CN106693632A - Zinc oxide based normal-temperature deep desulfurizing agent as well as preparation method and application thereof - Google Patents

Zinc oxide based normal-temperature deep desulfurizing agent as well as preparation method and application thereof Download PDF

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CN106693632A
CN106693632A CN201710025806.XA CN201710025806A CN106693632A CN 106693632 A CN106693632 A CN 106693632A CN 201710025806 A CN201710025806 A CN 201710025806A CN 106693632 A CN106693632 A CN 106693632A
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desulfurizing agent
zinc oxide
salt
temperature deep
zinc
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CN106693632B (en
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张磊
叶丽萍
陈孙维
罗勇
李建龙
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Shanghai Research Institute of Chemical Industry SRICI
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Shanghai Research Institute of Chemical Industry SRICI
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    • 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
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    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/16—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/32—Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active carbon
    • 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
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/104—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B01D2253/1124—Metal 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
    • 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
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character

Abstract

The invention relates to a zinc oxide based normal-temperature deep desulfurizing agent as well as a preparation method and application thereof. During preparation, a mixed solution of a zinc salt, an aluminum salt and an aid metallic salt is subjected to a one-step coprecipitation reaction to form a compound precipitate; the compound precipitate is subjected to aging, drying and roasting to obtain the zinc oxide based normal-temperature deep compound desulfurizing agent. The prepared zinc oxide based normal-temperature deep desulfurizing agent is used for the normal-temperature deep removal of H2S in various gaseous and liquid materials in the field of petroleum and coal chemical industries; that is, the fixed-bed operation is adopted; in conditions that a reaction temperature is 20 to 60 DEG C and operation pressure is 0.1MPa to 5MPa, the volume space velocity of liquid is controlled to be 1h<-1> to 12h<-1> or a gas-phase space velocity is controlled to be 1,000h<-1> to 30,000h<-1>; the H2s of which the content is 1ppm to 1,000ppm in a to-be-treated material is removed until the content is not more than 0.03ppm. Compared with the prior art, the desulfurizing agent prepared by the preparation method has breakthrough sulfur capacity, which reaches 26.1 percent, at a normal temperature and desulfurization precision which reaches 0.03ppm or below; the preparation method is simple, and can be used for large-scale industrialized production.

Description

A kind of Zinc oxide-base normal-temperature deep desulfurizing agent and preparation method and application
Technical field
The invention belongs to derived energy chemical field of material technology, it is related to a kind of Zinc oxide-base normal-temperature deep desulfurizing agent and its preparation Method with application, more particularly, to one kind in oil and coal chemical technology to various gaseous states, liquid material in hydrogen sulfide carry out Zinc oxide-base desulfurizing agent of normal-temperature deep removing and preparation method and application.
Background technology
Hydrogen sulfide (H2S the oil such as alkene, liquefied petroleum gas, natural gas, synthesis gas and coalification chemical product) are widely present in In.In transport, storage in these industrial chemicals, H2S can etching apparatus and pipeline.Particularly to its follow-up deep processing During utilization, very small amount H2The presence of S can all cause catalyst poisoning.Therefore, in industrial processes, deep removal sulphur It is essential important step to change hydrogen, is the important component that industrial chemicals purifies technique.
H in industrial chemicals2The removing of S generally uses two kinds of technologies of dry desulfurization and wet desulphurization.Although wet desulphurization skill Art is ripe, but there is sweetening process high energy consumption, the problems such as equipment investment is big, and its maximum be disadvantageous in that can only be by H2S is removed to 1~10ppm or so, it is impossible to realize deep desulfuration.By contrast, dry desulfurization has that desulfurization precision is high, equipment is thrown The money low feature of small, energy consumption.In dry desulfurization, Zinc oxide desulfurizer has high, the big, stable performance of Sulfur capacity of desulfurization precision etc. excellent Point, is widely used in the fine de-sulfur of industrial chemicals.But, traditional Zinc oxide desulfurizer often needs the middle height at 180~400 DEG C Under the conditions of temperature, just with Sulfur capacity higher and desulphurizing activated, this also causes sweetening process high energy consumption, and many industrial chemicals upper Side reaction is susceptible at a temperature of stating and go bad.But under normal temperature condition, its desulphurizing activated and Sulfur capacity is but significantly reduced, and Sulfur capacity is general All over less than 12%.In order to improve the low-temp desulfurization activity and Sulfur capacity of Zinc oxide desulfurizer, person skilled in art starts from list Pure zinc oxide desulfurizing agent is transferred to the research of Zinc oxide-base metal composite oxide desulfurizing agent.
It (can be zinc oxide, zinc hydroxide, zinc carbonate by zinc oxide that one kind is disclosed in the C of Chinese patent CN 1046213 Or basic zinc carbonate) and structural promoter calcium aluminoferrite cement (mainly including CaO, Fe2O3、Al2O3) etc. composition normal temp zinc oxide Base composite desulfurizing agent, the wherein content of active component ZnO are in more than 80~95% (m/m).The Zinc oxide desulfurizer 20 DEG C, 1500h-1When under the conditions of, Sulfur capacity only has 8.2%, and its desulfurization precision can only achieve below 0.05ppm.
