal of preparation example 1 was replaced with the coconut shell charcoal of preparation example 2. The composition of the obtained samples is shown in Table 1.
Example 15
A cleaning agent was prepared by following the procedure of example 3, except that the coconut shell charcoal of preparation example 1 was replaced with the coconut shell charcoal of preparation example 3. The composition of the obtained samples is shown in Table 1.
Example 16
A cleaning agent was prepared by the method of example 1, except that an equal amount of sodium carbonate for preparing a sodium carbonate solution was added to the step of preparing the suspension, and the step of preparing a sodium carbonate solution was omitted. The composition of the obtained samples is shown in Table 1.
Comparative example 1
1) Mixing and stirring 30 kg of copper nitrate trihydrate, 40 kg of zinc nitrate hexahydrate, 10 kg of aluminum nitrate nonahydrate and 500 kg of water uniformly to obtain a metal salt solution;
30 kg of sodium carbonate and 550 kg of water are mixed uniformly to obtain a sodium carbonate solution.
2) The sodium carbonate solution and the metal salt solution were mixed uniformly, reacted at 70 ℃ for 1 hour, and filtered to obtain an insoluble reaction mixture.
3) Washing the insoluble reaction mixture until the conductivity of the washing liquid is less than 100 mus/cm to obtain insoluble substances, drying the insoluble substances, adding 6 kg of alumina and 1 kg of graphite, mixing, rolling, adding 30 wt% of water, granulating, roasting at 360 ℃ for 5 hours, tabletting and forming to obtain a sample composition shown in table 1.
Comparative example 2
A cleaning agent was prepared by following the procedure of example 1 except that the coconut shell charcoal of preparation example 1 was replaced with the raw coconut shell charcoal powder. The composition of the obtained samples is shown in Table 1.
Comparative example 3
A cleaning agent was prepared by following the procedure of example 1, except that the coconut charcoal of production example 1 was replaced with the coconut charcoal obtained in production example 4. The composition of the obtained samples is shown in Table 1.
Comparative example 4
A cleaning agent was prepared by following the procedure of example 1, except that the coconut charcoal of production example 1 was replaced with the coconut charcoal obtained in production example 5. The composition of the obtained samples is shown in Table 1.
TABLE 1
Figure BDA0002455976140000241
Test example 1
Nitrogen containing different contents of sulfur, arsenic and/or phosphorus impurities was prepared according to table 2. The purifiers prepared in the above examples and comparative examples were pulverized into particles of 20 to 40 meshes, respectively, and filled into reactors having an inner diameter of 1cm, respectively, with a packing mass of 2g, at 25 deg.C, 0.1MPa, and a volume space velocity of 3000h-1The prepared nitrogen gas containing different contents of sulfur impurities, arsenic impurities and/or phosphorus impurities is purified by corresponding reactors respectively under the conditions of (1), and the results are shown in table 2.
TABLE 2
Figure BDA0002455976140000251
Test example 2
Synthesis gas containing different contents of sulphur, arsenic and/or phosphorus impurities (1: 1 volume ratio of hydrogen to carbon monoxide) was prepared according to table 3. The purifiers prepared in the above examples and comparative examples were pulverized into particles of 20 to 40 meshes, respectively, and filled into reactors having an inner diameter of 1cm, respectively, with a packing mass of 2g, at 25 deg.C, 0.1MPa, and a volume space velocity of 3000h-1The prepared synthesis gas containing different contents of sulfur impurities, arsenic impurities and/or phosphorus impurities was purified by passing through the corresponding reactors, respectively, and the results are shown in table 3.
TABLE 3
Figure BDA0002455976140000261
Test example 3
Liquid propylene containing different contents of sulfur impurities, arsenic impurities and/or phosphorus impurities was prepared according to table 4. The purifiers prepared in the above examples and comparative examples were pulverized into particles of 20 to 40 meshes, respectively, and filled into reactors having an inner diameter of 1cm, respectively, with a packing mass of 2g, a pressure of 3.0MPa at 25 ℃ and a mass space velocity of 3.5h-1Respectively carrying out corresponding reactions on the prepared liquid propylene containing different contents of sulfur impurities, arsenic impurities and/or phosphorus impuritiesThe vessel was purged and the results are shown in Table 4.
TABLE 4
Figure BDA0002455976140000271
As can be seen from the results in tables 2-4, the contents of sulfur impurities, arsenic impurities and phosphorus impurities in the gas purified by the purifying agent prepared in the embodiment of the invention are less than 1ppm, and the utilization rate of active components of the purifying agent in each embodiment can reach more than 85%.
