CN100363100C - Desulfur catalyst - Google Patents
Desulfur catalyst Download PDFInfo
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- CN100363100C CN100363100C CNB2004100218563A CN200410021856A CN100363100C CN 100363100 C CN100363100 C CN 100363100C CN B2004100218563 A CNB2004100218563 A CN B2004100218563A CN 200410021856 A CN200410021856 A CN 200410021856A CN 100363100 C CN100363100 C CN 100363100C
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- CN
- China
- Prior art keywords
- present
- sulphur
- catalyst
- natural gas
- sulfur
- 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.)
- Expired - Fee Related
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- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 239000011148 porous material Substances 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 238000007906 compression Methods 0.000 claims description 4
- 230000006835 compression Effects 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 30
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 22
- 239000003345 natural gas Substances 0.000 abstract description 15
- 239000005864 Sulphur Substances 0.000 abstract description 12
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003546 flue gas Substances 0.000 abstract description 11
- 239000011593 sulfur Substances 0.000 abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 9
- 238000006477 desulfuration reaction Methods 0.000 abstract description 9
- 230000023556 desulfurization Effects 0.000 abstract description 9
- 239000007787 solid Substances 0.000 abstract description 7
- 239000003245 coal Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 150000003568 thioethers Chemical class 0.000 abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000446 fuel Substances 0.000 abstract description 4
- 125000001741 organic sulfur group Chemical group 0.000 abstract description 4
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910021529 ammonia Inorganic materials 0.000 abstract description 2
- 238000009434 installation Methods 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 abstract 2
- 231100000331 toxic Toxicity 0.000 abstract 2
- 230000002588 toxic effect Effects 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000009418 renovation Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910000943 NiAl Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- LNRYQGINUXUWLV-UHFFFAOYSA-N [Mn].[Fe].[Zn] Chemical compound [Mn].[Fe].[Zn] LNRYQGINUXUWLV-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- -1 wherein Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The present invention discloses a solid desulfurization catalyst which is used for eliminating sulfide, sulfur oxide, thioether and other toxic and harmful substances in natural gas and flue gas at a certain temperature and under a certain pressure. The present invention contains the following components of the percentage by weight adopting the catalyst weight as the reference: 6.5% to 65% of ZnO, 0.5% to 2% of NiO, 11% to 40% of CaAlO3, 0.5% to 2% of TiO2, 0.9% to 2% of C0O, 0.7% to 3% of M0O and 20% to 70% of Al2O3. The present invention can be used for eliminating sulfide, sulfur oxide, thioether and other toxic and harmful substances in natural gas and flue gas; the present invention is capable of eliminating organic sulfur, inorganic sulphur, sulphur of the ppm level content, sulphur with the sulfur content of 80 milligram per cubic metre, sulphur at normal temperatures and sulphur at the temperature of 400 DEG C to 500 DEG C; when the present invention is used in a large sized synthetic ammonia installation of 300 thousands of tons, both organic sulfur and inorganic sulphur in natural gas can be removed; when the present invention is used for large-sized power generating plants adopting coal as fuel, SO2 in exhaust flue gas can be removed.
Description
Technical field
The present invention relates to a kind ofly under certain temperature, pressure condition, to remove in the natural gas, the solid desulphurization catalyst of poisonous and harmful substance such as the sulfide in the flue gas, oxysulfide, thioether, specifically, the present invention relates to a kind of zinc solid desulphurization catalyst that contains.
