CN100494323C - Technology for normal temperature precision desulfation by liquid light hydrocarbon - Google Patents
Technology for normal temperature precision desulfation by liquid light hydrocarbon Download PDFInfo
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- CN100494323C CN100494323C CNB2006100181144A CN200610018114A CN100494323C CN 100494323 C CN100494323 C CN 100494323C CN B2006100181144 A CNB2006100181144 A CN B2006100181144A CN 200610018114 A CN200610018114 A CN 200610018114A CN 100494323 C CN100494323 C CN 100494323C
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- light hydrocarbon
- liquid light
- desulfurizing agent
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Abstract
The invention relates to liquid state light hydrocarbon normal temperature fine desulfurizing technology. It is aimed at H<SUB>2</SUB>S, mercaptan, and thiophene organic sulfide in putrescence industry liquid state light hydrocarbon. It uses DS-1 and HB2 fine desulfurizer to remove H<SUB>2</SUB>S to less than 0.1ppm, RSH to 5ppm under the following condition: temperature is normal temperature or -5-90 centigrade degree; pressure is 0.1-4 megapascal; liquid airspeed is 0.5-10m <SUP>3</SUP> liquid state light hydrocarbon/m <SUP>3</SUP> desulfurizer per hour. The copper sheet corrosion is not more than 1 grade, and no obvious odor. Product whole sulfur does not exceed national standard or trade standard to satisfy technology application demand. The technology has the features of normal operation, large handling capacity, no aldali waste, need not oxygen and activator, low energy consumption, simple, and convenient operation.
Description
Technical field
The present invention relates to from liquid light hydrocarbon the normal temperature essence and take off H
2The method of inorganic and organic sulfide such as S, RSH, thiophene.
Background technology
Oil more and more is subjected to the attention of countries in the world as the main energy in the world.The consumption of the various products relevant with oil also constantly rises, and owing to the further understanding of people to healthy and environmental protection, the quality of people's pair various products relevant with oil has proposed requirements at the higher level.
Fine, Chemical Plant, Daqing Oil Field is to be the producer of the multiple derived product of raw material production with the liquid light hydrocarbon.Its raw material is for containing C
10.01%, C
20.22%, C
35.98%, C
421.93%, C
524.7%, C
620.71%, C
713.78%, C
87.36%, C
93.70%, C
101.61%, H
2The liquid light hydrocarbon of S 9ppm, RSH 60ppm, thiophene 80ppm, RSR 10ppm, COS 1ppm.Sulfide in the liquid light hydrocarbon causes equipment and corrosive pipeline, distributes unpleasant stink, and contaminate environment influences HUMAN HEALTH, and its product total sulfur surpasses country or industry standard, and copper corrosion is defective.
Existing liquid light hydrocarbon sulfur method is generally the MEROX catalytic oxidation of American UOP company exploitation or the sulfur method of same principle, its main deficiency is: (1) existing sulfur method need use a large amount of alkali lye, cause producing a large amount of salkali waste, salkali waste handles that not only expense is very high, and has polluted environment; (2) operation of band alkali causes inevitably carrying alkali lye in the oil product secretly, has influenced oil quality, has increased the weight of the corrosion to oil storage equipment simultaneously; (3) for improving desulfuration efficiency, add activator in the oil product of being everlasting, this has potential hidden danger to oil quality; (4) existing sulfur method needs the oxygenation operation, also will realize oil product and separating of alkali lye and recycling of alkali lye, causes the investment of equipment big, complex process, process cost height.
Summary of the invention
The objective of the invention is deficiency, provide a kind of liquid light hydrocarbon constant temperature fine desulfurizing technology, H after the smart desulfurization at existing sulfur method
2S content is less than 0.1ppm, and RSH is less than 5ppm, and copper corrosion is not more than 1 grade, and does not have obvious stink, and the product total sulfur is no more than national standard or industry standard.