One kind is disclosed in the B of Chinese patent CN 102078749 by basic zinc carbonate, copper carbonate, alumina cement, hydroxyl oxygen Change the Zinc oxide-base fine desulfurizing agent of iron and binding agent composition.When basic zinc carbonate by weight be 60 parts, copper carbonate be 25 parts, When γ-FeOOH is 6 parts, alumina cement is 11 parts, the prepared Zinc oxide-base fine desulfurizing agent desulfurization essence at 20 DEG C Degree reaches 0.02ppm, but its Sulfur capacity is 13.8%.
One kind is disclosed in the B of Chinese patent CN 101591557 by activated zinc oxide, manganese carbonate, mixed aid (kaolinite Soil, concave convex rod, bentonite high hold sulphur powder), alkaline assistant (causticization coefficient is 1.45~1.55 sodium metaaluminate) and bond The improved ambient temperature desulfuration agent that agent (carboxymethylcellulose calcium or methocel solution) is prepared from.Under 25 DEG C of test conditions, The desulfurizing agent Sulfur capacity highest when zinc oxide content >=95% in desulfurizing agent, is 12%.
One kind is disclosed in the B of Chinese patent CN 102961959 by activated zinc oxide, high-alumina fly, bentonite, calcium hydroxide The zinc oxide fine desulfurizer for mixing extrusion with sodium carboxymethylcellulose and preparing.The desulfurizing agent is in 25 DEG C, air speed 1h-1Condition Under, by the H of 12ppm in propylene liguid2S is removed to 0.03ppm, and Sulfur capacity is 3.1%.
The A of Chinese patent CN 101485954 disclose it is a kind of by nano zine oxide, cupric oxide, binding agent and pore creating material with Water is mixed to form mixture, then mediates the mixture, is molded, drying, being calcined and obtain desulfurizing agent.The desulfurizing agent is 30 Desulfurization precision at DEG C can only achieve below 0.05ppm, and working sulfur capacity is 15.5%, can not still meet demand, this be probably by Caused by the mixing of active component nano zine oxide and cupric oxide in kneaded and formed preparation process is not uniform enough.
In sum, although by years of researches, the desulfurization performance of Zinc oxide-base desulfurizing agent has and greatly improves, mesh The preceding technology about Zinc oxide-base desulfurizing agent still suffers from following weak point：1) Sulfur capacity of desulfurizing agent also needs further raising, special It is not that normal temperature Sulfur capacity is generally less than 15%；2) desulfurization precision is inadequate, it is difficult to by hydrogen sulfide stripping as little as below 0.03ppm；3) take off Sulphur agent low temperature active is not enough, and the desulfurized effect and high sulfur capacity to have reached generally require to carry out at relatively high temperatures, increased energy Consumption and operating cost；4) still need to find a kind of preparation method of more easy desulfurizing agent, improve the utilization rate of active component, drop Low cost.Accordingly, it would be desirable to develop under a kind of normal temperature and pressure conditionses, with good low temperature activity, high sulfur capacity and high stability, while Synthesize low cost, be easy to industrialized trace hydrogen sulfide deep desulfurizer, and develop corresponding sulfur removal technology, to oil and coalification The deep removal purification of hydrogen sulfide has great importance in work raw material.
The content of the invention
The purpose of the present invention is exactly to provide one kind for the defect for overcoming above-mentioned prior art to exist to realize big rule Mould is produced, economical and practical, have under normal temperature and pressure high sulfur capacity and desulfurization precision high Zinc oxide-base normal-temperature deep desulfurizing agent and its Preparation method and application.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of preparation method of Zinc oxide-base normal-temperature deep desulfurizing agent, the method specifically includes following steps：
Step (1)：Zinc salt, aluminium salt, promoter metal salt is soluble in water, be configured to respectively molar concentration for 0.05~ The salting liquid of 3mol/L, and mixed, stir, mixed salt solution is obtained；
Step (2)：Prepare the precipitant solution that molar concentration is 0.05~3mol/L；
Step (3)：Precipitant solution obtained in step (2) is added in the mixed salt solution of step (1), is stirred Reaction a period of time, presoma slurries are obtained, are then sufficiently stirred for presoma slurries, carry out burin-in process；
Step (4)：Presoma slurries in step (3) through burin-in process are centrifuged, precipitation is collected, and to heavy Shallow lake is washed, is dried, is calcined, that is, described Zinc oxide-base normal-temperature deep desulfurizing agent is obtained.
The mol ratio of zinc salt, aluminium salt and promoter metal salt is 100 in mixed salt solution described in step (1):1~ 30:1~50.
Zinc salt described in step (1) includes one or more in zinc nitrate, zinc chloride, zinc sulfate or zinc acetate, described Aluminium salt include aluminum nitrate, aluminium chloride or aluminum sulfate in one or more.
Promoter metal salt described in step (1) includes the one kind or many in calcium salt, manganese salt, molysite, cobalt salt, nickel salt or mantoquita Kind.
Described calcium salt includes the one kind in calcium acetate, calcium sulfate, calcium nitrate or calcium chloride, and described manganese salt includes acetic acid One kind in cobalt, manganese sulfate, manganese nitrate or manganese chloride, described molysite is included in ferric acetate, ferric sulfate, ferric nitrate or iron chloride One kind, described cobalt salt includes the one kind in cobalt acetate, cobaltous sulfate, cobalt nitrate or cobalt chloride, and described nickel salt includes acetic acid One kind in nickel, nickel sulfate, nickel nitrate or nickel chloride, described mantoquita is included in copper acetate, copper sulphate, copper nitrate or copper chloride One kind.
