CN101322915A - Composite adsorption desulfurizing agent and preparation method thereof - Google Patents
Composite adsorption desulfurizing agent and preparation method thereof Download PDFInfo
- Publication number
- CN101322915A CN101322915A CNA2007100181740A CN200710018174A CN101322915A CN 101322915 A CN101322915 A CN 101322915A CN A2007100181740 A CNA2007100181740 A CN A2007100181740A CN 200710018174 A CN200710018174 A CN 200710018174A CN 101322915 A CN101322915 A CN 101322915A
- Authority
- CN
- China
- Prior art keywords
- desulfurizing agent
- composite adsorption
- adsorption desulfurizing
- attapulgite
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a compound absorptive desulfurizer and a preparation method thereof. The desulfurizer comprises attapulgite, active alumina, shaping agent and active components. The attapulgite and the active alumina are taken as carriers; measured according to weight percentage, the content of the attapulgite is 50 to 70 percent; the content of the active alumina is 20 to 40 percent; the content of the shaping agent is 0.01 to 5 percent and the content of the active components is 0.1 to 10 percent. The active components are selected from one or a plurality of non-noble metal oxides of IB group, IIB group, VIIIB group and lanthanide; the preparation steps are: uniformly mixing the attapulgite, the active alumina, the shaping agent and water according to a ratio; roasting the mixture after aging, pelleting and drying; modifying the roasted object with acid, dipping the modified object into solution containing the active components and roasting again.
Description
Technical field
The present invention relates to adsorption desulfurizing agent, specifically is a kind of adsorption desulfurizing agent with absorption and catalytic desulfurization double action and preparation method thereof.
Background technology
In recent years, because sulfurous gas is increasing to the harm of productive life, people also more and more pay attention to the desulfurization of all gases.As removing of the hydrogen sulfide that produces in natural gas, coke-stove gas, the synthesis gas production process, the sulfur dioxide of generations such as thermal power plant, boiler remove the organic sulfur compound that produces in the oil product production process (cos, mercaptan, thioether, thiophene, CS
2) remove.
Dry desulfurization is a kind of desulfurizing process, generally has degree of purification height, easy to operate, simultaneously organic sulfide removal and advantages such as inorganic sulfur, non-secondary pollution, and in addition, the desulfurizing agent of dry desulfurization can also be regenerated, and recycles.But dry desulfurization can only periodical operation, and equipment is huge, is not suitable for handling the gas that flow is big, sulfur content is high.
The principle of load metal oxide flue gas dry desulfurizing is to make absorbent with metal oxide, with activated Al
2O
3, TiO
2, the desulfurizing agent that active carbon and silica gel etc. become for preparing carriers.Metal oxide that can desulfurization has CuO, ZnO, MnO
2, NiO
2, CeO
2, Fe
2O
3With MgO etc.Metal oxide desulfurizer can be divided into 2 kinds of single metal oxide desulfurizer and composite metal oxide desulfurizing agents substantially.The single oxide desulfurizing agent mainly contains iron oxide, zinc oxide, calcium oxide, cupric oxide, manganese oxide, tin oxide and rare-earth oxide etc.The composite metal oxide desulfurizing agent mainly contains zinc titanate, zinc ferrite etc.
Disclosed TiO in the BP 2122597
2The base desulphurization catalyst is exclusively used in and removes hydrogen sulfide gas, needs the high concentration aqueous amount to do assurance during use; Disclosed carrier is a-Al among the US4818740
2O
3, active component is Fe
2O
3-Cr
2O
3Though desulphurization catalyst then be not subjected to the influence of water content, at 270 ℃, 1000h
-1The removal efficiency that removes 1% hydrogen sulfide gas under the air speed condition can reach 100%; The disclosed carrier of CN1203828A is a-Al
2O
3Make the direct oxidation desulphurization catalyst after making the complex compound dipping with the nitrate of iron, chromium and phosphorylated ligand, the removal efficiency of this catalyst removal 1% hydrogen sulfide gas reaches 83.6%～100%, the catalyst that these patents relate to is the loaded catalyst that infusion process makes, hydrogen sulfide gas to low content is more suitable, but the example of the high concentration sulfurous gas not being handled.
Summary of the invention
The purpose of this invention is to provide a kind of composite adsorption desulfurizing agent and preparation method thereof.
The present invention is a kind of composite adsorption desulfurizing agent and preparation method thereof, this composite adsorption desulfurizing agent contains attapulgite, activated alumina, forming agent and active component, with described attapulgite and activated alumina is carrier, by weight percentage, the content of attapulgite is 50～70%, the content of activated alumina is 20～40%, the content of forming agent is 0.01～5%, the content of active component is 0.1～10%, and described active component is selected from one or more of IB family, IIB family, VIIIB family and group of the lanthanides non-noble metal oxide.
