CN112619609B - Adsorbent for synergistically removing sulfur and mercury and preparation method and application thereof - Google Patents

Adsorbent for synergistically removing sulfur and mercury and preparation method and application thereof Download PDF

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Publication number
CN112619609B
CN112619609B CN202011356315.1A CN202011356315A CN112619609B CN 112619609 B CN112619609 B CN 112619609B CN 202011356315 A CN202011356315 A CN 202011356315A CN 112619609 B CN112619609 B CN 112619609B
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mercury
solution
zinc
aluminum
sulfur
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CN112619609A (en
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张佳
周永贤
陈伟
余金鹏
李春成
何秋平
王鹏飞
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Shanghai Lyuqiang New Materials Co ltd
Shanghai Research Institute of Chemical Industry SRICI
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Shanghai Lyuqiang New Materials Co ltd
Shanghai Research Institute of Chemical Industry SRICI
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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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • B01D53/82—Solid phase processes with stationary reactants
    • 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
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0233—Compounds of Cu, Ag, Au
    • B01J20/0237—Compounds of Cu
    • 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
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0288—Halides of compounds other than those provided for in B01J20/046
    • 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
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/045—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing sulfur, e.g. sulfates, thiosulfates, gypsum
    • 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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic 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
    • B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 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
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
    • 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
    • B01D2257/60—Heavy metals or heavy metal compounds
    • B01D2257/602—Mercury or mercury compounds

Abstract

The invention relates to an adsorbent for synergistically removing sulfur and mercury and a preparation method and application thereof. Compared with the prior art, the preparation method has the advantages of high capacity of synergistic desulfurization and demercuration, and the like, and the obtained adsorbent has the advantages of rich pore structure, high dispersion of active components and the like.

Description

Adsorbent for synergistically removing sulfur and mercury and preparation method and application thereof
Technical Field
The invention belongs to the technical field of adsorbent preparation, and relates to an adsorbent for synergistically removing sulfur and mercury, and a preparation method and application thereof.
Background
Most of various natural gas fields contain trace metal mercury and compounds thereof, the vapor pressure of the natural gas fields is relatively high, the natural gas fields are volatile to generate mercury vapor, the natural gas fields have strong corrosivity and high toxicity, and the natural gas fields can also cause catalyst poisoning in the chemical industry of natural gas. The natural gas carries mercury vapor during production, and although it is in small quantities, it is potentially hazardous. The mercury can cause dissolution corrosion to various metals, and in the natural gas treatment process, the corrosion can cause container leakage, thereby greatly harming the production safety and bringing huge economic loss and potential safety hazard. Meanwhile, natural gas also contains a large amount of acid gases, especially hydrogen sulfide, which can cause corrosion of equipment and pipelines, poison catalysts and cause environmental pollution. The removal of sulfur and mercury from natural gas is a necessary purification treatment.
At present, the mercury removing agent and the desulfurizing agent are commonly used for refining domestic natural gas to respectively remove mercury vapor and hydrogen sulfide in the natural gas. CN111394144A discloses a mercury removing agent, which takes an aluminum oxide dentiform sphere or an aluminum oxide sphere as a carrier material, wherein the carrier material is loaded with 12-14% of an active substance CuS, or the carrier material is also loaded with 1.5-6% of an active substance ZnS. The demercuration effect of the demercuration agent is as follows: after penetrating the thickness of the mercury removing agent of 20cm, the mercury content can be reduced to be below 28 mu g/m < 3 >, and the duration is 28 days. After penetrating the thickness of 30cm of the demercuration agent, the mercury content can be reduced to 0.01 mu g/m < 3 > for 34 days. CN 104105536a discloses a method for removing mercury from fluid streams using a high capacity copper adsorbent, wherein the mercury removal agent active component is copper sulfide formed by direct sulfidation of copper carbonate at temperatures less than 150 ℃ without thermal decomposition of copper carbonate to oxides. CN 109663475A discloses a preparation method of a copper sulfide mercury removing agent. Wherein, a hydrothermal solution method is used for generating nano-level active copper sulfide with the grain size of 150-250 nm and the length of 1-1.5 mu m between pH 7-10, and then the nano-level active copper sulfide is mixed with a carrier and a structural auxiliary agent according to a proportion for granulation and is calcined in a nitrogen atmosphere to obtain the spherical copper sulfide mercury removing agent with excellent mercury removing efficiency. CN111333101A discloses a nano zinc oxide, a preparation method thereof and a desulfurizer, wherein a zinc sulfate solution and a soda solution are subjected to a neutralization reaction in a supergravity reactor to generate precursor slurry; adjusting the precursor slurry to be neutral, standing and aging for at least 2.5h, washing, and performing filter pressing to obtain a precursor; and calcining the precursor to obtain the nano zinc oxide. Mixing nano zinc oxide and sodium carboxymethylcellulose, extruding into strips, and molding to obtain the zinc oxide desulfurizer.
