CN1040616A - Compound desulfurizing agent of iron-manganese-magnesium system and preparation thereof - Google Patents
Compound desulfurizing agent of iron-manganese-magnesium system and preparation thereof Download PDFInfo
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- CN1040616A CN1040616A CN 88105939 CN88105939A CN1040616A CN 1040616 A CN1040616 A CN 1040616A CN 88105939 CN88105939 CN 88105939 CN 88105939 A CN88105939 A CN 88105939A CN 1040616 A CN1040616 A CN 1040616A
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- iron
- sweetening agent
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Abstract
This patent provides a kind of efficient essence to take off the iron-manganese-magnesium system low temperature LS type sweetening agent of sulfide in the gases such as semi-water gas, coke(oven)gas, Sweet natural gas.Adopt semi-water gas, Sweet natural gas be the Methanol Plant, synthesis ammonia plant of raw material if use LS type sweetening agent, then can simplify existing desulfurization flow process, energy consumption is reduced.Main active component is ferrimanganic ore deposit, iron ore slag and zinc oxide (or zinc carbonate) in this sweetening agent.Add auxiliary agent, water, graphite, binding agents etc. such as magnesium oxide again, behind mixing granulation, compression moulding.
Description
This patent provides a kind of solid desulfurating agent that is used for removing multiple industrial unstripped gas sulfide such as coal gas, semi-water gas, coke(oven)gas, Sweet natural gas, is called for short LS type sweetening agent.
LS type sweetening agent has the dual-use function of hydrocracking organosulfur and absorbing hydrogen sulphide, can take off the organosulfur in the semi-water gas before the conversion to less than 0.1PPm.Working conditions is: temperature, 200～300 ℃; Pressure, 0.02～5.0MPa; Air speed, 200～1000hr
-1; Penetrate Sulfur capacity 〉=11%(weight).
Desulfurization is one of important process in the chemical engineering process.All kinds of catalyzer have been used in many technologies.Catalyzer such as wherein steam reforming, low change, methanation, synthesizing methanol, synthetic ammonia are very responsive to sulphur.For example: require in the unstripped gas sulphur content less than 0.1PPm in the synthesizing methanol, this just must use solid desulfurating agent to reach the purpose of smart desulfurization.Since nineteen eighty-two, family is that all kinds of ammonia factory of raw material uses MF-1 type sweetening agent (wherein mainly active constituent is manganese, iron) desulfurization with Sweet natural gas, oil field gas etc. surplus in the of domestic existing 30, to reach the purpose that essence is taken off, realizes satisfactory results.
Contain the 30%(volume in the semi-water gas) about carbon monoxide, and carbon monoxide easily with coal gas in hydrogen on catalyzer, react, generation methane is so can not use the cobalt-molybdenum catalyst desulfurizing.For many years, with coal or heavy oil is the synthetic ammonia of raw material and the purification process of methanol plant, there is the desulfurization long flow path, equipment is many, several cold several heat of gas, shortcomings such as heat exchange is frequent, many scholars preferably can develop a kind of sweetening agent that can smart take off organosulfur in the preceding semi-water gas of conversion, to become the technical process of the low change of string in realizing through proposing after the demonstration for many years.Its result can save once desulfurization, zinc oxide desulfurization groove and corresponding heat exchanger etc.Purification process shortens dramatically, the also corresponding reduction of energy consumption and resistance.For the ease of transforming the desulfurization flow process of old factory, the sweetening agent use temperature preferably is not more than 280 ℃.
If various sweetening agents such as general zinc oxide and ferric oxide desulfurization under less than 280 ℃ of temperature, desulphurizing activated not high, so above-mentioned sweetening agent can not be used for the preceding semiwater gas desulphurizing of conversion, though Mn oxide is having the ability of hydrocracking organosulfur preferably more than 300 ℃, it is stronger than the catalytic production of methane response capacity of Zinc oxide desulfurizer.Therefore, do not see that as yet the sweetening agent based on Mn oxide is used for semiwater gas desulphurizing both at home and abroad.
The agent of ideal semiwater gas desulphurizing should possess under lesser temps (＜250 ℃) the good ability that removes dithiocarbonic anhydride, carbonylsulfide etc. is arranged, and characteristic such as the catalytic production of methane reactive activity is low, inexpensive, intensity is good.