Precipitating reagent described in step (2) includes sodium carbonate, sodium acid carbonate, NaOH, potassium carbonate, saleratus, hydrogen-oxygen Change one or more in potassium, ammoniacal liquor, ammonium carbonate or ammonium hydrogen carbonate.
Mixed metal salt and the mol ratio of precipitating reagent are 1 in step (3):1~4；The condition of stirring reaction is：20~80 DEG C 0.5~2h of stirring reaction；The condition of burin-in process is：Aging 2~8h at 60~90 DEG C.
Dry condition is in step (4)：2~8h is dried at 80~120 DEG C；The condition of roasting is：300~500 2~6h is calcined at DEG C.
The Zinc oxide-base normal-temperature deep desulfurizing agent being prepared from using the above method.
The application of Zinc oxide-base normal-temperature deep desulfurizing agent, described Zinc oxide-base normal-temperature deep desulfurizing agent is used for oil and coal H in various gaseous states, liquid material in chemical field2The normal-temperature deep removing of S, i.e., using fixed-bed operation, be in reaction temperature 20~60 DEG C, operating pressure is 1~12h under conditions of 0.1~5MPa, to control liquid volume air speed-1Or gas phase air speed is 1000~30000h-1, by the H that content in treating material is 1~1000ppm2S is removed to≤0.03ppm.
It is described containing H2Various gaseous states, liquid material are selected from alkene, alkane, liquefaction in the oil and coal chemical technology of S One or more in oil gas, natural gas, synthesis gas of mixture, H in material2The content of S is 1~1000ppm, preferably not More than 100ppm.
The preparation method of Zinc oxide-base normal-temperature deep desulfurizing agent of the present invention is first by the mixed of zinc salt, aluminium salt and promoter metal salt Close solution and form complex precipitate through a step coprecipitation reaction, obtaining Zinc oxide-base normal-temperature deep by aging, dry, roasting answers Close desulfurizing agent.The preparation method of Zinc oxide-base normal-temperature deep composite desulfurizing agent of the present invention, its preparation process is simple can be used for Large-scale industrial production.Desulfurizing agent prepared by present invention working sulfur capacity at normal temperatures reaches 26.1%, and desulfurization precision reaches Below 0.03ppm.The normal-temperature deep for being particularly well-suited to hydrogen sulfide in various gaseous states, liquid material in oil and coal chemical technology takes off Remove.
Compared with prior art, the invention has the characteristics that：
1) using the step of coprecipitation one addition aluminium oxide structure auxiliary agent and transition metal electronic auxiliary, ZnO is not only increased The specific surface area and pore passage structure of adsorbent, while the interaction between ZnO active components and transition metal promoter is strengthened, So as to the low temperature Sulfur capacity and desulfurization precision of Zinc oxide-base desulfurizing agent greatly improved；
2) the normal temperature Sulfur capacity of the desulfurizing agent prepared by the present invention is greatly improved compared with conventional oxidation zinc desulfurizing agent, reduces desulfurization The energy consumption of process, improves the utilization rate of desulfurizing agent, so that reduces cost；
3) preparation process is simple that the present invention is provided, operating condition is gentle, is adapted to industrial amplification production, with good Application prospect.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.
Embodiment 1：
A kind of preparation method of Zinc oxide-base normal-temperature deep composite desulfurizing agent, using following steps：
(1) it is zinc nitrate, aluminum nitrate and manganese nitrate is soluble in water, after the salting liquid that concentration is 0.1mol/L is configured to respectively Mixed, be stirred well to uniformly, obtained mixed salt solution；Wherein, zinc nitrate and aluminum nitrate and manganese nitrate mole Than being 100:15:5；Compound concentration is the sodium carbonate liquor of 0.1mol/L simultaneously；
(2) to adding the sodium carbonate liquor, the salt-mixture to be with the mol ratio of the sodium carbonate in above-mentioned mixing salt solution 1:1.5, reaction 1h is carried out under being stirred at 70 DEG C, obtain presoma slurries；Then the presoma slurries of gained are fully stirred Mix, the aging 4h at 80 DEG C of temperature；
(3) the presoma slurries are centrifuged, collect precipitation, the precipitation is washed through deionized water, 90 After DEG C drying 6h, then through 350 DEG C of roasting 4h, obtain Zinc oxide-base normal-temperature deep composite desulfurizing agent；
By this Zinc oxide-base normal-temperature deep composite desulfurizing agent, crushed after being granulated through compressing tablet, filter out 40~60 mesh samples, adopted It is 30 DEG C, gas volume air speed 3000h in reaction temperature with fixed-bed operation-1, H2S concentration is that (nitrogen makees bottom to 1% Standard Gases Gas) appreciation condition under, working sulfur capacity reaches 26.1%, and desulfurization precision reaches below 0.03ppm.