The equipment investment required by independent desulfurization and demercuration is large, and meanwhile, the demercuration and desulfurization discharging agent needs to be treated as dangerous waste, so that the cost is high. Because mercury molecules are large, the specific surface area of a common zinc oxide desulfurizing agent is low, the pore diameter is small, the conventional zinc oxide desulfurizing agent is difficult to be applied to mercury removal, and the conventional mercury removal agent uses sulfide as an active component and does not have the desulfurizing activity. Accordingly, the present invention has been made to solve the above-mentioned problems.
Disclosure of Invention
The invention aims to provide an adsorbent for synergistically removing sulfur and mercury, a preparation method and application thereof, and aims to realize simultaneous removal of hydrogen sulfide and mercury and the like.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a sorbent for synergistically removing sulfur and mercury comprises the following steps:
(1) Weighing aluminum isopropoxide, dissolving the aluminum isopropoxide in ethanol to prepare a solution A, weighing zinc nitrate hexahydrate and glucose, dissolving the zinc nitrate hexahydrate and the glucose in water to prepare a solution B, mixing the solution B with the solution A, uniformly stirring, drying and roasting to obtain a zinc-aluminum carrier;
(2) Taking part of the zinc-aluminum carrier and taking the acidic alumina sol as a binder, forming, granulating and screening to obtain seed crystal particles;
(3) Taking another part of the zinc-aluminum carrier and EDTA to mix evenly, taking the acidic aluminum sol as a binder, adding the prepared seed crystal particles, continuing to granulate, and drying to obtain a granular desulfurization and demercuration agent carrier;
(4) And (3) spraying a copper chloride solution on the obtained desulfurization and demercuration agent carrier in a rolling way, drying, then soaking in a sodium sulfide solution, washing to obtain a granular adsorbent crude product, and then placing the granular adsorbent crude product in an inert atmosphere for activation to obtain the target product adsorbent.
Further, in the step (1), the molar ratio of zinc nitrate hexahydrate to glucose is 5-10; the addition ratio of the solution A to the solution B satisfies the following conditions: the molar ratio of aluminum atoms to zinc atoms is 3 to 10. In the invention, zinc oxide is introduced on the alumina carrier through cohydrolysis to prepare the zinc-aluminum carrier, thereby realizing high dispersion of the zinc active component. Glucose is introduced into the cohydrolysis system, and the pore structure of the zinc-aluminum carrier is improved after the product is activated, so that the carrier with high specific surface area and large void ratio is prepared.
Further, the concentration of aluminum isopropoxide in the solution A is 5 to 30wt%, and the concentration of zinc nitrate in the solution B is 5 to 30wt%.
Further, in the step (1), the reaction temperature is 80-120 ℃, and the reaction time is 6-12 h; the drying temperature is 100-200 ℃, the roasting temperature is 400-600 ℃, and the roasting time is 1-6 h. Drying and calcination are necessary process steps to effect conversion of the hydrolysate to oxides and to remove organics therefrom to enhance pore distribution. Preferably, the calcination temperature is 400 to 500 ℃, and the heating device preferably uses a moving bed so as to obtain uniform activation of the adsorbent particles. More preferably, the activation treatment may be carried out by blowing low humidity air having a relative humidity of 10 to 30% RH (25 ℃).
