CN101260323A - Cerium oxide high-temperature gas desulfurizer and preparation thereof - Google Patents
Cerium oxide high-temperature gas desulfurizer and preparation thereof Download PDFInfo
- Publication number
- CN101260323A CN101260323A CNA2008100548576A CN200810054857A CN101260323A CN 101260323 A CN101260323 A CN 101260323A CN A2008100548576 A CNA2008100548576 A CN A2008100548576A CN 200810054857 A CN200810054857 A CN 200810054857A CN 101260323 A CN101260323 A CN 101260323A
- Authority
- CN
- China
- Prior art keywords
- cerium oxide
- sweetening agent
- temperature
- gas
- preparation
- 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.)
- Granted
Links
Images
Abstract
The invention relates to a cerium oxide high-temperature gas desulfurizer and a preparation method thereof, belonging to the gas purification and catalyst preparation field. The desulfurizer consists of active cerium oxide 50-70 wt percent, a binding agent 20-40 wt percent and a pore-forming agent 3-10 wt percent, wherein the active component cerium oxide is obtained by screening from the cerium oxide prepared by means of different technologies. The preparation method of the desulfurizer comprises the following steps of: grinding and mixing evenly the active cerium oxide and the binding agent as well as the pore-forming agent, adding water to knead, extruding into strips and forming, then drying and calcinating at high temperature, finally obtaining the desulfurizer. The desulfurizer has the advantages of high mechanical strength, high desulfurization purification efficiency and capability of regenerating to obtain elemental sulfur after the saturated desulfurization, and is especially applied in the desulfurization purification field with high temperature, strong reducing fuel gas and feed gas.
Description
One, technical field
Cerium oxide high-temperature gas sweetening agent of the present invention and preparation belong to gas sweetening and Preparation of Catalyst field, relate to the high temperature coal gas purification agent in integrated gasification combined cycle for power generation (IGCC), fuel cell power generation technology and the polygenerations systeme and are the preparation method of desulfurizing decontaminating agent of the strong reducing property material gas of feedstock production with coal, oil, Sweet natural gas.
Two, background technology
Coal is China's main energy resource, and in the fossil energy proven reserve, coal accounts for 92.7% at home.Coal is converted into the main means that electric energy is a coal utilization, but problems such as coal fired power generation ubiquity high flow rate and environmental pollution in the present world wide, and employing coal gasification power generation such as integrated gasification combined cycle for power generation (IGCC) technology and Poly-generation mode, then can reach the maximization that coal resources are worth utilising efficiency and economic benefit, realize the pollutent low emission or do not have discharging that the environment that satisfies the coal resources utilization is the most friendly.Gas purification is one of gordian technique in IGCC and the polygenerations systeme, and its main task is dedusting, desulfurization, remove other pollutents.Contain solid dust, sulfide, nitride in the raw gas after the gasification (as NH
3) and pollutent such as gaseous bases metal, sulfide wherein is if bring follow-up system into, not only can etching apparatus, and cause synthetic catalyst to be poisoned, and the waste gas of discharging also pollute the environment, it is very crucial therefore coal gas to be carried out cleaning and desulfurization.The coal gas of high temperature thermally desulfurizing is acknowledged as state-of-the-art sulfur method.Compare with traditional normal temperature wet desulphurization, the high-temperature dry coal gas desulfurization is directly at high temperature sulphur to be removed, coal gas after purifying then enters internal combustion turbine with higher temperature, heat exchanging process and expensive wastewater treatment process such as cooling and heating have been saved, make full use of the sensible heat and the latent heat of coal, the thermo-efficiency of total system is improved greatly, and make sulfur recovery elasticity big, be convenient to produce byproduct sulphur or sulfuric acid.The research of coal gas of high temperature desulfurization by dry method has nearly 30 years history, but in its industrialized process, still has many problems.
Three, summary of the invention
Cerium oxide high-temperature gas sweetening agent of the present invention and preparation, purpose is problems such as the cyclical stability that mainly exists at present coal gas of high temperature desulfurization is poor, regeneration difficulty, a kind of physical strength height, anti-efflorescence, desulfuration efficiency height are provided, easily regeneration, and regeneration can generate the desulfurizing agent for high-temp gas and the simple preparation method thereof of elemental sulfur.