Embodiment 2：
A kind of preparation method of Zinc oxide-base normal-temperature deep composite desulfurizing agent, using following steps：
(1) it is zinc acetate, aluminum nitrate and nickel nitrate is soluble in water, the salting liquid that concentration is 0.05mol/L is configured to respectively After mixed, be stirred well to uniform, obtain mixed salt solution；Wherein, zinc acetate and aluminum nitrate and nickel nitrate rub You are than being 100:1:20；Compound concentration is the sal volatile of 0.05mol/L simultaneously；
(2) to adding the sal volatile, the salt-mixture to be with the mol ratio of the ammonium carbonate in above-mentioned mixing salt solution 1:2, reaction 2h is carried out under being stirred at 20 DEG C, obtain presoma slurries；Then the presoma slurries of gained are sufficiently stirred for, The aging 2h at 90 DEG C of temperature；
(3) the presoma slurries are centrifuged, collect precipitation, the precipitation is washed through deionized water, 80 After DEG C drying 8h, then through 350 DEG C of roasting 4h, obtain Zinc oxide-base normal-temperature deep composite desulfurizing agent；
By this Zinc oxide-base normal-temperature deep composite desulfurizing agent, crushed after being granulated through compressing tablet, filter out 40~60 mesh samples, adopted It is 30 DEG C, gas volume air speed 3000h in reaction temperature with fixed-bed operation-1, H2S concentration is that (nitrogen makees bottom to 1% Standard Gases Gas) appreciation condition under, working sulfur capacity reaches 25.8%, and desulfurization precision reaches below 0.03ppm.
Embodiment 3：
A kind of preparation method of Zinc oxide-base normal-temperature deep composite desulfurizing agent, using following steps：
(1) it is zinc chloride, aluminum nitrate and cobalt nitrate is soluble in water, it is laggard that the salting liquid that concentration is 3mol/L is configured to respectively Row mixing, is stirred well to uniformly, obtains mixed salt solution；Wherein, zinc chloride and aluminum nitrate and the mol ratio of cobalt nitrate It is 100:25:15；Compound concentration is the ammonium bicarbonate soln of 3mol/L simultaneously；
(2) to adding ammonium bicarbonate soln in above-mentioned mixing salt solution, the salt-mixture and the ammonium hydrogen carbonate mole Than being 1:4, reaction 2h is carried out under being stirred at 60 DEG C, obtain presoma slurries；Then the presoma slurries of gained are carried out fully Stirring, the aging 4h at 80 DEG C of temperature；
(3) the presoma slurries are centrifuged, collect precipitation, the precipitation is washed through deionized water, 120 After DEG C drying 2h, then through 300 DEG C of roasting 6h, obtain Zinc oxide-base normal-temperature deep composite desulfurizing agent；
By this Zinc oxide-base normal-temperature deep composite desulfurizing agent, crushed after being granulated through compressing tablet, filter out 40~60 mesh samples, adopted It is 30 DEG C, gas volume air speed 3000h in reaction temperature with fixed-bed operation-1, H2S concentration is that (nitrogen makees bottom to 1% Standard Gases Gas) appreciation condition under, working sulfur capacity reaches 23.6%, and desulfurization precision reaches below 0.03ppm.
Embodiment 4：
A kind of preparation method of Zinc oxide-base normal-temperature deep composite desulfurizing agent, using following steps：
(1) it is zinc nitrate, aluminum nitrate and ferric nitrate is soluble in water, after the salting liquid that concentration is 0.2mol/L is configured to respectively Mixed, be stirred well to uniformly, obtained mixed salt solution；Wherein, zinc nitrate and aluminum nitrate and ferric nitrate mole Than being 100:15:1；Compound concentration is the sodium bicarbonate solution of 0.2mol/L simultaneously；
(2) to adding sodium bicarbonate solution in above-mentioned mixing salt solution, the salt-mixture and the sodium acid carbonate mole Than being 1:2, reaction 2h is carried out under being stirred at 50 DEG C, obtain presoma slurries；Then the presoma slurries of gained are carried out fully Stirring, the aging 8h under temperature 60 C；
(3) the presoma slurries are centrifuged, collect precipitation, the precipitation is washed through deionized water, 100 After DEG C drying 8h, then through 450 DEG C of roasting 2h, obtain Zinc oxide-base normal-temperature deep composite desulfurizing agent；
By this Zinc oxide-base normal-temperature deep composite desulfurizing agent, crushed after being granulated through compressing tablet, filter out 40~60 mesh samples, adopted It is 30 DEG C, gas volume air speed 3000h in reaction temperature with fixed-bed operation-1, H2S concentration is that (nitrogen makees bottom to 1% Standard Gases Gas) appreciation condition under, working sulfur capacity reaches 24.5%, and desulfurization precision reaches below 0.03ppm.