Further, in the step (2) and the step (3), the concentration of the acidic aluminum sol is 10-20 wt%.
Further, in the step (3), the mass ratio of the zinc-aluminum carrier to the EDTA is (90-95) to (5-10) in the mixing process of the zinc-aluminum carrier and the EDTA.
Further, in the step (3), the drying temperature is 150-200 ℃.
Further, in the step (3), the grain size of the seed crystal particles is 1.2-1.5 mm, and the grain size of the prepared desulfurization and mercury removal agent carrier is 2-4 mm.
In the step (3), the binder is an essential component for forming the adsorbent so as to maintain the strength and wear resistance of the granular adsorbent in application, the acid alumina sol listed in the invention is a commercially common binder type, and other products with similar properties can be applied to the forming process of the adsorbent in the invention. In the invention, acidic alumina sol is used as a binder, and the 1.2-1.5 mm granulation seed crystal is obtained by molding. In the continuous granulation process of the crystal seeds, EDTA is introduced into the surface layer of the mercury removing agent carrier to complex copper ions, copper salt is fixed on the surface layer of the mercury removing agent, and sodium sulfide is introduced subsequently to form the copper sulfide active component. The copper sulfide is fixed on the surface layer of the catalyst, so that the mercury removal utilization rate of the copper sulfide is improved.
Further, in the step (4), the total amount of the sprayed copper chloride solution is 10-30 wt% of the mass of the desulfurization and mercury removal agent carrier, and the concentration of the copper chloride solution is 20-30 percent by weight.
Further, in the step (4), during the process of dipping the sodium sulfide solution, the mole ratio of the dipped sodium sulfide to the sprayed copper chloride is 1:1. According to the invention, copper salt is introduced by rolling spraying so as to be uniformly distributed on the particle surface, and then sodium sulfide is impregnated in an equal volume so as to form copper sulfide, and simultaneously, the loss of active components of the copper sulfide is reduced. Excess salt was removed using an equal volume of clean water wash. Wherein, the copper chloride has stronger acidity, and the roller equipment for spraying is treated by acid corrosion resistance. The heat is released in the dipping process, and the solution is washed after being cooled to the normal temperature.
Further, in the step (4), an equal-volume impregnation method is adopted for impregnating the sodium sulfide solution.
Further, in the step (4), the activation temperature is 120-200 ℃, and the activation treatment time is 2-6 h.
Compared with the prior art, the invention has the following advantages:
1) The mercury removing agent carrier raw material is prepared by a cohydrolysis method, zinc oxide is introduced into the carrier, so that the uniform dispersion of the active components of the zinc oxide is realized, and the high specific surface area of the carrier is utilized to realize the efficient utilization of desulfurization.
2) The zinc oxide active component removes hydrogen sulfide to produce zinc sulfide, and the zinc sulfide can be used as a demercuration active component to be continuously applied to demercuration to realize the high-efficiency utilization of the zinc active component. Sulfuration is realized through hydrogen sulfide in natural gas, sulfur loss in the application process of the mercury removing agent is effectively avoided, and the use activity is improved.
3) The introduction of glucose in the co-hydrolysis process can effectively improve the pore distribution of the hydrolysate after activation, and improve the specific surface area and pore volume of the carrier, so as to improve the application effect of desulfurization and demercuration.
4) And in the continuous granulation process of the seed crystal, introducing EDTA (ethylene diamine tetraacetic acid) on the surface layer of the carrier to enable copper ions in the spraying process to be fixedly carried on the surface layer of the carrier, and subsequently introducing sodium sulfide to form a copper sulfide active component. Copper sulfide is fixed on the surface layer of the catalyst, so that the utilization rate of demercuration of copper sulfide is improved, the enrichment of mercury on particles is realized, mercury is further diffused into holes, and meanwhile, EDTA complex copper which does not react completely can also be used as a desulfurized active site to participate in the removal of hydrogen sulfide.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, unless otherwise specified, all the starting materials and processing techniques are conventional and commercially available in the art.