The preparation method of above-mentioned composite adsorption desulfurizing agent the steps include: by said ratio, attapulgite, activated alumina, forming agent and water is mixed, with its ageing, granulation, dry roasting; With the article after the roasting with sour modification after, dipping and roasting in a kind of solution that contains active component, described active component is selected from one or more of IB family, IIB family, VIIIB family and lanthanide rare metallic compound.
Composite adsorption desulfurizing agent described in the present invention has higher activity and catalytic performance by the preparation of impregnation-calcination method, and the introducing of active component makes that desulphurizing activated raising is more remarkable.
The specific embodiment
Embodiment 1
With 50g attapulgite, 40g activated alumina, 1g forming agent and water mixing by a certain percentage, behind its ageing 24h, be squeezed into sheet with prilling granulator, air dry in air, the granulated sorbent of air dry is through 105 ℃ of oven for drying, 500 ℃ roasting temperatures 2 hours, reduce to room temperature naturally.With the sample after the roasting with behind 0.5mol/L sulfuric acid modified, at 10wt%Cu (NO
3)
2Dipping 2 hours and promptly get composite adsorption desulfurizing agent A after 1 hour in the solution at 500 ℃ roasting temperature.
Embodiment 2
With 55g attapulgite, 35g activated alumina, 1g forming agent and water mixing by a certain percentage, behind its ageing 24h, be squeezed into sheet with prilling granulator, air dry in air, the granulated sorbent of air dry is through 105 ℃ of oven for drying, 550 ℃ roasting temperatures 2 hours, reduce to room temperature naturally.After the hydrochloric acid modification of 1.0mol/L of the usefulness of the sample after the roasting, at 10wt%Ni (NO
3)
2Dipping 2 hours and promptly get composite adsorption desulfurizing agent B after 1 hour in the solution at 550 ℃ roasting temperature.
Embodiment 3
With 60g attapulgite, 40g activated alumina, 2g forming agent and water mixing by a certain percentage, behind its ageing 24h, be squeezed into sheet with prilling granulator, air dry in air, the granulated sorbent of air dry is through 105 ℃ of oven for drying, 600 ℃ roasting temperatures 3 hours, reduce to room temperature naturally.With the sample after the roasting with behind 2.0mol/L sulfuric acid modified, at 15wt%Ce (NO
3)
2Dipping 3 hours and promptly get composite adsorption desulfurizing agent C after 2 hours in the solution at 600 ℃ roasting temperature.
Embodiment 4
With 70g attapulgite, 35g activated alumina, 2g forming agent and water mixing by a certain percentage, behind its ageing 24h, be squeezed into sheet with prilling granulator, air dry in air, the granulated sorbent of air dry is through 105 ℃ of oven for drying, 700 ℃ roasting temperatures 4 hours, reduce to room temperature naturally.After the usefulness of the sample after the roasting Nitric Acid Modified of 1.5mol/L, at 15wt%Fe (NO
3)
3Dipping 4 hours and promptly get composite adsorption desulfurizing agent D after 3 hours in the solution at 700 ℃ roasting temperature.
Embodiment 5
With 80g attapulgite, 40g activated alumina, 3g forming agent and water mixing by a certain percentage, behind its ageing 24h, be squeezed into sheet with prilling granulator, air dry in air, the granulated sorbent of air dry is through 105 ℃ of oven for drying, 600 ℃ roasting temperatures 4 hours, reduce to room temperature naturally.After the hydrochloric acid modification of 1.5mol/L of the usefulness of the sample after the roasting, at 20wt%Co (NO
3)
2Dipping 4 hours and promptly get composite adsorption desulfurizing agent E after 4 hours in the solution at 600 ℃ roasting temperature.
Embodiment 6
With 65g attapulgite, 30g activated alumina, 5g forming agent and water mixing by a certain percentage, behind its ageing 24h, be squeezed into sheet with prilling granulator, air dry in air, the granulated sorbent of air dry is through 105 ℃ of oven for drying, 650 ℃ roasting temperatures 4 hours, reduce to room temperature naturally.After the acetic acid modification of 2.0mol/L of the usefulness of the sample after the roasting, at 20wt%Zn (NO
3)
2Dipping 4 hours and promptly get composite adsorption desulfurizing agent F after 2 hours in the solution at 650 ℃ roasting temperature.
