CN113522233B - 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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Publication number
CN113522233B
CN113522233B CN202010306546.5A CN202010306546A CN113522233B CN 113522233 B CN113522233 B CN 113522233B CN 202010306546 A CN202010306546 A CN 202010306546A CN 113522233 B CN113522233 B CN 113522233B
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water
soluble
zinc
copper
source
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CN113522233A (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

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 comprises copper element and zinc element, and the specific surface area of the active carbon is more than or equal to 1000m 2 Per g, the mesoporosity is more than or equal to 40%; also disclosed is a method for preparing the purifying agent, comprising the steps of: preparation of the catalyst with specific surface area of more than or equal to 1000m 2 /g, coconut shell charcoal with mesoporosity of more than or equal to 40%; contacting the coconut shell carbon, a water-soluble copper source, a water-soluble zinc source, a water-soluble aluminum source and a precipitant in the presence of water to obtain an insoluble reaction mixture; roasting the insoluble reaction mixture; the purifying agent can be used for purifying gas or liquid containing sulfur impurities, arsenic impurities and/or phosphorus impurities, the content of the sulfur impurities, the arsenic impurities and the phosphorus impurities in the purified gas or liquid is 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, in particular to a purifying agent, and a preparation method, application and a purifying method thereof.
Background
Sulfur, arsenic, phosphorus and other impurities widely exist in raw materials such as natural gas, synthetic gas, coal gas, light gas, liquid hydrocarbon and the like, and the existence of the impurities can lead to poisoning and deactivation of various catalysts, greatly shorten the service life of the catalysts and even lead to incapability of normal catalytic reaction; in addition, in production, residual impurities can enter downstream synthetic products as production proceeds, thereby presenting a series of environmental and health concerns. Therefore, the efficient and high-precision removal of sulfur, arsenic, phosphorus and other impurities is of great importance for protecting the main catalyst of the downstream equipment and improving the quality of the downstream products.
In general, sulfur impurities in industrial feedstocks are predominantly H 2 S and COS (carbonyl sulfide) exist, and the arsenic impurity is mainly in the form of AsH 3 In the form of phosphorus impurities, mainly in the form of pH 3 Is present in the form of (c). The current method for removing sulfur impurities, arsenic impurities and phosphorus impurities in gas is to use desulfurizing agent, dearsenifying agent and dephosphorizing agent for adsorption and removal.
Currently, the trend in the development of desulfurizing agents, dearsenic agents and dephosphorizing agents is toward low bulk density, low use temperature, high strength, and high sulfur and arsenic capacities.
CN201410575030.5 discloses a normal temperature desulfurizing and dearsenifying agent and a preparation method thereof, which comprises the following components in parts by weight: a) 1-10 parts of chlorite; b) 10-50 parts of copper oxide; c) 10-60 parts of zinc oxide; d) 0.01 to 3 parts of rare earth metal R. The addition of rare earth metal improves the charge distribution around Zn and Cu and improves the purifying capacity.
CN201410314482.8 discloses a sulfur-arsenic adsorbent and a preparation method thereof, and the sulfur-arsenic adsorbent comprises the following components in parts by weight: a) 1-10 parts of chlorite; b) 13-50 parts of copper oxide; c) 10-55 parts of zinc oxide; d) 0.1 to 5 parts of ferric oxide; e) 0.1 to 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 purifying hydrogen sulfide, phosphine and arsine simultaneously, which comprises the following steps: (1) Dissolving concentrated acid in distilled water according to the proportion of 1-5 mol/1000ml, and stirring until the mixture is uniformly mixed; (2) P123 or F127 is added into the solution in the step (1) according to the proportion of 5-30 g/100ml, and is stirred for 20-60 minutes at the temperature of 30-50 ℃; (3) Adding a pore-enlarging agent into the solution obtained in the step (2) according to the proportion of 1-5 g/100ml, adding tetraethoxysilane into the mixed solution of the solution obtained in the step (2) and tetraethoxysilane according to the proportion 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 substance obtained in the step (4) at 100-150 ℃ for 12-60 hours, finally placing the obtained white powder into a roasting furnace, heating to 400-600 ℃ at 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 acidic solution for ultrasonic impregnation for 30-60 minutes, and drying the impregnated adsorbent at 100-150 ℃ for 3-7 hours to obtain the adsorbent with large pore diameter capable of deeply purifying hydrogen sulfide, phosphine and arsine; three gases were adsorbed simultaneously using a large pore size adsorbent.
The adsorption capacity of the adsorbent is improved and increased by the scheme. However, there is still a problem in that the utilization of the active components of the scavenger is low.
Disclosure of Invention
The invention aims to solve the problem of low utilization rate of active components of a purifying agent in the prior art, and provides a purifying agent, a preparation method and application thereof and a purifying method, so as to achieve the aim of improving the utilization rate of the active components of the purifying agent.
In order to achieve the above object, according to one aspect of the present invention, there is provided a scavenger comprising an activated carbon and an active component supported on the activated carbon, wherein the active component comprises copper element and zinc element, and the specific surface area of the activated carbon is not less than 1000m 2 /g, mesoporesThe rate is more than or equal to 40 percent.
The second aspect of the present invention provides a method for producing a purifying agent, wherein the method comprises the steps of:
(1) Heating raw coconut shell carbon powder to 700-1000 ℃ in inert gas atmosphere, then activating treatment is carried out for 160-300 minutes at 700-1000 ℃ in carbon dioxide atmosphere, and then cooling is carried out in inert gas atmosphere, thus obtaining the coconut shell carbon powder with specific surface area more than or equal to 1000m 2 /g, coconut shell charcoal with mesoporosity of more than or equal to 40%;
(2) Contacting the coconut shell carbon, a water-soluble copper source, a water-soluble zinc source, a water-soluble aluminum source and a precipitant in the presence of water to obtain an insoluble reaction mixture;
(3) The insoluble reaction mixture is calcined.
In a third aspect the present invention provides a scavenger prepared by the above method.
In a fourth aspect, the invention provides the use of a purifying agent as described above in the purification of a gas or liquid.