Furthermore, it can be seen that the utilization rate of the active component in the purifiers prepared in the examples of the present invention is much higher than that of the comparative example 1 containing no coconut charcoal and that of the comparative example 2 using the raw coconut charcoal powder.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (16)

1. The purifying agent is characterized by comprising activated carbon and an active component loaded on the activated carbon, wherein the active component contains copper element and zinc element, and the specific surface area of the activated carbon is more than or equal to 1000m2The mesopore rate is more than or equal to 40 percent.
2. The purifying agent according to claim 1, wherein the content of the activated carbon is 50 to 90 parts by weight, preferably 60 to 80 parts by weight; the content of the copper element is 1-10 parts by weight, preferably 1-8 parts by weight calculated on oxide; the content of the zinc element is 1 to 10 parts by weight, preferably 1 to 8 parts by weight calculated on oxide;
preferably, the copper element is present in the form of copper oxide or copper oxide and aurichalcite and the zinc element is present in the form of zinc oxide or zinc oxide and aurichalcite, more preferably, the copper element is present in the form of copper oxide and the zinc element is present in the form of zinc oxide.
3. The purifying agent as claimed in claim 1 or 2, wherein the mesopore ratio of the activated carbon is 40% -50%, and the specific surface area of the activated carbon is 1000-1500m2/g；
Preferably, the activated carbon is coconut shell carbon.
4. The purifying agent as claimed in claim 3, wherein the preparation method of the coconut shell carbon comprises heating raw coconut shell carbon powder to 700-1000 ℃ in an inert gas atmosphere, then carrying out activation treatment at 700-1000 ℃ for 300 minutes in a carbon dioxide atmosphere, and then cooling in an inert gas atmosphere;
preferably, the carbon dioxide is used in an amount of 1 to 15 parts by weight per minute with respect to 100 parts by weight of the raw coconut charcoal powder.
5. The scavenger according to any one of claims 1 to 4, wherein the scavenger further comprises an aluminium-containing compound, preferably alumina; the content of the alumina is 1-6 parts by weight relative to the content of the activated carbon is 50-90 parts by weight;
preferably, the cleaning agent further comprises a binder, and the content of the binder is 1-5 parts by weight relative to the content of the activated carbon is 50-90 parts by weight.
6. A preparation method of a purifying agent is characterized by comprising the following steps:
(1) in the inert gas atmosphere, the coconut shell carbon powder as the raw material is heated to 700-1000 ℃, then is activated for 300 minutes at 700-1000 ℃ in the carbon dioxide atmosphere, and is cooled in the inert gas atmosphere to obtain the coconut shell carbon powder with the specific surface area of more than or equal to 1000m2(ii) coconut shell carbon with a mesopore ratio of not less than 40%;
(2) in the presence of water, the coconut shell carbon, a water-soluble copper source, a water-soluble zinc source, a water-soluble aluminum source and a precipitator are contacted to obtain an insoluble reaction mixture;
(3) the insoluble reaction mixture is calcined.
7. The method of claim 6, wherein the contacting in step (2) comprises the steps of:
(1) mixing a precipitator and water to obtain a solution I;
(2) mixing the activated carbon with the solution I to obtain a suspension II;
(3) mixing a water-soluble copper source, a water-soluble zinc source, a water-soluble aluminum source and water to obtain a solution III;
(4) mixing a precipitator and water to obtain a solution IV, wherein the concentration of the precipitator in the solution IV is greater than that of the precipitator in the solution I;
(5) mixing the suspension II, the solution III and the solution IV;
preferably, the water-soluble copper source is selected from one or more of copper nitrate, copper sulfate and copper chloride, more preferably copper nitrate;
preferably, the water-soluble zinc source is selected from one or more of zinc nitrate, zinc sulfate and zinc chloride, more preferably zinc nitrate;
preferably, the water-soluble aluminum source is selected from one or more of aluminum nitrate, aluminum sulfate and aluminum chloride, more preferably aluminum nitrate;
preferably, the precipitating agent is selected from water-soluble carbonates, more preferably one or more selected from sodium carbonate, potassium carbonate, ammonium carbonate.
8. The method as claimed in claim 7, wherein the molar content of the precipitant in the solution I is 0.1-0.3%;
the weight ratio of the precipitating agent in the step (1) to the precipitating agent in the step (4) is 1: 0.5-10; the molar ratio of the precipitant to the total amount of the water-soluble copper source, the water-soluble zinc source and the water-soluble aluminum source is 1: 0.8 to 2; the coconut shell carbon, the water-soluble copper source, the water-soluble zinc source and the water-soluble aluminum source are used in such amounts that the content of the activated carbon in the obtained purifying agent is 50-90 parts by weight, preferably 60-80 parts by weight; the content of the copper element is 1-10 parts by weight, preferably 1-8 parts by weight calculated on oxide; the content of the zinc element is 1 to 10 parts by weight, preferably 1 to 8 parts by weight calculated on oxide; the content of the alumina is 1 to 6 weight portions.