Background technology
Industries such as the energy, chemical industry, metallurgy, electronics use the SO that contains in the flue gas that fossil fuel (coal, oil, natural gas etc.) discharged
2Atmosphere is caused severe contamination, and China has become SO in the world at present
2Discharge first big country, the third-largest acid rain district, environmental problem has become the key issue that can Chinese national economy develop.Industrial practice in recent years shows that flue gases purification is control SO
2The effective way of discharging, desulphurization catalyst is the pith of flue gases purification, it can be divided into solid and liquid desulphurization catalyst, wherein, zinc oxide solid desulphurization catalyst is at various petrochemical materials gas, being most widely used in the smart desulfurization of industry gas, Zinc oxide desulfurizer mainly contains two kinds of high temperature and low forms, the former serviceability temperature is 350-400 ℃, latter's serviceability temperature is 180-250 ℃, because two types desulfurizing agent all needs to use at a certain temperature, needs thermal source, and consumes certain energy, generally all can not use at normal temperatures, therefore the scope of application of this catalyst is narrower;
For many years, the Soviet Union is just with zinc ore masonry desulphurization catalyst, but bad desulfurization effects, the negative resistance that adds that causes to system increases; The more existing producers of China make desulphurization catalyst with the oxide of zinc, salt etc. with other chemical substance, as Patent Office of the People's Republic of China with 85103555 disclosed a kind of " iron-manganese-zinc desulfurizing agent for gaseous hydrocarbons ", it is very satisfied that its desulfurized effect does not make us yet, reason has: a, can not remove the sulfide of high-load in the discharging gas that natural gas and coal produce, it requires the content of sulphur in the unstripped gas must be lower than 0.5ppm, when every cubic metre of sulfur content in the natural gas reached the milligram level, catalyst poisoning will appear; B, the used regeneration gas of this desulphurization catalyst regeneration are H
2And C
0Etc. expensive gases, the regeneration expense is very expensive; Though c, this desulphurization catalyst can be regenerated, need ability regeneration in 350 ℃ of following 10-12 hours, and its activity also descends to some extent.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art and provide a kind of and can the sulfide of high-load in the discharging gas be adsorbed, can regenerate and the recovery time is short, active high, and the solid desulphurization catalyst that can use under high and low and normal temperature in regeneration back.
The object of the present invention is achieved like this:
Nickel series conversion catalyzer has the above-mentioned various deficiencies of appearance of the desulphurization catalyst of special responsive characteristics and prior art to sulfide by analysis, and the present inventor has been found that on zinc is the basis of desulphurization catalyst prescription and adds an amount of NiO, TiO
2, Al
2O
3Deng, be effectively to the purpose that reaches foregoing invention, be successful based on the present invention of this discovery.
In other words, containing zinc solid desulphurization catalyst according to the invention provides an energy to what the sulfide of high-load in the discharging gas adsorbed, is benchmark with the catalyst weight, contains the component of following percentage by weight:
ZnO..................6.5% to 65%
NiO...................0.5% to 2%
CaAlO
3... ... ... .11% to 40%
TiO
2... ... ... 0.5% to 2%
CoO...................0.9% to 2%
MoO...................0.7% to 3%
Al
2O
3... ... ... ..20% to 70%
The average pore size of this catalyst is 16.1nm, and pore volume is 0.5~1.6ml/g; Specific area is 309~501m
2/ g, bulk density is 1.08g/ml, compression strength is 〉=150N/cm.
The Ni that is used for NiO of the present invention has great suction-operated to sulfide, can both be removed by its collection less than 10 other sulfide of ppm level, can be used for purified natural gas and is the waste gas that fuel is discharged with the coal, and NiO aims to remove H
2S adds;
Be used for Al of the present invention
2O
3Itself have hole rate preferably, and should be to have active Al
2O
3, the reason that adds it is in order to adsorb SO
2
Be used for TiO of the present invention
2Have mercaptan, thioether and sulfosalt are had suction-operated, and the alkene in the natural gas is also had suction-operated, because in the prescription Al is arranged
2O
3, TiO
2Adding protection NiO component is also had effect, prevent itself and Al
2O
3React and generate NiAl
2O
4Thereby influence its activity;
The ZnO that is used for the present invention can be to the most of H in the natural gas
2S removes;
The Ca that is used for the present invention adds with the form of pure calcium aluminate, and it can improve the intensity of catalyst;
The effect and the TiO that are used for the present invention's Mo, Co
2Similar, but they can not be to Al
2O
3Play a protective role.