In a fifth aspect the present invention provides a purification method, wherein the method comprises contacting a gas or liquid to be purified with a purification agent as described above.
The purifying agent has better purifying effect and higher utilization rate of active components, the purifying agent is 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 arsenic impurities and the phosphorus impurities in the purified gas or liquid is less than 1ppm, and the utilization rate of the active components is more than 85%.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, the adsorption capacity means the amount of the adsorbent adsorbed per unit adsorbent, and the unit is mg/g.
In order to achieve the above object, according to one aspect of the present invention, there is provided a scavenger comprising an activated carbon and an active component supported on the activated carbon, wherein the active component comprises copper element and zinc element, and the specific surface area of the activated carbon is not less than 1000m 2 The mesoporosity per gram is more than or equal to 40 percent.
In the present invention, the mesoporosity means the percentage of pore volume of pores having a pore diameter of 2nm or more to the total pore volume. I.e. mesoporosity = mesopore volume +.total pore volume; mesoporous pore volume = total pore volume-microporous pore volume, pore structure of coconut shell carbon was determined using an ASAP2600 surface analyzer, microporous pore volume was calculated using t-plot method, and total pore volume was calculated using single point method.
In the present invention, the specific surface area is measured by the BET method.
In the present invention, the content of sulfur impurities is calculated as sulfur, the content of arsenic impurities is calculated as arsenic, and the content of phosphorus impurities is calculated as phosphorus.
In the present invention, in order to improve the purification effect of the purification agent and the utilization ratio of the active components of the purification agent, it is preferable that the content of the activated carbon in the purification agent is 50 to 90 parts by weight, more preferably 60 to 80 parts by weight; the copper element content is 1 to 10 parts by weight, more preferably 1 to 8 parts by weight, calculated as 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 form of the copper element and the zinc element in the scavenger is not particularly limited, and in order to improve the purifying effect of the scavenger and the utilization ratio of the active components of the scavenger, it is preferable that the copper element exists in the form of copper oxide or in the form of copper oxide and wurtzite, and the zinc element exists in the form of zinc oxide or in the form of zinc oxide and wurtzite.
In the present invention, in order to further improve the purification effect of the purifying agent and the utilization ratio of the active components of the purifying 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 present invention, in order to improve the diffusion performance of the purifying agent and the utilization ratio of the active ingredient and to increase the residence time of the purified stream in the purifying agent, it is preferable that the mesoporosity of the activated carbon is 40% to 50%, and the specific surface area of the activated carbon is 1000 to 1500m 2 And/g. As will be appreciated by those skilled in the art, the diffusion property refers to the ability of the scavenger to diffuse a purified stream within the scavenger.
In the present invention, in order to further improve the diffusion performance of the purifying agent and the utilization ratio of the active ingredient and to increase the residence time of the purified stream in the purifying agent, the activated carbon is preferably wood-based activated carbon, more preferably coconut shell carbon.
The inventors of the present invention found in the study that the specific surface area was not less than 1000m 2 And/g, the active carbon with the mesoporosity of more than or equal to 40% and the active component loaded on the active carbon and containing copper element and zinc element can generate obvious synergistic purification effect under a specific weight ratio, and the utilization rate of the active component is effectively improved, especially the active carbon is coconut shell carbon, and the active component has better synergistic purification effect and higher utilization rate of the active component under the condition that the active component is copper oxide and zinc oxide.
In the present invention, there is no particular limitation on the method for preparing the coconut shell charcoal, and in order to further improve the diffusion performance of the purifying agent and the utilization rate of the active components in the purifying agent and increase the residence time of the purified stream in the purifying agent, it is preferable that the method for preparing the coconut shell charcoal comprises heating raw coconut shell charcoal powder to 700-1000 ℃ in an inert gas atmosphere, then performing activation treatment at 700-1000 ℃ for 160-300 minutes in a carbon dioxide atmosphere, and then cooling in an 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 raw coconut shell carbon powder, and may be, for example, one or more of nitrogen and a group 0 element gas of the periodic table.
In the present invention, the amount of the carbon dioxide is not particularly limited, and in order to enhance the activation effect of the raw coconut shell charcoal powder, it is preferable that the amount of the carbon dioxide is 1 to 15 parts by weight per minute with respect to 100 parts by weight of the raw coconut shell charcoal powder.
In the present invention, the purifying agent may further contain an aluminum-containing compound, and preferably, the aluminum-containing compound is aluminum oxide, and the aluminum oxide is contained in an amount of 1 to 6 parts by weight based on 50 to 90 parts by weight of the activated carbon.
In the present invention, when the scavenger is a molded body, the scavenger further contains a binder. The source of the binder is not particularly limited as long as the purifying effect of the purifying agent is not adversely affected, for example, the binder is one or more of alumina, bauxite, kaolin, and preferably alumina.
In the present invention, the amount of the binder is not particularly limited, and it is preferable that 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 present invention provides a method for producing a purifying agent, wherein the method comprises the steps of:
(1) Heating raw coconut shell carbon powder to 700-1000 ℃ in inert gas atmosphere, then activating treatment is carried out for 160-300 minutes at 700-1000 ℃ in carbon dioxide atmosphere, and then cooling is carried out in inert gas atmosphere, thus obtaining the coconut shell carbon powder with specific surface area more than or equal to 1000m 2 /g, coconut shell charcoal with mesoporosity of more than or equal to 40%;
(2) Contacting the coconut shell carbon, a water-soluble copper source, a water-soluble zinc source, a water-soluble aluminum source and a precipitant in the presence of water to obtain an insoluble reaction mixture;
(3) The insoluble reaction mixture is calcined.
The inventors of the present invention have found that the specific surface area and mesoporosity of coconut charcoal can be enhanced by subjecting conventional, commercially available coconut charcoal powder to an activation treatment in a carbon dioxide atmosphere at 700 deg.c to 1000 deg.c for 160 to 300 minutes.
In the present invention, for the sake of distinction, the coconut shell carbon before treatment is referred to as raw coconut shell carbon powder (conventional, commercially available coconut shell carbon powder), and the coconut shell carbon after treatment that can be used as the activated carbon of the present invention is referred to as coconut shell carbon.