Comparative Examples 1
Prepare composite adsorption desulfurizing agent A according to embodiment 1 composition and method, need not acid carry out modification to composite adsorption desulfurizing agent A, all the other preparation processes make composite adsorption desulfurizing agent G with embodiment 1.
Comparative Examples 2
Composition and method according to embodiment 2 prepare composite adsorption desulfurizing agent B, and 400 ℃ of following roastings, all the other preparation processes make composite adsorption desulfurizing agent H with embodiment 2.
Comparative Examples 3
Composition and method according to embodiment 2 prepare composite adsorption desulfurizing agent C, and 800 ℃ of following roastings, all the other preparation processes make composite adsorption desulfurizing agent I with embodiment 3.
Comparative Examples 4
Composition and method according to embodiment 3 prepare composite adsorption desulfurizing agent D, not add-on type agent, and all the other preparation processes make composite adsorption desulfurizing agent J with embodiment 3.
Comparative Examples 5
Composition and method according to embodiment 5 prepare composite adsorption desulfurizing agent E, not the carrying transition metal oxide.Make composite adsorption desulfurizing agent K.
The physical property such as the table 1 of each composite adsorption desulfurizing agent:
The contrast of table 1 composite adsorption desulfurizing agent physical property
Evaluation result
Above-mentioned composite adsorption desulfurizing agent is seated in the miniature packed tower of self-control, carries out the continuous-flow reaction.Feeding gas is that concentration is the SO of 1000～1300mg/L
2Gas is 400h in normal temperature, normal pressure and air speed
-1Condition under evaluate and test test.SO
2The removal efficiency and the computational methods of Sulfur capacity as follows:
By evaluation and test test, each composite adsorption desulfurizing agent remove SO
2Efficient and Sulfur capacity see Table 2.
The SO of table 2 composite adsorption desulfurizing agent
2Removal efficiency
As can be seen from Table 2, use the catalyst of preparation method of the present invention and condition preparation, even under high concentration, SO
2Clearance also can reach more than 90%, have the good adsorption catalytic performance, be applicable to high concentration SO
2The processing of gas.
Claims (10)
1, a kind of composite adsorption desulfurizing agent, it is characterized in that this composite adsorption desulfurizing agent contains attapulgite, activated alumina, forming agent and active component, with described attapulgite and activated alumina is carrier, by weight percentage, the content of attapulgite is 50～70%, the content of activated alumina is 20～40%, the content of forming agent is 0.01～5%, the content of active component is 0.1～10%, and described active component is selected from one or more of IB family, IIB family, VIIIB family and group of the lanthanides non-noble metal oxide.
2, composite adsorption desulfurizing agent according to claim 1 is characterized in that, one or more of described active component chosen from Fe, cobalt, nickel, copper, zinc, lanthanide rare metal oxide.
3, composite adsorption desulfurizing agent according to claim 1 and 2 is characterized in that, described attapulgite raw ore is taken from one or more in Linze, Gansu or the peaceful product of the meeting attapulgite ore deposit.
4, composite adsorption desulfurizing agent according to claim 4 is characterized in that, the content of attapulgite is 31～67% in the described attapulgite raw ore.
5, composite adsorption desulfurizing agent according to claim 1 and 2 is characterized in that, described activated alumina is selected from one or more in Y type or the X-P type activated alumina.
6, composite adsorption desulfurizing agent according to claim 1 and 2 is characterized in that, described forming agent is selected from one or more in converted starch, carboxymethyl cellulose, Ludox, the aluminium colloidal sol.
7, the preparation method of composite adsorption desulfurizing agent the steps include: attapulgite, activated alumina, forming agent and water to be mixed, with its ageing, granulation, dry roasting by the described proportioning of claim 1; With the article after the roasting with sour modification after, dipping and roasting in a kind of solution that contains active component, described active component is selected from one or more of IB family, IIB family, VIIIB family and lanthanide rare metallic compound.
8, the preparation method of composite adsorption desulfurizing agent according to claim 7 is characterized in that, described modification is selected from organic acid with acid, as acetic acid, or inorganic acid, as in sulfuric acid, hydrochloric acid, nitric acid, the phosphoric acid one or more; The concentration of acid is 0.1～5.0mol/L.
9, the preparation method of composite adsorption desulfurizing agent according to claim 7 is characterized in that, described dipping solution concentration is 1% to saturated, and dip time was at least 1 hour.