Embodiment 5：
A kind of preparation method of Zinc oxide-base normal-temperature deep composite desulfurizing agent, using following steps：
(1) it is zinc nitrate, aluminum nitrate and copper nitrate is soluble in water, after the salting liquid that concentration is 0.5mol/L is configured to respectively Mixed, be stirred well to uniformly, obtained mixed salt solution；Wherein, zinc nitrate and aluminum nitrate and copper nitrate mole Than being 100:15:5；Compound concentration is the solution of potassium carbonate of 0.5mol/L simultaneously；
(2) to adding the solution of potassium carbonate, the salt-mixture to be with the mol ratio of the potassium carbonate in above-mentioned mixing salt solution 1:1.5, reaction 1h is carried out under being stirred at 70 DEG C, obtain presoma slurries；Then the presoma slurries of gained are fully stirred Mix, the aging 4h at 80 DEG C of temperature；
(3) the presoma slurries are centrifuged, collect precipitation, the precipitation is washed through deionized water, 100 After DEG C drying 8h, then through 400 DEG C of roasting 4h, obtain Zinc oxide-base normal-temperature deep composite desulfurizing agent；
By this Zinc oxide-base normal-temperature deep composite desulfurizing agent, crushed after being granulated through compressing tablet, filter out 40~60 mesh samples, adopted It is 30 DEG C, gas volume air speed 3000h in reaction temperature with fixed-bed operation-1, H2S concentration is that (nitrogen makees bottom to 1% Standard Gases Gas) appreciation condition under, working sulfur capacity reaches 25.3%, and desulfurization precision reaches below 0.03ppm.
Embodiment 6：
A kind of preparation method of Zinc oxide-base normal-temperature deep composite desulfurizing agent, using following steps：
(1) it is zinc nitrate, aluminum nitrate and calcium chloride is soluble in water, after the salting liquid that concentration is 0.1mol/L is configured to respectively Mixed, be stirred well to uniformly, obtained mixed salt solution；Wherein, zinc nitrate and aluminum nitrate and calcium chloride mole Than being 100:15:30；Compound concentration is the sal volatile of 0.1mol/L simultaneously；
(2) to adding the sal volatile, the salt-mixture to be with the mol ratio of the ammonium carbonate in above-mentioned mixing salt solution 1:1, reaction 2h is carried out under being stirred at 60 DEG C, obtain presoma slurries；Then the presoma slurries of gained are sufficiently stirred for, The aging 2h at 90 DEG C of temperature；
(3) the presoma slurries are centrifuged, collect precipitation, the precipitation is washed through deionized water, 110 After DEG C drying 4h, then through 450 DEG C of roasting 4h, obtain Zinc oxide-base normal-temperature deep composite desulfurizing agent；
By this Zinc oxide-base normal-temperature deep composite desulfurizing agent, crushed after being granulated through compressing tablet, filter out 40~60 mesh samples, adopted It is 30 DEG C, gas volume air speed 3000h in reaction temperature with fixed-bed operation-1, H2S concentration is that (nitrogen makees bottom to 1% Standard Gases Gas) appreciation condition under, working sulfur capacity reaches 24.8%, and desulfurization precision reaches below 0.03ppm.
Embodiment 7：
A kind of preparation method of Zinc oxide-base normal-temperature deep composite desulfurizing agent, using following steps：
(1) it is zinc nitrate, aluminum nitrate and manganese nitrate is soluble in water, after the salting liquid that concentration is 0.5mol/L is configured to respectively Mixed, be stirred well to uniformly, obtained mixed salt solution；Wherein, zinc nitrate and aluminum nitrate and manganese nitrate mole Than being 100:30:50；Compound concentration is the sodium carbonate liquor of 0.5mol/L simultaneously；
(2) to adding the sodium carbonate liquor, the salt-mixture to be with the mol ratio of the sodium carbonate in above-mentioned mixing salt solution 1:2, reaction 0.5h is carried out under being stirred at 80 DEG C, obtain presoma slurries；Then the presoma slurries of gained are fully stirred Mix, the aging 2h at 90 DEG C of temperature；
(3) the presoma slurries are centrifuged, collect precipitation, the precipitation is washed through deionized water, 100 After DEG C drying 8h, then through 500 DEG C of roasting 2h, obtain Zinc oxide-base normal-temperature deep composite desulfurizing agent；
By this Zinc oxide-base normal-temperature deep composite desulfurizing agent, crushed after being granulated through compressing tablet, filter out 40~60 mesh samples, adopted It is 30 DEG C, gas volume air speed 3000h in reaction temperature with fixed-bed operation-1, H2S concentration is that (nitrogen makees bottom to 1% Standard Gases Gas) appreciation condition under, working sulfur capacity reaches 25.9%, and desulfurization precision reaches below 0.03ppm.
Embodiment 8：
A kind of preparation method of Zinc oxide-base normal-temperature deep composite desulfurizing agent, using following steps：
(1) it is zinc nitrate, aluminum nitrate and copper nitrate is soluble in water, it is laggard that the salting liquid that concentration is 1mol/L is configured to respectively Row mixing, is stirred well to uniformly, obtains mixed salt solution；Wherein, zinc nitrate and aluminum nitrate and the mol ratio of copper nitrate It is 100:15:15；Compound concentration is the solution of potassium carbonate of 1mol/L simultaneously；
(2) to adding the solution of potassium carbonate, the salt-mixture to be with the mol ratio of the potassium carbonate in above-mentioned mixing salt solution 1:1.5, reaction 1h is carried out under being stirred at 60 DEG C, obtain presoma slurries；Then the presoma slurries of gained are fully stirred Mix, the aging 4h at 80 DEG C of temperature；
(3) the presoma slurries are centrifuged, collect precipitation, the precipitation is washed through deionized water, 100 After DEG C drying 8h, then through 350 DEG C of roasting 4h, obtain Zinc oxide-base normal-temperature deep composite desulfurizing agent；
By this Zinc oxide-base normal-temperature deep composite desulfurizing agent, crushed after being granulated through compressing tablet, filter out 40~60 mesh samples, adopted It is 30 DEG C, gas volume air speed 3000h in reaction temperature with fixed-bed operation-1, H2S concentration is that (nitrogen makees bottom to 1% Standard Gases Gas) appreciation condition under, working sulfur capacity reaches 26.0%, and desulfurization precision reaches below 0.03ppm.
