CN1095393C - Refined active carbon desulfurizer for eliminating mercaptan and thioether and its prepn. - Google Patents
Refined active carbon desulfurizer for eliminating mercaptan and thioether and its prepn. Download PDFInfo
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- CN1095393C CN1095393C CN 00114588 CN00114588A CN1095393C CN 1095393 C CN1095393 C CN 1095393C CN 00114588 CN00114588 CN 00114588 CN 00114588 A CN00114588 A CN 00114588A CN 1095393 C CN1095393 C CN 1095393C
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- active carbon
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Abstract
The present invention relates to a refined active carbon desulfurizer for eliminating mercaptan and thioether and a method thereof, the desulfuring agent of the present invention is composed of an oxide of Na, Cu and Si or salt and the activated carbon. In the preparation method of the present invention, water-soluble compound of raw materials is added before activated carbon molding, or is loaded on the activated carbon by division immersion or co-impregnated immersion, and the desulfuring agent of the present invention is formed by drying and activating at the temperature of-300 DEG C. The agent can remove the sulphides such as H2S, COS, CS2, thiol, thioether, thiophene, etc., and is particularly applied to removing expuisite sweetening and thioether, and removing precision is less than 0.05 ppm; compared with other allied desulfurizing agent, the desulfuring agent of the present invention has the superior sulfur volume, 0 to 100DEG C of the using temperature, and 100 to 3000h<-1> of the airspeed. The present invention can be widely used for fine desulphurization in the production technology, such as synthetic ammonia, methanol, linked alcohol, low-carbon alcohol, synthetic fuel, urban, methanation, CO2., synthesize polypropylene, etc. and can also be used for fine removing desulphurization from chemical raw material gas, such as semiwater gas, water gas, coke oven gas, natural gas, liquid gas, etc.
Description
The present invention relates to the activated carbon desulphurization agent and the preparation of smart removal of mercaptans of material gas and thioether.
The harm of sulfide is well-known.Owing to protection noble metal catalyst or adsorbent, improve the quality of products, reduce the needs of environmental pollution, the requirement that sulfide is removed precision is also more and more higher, generally wants refinement desulfurization index to reach total sulfur＜0.1ppm in recent years.Traditional desulfurizing process adopts high temperature cobalt molybdenum hydrogenation catalyst string zinc oxide, but this method needs high temperature heat source, and operating cost height, cobaltmolybdate catalyst need sulfuration, and easily produce the methanation side reaction.Chinese patent ZL96118013.7, ZL94102711.2 have developed two kinds of refined active carbon desulfurizers, and they are applicable to H
2S, COS, CS
2Essence take off, but Sulfur capacity is less when smart removal of mercaptans, thioether.
The purpose of this invention is to provide a kind of refined active carbon desulfurizer and preparation method who removes mercaptan and thioether, this desulfurizing agent desulfurization precision height removes mercaptan, the thioether capacity is big, and intensity is good, it both can with organic sulfur hydrolyst or the supporting use of other desulfurizing agent, can use separately again.
The objective of the invention is to realize that by following method this desulfurizing agent is made up of oxide or the salt of load Na, Cu, Si on absorbent charcoal carrier and the carrier, its content is counted 0.25%～1.00%SiO of carrier active carbon weight with oxide
2, 2.10%～7.85%Na
2O, 4.38%～12.30%CuO.
Active carbon can be ature of coal, wooden, shell, cocoanut active charcoal: profile is bar shaped, sphere or amorphous, rate of wear＜10%, crush strength＞30N/cm or＞20N/, specific area 〉=500～1500m
2/ g, water absorption rate 0.4～1.0mL/g.
The preparation method of this desulfurizing agent is to be nitrate or sulfate, silicate, carbonate, chloride, acylate, hydroxide such as Na with above-mentioned active carbon with the water soluble compound of described element Na, Cu, Si
2SiO
3, NaNO
3, Na
2CO
3, NaOH, Cu (AC)
2, CuCl
2, Cu (NO
3)
2, CuSO
4Before active carbon forming, add, or divide and soak or soak altogether active carbon more than 2 hours, dry down in room temperature～120 ℃ then, in 150～300 ℃ of blanket of nitrogen, activate more than 4 hours at last, maceration extract compound concentration 0.5～40g/100mL, the compound that the refined active carbon desulfurizer that makes is contained is counted 0.25%～1.00%SiO of active carbon weight with oxide
2, 2.10%～7.85%Na
2O, 4.38%～12.30%CuO.