This liquid light hydrocarbon constant temperature fine desulfurizing technology is to contain C
10.01%, C
20.22%, C
35.98%, C
421.93%, C
524.7%, C
620.71%, C
713.78%, C
87.36%, C
93.70%, C
101.61%, H
2The liquid light hydrocarbon of S 9ppm, RSH60ppm, thiophene 80ppm, RSR 10ppm, COS 1ppm goes out the reactor 1 and 2 through interior dress DS-1 desulfurizing agent on advancing down, remove H
2S, make it less than 0.1ppm, go out reactor 3 and 4 on advancing down then through interior dress HB2 desulfurizing agent, RSH in a liquid light hydrocarbon part is absorbed, another part is converted into corresponding disulphide, remove part RSR, COS and thiophene simultaneously, make outlet RSH content less than 5ppm, total sulfur is less than 130ppm, and copper corrosion is not more than 1 grade, and does not have obvious stink, the product total sulfur is no more than national standard or industry standard, its service temperature is-5～90 ℃, and pressure is 0.1～4 MPa, and liquid air speed is 0.5～10 meter
3Liquid light hydrocarbon/rice
3Sweetening agent hour,
Described DS-1 desulfurizing agent has following feature:
1, outward appearance: yellowish or tawny strip,
2, the chemical composition weight percent is: Fe
2O
320%～50%, ZnO 0.1%～3%, Cr
2O
30.1%～1%, MgO 0.1%～20%, Si O
25.0%～30%, CaO 5%～30%, and each component sum equals 100%,
3, granularity: 3～5 millimeters of diameters, long 3～15 millimeters,
4, intensity: more than or equal to 25 newton/centimetre,
5, specific surface area: 50～100 meters
2/ milliliter,
6, bulk density: 0.7 ± 0.1 grams per milliliter,
7, H
2S Sulfur capacity: more than or equal to 15%;
Its desulfurization principle is:
MO+H
2S＝＝MS+H
2O
MO+COS＝＝MS+CO
2
M: represent atoms metal
Described HB2 desulfurizing agent has following feature:
1, outward appearance: green spherical,
2, the chemical composition weight percent is: Al
2O
360%～95%, ZnO 0.1%～10%, MnO 0.1%～10%, CuO 1%～20%, MoO 0.1%～10%, NiO 0.1%～1%, each component sum equals 100%,
3, granularity: 2～3 millimeters of diameters,
4, intensity: more than or equal to 20 newton/,
5, specific surface area: more than or equal to 100 meters
2/ milliliter,
6, bulk density: 0.8 ± 0.1 grams per milliliter,
7, RHS Sulfur capacity: more than or equal to 15%.
Its desulfurization principle is:
RSH→RSM
RSH → RSSR M: represent atoms metal.
The present invention compares with existing sulfur removal technology, has following characteristics:
1, alkali-free operation, this constant temperature fine desulfurizing technology does not need alkali, and the pollution of salkali waste to environment thoroughly eliminated in alkali-free operation fully;
2, do not use activator, this constant temperature fine desulfurizing technology does not need activator, has eliminated the potential impact of activator to oil product;
3, oxygen free operation, this constant temperature fine desulfurizing technology do not need the participation of oxygen, have simplified flow process, have reduced facility investment;
4, the investment of this constant temperature fine desulfurizing technology is little, and technology is simple, and process cost is low.
Description of drawings
The skeleton diagram of Fig. 1 technical process of the present invention.
Among the figure, 1 and 2 is the reactor of in-built DS-desulfurizing agent, and 3 and 4 is the reactor of in-built HB2 desulfurizing agent. Contain C1 0.01％、C
2 0.22％、C
3 5.98％、C
4 21.93％、C
5 24.7％、C
6 20.71％、C
7 13.78％、
C
8 7.36％、C
9 3.70％、C
10 1.61％、H
2The liquid light hydrocarbon of S 9ppm, RSH 60ppm, thiophene 80ppm, RSR 10ppm, COS 1ppm, bottom in and top out removes H through the reactor 1 and 2 of in-built DS-1 desulfurizing agent2S makes It is less than 0.1ppm, bottom in and top out is through the reactor 3 and 4 of in-built HB2 desulfurizing agent then, with in the liquid light hydrocarbon A RSH part absorbs, and another part is converted into corresponding disulphide, removes simultaneously part RSR, COS and thiophene, makes Outlet RSH content is less than 5ppm, and total sulfur is less than 130ppm, and copper corrosion is not more than 1 grade, and does not have obvious stink, product Total sulfur is no more than national standard or industry standard. Desulfurizing agent is divided into two-layer or the multilayer filling in each reactor, the bed height overall The footpath is than being 4～6, and its operating temperature is-5～90 ℃, and pressure is 0.1～4 MPa, and liquid air speed is 0.5～10 meter3Liquid light hydrocarbon/rice3Desulfurizing agent hour.