Embodiment 9：
A kind of application of Zinc oxide-base normal-temperature deep composite desulfurizing agent：
By Zinc oxide-base normal-temperature deep composite desulfurizing agent in embodiment 1, crushed after being granulated through compressing tablet, filter out 40~60 mesh Sample, weighs the desulfurizing agent 1g, by ratio of height to diameter 3:1 is seated in fixed bed device, the charging of constant voltage DC pump upper entering and lower leaving, Reaction temperature is 30 DEG C, and pressure is 3MPa, liquid volume air speed 12h-1Under conditions of, can be by the H of 10ppm in propylene2S is removed to Below 0.03ppm, working sulfur capacity reaches 24.8%.
Embodiment 10：
A kind of application of Zinc oxide-base normal-temperature deep composite desulfurizing agent：
By Zinc oxide-base normal-temperature deep composite desulfurizing agent in embodiment 5, crushed after being granulated through compressing tablet, filter out 40~60 mesh Sample, weighs the desulfurizing agent 1g, by ratio of height to diameter 3:1 is seated in fixed bed device, is 20 DEG C in reaction temperature, and pressure is 0.1MPa, gas volume air speed 10000h-1Under conditions of, can be by the H of 10ppm in ethene2S is removed to below 0.03ppm, penetrates Sulfur capacity reaches 25.4%.
Comparative example 1：
The preparation method of one zinc oxide desulfurizer, using following steps：
(1) it is zinc nitrate is soluble in water, it is configured to the salting liquid that concentration is 0.1mol/L；Compound concentration is simultaneously The sodium carbonate liquor of 0.1mol/L；
(2) to adding the sodium carbonate liquor, the zinc nitrate to be with the mol ratio of the sodium carbonate in above-mentioned zinc nitrate solution 1:1.5, reaction 1h is carried out under being stirred at 70 DEG C, obtain presoma slurries；Then the presoma slurries of gained are fully stirred Mix, the aging 4h at 80 DEG C of temperature；
(3) the presoma slurries are centrifuged, collect precipitation, the precipitation is washed through deionized water, 90 After DEG C drying 6h, then through 350 DEG C of roasting 4h, obtain Zinc oxide desulfurizer；
By this Zinc oxide desulfurizer, crushed after being granulated through compressing tablet, filter out 40~60 mesh samples, using fixed-bed operation, It is 30 DEG C, gas volume air speed 3000h in reaction temperature-1, H2S concentration is the appreciation condition of 1% Standard Gases (nitrogen makees spirit) Under, working sulfur capacity is 8.1%, and desulfurization precision reaches below 0.03ppm.
Comparative example 2：
A kind of preparation method of Zinc oxide-base normal-temperature deep composite desulfurizing agent, using following steps：
(1) it is zinc nitrate and aluminum nitrate is soluble in water, mixed after the salting liquid that concentration is 0.1mol/L is configured to respectively Close, be stirred well to uniformly, obtain mixed salt solution；Wherein, zinc nitrate and the mol ratio of aluminum nitrate are 100:15；Simultaneously Compound concentration is the sodium carbonate liquor of 0.1mol/L；
(2) to adding the sodium carbonate liquor, the salt-mixture to be with the mol ratio of the sodium carbonate in above-mentioned mixing salt solution 1:1.5, reaction 1h is carried out under being stirred at 70 DEG C, obtain presoma slurries；Then the presoma slurries of gained are fully stirred Mix, the aging 4h at 80 DEG C of temperature；
(3) the presoma slurries are centrifuged, collect precipitation, the precipitation is washed through deionized water, 90 After DEG C drying 6h, then through 350 DEG C of roasting 4h, obtain Zinc oxide-base normal-temperature deep composite desulfurizing agent；
By this Zinc oxide-base normal-temperature deep composite desulfurizing agent, crushed after being granulated through compressing tablet, filter out 40~60 mesh samples, adopted It is 30 DEG C, gas volume air speed 3000h in reaction temperature with fixed-bed operation-1, H2S concentration is that (nitrogen makees bottom to 1% Standard Gases Gas) appreciation condition under, working sulfur capacity reaches 14.3%, and desulfurization precision reaches below 0.03ppm.
Desulfurization performance result shows that the preparation method of Zinc oxide-base normal-temperature deep composite desulfurizing agent is obtained in accordance with the present invention To Zinc oxide-base normal-temperature deep composite desulfurizing agent Sulfur capacity at normal temperatures be up to 26.1%, far above the oxygen in comparative example 1~2 Change the Sulfur capacity of zinc ambient temperature desulfuration agent, this explanation is combined by the Zinc oxide-base normal-temperature deep that step coprecipitation of the invention is obtained Zinc, aluminium and transition metal promoter element are uniformly dispersed in desulfurizing agent, not only increase the specific surface area and duct knot of ZnO adsorbents Structure, while strengthening the interaction between ZnO active components and transition metal promoter, takes off so as to Zinc oxide-base greatly improved The low temperature Sulfur capacity and desulfurization precision of sulphur agent.