A kind of cerium oxide high-temperature gas sweetening agent of the present invention, it is characterized in that with the active oxidation cerium that is made by the pyrolysis cerous nitrate be main active ingredient, the lamellar compound that interpolation contains the Different Silicon aluminum ratio with wilkinite, brick and tile soil etc. is tackiness agent and is a kind of cerium oxide high-temperature gas sweetening agent that pore-forming material is made with starch or xylogen, its component concentration is 50～70wt%, SiO
215～25wt%, Al
2O
33～10%, all the other are calcium oxide, magnesium oxide, ferric oxide and the titanium oxide of trace.
The preparation method of above-mentioned a kind of cerium oxide high-temperature gas sweetening agent is characterized in that:
I, active ingredient cerium oxide make via the pyrolysis cerous nitrate, and promptly cerous nitrate salt is 340～360 ℃ of following pyrolysis, and soaking time 14～16 hours is cooled to room temperature;
II, tackiness agent are silica alumina ratio scopes such as wilkinite, brick and tile soil at 1.0～22.0 lamellar compound;
III, pore-forming material are starch or xylogen;
IV, with the above-mentioned active oxidation cerium (50～70wt%) that makes, tackiness agent (20～40wt%), (3～10wt%) through grinding, complete mixing for pore-forming material, adding suitable quantity of water mediates, with banded extruder be crushed to cylinder shape (sweetening agent of φ 3～5mm), natural air drying to room temperature 95～100 ℃ of down oven dry 5～8 hours, put into retort furnace then under 550～800 ℃, calcined 4～6 hours, and made through quenching or naturally cooling more at last.
The activity rating of V, the cerium oxide high-temperature gas sweetening agent made is to carry out in fixed-bed reactor, and reactor inside diameter 20mm, sweetening agent are the right cylindrical of φ 3～5mm, 700～800 ℃ of bed temperature of reaction, air speed 1500h
-1, contain 39%H in the reactant gases
2, import H
2S concentration is 10000ppm, N
2As balance gas.
Cerium oxide high-temperature gas sweetening agent of the present invention and preparation advantage are: be a kind of physical strength height, anti-efflorescence, desulfurization precision height, regeneration can generate elemental sulfur, and the simple desulfurizing agent for high-temp gas of preparation method.This sweetening agent can be used for the high temperature purification desulfurization of the strong reducing property coal gas in IGCC, polygenerations systeme and the fuel cell power generation technology and the cleaning and desulfurization of synthetic ammonia, synthol, the synthetic wet goods C1 chemistry of F-T and other chemical field strong reducing property unstripped gas.
Four, description of drawings
Fig. 1 is the pre-break-through curve of cerium oxide high-temperature gas sweetening agent sulfurized in fixed bed.
Number in the figure is: t---vulcanize pre-time of break-through (hour);
C---outlet H
2S concentration (ppm).
Five, embodiment
Embodiment one:
Preparation method by foregoing cerium oxide high-temperature gas sweetening agent, take by weighing the active oxidation cerium 1000g of preparation, structural promoter adopts wilkinite, brick and tile soil and diatomite 540g respectively, and starch 150g is behind mixing, adding 100ml water mediates, room temperature was placed 2 hours, made cylinder shape (φ 3mm) sweetening agent with banded extruder, drying or air-dry after, calcined 4 hours down at 750 ℃, naturally cooling is made sweetening agent.The specific surface area and the pore volume of sweetening agent see Table 1 before and after the calcining.
Physicals before and after the cerium oxide high-temperature gas sweetening agent calcining of two kinds of Different Silicon aluminum ratios of table 1
Embodiment two:
Preparation method by foregoing cerium oxide high-temperature gas sweetening agent, take by weighing the active oxidation cerium 1000g of preparation, wilkinite 540g, starch 150g, behind mixing, add 100ml water and mediate, room temperature was placed 2 hours, made cylinder shape (φ 3mm) sweetening agent with banded extruder, drying or air-dry after, choose 750 ℃ of calcining temperatures, 650 ℃ and 550 ℃, choosing temperature lower calcination 4 hours respectively, naturally cooling is made sweetening agent.The physical strength of the sweetening agent after the different calcining temperatures sees Table 2.
The physical strength of ferrocerium desulfurizing agent for high-temp gas under the different calcining temperatures of table 2
Embodiment two:
In fixed-bed reactor, 750-1# cerium oxide high-temperature gas sweetening agent has been carried out activity rating, 800 ℃ of vulcanization reaction temperature, air speed 1500h
-1, reactant gases consists of 39%H
2, H
2S concentration is 10000ppm, N
2As balance gas, as outlet H
2S concentration surpasses 200ppm when (being equivalent to inlet concentration 2%), promptly thinks to penetrate, and stops desulfurization.Under 600 ℃ of the temperature, feed regeneration gas (SO
2Gas and N
2Gas) sweetening agent after the sulfuration is regenerated, reactor exit obviously has the yellow crystals elemental sulfur.