Example 1
Dissolving aluminum isopropoxide in an ethanol solution, and dissolving zinc nitrate and glucose in water, wherein the molar ratio of zinc nitrate hexahydrate to glucose is 5:1. According to the weight percentage of aluminum: the molar ratio of zinc is 3:1, uniformly stirring, placing the mixture in a polytetrafluoroethylene kettle, reacting for 8 hours at 100 ℃, drying at 100 ℃, and roasting for 1 hour at 400 ℃ to obtain the zinc-aluminum carrier material.
The zinc-aluminum carrier material is granulated by taking acidic aluminum sol (purchased from Dalianno chemical new material science and technology Co., ltd., diluted by water) with the concentration of 10wt% as a binder to obtain 1.2-1.5 mm granulation seed crystals.
Mixing the zinc-aluminum carrier material with EDTA at a mass ratio of 95:5, granulating with the acidic alumina sol as a binder (the acidic alumina sol concentration is the same as above) to obtain 2-4 mm granules, drying, and rolling-spraying 30-wt% of a copper chloride solution, the amount of the sprayed liquid being 10-wt% of the mass of the granules. The solution was immersed in an equal volume of sodium sulfide solution, in an equimolar ratio to the total amount of copper chloride sprayed, after the solution had cooled, it was washed with an equal volume of water and dried at 180 ℃ for 2h to give example (1).
Example 2
Dissolving aluminum isopropoxide in an ethanol solution, and dissolving zinc nitrate and glucose in water, wherein the molar ratio of zinc nitrate hexahydrate to glucose is 10:1. according to the weight percentage of aluminum: the zinc molar ratio is 5:1, stirring uniformly, placing the mixture in a polytetrafluoroethylene kettle, reacting for 8 hours at 100 ℃, drying at 200 ℃, and roasting for 2 hours at 600 ℃.
The zinc-aluminum carrier material is granulated by taking acidic alumina sol with the concentration of 20 percent as a binder (purchased from Dalianno chemical new material science and technology Co., ltd., diluted by water and used), and 1.2-1.5 mm granulation seed crystal is obtained.
Mixing the zinc-aluminum carrier material with EDTA at a mass ratio of 95:5, granulating with acidic aluminum sol as a binder (the concentration of acidic aluminum sol is the same as above) to obtain 2-4 mm granules, drying, and rolling-spraying copper chloride solution to a concentration of 20wt% based on the mass of the granules, wherein the amount of the sprayed liquid is 30wt% based on the mass of the granules. The solution of sodium sulfide is dipped in equal volume, the total amount of sodium sulfide and the total amount of sprayed copper chloride are in equal molar ratio, after the solution is cooled, the solution is washed by equal volume of water and dried for 6 hours at 120 ℃, and then the example (2) is obtained.
Example 3
Dissolving aluminum isopropoxide in an ethanol solution, and dissolving zinc nitrate and glucose in water, wherein the molar ratio of zinc nitrate hexahydrate to glucose is 8:1. according to the weight percentage of aluminum: the zinc molar ratio is 8:1, stirring uniformly, placing the mixture in a polytetrafluoroethylene kettle, reacting for 8 hours at 100 ℃, drying at 180 ℃, and roasting for 3 hours at 500 ℃.
The zinc-aluminum carrier material is granulated by taking acidic alumina sol with the concentration of 15 percent as a binder (purchased from Daliano chemical New Material science and technology Co., ltd., diluted by water and used) to obtain 1.2-1.5 mm granulation seed crystals.
Mixing the zinc-aluminum carrier material with EDTA at a mass ratio of 90:10, granulating with the acidic alumina sol as a binder (the acidic alumina sol concentration is the same as above) to obtain 2-4 mm granules, oven-drying, and roll-spraying 30-wt% of a copper chloride solution, the amount of the liquid sprayed being 30-wt% of the mass of the granules. The solution was immersed in an equal volume of sodium sulfide solution, after the solution was cooled, washed with an equal volume of water, and dried at 150 ℃ for 3 hours to give example (3).