This desulfurizing agent is at 0～100 ℃ of serviceability temperature, air speed 100～3000h
-1, pressure＜15MPa, relative humidity 10～100%, O
2Content 0～5.0% o'clock can be used for synthetic ammonia, methyl alcohol, connection alcohol, low-carbon alcohols, synthetic fuel, town gas, methanation, food-class CO
2, smart desulfurization in the production technology such as synthetic polypropylene, also can be used for the smart sulfide removal of multiple material gas such as semiwater gas, water-gas, oven gas, natural gas, liquefied gas simultaneously.This desulfurizing agent is particularly useful for smart removal of mercaptans, thioether.
The Sulfur capacity of this desulfurizing agent is measured in glass reactor, and condition is reactor inside diameter φ 29mm, and desulfurizing agent is former granularity, volume 30ml, and 30 ℃ of reaction temperatures, normal pressure, air speed is 1000h
-1, water content 10～1000ppm, O
2Content 0.5～5%, source of the gas: N
2Contain methyl mercaptan or methyl sulfide 1000-10000ppm, decontamination index: methyl mercaptan or methyl sulfide remove precision＜0.05ppm, and Sulfur capacity represents that with percetage by weight wt% sulfide detects the gas chromatograph with the band flame photometric detector, sensitivity 1 * 10
-9
Hereinafter elaborate the present invention with comparative example, embodiment.
Comparative example: the bar shaped activated carbon 100g of Φ 3-4mm was put into room temperature～120 ℃ baking oven drying more than 2 hours, and activation got non-additive No. 0 desulfurizing agent more than 4 hours in 150～300 ℃ of blanket of nitrogen again, and its desulfurization performance sees Table 1.
Embodiment 1-9
Get used active carbon 100g in the comparative example * 9 parts, put into 9 500mL flasks respectively, respectively with 1gNa
2SiO
3With 5gNa
2CO
3And 15gCu (NO
3)
2, 2gNa
2SiO
3With 5gNaOH and 15gCu (AC)
2, 0.5gNa
2SiO
3With 8gNaOH and 10gCuSO
4, 2gNa
2SiO
3With 3gNaNO
3And 10gCuCl
2, 2gNa
2SiO
3With 8gNa
2CO
3And 10gCu (AC)
2, 1gNa
2SiO
3With 5gNaOH and 15gCu (NO
3)
2, 0.5gNa
2SiO
3With 13gNa
2CO
3And 20gCu (AC)
2, 1gNa
2SiO
3With 5gNaNO
3And 25gCu (NO
3)
2, 1gNa
2SiO
3With 10gNa
2CO
3And 29gCu (NO
3)
2Be dissolved into the 100mL aqueous solution, add in the flask fill active carbon Immesion active carbon more than 2 hours, leach raffinate, room temperature is placed more than 10 hours, dry more than 2 hours in ℃ baking oven of room temperature～120, activation was numbered 1～No. 9 more than 4 hours in 150～300 ℃ of blanket of nitrogen at last, and its desulfurization performance sees Table 1.
Embodiment 10～18:
Water soluble metallic compound branch among the embodiment 1～9 is immersed on the active carbon, promptly earlier above-mentioned additive is dissolved in respectively in the 100ml water, add first kind of compound of 100g active carbon dipping then, flooded 2 hours, and leached raffinate, in room temperature～120 ℃ drying after 2 hours, flood second and third kind compound more respectively, operating procedure is the same, and activation got desulfurizing agent 10～No. 18 in 4 hours in 150～300 ℃ of blanket of nitrogen at last, and its desulfurization performance sees Table 2.
Embodiment 19～20
Get 1gNa
2SiO
3With 5gNa
2CO
3And 15gCu (AC)
2, 2gNa
2SiO
3With 5gNaOH and 15gCu (NO
3)
2After the dissolving, each adds the 100g activated carbon powder, is extruded into bar shaped or sphere after mixing thoroughly respectively,, in 150～300 ℃ of blanket of nitrogen, activate more than 4 hours at last more than 2 hours in room temperature～120 ℃ drying then, promptly get the desulfurizing agent product, number 19～No. 20, its desulfurization performance sees Table 3.