Claims (2)
1, a kind of cerium oxide high-temperature gas sweetening agent, it is characterized in that with the active oxidation cerium that is made by the pyrolysis cerous nitrate be main active ingredient, the lamellar compound that interpolation contains the Different Silicon aluminum ratio with wilkinite, brick and tile soil etc. is tackiness agent and is a kind of cerium oxide high-temperature gas sweetening agent that pore-forming material is made with starch or xylogen, its component concentration is 50～70wt%, SiO
215～25wt%, Al
2O
33～10%, all the other are calcium oxide, magnesium oxide, ferric oxide and the titanium oxide of trace.
2, the preparation method of the described a kind of cerium oxide high-temperature gas sweetening agent of claim 1 is characterized in that:
I, active ingredient cerium oxide make via the pyrolysis cerous nitrate, and promptly cerous nitrate salt is 340～360 ℃ of following pyrolysis, and soaking time 14～16 hours is cooled to room temperature;
II, tackiness agent are the lamellar compound of wilkinite or brick and tile soil, and the silica alumina ratio scope is 1.0～22.0;
III, pore-forming material are starch or xylogen;
IV, with the above-mentioned active oxidation cerium (50～70wt%) that makes, tackiness agent (20～40wt%), (3～10wt%) through grinding, complete mixing for pore-forming material, adding suitable quantity of water mediates, with banded extruder be crushed to cylinder shape (sweetening agent of φ 3～5mm), natural air drying to room temperature 95～100 ℃ of down oven dry 5～8 hours, put into retort furnace then under 550～800 ℃, calcined 4～6 hours, and made through quenching or naturally cooling more at last.
The activity rating of V, the cerium oxide high-temperature gas sweetening agent made is to carry out in fixed-bed reactor, and reactor inside diameter 20mm, sweetening agent are the right cylindrical of φ 3～5mm, 700～800 ℃ of bed temperature of reaction, air speed 1500h
-1, contain 39%H in the reactant gases
2, import H
2S concentration is 10000ppm, N
2As balance gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100548576A CN101260323B (en) | 2008-04-18 | 2008-04-18 | Cerium oxide high-temperature gas desulfurizer and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100548576A CN101260323B (en) | 2008-04-18 | 2008-04-18 | Cerium oxide high-temperature gas desulfurizer and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101260323A true CN101260323A (en) | 2008-09-10 |
| CN101260323B CN101260323B (en) | 2011-03-30 |
Family
ID=39961025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100548576A Expired - Fee Related CN101260323B (en) | 2008-04-18 | 2008-04-18 | Cerium oxide high-temperature gas desulfurizer and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101260323B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811039A (en) * | 2010-03-12 | 2010-08-25 | 浙江大学 | Method for preparing sulfur modified ceria catalyst and prepared catalyst |
| CN107456866A (en) * | 2017-09-30 | 2017-12-12 | 中晶蓝实业有限公司 | Flue gas desulfurization and denitrification agent and its preparation method and application |
| CN107485990A (en) * | 2017-09-30 | 2017-12-19 | 中晶蓝实业有限公司 | Flue gas desulfurization and denitrification agent and its production method and application |
| CN107583457A (en) * | 2017-09-30 | 2018-01-16 | 中晶蓝实业有限公司 | Smoke denitrifier and its production method and application |
| CN111073717A (en) * | 2019-12-30 | 2020-04-28 | 李晓澎 | Natural gas purifying agent and method for purifying natural gas |
| CN111229221A (en) * | 2020-01-16 | 2020-06-05 | 西安理工大学 | Blast furnace gas desulfurization system and preparation method of catalytic net for same |
| CN116099351A (en) * | 2022-12-29 | 2023-05-12 | 杭州尚善若水环保科技有限公司 | Desulfurization agent and desulfurization method for garbage incineration flue gas treatment |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386785B (en) * | 2008-10-24 | 2012-11-14 | 中国科学院山西煤炭化学研究所 | Desulphurizer for high-sulphur coal coke making and preparation method and applications |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6350422B1 (en) * | 1998-09-21 | 2002-02-26 | Phillips Petroleum Company | Sorbent compositions |
| CN1100590C (en) * | 2000-12-20 | 2003-02-05 | 岳建华 | High temperature plasma fume desulfurizer |
| CN100475981C (en) * | 2006-12-07 | 2009-04-08 | 上海交通大学 | Passivated magnesium desulfurizer containing rare earth oxide and method for preparing same |