Example 4
Dissolving aluminum isopropoxide in an ethanol solution, and dissolving zinc nitrate and glucose in water, wherein the molar ratio of zinc nitrate hexahydrate to glucose is 6:1. according to the weight percentage of aluminum: the zinc molar ratio is 10:1, stirring uniformly, placing the mixture in a polytetrafluoroethylene kettle, reacting for 8 hours at 100 ℃, drying at 200 ℃, and roasting for 3 hours at 500 ℃.
The zinc-aluminum carrier material is granulated by taking acidic alumina sol with the concentration of 12 percent as a binder (purchased from Dalianno chemical new material science and technology Co., ltd., diluted by water and used), and 1.2-1.5 mm granulation seed crystals are obtained.
Mixing the zinc-aluminum carrier material with EDTA at a mass ratio of 92, granulating with acidic aluminum sol as a binder (the concentration of the acidic aluminum sol is the same as above) to obtain 2-4 mm granules, drying, and rolling-spraying a copper chloride solution to a concentration of 30wt% based on the mass of the granules, wherein the amount of the sprayed liquid is 10wt% based on the mass of the granules. The solution was immersed in an equal volume of sodium sulfide solution, washed with equal volume of water after the solution was cooled, and dried at 150 ℃ for 6 hours to give example (4).
Example 5
Dissolving aluminum isopropoxide in an ethanol solution, and dissolving zinc nitrate and glucose in water, wherein the molar ratio of zinc nitrate hexahydrate to glucose is 7:1. according to the weight percentage of aluminum: the zinc molar ratio is 4:1, stirring uniformly, placing the mixture in a polytetrafluoroethylene kettle, reacting for 8 hours at 100 ℃, drying at 200 ℃, and roasting for 2 hours at 600 ℃.
The zinc-aluminum carrier material is granulated by taking acid aluminum sol with the concentration of 18 percent as a binder (purchased from Dalianno chemical new material science and technology Co., ltd., diluted by water and used), and 1.2-1.5 mm granulation seed crystals are obtained.
Mixing the zinc-aluminum carrier material with EDTA at a mass ratio of 93, granulating with acidic aluminum sol as a binder (the concentration of the acidic aluminum sol is the same as above) to obtain 2-4 mm granules, drying, and rolling-spraying 25 wt% of copper chloride solution, wherein the amount of the sprayed liquid is 20wt% of the mass of the granules. The solution was immersed in an equal volume of sodium sulfide solution, washed with equal volume of water after the solution was cooled, and dried at 140 ℃ for 5 hours to give example (5).
Example 6
Dissolving aluminum isopropoxide in an ethanol solution, and dissolving zinc nitrate and glucose in water, wherein the molar ratio of zinc nitrate hexahydrate to glucose is 5:1. according to the weight percentage of aluminum: the zinc molar ratio is 6:1, stirring uniformly, placing the mixture in a polytetrafluoroethylene kettle, reacting for 8 hours at 100 ℃, drying at 150 ℃, and roasting for 6 hours at 500 ℃.
The zinc-aluminum carrier material is granulated by taking acidic alumina sol with the concentration of 15 percent as a binder (purchased from Daliano chemical New Material science and technology Co., ltd., diluted by water and used) to obtain 1.2-1.5 mm granulation seed crystals.
Mixing the zinc-aluminum carrier material with EDTA at a mass ratio of 93. The solution was immersed in an equal volume of sodium sulfide solution, washed with equal volume of water after the solution was cooled, and dried at 160 ℃ for 2 hours to give example (6).
Comparative example 1
Compared to example 1, most of them are the same except that glucose is omitted. Comparative example (1) was obtained.
The test of the example (1) and the comparative example (1) is carried out by adopting a physical adsorption apparatus ASAP 2020, the pore channel structure is tested by adopting a low-temperature nitrogen adsorption-desorption method (the test method refers to GB/T19587-2017), the specific surface area and the pore volume of the sample are measured, and the data are shown in Table 1.