Production method of the present invention is as follows: the each component raw material in the above-mentioned prescription is mixed the back grinding in ball grinder 4~6 hours by the amount described in the prescription, be ground to the above fineness of 120 orders and must account for 30% of weight, after tablet machine is beaten sheet, crusher in crushing (being granulation) then, send into compression moulding in the ring squeezer after crossing 120 purposes sieve, again at 4kg/cm
2Still kettle in steam the roasting temperature of delivering to 400~500 ℃ of stove inherences after 4 hours and promptly get the present invention after 12 hours.
The present invention can be used for removing poisonous and harmful substances such as sulfide in the natural gas, in the flue gas, oxysulfide, thioether, it can organic sulfide removal, can remove inorganic sulfur again, can remove the sulphur of ppm rank content, can remove again in every cubic metre of the sulfur content and reach 80 milligrams sulphur, desulfurization at normal temperatures again can desulfurization under 400-500 ℃ of temperature.Be used on the 300000 ton large-scale synthetic ammonia installations, organic sulfur in the natural gas and inorganic sulfur can be removed together, being used in the coal is the big power station of fuel, and it can remove the SO in the flue discharging gas
2
Renovation process of the present invention is: directly send into air with air blast toward the bed of desulphurization catalyst, the outlet that must open desulfurizer this moment, the valve of next production process is sent in cut-out, with the sulfur content of the gas that just can make air outlet slit in 20 minutes to 2 hours index, finish regenerative process less than technological requirement.
The specific embodiment
Below by embodiment the present invention is further described, but the present invention is not limited only to these examples.
Embodiment 1: with the catalyst weight is benchmark, adopts following prescription controlling catalyst:
ZnO..................64%
NiO..................1%
CaAlO
3...............11%
TiO
2.................0.5%
CoO..................0.9%
MoO..................0.7%
Al
2O
3................21.9%
Each component raw material in the above-mentioned prescription is mixed the back grinding in ball grinder 4~6 hours by the amount described in the prescription, be ground to the above fineness of 120 orders and must account for 30% of weight, after tablet machine is beaten sheet, crusher in crushing (being granulation) then, send into compression moulding in the ring squeezer after crossing 120 purposes sieve, again at 4kg/cm
2Still kettle in steam the roasting temperature of delivering to 400~500 ℃ of stove inherences after 4 hours and promptly get desulphurization catalyst after 12 hours.
The average pore size of this catalyst is 16.1nm, and pore volume is 1.5ml/g; Specific area is 400m
2/ g, bulk density is 1.08g/ml, compression strength is 150N/cm.
This catalyst is loaded in the devulcanizer, is used for removing the organic sulfur and the inorganic sulfur of natural gas, contain 80mg/m in this natural gas
3H
2S, 1mg/m
3Mercaptan, 1mg/m
3Thioether, 20 ℃~600 ℃ temperature, the pressure of 3.5Mpa uses down this catalyst to carry out the desulfurization of natural gas, by the gas after the automatic sulphur analyzer test desulfurization, automatically crest does not appear in the sulphur analyzer, and the content that shows sulphur is significantly less than national standard below 0.1ppm.
This catalyst is after using the regular hour, must regenerate, the method of regeneration is: directly send into air with air blast toward the bed of desulphurization catalyst, the outlet that must open desulfurizer this moment, the valve of next production process is sent in cut-out, with the sulfur content of the gas that just can make air outlet slit in 20 minutes index, finish regenerative process less than technological requirement.Use after the cyclic regeneration 5 times, its sulfur limitation effect illustrates that with primary identical this activity of such catalysts still remains on the higher level.
Embodiment 2: with the catalyst weight is benchmark, adopts following prescription controlling catalyst:
ZnO..................9%
NiO..................0.5%
CaAlO
3...............15%
TiO
2.................0.5%
CoO..................2%
MoO..................3%
Al
2O
3................70%
The method of pressing among the embodiment 1 is produced catalyst, and the average pore size of this catalyst is 16.1nm, and pore volume is 0.5ml/g; Specific area is 450m
2/ g, bulk density is 1.08g/ml, compression strength is 170N/cm.