The temperature rising rate of the step (1) is preferably 1-10 ℃/min.
The cooling rate of step (1) is preferably 5-20 ℃/min.
In the invention, the raw material coconut shell carbon powder is heated to 700-1000 ℃ and then is subjected to activation treatment in carbon dioxide atmosphere, wherein the temperature of the activation treatment can be the end temperature after the temperature is raised, or can be slightly different, so 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, it is preferable that the raw coconut shell charcoal powder is subjected to the activation treatment in a carbon dioxide atmosphere at 700 to 1000 ℃ for 200 to 280 minutes.
In the present invention, the amount of the carbon dioxide is not particularly limited, and in order to further enhance the activation effect of the raw coconut shell charcoal powder, it is preferable that the amount of the carbon dioxide is 1 to 15 parts by weight per minute with respect to 100 parts by weight of the coconut shell charcoal powder.
In the invention, the activation treatment mode can be that the raw material coconut shell carbon powder is placed in a reaction furnace, the temperature is raised in an inert gas atmosphere, then the inert gas atmosphere in the reaction furnace is replaced by carbon dioxide, and the carbon dioxide is continuously introduced into the reaction furnace, and the reaction furnace is heated for 160-300 minutes, preferably 200-280 minutes, at 700-1000 ℃, preferably 850-980 ℃.
In the present invention, it is preferable that the inert gas atmosphere in the reaction furnace is replaced with carbon dioxide gas at a rate of 160 to 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 completed, inert gas is introduced into a 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 raw coconut shell charcoal 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 to 300ml/min to form an inert gas atmosphere with respect to a reaction furnace having a volume of 1000 ml.
In the present invention, the inert gas may be one or more of nitrogen and a group 0 element gas of the periodic table. The inert gas in the heating process and the inert gas in the cooling process of the reaction furnace can be the same or different, and are preferably the same inert gas.
In the present invention, the manner of contacting the coconut shell charcoal, 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 load the active components in the purification agent on the active carbon, one preferable contact manner includes: (1) mixing a precipitant and water to obtain a solution I;
(2) Mixing active 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 the precipitant with water to obtain a solution IV, wherein the concentration of the precipitant in the solution IV is greater than that in the solution I;
(5) Mixing the suspension II, the solution III and the solution IV.
In the invention, the precipitant is used for forming the copper element, zinc element and aluminum element in the water-soluble copper source, the water-soluble zinc source and the water-soluble aluminum source into precipitates, attaching the precipitates to the surface of the activated carbon, and roasting to obtain the oxides of the metal elements.
In the invention, the precipitant in the step (4) and the precipitant in the step (1) can be prepared into a solution I, so that the solution IV in the step (4) is omitted; or the precipitant in the step (4) and the precipitant in the step (1) can be prepared into a solution IV together, so that the solution I in the step (4) is omitted; in order to uniformly load the active component on the activated carbon and to increase the adsorption capacity of the purifying agent and to increase the utilization rate of the active component, it is preferable that the precipitating agent is formulated into solution i and solution IV, respectively.
In the present invention, the source of the water-soluble copper source is not particularly limited, and the water-soluble copper source may be one or more selected from copper nitrate, copper sulfate and copper chloride, and preferably, the water-soluble copper source is copper nitrate in order to improve the purification effect of the purifying agent and the utilization ratio of the active component.
In the present invention, the source of the water-soluble copper source is not particularly limited, and the water-soluble copper source may be one or more selected from zinc nitrate, zinc sulfate, and zinc chloride, and preferably, the water-soluble zinc source is zinc nitrate in order to improve the purification effect of the purifying agent and the utilization ratio of the active component.
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 preferably, the water-soluble aluminum source is aluminum nitrate in order to improve the purification effect of the purification agent and the utilization ratio of the active component.
In the present invention, in order to enhance the purification effect of the purifying agent and to enhance the utilization ratio of the active ingredient, it is preferable that the precipitating agent is a water-soluble carbonate, more preferably one or more of 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 is completely dissolved in water, and in order to improve the purification effect of the purification agent and the utilization rate of the active components, the molar content of the precipitant in the solution i is preferably 0.1% to 0.3%.
In the present invention, the weight ratio of the precipitant in the solution i to the solution iv is not particularly limited, and in order to improve the purification effect of the purification agent and to improve the utilization ratio of the active components, preferably, the weight ratio of the precipitant in the solution i to 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 ratio 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 the coconut shell carbon, the water-soluble copper source, the water-soluble zinc source, and the water-soluble aluminum source are not particularly limited, and preferably, the amount of the activated carbon is 50 to 90 parts by weight, preferably 60 to 80 parts by weight, in the resulting purifying agent; the content of the copper element is 1-10 parts by weight, preferably 1-8 parts by weight, calculated as oxide; the content of the zinc element is 1 to 10 parts by weight, preferably 1 to 8 parts by weight, calculated as oxide; the content of the alumina is 1-6 parts by weight.
In the present invention, the conditions under which the contact is performed are not particularly limited as long as the reaction can be performed normally, and in order to uniformly load the reactant on the activated carbon and to improve the purification effect of the purification agent and the utilization rate of the active component, the conditions of the contact preferably include: the temperature is 40-90 ℃ and the time is 0.5-3h.
In the present invention, the conditions of the calcination are not particularly limited, and in order to further increase the adsorption capacity of the scavenger and to increase the utilization ratio of the active component, the conditions of the calcination preferably include: the roasting temperature is 250-500 ℃, preferably 350-500 ℃ and the roasting time is 1-5h.
In the present invention, in order to enhance the purifying effect of the purifying agent, the method further comprises kneading and molding the insoluble reaction mixture after washing to a conductivity of 100. Mu.S/cm or less before firing.
In the present invention, the kneading and molding method is not particularly limited, and for example, the washed insoluble reaction mixture is mixed with a binder and an acid in the presence of water and then kneaded and molded.
In the present invention, in order to improve the kneading molding rate and the purifying effect of the purifying agent, the binder is preferably one or more of alumina, bauxite, and kaolin, and preferably alumina. The acid is one or more of nitric acid, sulfuric acid, and hydrochloric acid, and in order to improve kneading molding rate and purifying effect of the purifying agent, the acid is preferably nitric acid.