9. The method of any one of claims 6-8, wherein the conditions of the contacting comprise: the temperature is 40-90 ℃ and the time is 0.5-3 h; the roasting conditions comprise: the roasting temperature is 250-500 ℃, preferably 350-500 ℃, and the roasting time is 1-5 h.
10. The method according to any one of claims 6 to 9, wherein the method further comprises kneading and molding after washing the insoluble reaction mixture to an electric conductivity of 100 μ S/cm or less before calcination.
11. A scavenger prepared by the process of any one of claims 6 to 10.
12. Use of a purification agent as claimed in any one of claims 1 to 5 and 11 in the purification of a gas or liquid.
13. The use of claim 12, wherein the gas or liquid contains one or more of sulfur impurities, arsenic impurities, phosphorus impurities;
preferably, the sulfur impurities are one or more of hydrogen sulfide, sulfur dioxide, carbonyl sulfide;
preferably, the arsenic impurity is arsine;
preferably, the phosphorus impurity is phosphine;
preferably, the total content of sulphur, arsenic and phosphorus impurities in the gas or liquid is between 5 and 50000 ppm.
14. A method of decontamination, the method comprising contacting a gas or liquid to be decontaminated with the decontaminant of any one of claims 1 to 5 and 11.
15. The purification method according to claim 14, wherein the gas or liquid to be purified contains one or more of sulphur impurities, arsenic impurities, phosphorus impurities;
preferably, the sulfur impurities are one or more of hydrogen sulfide, sulfur dioxide, carbonyl sulfide;
preferably, the arsenic impurity is arsine;
preferably, the phosphorus impurity is phosphine;
preferably, the total content of sulphur, arsenic and phosphorus impurities in the gas or liquid to be purified is between 5 and 50000 ppm.
16. The purification process according to claim 14 or 15, wherein the contacting conditions comprise a temperature of 20 ℃ to 100 ℃, a pressure of 0.1 to 5MPa and a volume space velocity of the gas to be purified of 10 to 10000h-1Or the mass space velocity of the liquid to be purified is 0.1-10h-1。
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101804325A (en) * 2010-04-22 2010-08-18 上海化工研究院 Preparation method of modified activated carbon adsorption desulfurizing agent
CN102423688A (en) * 2011-08-26 2012-04-25 昆明理工大学 Preparation method for walnut shell active carbon adsorbent for purifying low concentration phosphine
CN102806065A (en) * 2011-06-03 2012-12-05 中国石油化工股份有限公司 Purifier for adsorbing arsenic hydride and hydrogen phosphide in olefin tail gas and preparation method thereof
CN103506071A (en) * 2012-06-19 2014-01-15 中国石油化工股份有限公司 Purificant used for absorbing hydrogen sulfide and carbonyl sulfide in tail gas of natural gas and preparation method thereof
CN104107631A (en) * 2014-07-30 2014-10-22 沈阳三聚凯特催化剂有限公司 Desulfurization and demercuration agent and preparation method thereof
CN105366674A (en) * 2014-08-27 2016-03-02 中国石油化工股份有限公司 Preparation method of rich mesoporous high-specific surface area activated carbon
CN107952408A (en) * 2016-10-14 2018-04-24 中国石油化工股份有限公司 Sulphur, arsenic, phosphorus cleanser and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101804325A (en) * 2010-04-22 2010-08-18 上海化工研究院 Preparation method of modified activated carbon adsorption desulfurizing agent
CN102806065A (en) * 2011-06-03 2012-12-05 中国石油化工股份有限公司 Purifier for adsorbing arsenic hydride and hydrogen phosphide in olefin tail gas and preparation method thereof
CN102423688A (en) * 2011-08-26 2012-04-25 昆明理工大学 Preparation method for walnut shell active carbon adsorbent for purifying low concentration phosphine
CN103506071A (en) * 2012-06-19 2014-01-15 中国石油化工股份有限公司 Purificant used for absorbing hydrogen sulfide and carbonyl sulfide in tail gas of natural gas and preparation method thereof
CN104107631A (en) * 2014-07-30 2014-10-22 沈阳三聚凯特催化剂有限公司 Desulfurization and demercuration agent and preparation method thereof
CN105366674A (en) * 2014-08-27 2016-03-02 中国石油化工股份有限公司 Preparation method of rich mesoporous high-specific surface area activated carbon
CN107952408A (en) * 2016-10-14 2018-04-24 中国石油化工股份有限公司 Sulphur, arsenic, phosphorus cleanser and preparation method thereof

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