TABLE 1
Figure BDA0002802726770000061
Figure BDA0002802726770000071
Comparative example 2
Compared to example 1, most of them are identical, except that the EDTA component is omitted. Comparative example (2) was obtained.
Comparative example 3 is largely identical to example 1, except that the cupric chloride solution is also changed to an equal volume impregnation. Comparative example (3) was obtained.
Example 7
The experiment used a fixed bed reactor to evaluate the desulfurization performance. Adsorption column: the tube is a straight glass tube, the inner diameter of the tube is 8mm, the length of the tube is 150mm, and the tube is connected with the tube by using a grinding opening of 14 mm. About 4g of the adsorbent was weighed into an adsorption column, and the adsorbent was fixed up and down using glass wool. At an airspeed of 2000h -1 A standard gas of 2000ppm hydrogen sulfide was introduced and the exit hydrogen sulfide content was measured with an SCD detector until exit in excess of 20ppm was recorded as breakthrough. The column was used in example 8 to evaluate the demercuration performance after breakthrough.
The test results of the adsorbents prepared in examples 1 to 6 and comparative examples 1 to 3 are shown in Table 2.
The adsorption columns after removal of hydrogen sulfide are designated as examples (1) to H, respectively 2 S，②-H 2 S，③-H 2 S，④-H 2 S，⑤-H 2 S，⑥-H 2 S and comparative examples (1) to H 2 S，②-H 2 S，③-H 2 S。
TABLE 2
Sample name Desulfurization Capacity, wt%
Example (1) 10.2
Example (2) 7.5
Example (3) 6.4
Example (4) 5.6
Example (5) 8.9
Example (6) 6.5
COMPARATIVE EXAMPLE (1) 5.9
COMPARATIVE EXAMPLE (2) 6.2
COMPARATIVE EXAMPLE (3) 8.2
Example 8
The experiment adopts a fixed bed reactor to evaluate the demercuration performance. Nitrogen was passed through a mercury vapor generator and then through a fixed bed adsorber. Wherein the mercury vapor generator: an electric heating blast box is used for heating, three bubblers are connected in series, and the bottom of each bubbler is filled with mercury liquid. The constant temperature is 90 ℃. Adsorption column: the glass tube is a straight glass tube, the inner diameter of the tube is 8mm, the length of the tube is 150mm, and the upper part and the lower part of the tube are connected by using a 14mm ground port. About 4g of the adsorbent was weighed into an adsorption column at 250mL/min and the adsorbent was fixed up and down using glass wool. The absorbance of the outlet mercury vapor was measured using an atomic absorption spectrophotometer. When the exit absorbance was 0.060, the breakthrough was recorded and the length of time for mercury removal was recorded. The evaluation was also carried out using the adsorption column after removal of hydrogen sulfide in example 7. The absorbance of the outlet mercury vapor was measured using an atomic absorption spectrophotometer. When the exit absorbance was 0.060, the breakthrough was recorded and the length of time to demercuration was recorded.
The results of the tests on the adsorbents prepared in examples 1 to 6 and comparative examples 1 to 3, and the results of the test on the adsorbent after removal of hydrogen sulfide in example 7 are shown in Table 3.
TABLE 3
Sample name Length of mercury removal Sample name Length of mercury removal
Example (1) 43 Examples (1) to H 2 S 82
Example (2) 47 Example (2) to H 2 S 71
Example (3) 51 Example (3) to H 2 S 69
Example (4) 33 Example (4) -H 2 S 54
Example (5) 39 Example (5) -H 2 S 77
Example (6) 50 Example (6) -H 2 S 76
COMPARATIVE EXAMPLE (1) 31 Comparative examples (1) to H 2 S 58
COMPARATIVE EXAMPLE (2) 34 Comparative examples (2) to H 2 S 48
COMPARATIVE EXAMPLE (3) 39 Comparative examples (3) to H 2 S 71
Example 9
Compared with the example 1, the two solutions are mostly the same, except that the two solutions are put into a polytetrafluoroethylene kettle to react for 12 hours at 80 ℃ after being stirred uniformly.