In the present invention, the amount of the binder is not particularly limited, and in order to enhance 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 active carbon.
In the present invention, the amount of the acid 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 is 1 to 3:1.
In the present invention, water is also used in the kneading molding process, and the amount of the water is not particularly limited, and in order to enhance the bonding effect, it is preferable that the amount of the 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 scavenger prepared by the above method.
In a fourth aspect, the invention provides the use of a purifying agent as described above in the purification of a gas or liquid.
The purifying agent of the present invention is particularly suitable for purifying a 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 other than sulfur impurities, arsenic impurities and phosphorus impurities in the gas 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, oilfield gas, refinery gas.
In the present invention, the source of the liquid is not particularly limited as long as components other than sulfur impurities, arsenic impurities and phosphorus impurities in the liquid do not adversely affect the scavenger, 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 ordinary temperature and pressure, more preferably the liquid is a liquid formed by pressurizing a hydrocarbon which is gaseous at ordinary temperature and pressure, further, the liquid is liquid propylene.
In the present invention, the type of the sulfur impurity is not particularly limited, and for example, the sulfur impurity is one or more of hydrogen sulfide, sulfur dioxide, and 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 enhance the purifying effect of the purifying agent, the total content of sulfur impurities, arsenic impurities and phosphorus impurities in the gas or liquid is preferably 5 to 50000ppm.
In a fifth aspect the present invention provides a method of purifying, wherein the method comprises contacting a gas or liquid to be purified with a purifying agent as described above.
The purifying agent of the present invention is particularly suitable for purifying a 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 other than sulfur impurities, arsenic impurities and phosphorus impurities in the gas to be purified 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, oilfield gas and refinery gas.
In the present invention, the source of the liquid to be purified is not particularly limited as long as components other than sulfur impurities, arsenic impurities and phosphorus impurities in the liquid to be purified do not adversely affect the purifying agent, 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 at normal temperature, and further, the liquid to be purified is liquid propylene.
In the present invention, the type of the sulfur impurity is not particularly limited, and for example, the sulfur impurity is one or more of hydrogen sulfide, sulfur dioxide, and 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 purifying agent, the total content of sulfur impurities, arsenic impurities and phosphorus impurities in the gas or liquid to be purified is preferably 5 to 50000ppm.
In the present invention, the conditions of the contact are not particularly limited, and in order to enhance the purification effect of the purifying agent and to enhance the utilization ratio of the active component, preferably, the conditions of the contact 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 -1 Or the mass space velocity of the liquid to be purified is 0.1-10h -1 . The pressure in the present invention is absolute.
The present invention will be described in detail by examples. In the following examples of the present invention,
When the material flow to be purified is gas, the adsorption capacity calculation method comprises the following steps:
S＝V×t×(C in -C out )÷22.4÷1000×M÷m ad ×10 -6 ；
when the material flow to be purified is liquid, the adsorption capacity calculation method comprises the following steps:
s=t×mass space velocity× (C in -C out )×10 -6 ；
V: the flow rate (mL/min) of the gas to be purified;
t: contact time (min);
m ad : sorbent loading (g);
m: molar mass (L/mol) of sulfur, arsenic or phosphorus;
mass space velocity: mass space velocity of the stream to be purified (h -1 )；
C in : inlet sulfur impurity, arsenic impurity and/or phosphorus impurity content (ppm) in the gas or liquid to be purified;
C out : sulfur impurity, arsenic impurity and/or phosphorus impurity content (ppm) in the gas or liquid after outlet purification;
the theoretical value calculation method 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 adsorption capacity of the purifying agent is obtained;
the method for measuring the utilization rate of the active component comprises the following steps: active ingredient utilization = adsorption capacity measurement ≡adsorption capacity theoretical value x 100%;
the method for measuring the mesoporosity comprises the following steps: the mesoporosity is the ratio of pore volume to total pore volume of pores with pore diameters above 2nm, i.e. mesoporosity = mesopore pore volume +.total pore volume; mesoporous volume = total pore volume-microporous volume, measuring the pore structure of coconut shell carbon by using an ASAP2600 type surface analyzer, calculating the microporous volume by using a t-plot method, and calculating the total pore volume by using a single-point method;
The specific surface area measurement method comprises the following steps: measuring an adsorption curve of the coconut shell carbon by using an ASAP2600 type surface analyzer in the United states, and calculating the specific surface area of the coconut shell carbon by using a BET method according to the adsorption curve;
the active 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 the activated carbon, the content of the copper oxide and the content of the zinc oxide in the purifying agent are measured by XRF (X-ray fluorescence spectrum);
the sulfur impurity content in the gas or liquid is detected by adopting Agilent GC7890 gas chromatography, and the detector is SCD;
the content of arsenic impurities and phosphorus impurities in the gas or liquid is detected by adopting Agilent GC7890 gas chromatography, and the detector is PDHID;
raw coconut shell charcoal powder: specific surface area of 800m 2 Per g, mesoporosity is 20%.
Preparation example 1
100g of raw coconut shell carbon powder is placed in a reaction furnace with a volume of 5000ml, the temperature is raised from room temperature to 900 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere, the inert gas atmosphere in the reaction furnace is replaced by carbon dioxide at a speed of 1000ml per minute, then carbon dioxide is continuously introduced at a speed of 1000ml per minute, the coconut shell carbon powder is subjected to activation treatment for 200 minutes in the carbon dioxide atmosphere, then nitrogen is introduced at a speed of 1200ml per minute to form a nitrogen atmosphere, and the nitrogen atmosphere is cooled to 20 ℃ at a speed of 10 ℃/min. The specific surface area of the coconut shell charcoal obtained is determined to be 1245m 2 Per g, mesoporosity is 45%.