10, the preparation method of composite adsorption desulfurizing agent according to claim 7 is characterized in that, sintering temperature was 400～1000 ℃ when composite adsorption desulfurizing agent prepared, and roasting time was at least 1 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100181740A CN101322915A (en) | 2007-06-14 | 2007-06-14 | Composite adsorption desulfurizing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100181740A CN101322915A (en) | 2007-06-14 | 2007-06-14 | Composite adsorption desulfurizing agent and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101322915A true CN101322915A (en) | 2008-12-17 |
Family
ID=40186714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100181740A Pending CN101322915A (en) | 2007-06-14 | 2007-06-14 | Composite adsorption desulfurizing agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101322915A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805640A (en) * | 2010-05-13 | 2010-08-18 | 天津大学 | High-temperature coal gas desulfurizing agent of composite oxides of mesoporous rare soil and preparation method thereof |
| CN102773010A (en) * | 2012-07-23 | 2012-11-14 | 昆明理工大学 | Method for purifying thiophene in industrial tail gas |
| CN103203242A (en) * | 2013-03-06 | 2013-07-17 | 广州博能能源科技有限公司 | Catalytic system and process for desulfuration of industrial sulfur-bearing waste gas |
| CN103723785A (en) * | 2013-12-13 | 2014-04-16 | 陕西科技大学 | Method adopting lanthanum modified attapulgite to remove fluorinion in water |
| CN103962090A (en) * | 2013-01-29 | 2014-08-06 | 中国石油化工股份有限公司 | Multi-metal solid desulfurizing agent and preparing method thereof |
| CN105214684A (en) * | 2015-09-11 | 2016-01-06 | 淮阴师范学院 | The preparation method of the hydrogen-supplemented fuel desulphurization catalyst of bar-shaped recessed soil matrix synergistic sorption |
| CN105694948A (en) * | 2014-11-27 | 2016-06-22 | 中国海洋石油总公司 | Gasoline adsorption desulfurization method |
| CN105727888A (en) * | 2014-12-11 | 2016-07-06 | 中国石油化工股份有限公司 | Reproducible SO2 adsorbent and preparation method therefor |
| CN106925250A (en) * | 2015-12-29 | 2017-07-07 | 天津市英派克石化工程有限公司 | A kind of method that dry type desulfurizing catalyst is prepared with white clay |
| CN107469803A (en) * | 2016-06-07 | 2017-12-15 | 中国石油化工股份有限公司 | Catalyst for recovering sulfur and preparation method thereof |
| CN110064361A (en) * | 2019-05-23 | 2019-07-30 | 辽宁师范大学 | Magnetic absorption-oxidation desulfurizing agent and preparation method |
| CN112480982A (en) * | 2020-09-14 | 2021-03-12 | 沈阳三聚凯特催化剂有限公司 | Fine desulfurization dechlorinating agent and preparation method and application thereof |
| CN115057645A (en) * | 2022-06-09 | 2022-09-16 | 苏州中晟环境修复有限公司 | Production process and device of composite ecological filler |
-
2007
- 2007-06-14 CN CNA2007100181740A patent/CN101322915A/en active Pending
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805640B (en) * | 2010-05-13 | 2012-12-26 | 天津大学 | High-temperature coal gas desulfurizing agent of composite oxides of mesoporous rare soil and preparation method thereof |
| CN101805640A (en) * | 2010-05-13 | 2010-08-18 | 天津大学 | High-temperature coal gas desulfurizing agent of composite oxides of mesoporous rare soil and preparation method thereof |
| CN102773010A (en) * | 2012-07-23 | 2012-11-14 | 昆明理工大学 | Method for purifying thiophene in industrial tail gas |
| CN102773010B (en) * | 2012-07-23 | 2014-09-03 | 昆明理工大学 | Method for purifying thiophene in industrial tail gas |
| CN103962090A (en) * | 2013-01-29 | 2014-08-06 | 中国石油化工股份有限公司 | Multi-metal solid desulfurizing agent and preparing method thereof |
| CN103962090B (en) * | 2013-01-29 | 2017-02-08 | 中国石油化工股份有限公司 | Multi-metal solid desulfurizing agent and preparing method thereof |
| CN103203242A (en) * | 2013-03-06 | 2013-07-17 | 广州博能能源科技有限公司 | Catalytic system and process for desulfuration of industrial sulfur-bearing waste gas |
| CN103203242B (en) * | 2013-03-06 | 2015-02-25 | 广州博能能源科技有限公司 | Catalytic system and process for desulfuration of industrial sulfur-bearing waste gas |
| CN103723785A (en) * | 2013-12-13 | 2014-04-16 | 陕西科技大学 | Method adopting lanthanum modified attapulgite to remove fluorinion in water |
| CN105694948B (en) * | 2014-11-27 | 2017-07-28 | 中国海洋石油总公司 | A kind of method of gasoline absorbing desulfurization |