Example 10
Compared with the example 1, the two solutions are mostly the same, except that the two solutions are put into a polytetrafluoroethylene kettle to react for 6 hours at 120 ℃ after being stirred uniformly.
Example 11
Compared to example 1, most of them were the same except that after washing with equal volume of water, drying was carried out at 120 ℃.
Example 12
Compared to example 1, most of them were the same except that after washing with an equal volume of water, drying was carried out at 200 ℃.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (8)

1. A preparation method of a sorbent for synergistically removing sulfur and mercury is characterized by comprising the following steps:
(1) Weighing aluminum isopropoxide, dissolving the aluminum isopropoxide in ethanol to prepare a solution A, weighing zinc nitrate hexahydrate and glucose, dissolving the zinc nitrate hexahydrate and the glucose in water to prepare a solution B, mixing the solution B with the solution A, stirring uniformly, reacting, drying and roasting to obtain a zinc-aluminum carrier;
(2) Taking part of the zinc-aluminum carrier and taking the acidic alumina sol as a binder, forming, granulating and screening to obtain seed crystal particles;
(3) Taking another part of the zinc-aluminum carrier and EDTA (ethylene diamine tetraacetic acid) to be uniformly mixed, taking the acidic aluminum sol as a binder, adding the prepared seed crystal particles, continuously granulating, and drying to obtain a granular desulfurization and demercuration agent carrier;
(4) Spraying a copper chloride solution on the obtained desulfurization and demercuration agent carrier in a rolling manner, drying, then soaking in a sodium sulfide solution, washing to obtain a granular adsorbent crude product, and then placing the granular adsorbent crude product in an inert atmosphere for activation to obtain a target product adsorbent;
in the step (1), the molar ratio of zinc nitrate hexahydrate to glucose is 5 to 10;
the addition ratio of the solution A to the solution B satisfies the following conditions: the molar ratio of aluminum atoms to zinc atoms is 3 to 10;
in the step (3), in the process of mixing the zinc-aluminum carrier and the EDTA, the mass ratio of the zinc-aluminum carrier to the EDTA is (90 to 95): 5 to 10);
in the step (1), the reaction temperature is 80 to 120 ℃, the time is 6 to 12 hours, the baking temperature is 400 to 600 ℃, and the baking time is 1 to 6 hours;
in the step (4), the total amount of the sprayed copper chloride solution is 10-30wt% of the mass of the desulfurization and mercury removal agent carrier.
2. The preparation method of the sorbent for synergistic removal of sulfur and mercury according to claim 1, wherein in the step (1), the drying temperature is 100 to 200 ℃.
3. The method for preparing the sorbent for the synergistic removal of sulfur and mercury as claimed in claim 1, wherein the concentration of the acidic aluminum sol in the steps (2) and (3) is 10 to 20wt%.
4. The preparation method of the sorbent for synergistic removal of sulfur and mercury according to claim 1, wherein in the step (3), the drying temperature is 150 to 200 ℃;
the grain diameter of the seed crystal particles is 1.2 to 1.5mm, and the grain diameter of the prepared desulfurization and mercury removal agent carrier is 2 to 4mm.
5. The method for preparing the sorbent for the synergistic removal of sulfur and mercury as claimed in claim 1, wherein the concentration of the copper chloride solution in the step (4) is 20 to 30% by weight.
6. The method for preparing the sorbent for the synergistic removal of sulfur and mercury according to claim 1, wherein in the step (4), during the impregnation of the sodium sulfide solution, the molar ratio of the impregnated sodium sulfide to the sprayed copper chloride is 1:1;
impregnating the sodium sulfide solution by adopting an isovolumetric impregnation method;
in the step (4), the activation temperature is 120 to 200 ℃, and the activation processing time is 2 to 6 hours.
7. An adsorbent for synergistic removal of sulfur and mercury, which is prepared by the preparation method as claimed in any one of claims 1 to 6.
8. Use of the sorbent for the synergistic removal of sulfur and mercury according to claim 7 for the synergistic removal of contaminants including hydrogen sulfide and mercury.
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