Embodiment 11：
The preparation method of the present embodiment Zinc oxide-base normal-temperature deep desulfurizing agent, the method specifically includes following steps：
Step (1)：Zinc salt, aluminium salt, promoter metal salt is soluble in water, molar concentration is configured to respectively for 0.05mol/L Salting liquid, and mixed, stir, mixed salt solution is obtained；
Step (2)：It is the precipitant solution of 0.05mol/L to prepare molar concentration；
Step (3)：Precipitant solution obtained in step (2) is added in the mixed salt solution of step (1), is stirred Reaction a period of time, presoma slurries are obtained, are then sufficiently stirred for presoma slurries, carry out burin-in process；
Step (4)：Presoma slurries in step (3) through burin-in process are centrifuged, precipitation is collected, and to heavy Shallow lake is washed, is dried, is calcined, that is, described Zinc oxide-base normal-temperature deep desulfurizing agent is obtained.
Wherein, the mol ratio of zinc salt, aluminium salt and promoter metal salt is 100 in step (1) mixed salt solution:1:1.Zinc Salt is zinc sulfate, and aluminium salt is aluminum nitrate.Promoter metal salt is nickel salt, and it is 1 by nickel acetate and nickel sulfate that the nickel salt is in mass ratio: 1 mixes.
Step (2) precipitating reagent is ammoniacal liquor.
Mixed metal salt and the mol ratio of precipitating reagent are 1 in step (3):4；The condition of stirring reaction is：In 20 DEG C of stirrings Reaction 2h；The condition of burin-in process is：The aging 8h at 60 DEG C.
Dry condition is in step (4)：8h is dried at 80 DEG C；The condition of roasting is：6h is calcined at 300 DEG C.
The Zinc oxide-base normal-temperature deep desulfurizing agent being prepared from using the above method.
The application of Zinc oxide-base normal-temperature deep desulfurizing agent, described Zinc oxide-base normal-temperature deep desulfurizing agent is used for oil and coal H in various gaseous states, liquid material in chemical field2The normal-temperature deep removing of S, i.e., using fixed-bed operation, be in reaction temperature 20 DEG C, operating pressure is 1h under conditions of 0.1MPa, to control liquid volume air speed-1, by content in treating material be 1~ The H of 1000ppm2S is removed to≤0.03ppm.
Embodiment 12：
The preparation method of the present embodiment Zinc oxide-base normal-temperature deep desulfurizing agent, the method specifically includes following steps：
Step (1)：Zinc salt, aluminium salt, promoter metal salt is soluble in water, the salt that molar concentration is 3mol/L is configured to respectively Solution, and mixed, stir, mixed salt solution is obtained；
Step (2)：It is the precipitant solution of 3mol/L to prepare molar concentration；
Step (3)：Precipitant solution obtained in step (2) is added in the mixed salt solution of step (1), is stirred Reaction a period of time, presoma slurries are obtained, are then sufficiently stirred for presoma slurries, carry out burin-in process；
Step (4)：Presoma slurries in step (3) through burin-in process are centrifuged, precipitation is collected, and to heavy Shallow lake is washed, is dried, is calcined, that is, described Zinc oxide-base normal-temperature deep desulfurizing agent is obtained.
Wherein, the mol ratio of zinc salt, aluminium salt and promoter metal salt is 100 in step (1) mixed salt solution:30:50. Zinc salt is zinc chloride, and aluminium salt is aluminum sulfate.Promoter metal salt is that manganese salt is in molar ratio 1 with molysite, cobalt salt:1:1 mixes, Wherein, manganese salt is manganese sulfate, and molysite is ferric nitrate, and cobalt salt is cobaltous sulfate.
Step (2) precipitating reagent is ammonium hydrogen carbonate.
Mixed metal salt and the mol ratio of precipitating reagent are 1 in step (3):1；The condition of stirring reaction is：In 80 DEG C of stirrings Reaction 0.5h；The condition of burin-in process is：The aging 2h at 90 DEG C.
Dry condition is in step (4)：2h is dried at 120 DEG C；The condition of roasting is：2h is calcined at 500 DEG C.
The Zinc oxide-base normal-temperature deep desulfurizing agent being prepared from using the above method.
The application of Zinc oxide-base normal-temperature deep desulfurizing agent, described Zinc oxide-base normal-temperature deep desulfurizing agent is used for oil and coal H in various gaseous states, liquid material in chemical field2The normal-temperature deep removing of S, i.e., using fixed-bed operation, be in reaction temperature 60 DEG C, operating pressure is 12h under conditions of 5MPa, to control liquid volume air speed-1, by content in treating material be 1~ The H of 1000ppm2S is removed to≤0.03ppm.
The above-mentioned description to embodiment is to be understood that and use invention for ease of those skilled in the art.It is ripe The personnel for knowing art technology obviously can easily make various modifications to these embodiments, and general original described herein Ought to use in other embodiment without by performing creative labour.Therefore, the invention is not restricted to above-described embodiment, this area Technical staff's announcement of the invention, does not depart from improvement that scope made and modification all should be in guarantor of the invention Within the scope of shield.