Further specify the present invention and effect below in conjunction with example.
Embodiment
Below 1～5 embodiment all use accompanying drawing 1 technical process, except that the sulphur content difference, other parameter such as desulfurizing agent model, the condition of device is identical.
Embodiment 1: H in the liquid light hydrocarbon
2S5ppm, RSH 18ppm, RSR 10ppm, COS 1ppm, RSSR 27ppm, 4 grades of import copper corrosions, use temperature is 3 ℃, and pressure is 1.8 MPas, and liquid air speed is 1 meter
3Liquid light hydrocarbon/rice
3Sweetening agent hour, H after the smart desulfurization
2S＜0.1ppm, RSH＜2ppm, copper corrosion is less than or equal to 1 grade.
Embodiment 2: H in the liquid light hydrocarbon
2S 11ppm, RSH 21ppm, RSR 5ppm, RSSR 23ppm, 4 grades of import copper corrosions, use temperature is 5 ℃, and pressure is 2.0 MPas, and liquid air speed is 2 meters
3Liquid light hydrocarbon/rice
3Sweetening agent hour, H after the smart desulfurization
2S＜0.1ppm, RSH＜2ppm, copper corrosion is less than or equal to 1 grade.
Embodiment 3: H in the liquid light hydrocarbon
2S7ppm, RSH35ppm, RSR5ppm, COS1ppm, RSSR21ppm, 4 grades of import copper corrosions, use temperature is 5 ℃, and pressure is 1.9 MPas, and liquid air speed is 1.5 meters
3Liquid light hydrocarbon/rice
3Sweetening agent hour, H after the smart desulfurization
2S＜0.1ppm, RSH＜2ppm, copper corrosion is less than or equal to 1 grade.
Embodiment 4: H in the liquid light hydrocarbon
2S 5ppm, RSH 89ppm, RSR 10ppm, COS 1ppm, RSSR 27ppm, 4 grades of import copper corrosions, use temperature is 3 ℃, and pressure is 1.8 MPas, and liquid air speed is 1.5 meters
3Liquid light hydrocarbon/rice
3Sweetening agent hour, H after the smart desulfurization
2S＜0.1ppm, RSH＜2ppm, copper corrosion is less than or equal to 1 grade.
Embodiment 5: H in the liquid light hydrocarbon
2S 18ppm, RSH 100ppm, RSR 13ppm, COS 1ppm, RSSR 45ppm, 4 grades of import copper corrosions, use temperature is 4 ℃, and pressure is 1.94 MPas, and liquid air speed is 1.5 meters
3Liquid light hydrocarbon/rice
3Sweetening agent hour, H after the smart desulfurization
2S＜0.1ppm, RSH＜2ppm, copper corrosion is less than or equal to 1 grade.