The described LS type of this patent sweetening agent is that to adopt a kind of virgin iron manganese ore be main raw material, and adds that the scrap iron slag, zinc oxide (or zinc carbonate) etc. of vitriol works make through dry mix.All contain 5～12%Al in virgin iron manganese ore, the scrap iron slag
2O
3And 13～20%SiO
2Auxiliary agents such as interpolation magnesium oxide can reach the premium properties of above-mentioned sweetening agent.Its weight compositing range is as follows:
Component ZnO Fe
2O
3MnO
2MgO Al
2O
3SiO
2CuO
Percentage composition 0.5～25 13～37 14～45 2～15 6～11 13～18 0～3
LS type sweetening agent system is as follows with the dry mix preparation method: virgin iron manganese ore, iron ore slag, zinc oxide were through 200～300 ℃ of dryings 3～6 hours, be crushed to granularity less than 60 orders with ball mill, add promotors such as a certain amount of MgO, CuO, 2～4%(weight) graphite and 5～9%(weight) granulation behind the adhesive solution mixing, be pressed into the cylindrical sweetening agent of φ 5 * 5～7 or φ 9 * 6 millimeters (also available other sizes) again with tabletting machine.The sweetening agent of moulding got product in 300～450 ℃ of following roastings of temperature in 15～30 hours.
The component of the LS type sweetening agent that makes with above-mentioned preparation method is exemplified below:
Component ZnO Fe
2O
3MnO
2MgO Al
2O
3SiO
2
LS-1(weight %) 0.5～3 13～22 35～45 5～15 6～11 13～18
LS-2(weight %) 0.5～3 31～37 14～18 5～15 6～11 13～18
The materialization data of several sweetening agents are listed in table 1.
Example: LS-1 type sweetening agent removes CS in the coke(oven)gas
2, COS examples of implementation as follows, with internal diameter be the stainless steel reaction pipe of 12mm as desulphurization reactor, interior filling φ 5 * 3 LS-1 type sweetening agent 10ml.Contain organosulfur 1134mgS/m in the coke(oven)gas
3Remove and contain COS 24.0mgS/m
3, thiophene 33.8mgS/m
3Outward, surplus is CS
2When pressure is 1.6MPa, air speed 500hr
-1The time, under 200,230,250 ℃ of conditions of temperature, penetrate that Sulfur capacity is respectively 7.28,10.99,13.24%(weight).Desulfurization precision reaches 0.1PPm(except that thiophene, and thiophene can not be removed).
Example: it is as follows that LS-2 type sweetening agent removes the examples of implementation of semi-water gas: used reaction unit and the same example of filling desulfurization dosage.Total organosulfur 332～864mgS/m in the semi-water gas
3Remove and contain 27.4mgS/m
3Outside the COS, surplus is CS
2At pressure 2.0MPa, air speed 500～1000hr
-1, under 250 ℃ of the temperature, penetrating Sulfur capacity is 11%(weight), desulfurization precision is 0.1PPm.
LS type sweetening agent should reduce before coming into operation.
At pressure 0.02～5.0MPa, during 280 ℃ of temperature, the carbon monoxide in the gas, carbonic acid gas generate methane hardly on LS-1 type sweetening agent, even under 300 ℃, the methane content of generation is also atomic.If sweetening agent is 250～300 ℃ of operations down, and then sweetening effectiveness is better.
Because LS type sweetening agent has better physical structure and intensity, when being used for selexol process, can obtain than the better result of MF-1 type sweetening agent.
In sum, the LS type sweetening agent that provides of this patent has organic sulfide removal (CS
2, COS) high reactivity, extremely low catalysis carbon monoxide, carbonic acid gas generate the ability of methane, high intensity, cheap advantages such as cost can be used in the sulfur removal technology of multiple industrial unstripped gass such as semi-water gas, coke(oven)gas, Sweet natural gas.
Claims (3)
1, compound desulfurizing agent of iron-manganese-magnesium system (LS type sweetening agent) is characterized in that: weight is formed: ZnO0.5～25, Fe
2O
313～37%, MnO
214～45%, MgO 2～15%, Al
2O
36～11%, SiO
213～18%, CuO 0～3% etc.
2, compound desulfurizing agent of iron-manganese-magnesium system according to claim 1 is characterized in that: main active component is from the iron ore slag and the industrial zinc oxide (or zinc carbonate) of virgin iron manganese ore, vitriol works.