Claims (10)

1. a kind of preparation method of Zinc oxide-base normal-temperature deep desulfurizing agent, it is characterised in that the method specifically includes following steps：
Step (1)：Zinc salt, aluminium salt, promoter metal salt is soluble in water, and it is 0.05~3mol/L's that molar concentration is configured to respectively Salting liquid, and mixed, stir, mixed salt solution is obtained；
Step (2)：Prepare the precipitant solution that molar concentration is 0.05~3mol/L；
Step (3)：Precipitant solution obtained in step (2) is added in the mixed salt solution of step (1), stirring reaction For a period of time, presoma slurries are obtained, then presoma slurries is sufficiently stirred for, burin-in process is carried out；
Step (4)：Presoma slurries in step (3) through burin-in process are centrifuged, collect precipitation, and to precipitate into Row washing, dry, roasting, that is, be obtained described Zinc oxide-base normal-temperature deep desulfurizing agent.
2. a kind of preparation method of Zinc oxide-base normal-temperature deep desulfurizing agent according to claim 1, it is characterised in that step (1) mol ratio of zinc salt, aluminium salt and promoter metal salt is 100 in the mixed salt solution described in:1~30:1~50.
3. a kind of preparation method of Zinc oxide-base normal-temperature deep desulfurizing agent according to claim 1, it is characterised in that step (1) zinc salt described in includes one or more in zinc nitrate, zinc chloride, zinc sulfate or zinc acetate, and described aluminium salt includes nitre One or more in sour aluminium, aluminium chloride or aluminum sulfate.
4. a kind of preparation method of Zinc oxide-base normal-temperature deep desulfurizing agent according to claim 1, it is characterised in that step (1) the promoter metal salt described in includes one or more in calcium salt, manganese salt, molysite, cobalt salt, nickel salt or mantoquita.
5. the preparation method of a kind of Zinc oxide-base normal-temperature deep desulfurizing agent according to claim 4, it is characterised in that described Calcium salt one kind for including in calcium acetate, calcium sulfate, calcium nitrate or calcium chloride, described manganese salt includes cobalt acetate, manganese sulfate, nitre One kind in sour manganese or manganese chloride, described molysite includes the one kind in ferric acetate, ferric sulfate, ferric nitrate or iron chloride, described Cobalt salt one kind for including in cobalt acetate, cobaltous sulfate, cobalt nitrate or cobalt chloride, described nickel salt includes nickel acetate, nickel sulfate, nitre One kind in sour nickel or nickel chloride, described mantoquita includes the one kind in copper acetate, copper sulphate, copper nitrate or copper chloride.
6. a kind of preparation method of Zinc oxide-base normal-temperature deep desulfurizing agent according to claim 1, it is characterised in that step (2) precipitating reagent described in includes sodium carbonate, sodium acid carbonate, NaOH, potassium carbonate, saleratus, potassium hydroxide, ammoniacal liquor, carbon One or more in sour ammonium or ammonium hydrogen carbonate.
7. a kind of preparation method of Zinc oxide-base normal-temperature deep desulfurizing agent according to claim 1, it is characterised in that step (3) mixed metal salt and the mol ratio of precipitating reagent are 1 in:1~4；The condition of stirring reaction is：In 20~80 DEG C of stirring reactions 0.5~2h；The condition of burin-in process is：Aging 2~8h at 60~90 DEG C.
8. a kind of preparation method of Zinc oxide-base normal-temperature deep desulfurizing agent according to claim 1, it is characterised in that step (4) dry condition is in：2~8h is dried at 80~120 DEG C；The condition of roasting is：At 300~500 DEG C roasting 2~ 6h。
9. the Zinc oxide-base normal-temperature deep desulfurizing agent being prepared from using the method described in any one of claim 1 to 8.
10. the application of Zinc oxide-base normal-temperature deep desulfurizing agent as claimed in claim 9, it is characterised in that described zinc oxide Base normal-temperature deep desulfurizing agent is used in oil and coal chemical technology H in gaseous state, liquid material2The normal-temperature deep removing of S.
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CN107398279A (en) * 2017-08-17 2017-11-28 江苏天东新材料科技有限公司 A kind of preparation method and application of efficient oxidation zinc desulfurizing agent
CN107970744A (en) * 2017-10-17 2018-05-01 上海交通大学 Sulfur dioxide and zinc sulfate method are recycled in aluminum sulfate/zinc oxide combination desulfurization at the same time
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CN112742203A (en) * 2019-10-30 2021-05-04 中国石油化工股份有限公司 Gas desulfurizing agent, preparation method thereof and gas desulfurizing method
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CN111410986A (en) * 2020-04-30 2020-07-14 武汉纺织大学 Preparation method of naphtha fine desulfurizing agent
CN112619609A (en) * 2020-11-26 2021-04-09 上海绿强新材料有限公司 Adsorbent for synergistically removing sulfur and mercury and preparation method and application thereof
CN112604491A (en) * 2020-12-29 2021-04-06 湖北浚然新材料有限公司 Nano desulfurizer, preparation method and reaction system
CN114807628A (en) * 2022-05-09 2022-07-29 昆明理工大学 Desulfurizing agent and preparation method thereof
CN114950379A (en) * 2022-06-22 2022-08-30 湖南仁和环境股份有限公司 Ammonia gas-hydrogen sulfide combined synchronous adsorption material and preparation and application thereof
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