Preparation example 2
100g of raw coconut shell carbon powder is placed in a reaction furnace with a volume of 5000ml, the temperature is raised from room temperature to 980 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere, the inert gas atmosphere in the reaction furnace is replaced by carbon dioxide at a speed of 1000ml per minute, then carbon dioxide is continuously introduced at a speed of 1000ml per minute, the coconut shell carbon powder is subjected to activation treatment in the carbon dioxide atmosphere for 300 minutes, then nitrogen is introduced at a speed of 1200ml per minute to form a nitrogen atmosphere, and the nitrogen atmosphere is cooled to 20 ℃ at a speed of 10 ℃/min. The specific surface area of the obtained coconut shell charcoal is determined to be 1500m 2 Per g, mesoporosity is 50%.
Preparation example 3
100g of raw coconut shell carbon powder is placed in a reaction furnace with a volume of 5000ml, the temperature is raised from room temperature to 850 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere, the inert gas atmosphere in the reaction furnace is replaced by carbon dioxide at a speed of 1000ml per minute, then carbon dioxide is continuously introduced at a speed of 1000ml per minute, the coconut shell carbon powder is activated in the carbon dioxide atmosphere for 160 minutes, then nitrogen is introduced at a speed of 1200ml per minute to form a nitrogen atmosphere, and the nitrogen atmosphere is cooled to 20 ℃ at a speed of 10 ℃/min. The specific surface area of the coconut shell charcoal obtained is measured to be 1005m 2 Per g, mesoporosity is 41%.
Preparation example 4
100g of raw coconut shell carbon powder is placed in a volume of 5In a reaction furnace of 000ml, the temperature is increased from room temperature to 800 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere, the inert gas atmosphere in the reaction furnace is replaced by carbon dioxide at a speed of 1000ml per minute, then carbon dioxide is continuously introduced at a speed of 1000ml per minute, the coconut shell carbon powder is subjected to activation treatment for 200 minutes in the carbon dioxide atmosphere, then nitrogen is introduced at a speed of 1200ml per minute to form a nitrogen atmosphere, and the nitrogen atmosphere is cooled to 20 ℃ at a speed of 10 ℃/min. The specific surface area of the coconut shell carbon obtained is 950m 2 Per g, mesoporosity is 35%.
Preparation example 5
100g of raw coconut shell carbon powder is placed in a reaction furnace with a volume of 5000ml, the temperature is raised from room temperature to 900 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere, the inert gas atmosphere in the reaction furnace is replaced by carbon dioxide at a speed of 1000ml per minute, then carbon dioxide is continuously introduced at a speed of 1000ml per minute, the coconut shell carbon powder is subjected to activation treatment in the carbon dioxide atmosphere for 150 minutes, then nitrogen is introduced at a speed of 1200ml per minute to form a nitrogen atmosphere, and the nitrogen atmosphere is cooled to 20 ℃ at a speed of 10 ℃/min. The specific surface area of the obtained coconut shell charcoal is measured to be 907m 2 Per g, mesoporosity is 30%.
Example 1
1) Uniformly mixing 10 kg of sodium carbonate and 700 kg of water, adding 90 kg of coconut shell charcoal of preparation example 1, and stirring 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 were uniformly mixed to obtain a sodium carbonate solution.
2) Sodium carbonate solution and metal salt solution were added simultaneously 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 mu s/cm to obtain insoluble substances, drying the insoluble substances, and adding 20 kg of aluminum oxideThe nitric acid having a concentration of 2.5 wt% was added in an amount of 33 wt% relative to the total weight of the insoluble matter and the alumina added, and kneaded and extruded into a bar to be moldedThe millimeter strips were dried at 120℃and calcined at 360℃for 3 hours to give the sample compositions shown in Table 1.
Example 2
1) Uniformly mixing 10 kg of sodium carbonate and 700 kg of water, adding 70 kg of coconut shell charcoal of preparation example 1, and stirring at 70 ℃ for 2 hours to obtain a suspension;
Mixing and stirring 60 kg of copper nitrate trihydrate, 80 kg of zinc nitrate hexahydrate, 20 kg of aluminum nitrate nonahydrate and 500 kg of water uniformly 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 sodium carbonate solution and metal salt solution into the suspension at the same time, and reacting for 1 hour at 70 ℃ 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 mu s/cm to obtain insoluble matter, drying the insoluble matter, adding 20 kg of aluminum oxide, adding 33% nitric acid with concentration of 2.5% by weight relative to the total weight of the insoluble matter and the added aluminum oxide, kneading, extruding to formThe millimeter strips were dried at 120℃and calcined at 360℃for 5 hours to give the sample compositions shown in Table 1.
Example 3
1) Uniformly mixing 10 kg of sodium carbonate and 700 kg of water, adding 100 kg of coconut shell charcoal of preparation example 1, and stirring at 70 ℃ for 2 hours to obtain a suspension;
mixing and stirring 6 kg of copper nitrate trihydrate, 8 kg of zinc nitrate hexahydrate, 2 kg of aluminum nitrate nonahydrate and 500 kg of water uniformly to obtain a metal salt solution;
8 kg of sodium carbonate and 500 kg of water were uniformly mixed to obtain a sodium carbonate solution.
2) Sodium carbonate solution and metal salt solution were added simultaneously 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 mu s/cm to obtain insoluble matter, drying the insoluble matter, adding 20 kg of aluminum oxide, adding 33% nitric acid with concentration of 2.5% by weight relative to the total weight of the insoluble matter and the added aluminum oxide, kneading, extruding to formThe millimeter strips were dried at 120℃and calcined at 380℃for 1 hour to give the sample compositions shown in Table 1.
Example 4
1) Uniformly mixing 10 kg of sodium carbonate and 700 kg of water, adding 120 kg of coconut shell charcoal of preparation example 1, and stirring 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 were uniformly mixed to obtain a sodium carbonate solution.
2) Sodium carbonate solution and metal salt solution were added simultaneously 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 mu s/cm to obtain insoluble matter, drying the insoluble matter, adding 20 kg of aluminum oxide, adding 33% nitric acid with concentration of 2.5% by weight relative to the total weight of the insoluble matter and the added aluminum oxide, kneading, extruding to formThe millimeter strips were dried at 120℃and calcined at 360℃for 5 hours to give the sample compositions shown in Table 1.