3, the preparation feature by the sweetening agent of right 1,2 is: virgin iron manganese ore, iron ore slag, zinc oxide were through 200～300 ℃ of dryings 3～6 hours, be crushed to granularity less than 60 orders with ball mill, add promotors such as a certain amount of magnesium oxide, cupric oxide, 2～4%(weight) graphite and 5～9%(weight) granulation behind the adhesive solution mixing, be pressed into the garden column of φ 5 * 5-7mm or φ 9 * 6-7mm again with tabletting machine, 300～450 ℃ of following roastings of temperature 15～30 hours, promptly get this sweetening agent finished product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105939 CN1020284C (en) | 1988-08-25 | 1988-08-25 | Compound desulfurizing agent of iron-manganese-magnesium system and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105939 CN1020284C (en) | 1988-08-25 | 1988-08-25 | Compound desulfurizing agent of iron-manganese-magnesium system and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1040616A true CN1040616A (en) | 1990-03-21 |
| CN1020284C CN1020284C (en) | 1993-04-14 |
Family
ID=4834056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88105939 Expired - Fee Related CN1020284C (en) | 1988-08-25 | 1988-08-25 | Compound desulfurizing agent of iron-manganese-magnesium system and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1020284C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277206A (en) * | 2010-06-10 | 2011-12-14 | 山东科技大学 | Hydrogen desulfurization agent for coke oven gas and preparation method thereof |
| CN1638860B (en) * | 2002-03-04 | 2012-02-15 | 中国石油化工股份有限公司 | Desulfurization and novel compositions for same |
| CN102755829A (en) * | 2012-08-06 | 2012-10-31 | 北京世能中晶能源科技有限公司 | Desulfurizer and application thereof |
| CN102755828A (en) * | 2012-08-06 | 2012-10-31 | 北京世能中晶能源科技有限公司 | Desulfurizer composite and application thereof |
| CN102824844A (en) * | 2012-09-11 | 2012-12-19 | 北京世能中晶能源科技有限公司 | Desulfurization and denitrification agent, preparation method and application thereof |
| CN102836636A (en) * | 2012-09-11 | 2012-12-26 | 北京世能中晶能源科技有限公司 | Desulfurization denitration composition, preparation method and application thereof |
| CN108329954A (en) * | 2018-04-28 | 2018-07-27 | 洛阳师范学院 | A kind of multivalent state metal oxide desulfurizer and preparation method thereof |
| CN113617217A (en) * | 2021-08-25 | 2021-11-09 | 济源市鲁泰纳米材料有限公司 | Desulfurizer containing nano zinc oxide and production process thereof |
| CN116272334A (en) * | 2022-12-26 | 2023-06-23 | 杭州尚善若水环保科技有限公司 | Coupling desulfurization and denitrification medicament, preparation method and use method thereof |
-
1988
- 1988-08-25 CN CN 88105939 patent/CN1020284C/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1638860B (en) * | 2002-03-04 | 2012-02-15 | 中国石油化工股份有限公司 | Desulfurization and novel compositions for same |
| CN102277206A (en) * | 2010-06-10 | 2011-12-14 | 山东科技大学 | Hydrogen desulfurization agent for coke oven gas and preparation method thereof |
| CN102277206B (en) * | 2010-06-10 | 2013-11-13 | 山东科技大学 | Hydrogen desulfurization agent for coke oven gas and preparation method thereof |
| CN102755828B (en) * | 2012-08-06 | 2014-10-15 | 北京世能中晶能源科技有限公司 | Desulfurizer composite and application thereof |
| CN102755829A (en) * | 2012-08-06 | 2012-10-31 | 北京世能中晶能源科技有限公司 | Desulfurizer and application thereof |
| CN102755828A (en) * | 2012-08-06 | 2012-10-31 | 北京世能中晶能源科技有限公司 | Desulfurizer composite and application thereof |
| CN102755829B (en) * | 2012-08-06 | 2016-01-20 | 北京世能中晶能源科技有限公司 | A kind of desulfurizing agent and application thereof |
| CN102836636B (en) * | 2012-09-11 | 2015-01-14 | 北京世能中晶能源科技有限公司 | Desulfurization denitration composition, preparation method and application thereof |
| CN102836636A (en) * | 2012-09-11 | 2012-12-26 | 北京世能中晶能源科技有限公司 | Desulfurization denitration composition, preparation method and application thereof |
| CN102824844A (en) * | 2012-09-11 | 2012-12-19 | 北京世能中晶能源科技有限公司 | Desulfurization and denitrification agent, preparation method and application thereof |
| CN108329954A (en) * | 2018-04-28 | 2018-07-27 | 洛阳师范学院 | A kind of multivalent state metal oxide desulfurizer and preparation method thereof |
| CN108329954B (en) * | 2018-04-28 | 2021-02-02 | 洛阳师范学院 | Multi-valence metal oxide desulfurizer and preparation method thereof |
| CN113617217A (en) * | 2021-08-25 | 2021-11-09 | 济源市鲁泰纳米材料有限公司 | Desulfurizer containing nano zinc oxide and production process thereof |
| CN113617217B (en) * | 2021-08-25 | 2023-09-15 | 济源市鲁泰纳米材料有限公司 | Desulfurizing agent containing nano zinc oxide and production process thereof |
| CN116272334A (en) * | 2022-12-26 | 2023-06-23 | 杭州尚善若水环保科技有限公司 | Coupling desulfurization and denitrification medicament, preparation method and use method thereof |
| CN116272334B (en) * | 2022-12-26 | 2023-08-15 | 杭州尚善若水环保科技有限公司 | Coupling desulfurization and denitrification medicament, preparation method and use method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1020284C (en) | 1993-04-14 |
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