-
2008
- 2008-04-18 CN CN2008100548576A patent/CN101260323B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811039A (en) * | 2010-03-12 | 2010-08-25 | 浙江大学 | Method for preparing sulfur modified ceria catalyst and prepared catalyst |
| CN107456866A (en) * | 2017-09-30 | 2017-12-12 | 中晶蓝实业有限公司 | Flue gas desulfurization and denitrification agent and its preparation method and application |
| CN107485990A (en) * | 2017-09-30 | 2017-12-19 | 中晶蓝实业有限公司 | Flue gas desulfurization and denitrification agent and its production method and application |
| CN107583457A (en) * | 2017-09-30 | 2018-01-16 | 中晶蓝实业有限公司 | Smoke denitrifier and its production method and application |
| WO2019062450A1 (en) * | 2017-09-30 | 2019-04-04 | 中晶环境科技股份有限公司 | Flue gas desulfurization and denitration agent, and production method therefor and application thereof |
| CN111073717A (en) * | 2019-12-30 | 2020-04-28 | 李晓澎 | Natural gas purifying agent and method for purifying natural gas |
| CN111229221A (en) * | 2020-01-16 | 2020-06-05 | 西安理工大学 | Blast furnace gas desulfurization system and preparation method of catalytic net for same |
| CN111229221B (en) * | 2020-01-16 | 2023-03-24 | 西安理工大学 | Blast furnace gas desulfurization system and preparation method of catalytic net for same |
| CN116099351A (en) * | 2022-12-29 | 2023-05-12 | 杭州尚善若水环保科技有限公司 | Desulfurization agent and desulfurization method for garbage incineration flue gas treatment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101260323B (en) | 2011-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101260323B (en) | Cerium oxide high-temperature gas desulfurizer and preparation thereof | |
| CN101177631B (en) | Ferrocerium oxide high-temperature coal gas desulfurization agent and preparation | |
| CN102427879A (en) | Catalyst for reforming tar-containing gas, method for producing catalyst for reforming tar-containing gas, method for reforming tar-containing gas using catalyst for reforming tar-containing gas, and method for regenerating catalyst for reforming tar | |
| CN102965131B (en) | Efficient and clean utilization technology for highly volatile young coal | |
| CN104893748A (en) | Method for producing tar and hydrocarbon fuel products from coal | |
| CN103272604A (en) | Fly ash catalyst for hydrogen production implemented by catalytic reforming of bio-oil and preparation method of fly ash catalyst | |
| CN101439844A (en) | Chemical link coupling catalytic reforming hydrogen making method and device | |
| CN107057797B (en) | A kind of composite oxygen carrier, preparation method and its application in solid fuel gasification | |
| CN102500379A (en) | Catalyst for methanation and preparation method thereof | |
| CN103242922A (en) | Method for preparing fuel gas by burning biomass | |
| CN101805641B (en) | Regeneration process of high temperature gas desulfurizer | |
| CN101230296A (en) | Reforming reactor and method for preparing synthetic gas by biomass raw fuel gas | |
| JP5535990B2 (en) | Shift catalyst, gas purification method and equipment | |
| CN101703934B (en) | Natural gas catalyst manufactured by coal and manufacturing method thereof | |
| CN103289768B (en) | Method for synthesizing natural gas from calcium carbide tail gas and coke oven gas | |
| CN103952184A (en) | Method and system for preparing reducing gas used for shaft furnace through catalytic coal gasification | |
| CN103551182A (en) | Catalyst for splitting decomposition of biomass tar and preparation method thereof | |
| CN203904284U (en) | System for preparing reducing gas for shaft furnace through catalysis and gasification of coal | |
| CN108114753B (en) | Biomass oil reforming catalyst | |
| CN104046399B (en) | Sulfur-tolerant methanation process for preparing natural gases from coke oven gases | |
| CN106609166B (en) | Desulfurizing agent and preparation method thereof | |
| CN106635108A (en) | Comprehensive utilization technology of biomass resources | |
| CN101519608A (en) | Manganese oxide based high-temperature coal gas desulfurizing agent and preparation method thereof | |
| CN105712301B (en) | H in a kind of natural gas2The technique that S is converted into sulphur | |
| CN110791305A (en) | Method and system for preparing active coke by co-pyrolysis of biomass and coal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110330 Termination date: 20120418 |