Example 5
1) Uniformly mixing 10 kg of sodium carbonate and 700 kg of water, adding 140 kg of coconut shell charcoal of preparation example 1, and stirring 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 were uniformly mixed to obtain a sodium carbonate solution.
2) Sodium carbonate solution and metal salt solution were added simultaneously 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 mu s/cm to obtain insoluble matter, drying the insoluble matter, adding 20 kg of aluminum oxide, adding 33% nitric acid with concentration of 2.5% by weight relative to the total weight of the insoluble matter and the added aluminum oxide, kneading, extruding to form The millimeter strips were dried at 120℃and calcined at 400℃for 3 hours to give the sample compositions shown in Table 1.
Example 6
1) Uniformly mixing 10 kg of sodium carbonate and 700 kg of water, adding 60 kg of coconut shell charcoal of preparation example 1, and stirring 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 were uniformly mixed to obtain a sodium carbonate solution.
2) Sodium carbonate solution and metal salt solution were added simultaneously 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 mu s/cm to obtain insoluble substances, and drying the insoluble substancesThen 20 kg of alumina was added, and the nitric acid having a concentration of 2.5 wt% was added in an amount of 33 wt% relative to the total weight of insoluble matter and alumina added, and kneaded and extruded into a bar to formThe millimeter strips were dried at 120℃and calcined at 360℃for 5 hours to give the sample compositions shown in Table 1.
Example 7
1) Uniformly mixing 10 kg of sodium carbonate and 700 kg of water, adding 40 kg of coconut shell charcoal of preparation example 1, and stirring 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 were uniformly mixed to obtain a sodium carbonate solution.
2) Sodium carbonate solution and metal salt solution were added simultaneously 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 mu s/cm to obtain insoluble matter, drying the insoluble matter, adding 20 kg of aluminum oxide, adding 33% nitric acid with concentration of 2.5% by weight relative to the total weight of the insoluble matter and the added aluminum oxide, kneading, extruding to formThe millimeter strips were dried at 120℃and calcined at 360℃for 5 hours to give the sample compositions shown in Table 1.
Example 8
1) Uniformly mixing 5 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 2 hours to obtain a suspension;
mixing and stirring 6 kg of copper nitrate trihydrate, 8 kg of zinc nitrate hexahydrate, 2 kg of aluminum nitrate nonahydrate and 500 kg of water uniformly to obtain a metal salt solution;
4 kg of sodium carbonate and 500 kg of water were uniformly mixed to obtain a sodium carbonate solution.
2) Sodium carbonate solution and metal salt solution were added simultaneously 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 mu s/cm to obtain insoluble matter, drying the insoluble matter, adding 10 kg of alumina, adding 33% nitric acid with concentration of 2.5 wt% relative to the total weight of the insoluble matter and the added alumina, kneading, extruding to formThe millimeter strips were dried at 120℃and calcined at 360℃for 5 hours to give the sample compositions shown in Table 1.
Example 9
1) Uniformly mixing 5 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 2 hours to obtain a suspension;
mixing and uniformly stirring 45 kg of copper nitrate trihydrate, 60 kg of zinc nitrate hexahydrate, 15 kg of aluminum nitrate nonahydrate and 500 kg of water to obtain a metal salt solution;
the sodium carbonate solution was obtained by uniformly mixing 30 kg of sodium carbonate with 500 kg of water.
2) Sodium carbonate solution and metal salt solution were added simultaneously 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 mu s/cm to obtain insoluble matter, drying the insoluble matter, adding 12 kg of alumina, adding 33% of nitric acid with a concentration of 2.5% by weight relative to the total weight of the insoluble matter and the added alumina, kneading, extruding to formThe millimeter strips were dried at 120℃and calcined at 360℃for 5 hours to give the sample compositions shown in Table 1.
Example 10
1) Uniformly mixing 5 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 2 hours to obtain a suspension;
mixing and stirring 20 kg of copper nitrate trihydrate, 60 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 were uniformly mixed to obtain a sodium carbonate solution.
2) Sodium carbonate solution and metal salt solution were added simultaneously 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 mu s/cm to obtain insoluble matter, drying the insoluble matter, adding 12 kg of alumina, adding 33% of nitric acid with a concentration of 2.5% by weight relative to the total weight of the insoluble matter and the added alumina, kneading, extruding to form The millimeter strips were dried at 120℃and calcined at 360℃for 5 hours to give the sample compositions shown in Table 1.
Example 11
1) Uniformly mixing 7 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 2 hours to obtain a suspension;
50 kg of copper nitrate trihydrate, 30 kg of zinc nitrate hexahydrate, 10 kg of aluminum nitrate nonahydrate and 500 kg of water are uniformly mixed and stirred to obtain a metal salt solution;
20 kg of sodium carbonate and 500 kg of water were uniformly mixed to obtain a sodium carbonate solution.
2) Sodium carbonate solution and metal salt solution were added simultaneously 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 mu s/cm to obtainInsoluble matter, drying the insoluble matter, then adding 10 kg of alumina, adding 33% by weight of nitric acid at a concentration of 2.5% by weight relative to the total weight of the insoluble matter and the added alumina, kneading, extruding into a bar, and moldingThe millimeter strips were dried at 120℃and calcined at 355℃for 5 hours to give the sample 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 2 hours to obtain a suspension;
Mixing and stirring 40 kg of copper nitrate trihydrate, 50 kg of zinc nitrate hexahydrate, 10 kg of aluminum nitrate nonahydrate and 500 kg of water uniformly to obtain a metal salt solution;
the sodium carbonate solution was obtained by uniformly mixing 30 kg of sodium carbonate with 500 kg of water.
2) Sodium carbonate solution and metal salt solution were added simultaneously to the above suspension, and reacted at 70℃for 1 hour to obtain an insoluble reaction mixture.
3) Filtering insoluble reaction mixture from solution, washing until the conductivity of washing solution is less than 100 μs/cm to obtain insoluble matter, drying the insoluble matter, adding 40 kg of alumina, adding 33 wt% nitric acid with concentration of 2.5 wt% relative to the total weight of insoluble matter and added alumina, kneading, extruding to obtain the final productThe millimeter strips were dried at 120℃and calcined at 355℃for 5 hours to give the sample compositions shown in Table 1.