This catalyst is loaded in the devulcanizer, is used for removing with the coal SO of the discharging flue gas that is fuel
2, contain 45mg/m in this discharging flue gas
3SO
2, use this catalyst to discharge flue gas desulfurization at normal temperatures and pressures, the sulfur content in the gas after the desulfurization is below 1ppm.
The renovation process of this catalyst is identical with method among the embodiment 1, and only the time of regeneration needs 1 hour.
Claims (1)
1. a desulphurization catalyst is characterized in that with the catalyst weight being benchmark, contains the component of following percentage by weight:
ZnO..................6.5% to 65%
NiO..................0.5% to 2%
CaAlO
3... ... 11% to 40%
TiO
2... ... ... 0.5% to 2%
CoO..................0.9% to 2%
MoO..................0.7% to 3%
Al
2O
3... ... ... 20% to 70%
The average pore size of this catalyst is 16.1nm, and pore volume is 0.5~1.6ml/g; Specific area is 309~501m
2/ g, bulk density is 1.08g/ml, compression strength is 〉=150N/cm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2004100218563A CN100363100C (en) | 2004-02-16 | 2004-02-16 | Desulfur catalyst |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2004100218563A CN100363100C (en) | 2004-02-16 | 2004-02-16 | Desulfur catalyst |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1559680A CN1559680A (en) | 2005-01-05 |
CN100363100C true CN100363100C (en) | 2008-01-23 |
Family
ID=34440875
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB2004100218563A Expired - Fee Related CN100363100C (en) | 2004-02-16 | 2004-02-16 | Desulfur catalyst |
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Country | Link |
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CN (1) | CN100363100C (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102949933B (en) * | 2011-08-23 | 2016-03-09 | 上海漕泾热电有限责任公司 | The denitration device of heat supply coal-burning boiler |
CN103769044B (en) * | 2012-10-23 | 2016-03-02 | 中国石油化工股份有限公司 | A kind of gas sweetening adsorbent and its preparation method and application |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1048175A (en) * | 1990-07-25 | 1991-01-02 | 湖北省化学研究所 | Be used for the solid sulfurizing agent and the preparation of cobalt-molybdenum series catalyst vulcanization |
CN1272398A (en) * | 1999-04-30 | 2000-11-08 | 北京海顺德钛催化剂有限公司 | Hydrodesulphurization method of gas containing hydrocarbon, and catalyst and its application |
CN1358825A (en) * | 2002-01-08 | 2002-07-17 | 中国石化集团南京化学工业有限公司催化剂厂 | Reformed raw oil fine desulfurizer and its preparation |
-
2004
- 2004-02-16 CN CNB2004100218563A patent/CN100363100C/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1048175A (en) * | 1990-07-25 | 1991-01-02 | 湖北省化学研究所 | Be used for the solid sulfurizing agent and the preparation of cobalt-molybdenum series catalyst vulcanization |
CN1272398A (en) * | 1999-04-30 | 2000-11-08 | 北京海顺德钛催化剂有限公司 | Hydrodesulphurization method of gas containing hydrocarbon, and catalyst and its application |
CN1358825A (en) * | 2002-01-08 | 2002-07-17 | 中国石化集团南京化学工业有限公司催化剂厂 | Reformed raw oil fine desulfurizer and its preparation |
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CN1559680A (en) | 2005-01-05 |
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Effective date of registration: 20180827 Address after: 646000 No. 12-18 construction street, Naxi District, Luzhou, Sichuan Patentee after: Sichuan Wu Shi Shi Environmental Protection Technology Co., Ltd. Address before: 646300 13 unit 2, 3 building, Luzhou, Naxi District, Sichuan Patentee before: Yang Dianming |
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Granted publication date: 20080123 Termination date: 20200216 |