Claims (2)
1, a kind of liquid light hydrocarbon constant temperature fine desulfurizing technology, its liquid light hydrocarbon contains C
10.01%, C
20.22%, C
35.98%, C
421.93%, C
524.7%, C
620.71%, C
713.78%, C
87.36%, C
93.70%, C
101.61%, H
2S 9ppm, RSH 60ppm, thiophene 80ppm, RSR 10ppm, COS 1ppm is characterized in that: go out the reactor 1 and 2 through interior dress DS-1 desulfurizing agent on advancing under the liquid light hydrocarbon, remove H
2S makes it less than 0.1ppm, goes out the reactor 3 and 4 through interior dress HB2 desulfurizing agent on advancing down then, RSH in a liquid light hydrocarbon part is absorbed, another part is converted into corresponding disulphide, removes part RSR, COS and thiophene simultaneously, makes outlet RSH content less than 5ppm, total sulfur is less than 130ppm, copper corrosion is not more than 1 grade, and does not have obvious stink, and its service temperature is-5～90 ℃, pressure is 0.1～4 MPa, and liquid air speed is 0.5～10 meter
3Liquid light hydrocarbon/rice
3Sweetening agent hour;
Described DS-1 desulfurizing agent has following feature:
(1) the chemical composition weight percent is: Fe
2O
320%～50%, ZnO 0.1%～3%, Cr
2O
30.1%～1%, MgO 0.1%～20%, Si O
25.0%～30%, CaO 5%～30%, and each component sum equals 100%,
(2) granularity: 3～5 millimeters of diameters, long 3～15 millimeters,
(3) intensity: more than or equal to 25 newton/centimetre,
(4) specific surface area: 50～100 meters
2/ milliliter,
(5) bulk density: 0.7 ± 0.1 grams per milliliter,
(6) H
2S Sulfur capacity: more than or equal to 15%;
Described HB2 desulfurizing agent has following feature:
(1) the chemical composition weight percent is: Al
2O
360%～95%, ZnO 0.1%～10%, MnO0.1%～10%, CuO 1%～20%, MoO 0.1%～10%, NiO 0.1%～1%, each component sum equals 100%,
(2) granularity: 2～3 millimeters of diameters,
(3) intensity: more than or equal to 20 newton/,
(4) specific surface area: more than or equal to 100 meters
2/ milliliter,
(5) bulk density: 0.8 ± 0.1 grams per milliliter,
(6) RHS Sulfur capacity: more than or equal to 15%.
2, liquid light hydrocarbon constant temperature fine desulfurizing technology as claimed in claim 1, it is characterized in that: wherein employed DS-1 desulfurizing agent is loaded in 1 and 2 reactors, and parallel-series is used, and the HB2 desulfurizing agent is loaded in 3 and 4 reactors, parallel-series is used, every kind of desulfurizing agent bed aspect ratio 4～6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100181144A CN100494323C (en) | 2006-01-05 | 2006-01-05 | Technology for normal temperature precision desulfation by liquid light hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100181144A CN100494323C (en) | 2006-01-05 | 2006-01-05 | Technology for normal temperature precision desulfation by liquid light hydrocarbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1793289A CN1793289A (en) | 2006-06-28 |
| CN100494323C true CN100494323C (en) | 2009-06-03 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101954284A (en) * | 2010-09-25 | 2011-01-26 | 东华大学 | Active carbon desulfurization catalyst and preparation method thereof |
| CN103525474B (en) * | 2013-10-30 | 2014-10-08 | 西南化工研究设计院有限公司 | Ultrafine desulfurization agent and preparation method thereof |
| CN110314540A (en) * | 2019-07-19 | 2019-10-11 | 河南开祥精细化工有限公司 | A kind of low-temp methanol washes hydrogen sulphide disposal unit |
| CN111440637B (en) * | 2020-05-13 | 2022-04-22 | 武汉科林化工集团有限公司 | LPG normal temperature dry desulfurization purification process |
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2006
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Non-Patent Citations (6)
| Title |
|---|
| DS-1、DS-2精脱硫剂在涠洲岛液化气脱硫装置的工业应用. 刘国庆等.天然气化工，第30卷第4期. 2005 |
| DS-1、DS-2精脱硫剂在涠洲岛液化气脱硫装置的工业应用. 刘国庆等.天然气化工，第30卷第4期. 2005 * |
| DS-1复合氧化物精脱硫剂和HB2油品脱臭剂的特性及其工业应用. 魏华等.辽宁化工，第33卷第11期. 2004 |
| DS-1复合氧化物精脱硫剂和HB2油品脱臭剂的特性及其工业应用. 魏华等.辽宁化工，第33卷第11期. 2004 * |
| 脱臭剂在溶剂油系统上的工业应用. 童莉等.化工时刊，第19卷第8期. 2005 |
| 脱臭剂在溶剂油系统上的工业应用. 童莉等.化工时刊，第19卷第8期. 2005 * |
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