Example 13
1) Uniformly mixing 10 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 2 hours to obtain a suspension;
mixing 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 were uniformly mixed to obtain a sodium carbonate solution.
2) Sodium carbonate solution and metal salt solution were added simultaneously to the above suspension, and reacted at 70℃for 1 hour to obtain an insoluble reaction mixture.
3) Filtering insoluble reaction mixture from solution, washing until the conductivity of washing solution is less than 100 μs/cm to obtain insoluble matter, drying the insoluble matter, adding 8 kg of alumina, adding 33 wt% nitric acid with concentration of 2.5 wt% relative to the total weight of insoluble matter and added alumina, kneading, extruding to obtain the final productThe millimeter strips were dried at 120℃and calcined at 360℃for 5 hours to give the sample compositions shown in Table 1.
Example 14
A purifying agent was prepared in the same manner as in example 2 except that the coconut shell charcoal of production example 1 was replaced with the coconut shell charcoal of production example 2. The composition of the obtained samples is shown in Table 1.
Example 15
A purifying agent was prepared in the same manner as in 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 scavenger was prepared as in example 1, except that an equal amount of sodium carbonate to formulate a sodium carbonate solution was added to the step of formulating the suspension, omitting the step of formulating the sodium carbonate solution. 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;
uniformly mixing 30 kg of sodium carbonate and 550 kg of water to obtain a sodium carbonate solution.
2) The sodium carbonate solution and the metal salt solution are uniformly mixed and reacted for 1 hour at 70 ℃, and the insoluble reaction mixture is obtained by filtration.
3) The insoluble reaction mixture was washed until the conductivity of the washing solution was less than 100. Mu.s/cm, to obtain an insoluble matter, the insoluble matter was dried, then 6 kg of alumina and 1 kg of graphite were added, mixed and rolled, then 30 wt% of water was added, granulated, baked at 360℃for 5 hours, and tabletted to obtain the sample composition shown in Table 1.
Comparative example 2
A purifying agent was prepared in the same manner as in example 1 except that the coconut shell charcoal of preparation example 1 was replaced with raw coconut shell charcoal powder. The composition of the obtained samples is shown in Table 1.
Comparative example 3
A purifying agent was prepared in the same manner as in example 1 except that the coconut shell charcoal of preparation example 1 was replaced with the coconut shell charcoal obtained in preparation example 4. The composition of the obtained samples is shown in Table 1.
Comparative example 4
A purifying agent was prepared in the same manner as in example 1 except that the coconut shell charcoal of preparation example 1 was replaced with the coconut shell charcoal obtained in preparation example 5. The composition of the obtained samples is shown in Table 1.
TABLE 1
Test example 1
Nitrogen gas containing different levels of sulfur impurities, arsenic impurities and/or phosphorous impurities was formulated as per table 2. The purifying agents prepared in the above examples and comparative examples were pulverized into particles of 20-40 mesh, respectively, and filled into a reactor having an inner diameter of 1cm with a filling mass of 2g at 25deg.C, 0.1MPa, and a volume space velocity of 3000h -1 The nitrogen gas formulated to contain different contents of sulfur impurity, arsenic impurity and/or phosphorus impurity was purified by the corresponding reactors, respectively, and the results are shown in table 2.
TABLE 2
Test example 2
Synthesis gas containing different levels of sulfur, arsenic and/or phosphorous impurities (hydrogen to carbon monoxide volume ratio 1:1) was formulated according to table 3. The purifying agents prepared in the above examples and comparative examples were pulverized into particles of 20 to 40 mesh, respectively, and filled into a reactor having an inner diameter of 1cm with a filling mass of 2g at 25℃and 0.1MPa and a volume space velocity of 3000h -1 The synthesis gas formulated to contain different levels of sulfur, arsenic and/or phosphorus impurities was purified by passing them through the respective reactors, the results being shown in table 3.
TABLE 3 Table 3
Test example 3
Liquid propylene containing different levels of sulfur impurities, arsenic impurities and/or phosphorous impurities was formulated as per table 4. The purifying agents prepared in the above examples and comparative examples were pulverized into particles of 20-40 mesh, respectively, and filled into a reactor having an inner diameter of 1cm with a filling mass of 2g at 25deg.C under a pressure of 3.0MPa and a mass space velocity of 3.5h -1 The liquid propylene containing sulfur impurity, arsenic impurity and/or phosphorus impurity was purified by the corresponding reactors, and the results are shown in table 4.
TABLE 4 Table 4
As can be seen from the results of tables 2 to 4, the content of sulfur impurities, arsenic impurities and phosphorus impurities in the gas purified by the purifying agent prepared by the examples of the present invention is less than 1ppm, and the active component utilization rate of the purifying agent of each example can reach more than 85%.
Moreover, it can be seen that the use ratio of the active ingredient in the purifying agent prepared in the example of the present invention is far higher than that in comparative example 1 without coconut shell charcoal and comparative example 2 using raw coconut shell charcoal powder.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (36)

1. A purifying agent is characterized by comprising 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 1000m 2 Per g, the mesoporosity is more than or equal to 40%; the activated carbon is coconut shell carbon;
the preparation method of the purifying agent comprises the following steps: (1) Heating raw coconut shell carbon powder to 700-1000 ℃ in inert gas atmosphere, then activating treatment is carried out for 160-300 minutes at 700-1000 ℃ in carbon dioxide atmosphere, and then cooling is carried out in inert gas atmosphere, thus obtaining the coconut shell carbon powder with specific surface area more than or equal to 1000m 2 /g, coconut shell charcoal with mesoporosity of more than or equal to 40%; (2) Contacting the coconut shell carbon, a water-soluble copper source, a water-soluble zinc source, a water-soluble aluminum source and a precipitant in the presence of water to obtain an insoluble reaction mixture; (3) calcining the insoluble reaction mixture;
the contacting mode in the step (2) comprises the following steps: a. mixing a precipitant with water to obtain a solution I; b. mixing active carbon with the solution I to obtain a suspension II; c. mixing a water-soluble copper source, a water-soluble zinc source, a water-soluble aluminum source and water to obtain a solution III; d. mixing the precipitant with water to obtain a solution IV, wherein the concentration of the precipitant in the solution IV is greater than that in the solution I; e. mixing the suspension II, the solution III and the solution IV.