| CN105694948A (en) * | 2014-11-27 | 2016-06-22 | 中国海洋石油总公司 | Gasoline adsorption desulfurization method |
| CN105727888A (en) * | 2014-12-11 | 2016-07-06 | 中国石油化工股份有限公司 | Reproducible SO2 adsorbent and preparation method therefor |
| CN105214684A (en) * | 2015-09-11 | 2016-01-06 | 淮阴师范学院 | The preparation method of the hydrogen-supplemented fuel desulphurization catalyst of bar-shaped recessed soil matrix synergistic sorption |
| CN105214684B (en) * | 2015-09-11 | 2017-06-27 | 淮阴师范学院 | The preparation method of the hydrogen-supplemented fuel desulphurization catalyst of bar-shaped recessed soil matrix synergistic sorption |
| CN106925250A (en) * | 2015-12-29 | 2017-07-07 | 天津市英派克石化工程有限公司 | A kind of method that dry type desulfurizing catalyst is prepared with white clay |
| CN107469803A (en) * | 2016-06-07 | 2017-12-15 | 中国石油化工股份有限公司 | Catalyst for recovering sulfur and preparation method thereof |
| CN110064361A (en) * | 2019-05-23 | 2019-07-30 | 辽宁师范大学 | Magnetic absorption-oxidation desulfurizing agent and preparation method |
| CN112480982A (en) * | 2020-09-14 | 2021-03-12 | 沈阳三聚凯特催化剂有限公司 | Fine desulfurization dechlorinating agent and preparation method and application thereof |
| CN115057645A (en) * | 2022-06-09 | 2022-09-16 | 苏州中晟环境修复有限公司 | Production process and device of composite ecological filler |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101322915A (en) | Composite adsorption desulfurizing agent and preparation method thereof | |
| CN104492446B (en) | A kind of catalyst and preparation method for ammonia selective reducing nitrogen oxide | |
| CN102357364A (en) | Preparation of activated carbon-based catalyst used for selective reduction desulphurization of flue gas | |
| CN101954284A (en) | Active carbon desulfurization catalyst and preparation method thereof | |
| CN104069795A (en) | Gas desulfurization and adsorption composition, preparation method thereof and method for desulfurizing sulfurous gases | |
| CN101804289B (en) | Preparation of flue gas desulfurizer and use and regeneration method thereof | |
| CN104888602A (en) | Application of metal oxide modified CePO4 catalyst to collaborative denitration and demercuration | |
| CN107008323B (en) | A kind of activated-carbon catalyst preparation method for flue gas desulfurization and denitrification | |
| CN101811051A (en) | Carbonyl sulfide hydrolysis catalyst prepared by using cobalt(Co)-nickel(Ni)-aluminum(Al) hydrotalcites as precursor and preparation method thereof | |
| CN112742413B (en) | Low-temperature SCR denitration catalyst and preparation method and application thereof | |
| CN103406122A (en) | Catalyst for desorbing nitrogen oxides and carbon monoxide at low temperature and preparation method thereof | |
| CN102962064A (en) | Gamma-form alumina loaded metallic oxide catalyst as well as preparation method and application thereof | |
| CN101972661A (en) | Sulfur-resisting and nitrogen-removed oxide compound metallic oxide SCR (Selective Catalytic Reduction) catalyst and preparation method thereof | |
| CN107983354B (en) | Preparation method of alkali poisoning resistant copper-based spinel low-temperature denitration catalyst | |
| CN102000600B (en) | Integral normal-temperature micro nitrogen oxide purification material and preparation method thereof | |
| CN102764657A (en) | Nano V205/activated coke denitration catalyst and preparation method of catalyst | |
| CN106799249A (en) | For N2Co oxides/the BaCO of O catalytic decompositions3Catalyst and preparation method thereof | |
| CN104841441A (en) | Preparation method and application of catalyst for purifying HCN through hydrolysis-oxidation coupling technology | |
| CN104190358A (en) | NOx adsorber | |
| CN103537289A (en) | Method for preparing low-temperature SCR (Selective Catalytic Reduction) denitration catalyst | |
| CN104399499B (en) | For nonvalent mercury oxidation Cerium monophosphate is catalyst based, preparation method and application | |
| CN109513447B (en) | Catalyst for removing carbon monoxide and preparation method thereof | |
| CN101053735A (en) | Montmorillonite as natural gas desulfurizing agent | |
| CN107486206B (en) | Manganese-based material and preparation method and application thereof | |
| CN103447072B (en) | Preparation method of Fe-NaY-C-attapulgite compound flue gas denitrification catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20081217 |