2. The purifying agent according to claim 1, wherein the content of the activated carbon is 50 to 90 parts by weight; the content of the copper element is 1-10 parts by weight calculated by oxide; the content of the zinc element is 1-10 parts by weight calculated by oxide.
3. The purifying agent according to claim 2, wherein the content of the activated carbon is 60 to 80 parts by weight; the content of the copper element is 1-8 parts by weight calculated by oxide; the content of the zinc element is 1-8 parts by weight calculated by oxide.
4. A scavenger according to claim 3 wherein the copper element is in the form of copper oxide or copper oxide and wurtzite and the zinc element is in the form of zinc oxide or zinc oxide and wurtzite.
5. The purifying agent according to claim 4, wherein the copper element is in the form of copper oxide and the zinc element is in the form of zinc oxide.
6. The purifying agent according to any one of claims 1 to 5, wherein the mesoporosity of the activated carbon is 40% to 50%, and the specific surface area of the activated carbon is 1000 to 1500m 2 /g。
7. The purifying agent according to claim 1, wherein 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 shell charcoal powder.
8. The scavenger according to any one of claims 1 to 5, wherein the scavenger further comprises an aluminum-containing compound.
9. The purifying agent according to claim 8, wherein,
the aluminum-containing compound is aluminum oxide; the content of the alumina is 1 to 6 parts by weight relative to 50 to 90 parts by weight of the content of the activated carbon.
10. The scavenger according to claim 8, further comprising a binder in an amount of 1 to 5 parts by weight relative to 50 to 90 parts by weight of the activated carbon.
11. The scavenger according to claim 1 wherein the water soluble copper source is selected from one or more of copper nitrate, copper sulfate, copper chloride.
12. The scavenger according to claim 11 wherein the water soluble copper source is copper nitrate.
13. The purifying agent of claim 1, wherein the water-soluble zinc source is selected from one or more of zinc nitrate, zinc sulfate, zinc chloride.
14. The purification agent according to claim 13, wherein the water-soluble zinc source is zinc nitrate.
15. The scavenger of claim 1 wherein the water soluble aluminum source is selected from one or more of aluminum nitrate, aluminum sulfate, aluminum chloride.
16. The scavenger according to claim 1 wherein the water soluble aluminum source is aluminum nitrate.
17. The scavenger according to claim 1 wherein the precipitant is selected from water soluble carbonates.
18. The scavenger according to claim 17 wherein the precipitant is selected from one or more of sodium carbonate, potassium carbonate, ammonium carbonate.
19. The scavenger according to claim 9 wherein the molar content of precipitant in the solution i is 0.1-0.3%;
the weight ratio of the precipitant in the step a to the precipitant in the step d in the mode of contacting in the step (2) is 1:0.5-10; the molar ratio of the total amount of the precipitants to the total amount of the water-soluble copper source, the water-soluble zinc source and the water-soluble aluminum source in the step a and the step d is 1:0.8-2; the amounts of the coconut shell carbon, the water-soluble copper source, the water-soluble zinc source and the water-soluble aluminum source are such that the content of the activated carbon in the obtained purifying agent is 50-90 parts by weight; the content of the copper element is 1-10 parts by weight calculated by oxide; the content of the zinc element is 1-10 parts by weight calculated by oxide; the content of the alumina is 1-6 parts by weight.
20. The purifying agent according to claim 19, wherein the coconut shell charcoal, the water-soluble copper source, the water-soluble zinc source, and the water-soluble aluminum source are used in such an amount that the content of the activated carbon in the obtained purifying agent is 60 to 80 parts by weight; the content of the copper element is 1-8 parts by weight calculated by oxide; the content of the zinc element is 1-8 parts by weight calculated by oxide.
21. The purification agent according to any one of claims 1 to 5, wherein the conditions of the contact in step b and step e include: the temperature is 40-90 ℃ and the time is 0.5-3h; the roasting conditions include: the roasting temperature is 250-500 ℃ and the roasting time is 1-5h.
22. The scavenger according to claim 21 wherein the conditions of calcination comprise: the roasting temperature is 350-500 ℃.
23. The scavenger according to any one of claims 1 to 5, wherein the method further comprises kneading the insoluble reaction mixture after washing to a conductivity of 100 μs/cm or less before calcination.
24. Use of a purifying agent according to any of claims 1 to 23 for purifying a gas or a liquid.
25. The use of claim 24, wherein the gas or liquid contains one or more of sulfur impurities, arsenic impurities, phosphorus impurities.
26. The use of claim 25, wherein the sulfur impurity is one or more of hydrogen sulfide, sulfur dioxide, carbonyl sulfide.
27. The use of claim 25, wherein the arsenic impurity is arsine.
28. The use of claim 25, wherein the phosphorus impurity is phosphine.
29. Use according to claim 25, wherein the total content of sulphur, arsenic and phosphorus impurities in the gas or liquid is 5-50000ppm.
30. A purification method, characterized in that the method comprises contacting a gas or liquid to be purified with a purifying agent according to any one of claims 1 to 23.
31. The purification method of claim 30, wherein the gas or liquid to be purified contains one or more of sulfur impurities, arsenic impurities, phosphorus impurities.
32. The purification process of claim 31, wherein the sulfur impurity is one or more of hydrogen sulfide, sulfur dioxide, carbonyl sulfide.
33. The purification method of claim 31, wherein the arsenic impurity is arsine.
34. The purification method of claim 31, wherein the phosphorus impurity is phosphine.
35. The purification method as claimed in claim 30, wherein the total content of sulfur impurities, arsenic impurities and phosphorus impurities in the gas or liquid to be purified is 5-50000ppm.
36. The purification process according to any one of claims 30 to 35, wherein the conditions of contact 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 -1 Or the mass space velocity of the liquid to be purified is 0.1-10h -1 。
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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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* 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
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