Embodiment 21～24
Get 4 parts of 0.5gNa
2SiO
3With 10gNa
2CO
3And 15gCu (NO
3)
2Be dissolved into the 100mL aqueous solution respectively, flood the 100g active carbon respectively, soak the back, then activation 4 hours in 150 ℃, 200 ℃, 250 ℃, 300 ℃ blanket of nitrogen respectively in 120 ℃ of dryings 2 hours by the method for embodiment 1～9.4 kinds of refined active carbon desulfurizers that obtain are numbered 21～No. 24, and its desulfurization performance sees Table 4.
Embodiment 25:
Certain chemical plant removes 100ppm PrSH in the natural gas, 20 ℃ of desulfurization reaction temperatures, normal pressure, air speed 467h with No. 6 desulfurizing agents of the present invention
-1, anaerobic is anhydrous in the unstripped gas.After measured, its to penetrate Sulfur capacity be 8.0%.
Table 1 soaks the Sulfur capacity of three kinds of slaine activated carbon desulphurization agents altogether
| Numbering | Additive | Concentration, g/100mL | Sulfur capacity, Wt% | |
| CH 3SH | (CH 3) 2S 2 | |||
| 0 | Do not have | 2.3 | 1.2 | |
| 1 | Na 2SiO 3 Na 2CO 3 Cu(NO 3) 2 | 1 5 15 | 6.3 | 2.4 |
| 2 | Na 2SiO 3 NaOH Cu(AC) 2 | 2 5 15 | 7.2 | 2.7 |
| 3 | Na 2SiO 3 NaOH CuSO 4 | 0.5 8 10 | 8.1 | 2.9 |
| 4 | Na 2SiO 3 NaNO 3 CuCl 2 | 2 3 10 | 5.6 | 1.6 |
| 5 | Na 2SiO 3 Na 2CO 3 Cu(AC) 2 | 2 8 10 | 6.1 | 2.2 |
| 6 | Na 2SiO 3 NaOH Cu(NO 3) 2 | 1 5 15 | 7.4 | 2.5 |
| 7 | Na 2SiO 3 Na 2CO 3 Cu(AC) 2 | 0.5 13 20 | 6.7 | 2.5 |
| 8 | Na 2SiO 3 Na 2NO 3 Cu(NO 3) 2 | 1 5 25 | 6.1 | 2.1 |
| 9 | Na 2SiO 3 Na 2CO 3 Cu(NO 3) 2 | 1 10 29 | 6.3 | 2.5 |
Table 2 minute soaks the Sulfur capacity of three kinds of slaine activated carbon desulphurization agents
| Numbering | Additive | Concentration, g/100mL | Sulfur capacity, Wt% | |
| CH 3SH | (CH 3) 2S 2 | |||
| 10 | Na 2SiO 3 Na 2CO 3 Cu(NO 3) 2 | 1 5 15 | 6.5 | 2.4 |
| 11 | Na 2SiO 3 NaOH Cu(AC) 2 | 2 5 15 | 7.0 | 2.5 |
| 12 | Na 2SiO 3 NaOH CuSO 4 | 0.5 8 10 | 7.8 | 2.8 |
| 13 | Na 2SiO 3 NaNO 3 CuCl 2 | 2 3 10 | 5.6 | 1.7 |
| 14 | Na 2SiO 3 Na 2CO 3 Cu(AC) 2 | 2 8 10 | 6.3 | 2.1 |
| 15 | Na 2SiO 3 NaOH Cu(NO 3) 2 | 1 5 15 | 7.0 | 2.3 |
| 16 | Na 2SiO 3 Na 2CO 3 Cu(AC) 2 | 0.5 13 20 | 6.5 | 2.5 |
| 17 | Na 2SiO 3 Na 2NO 3 Cu(NO 3) 2 | 1 5 25 | 6.3 | 2.2 |
| 18 | Na 2SiO 3 Na 2CO 3 Cu(NO 3) 2 | 1 10 29 | 6.3 | 2.3 |
Add the desulfurizing agent Sulfur capacity of slaine before table 3 active carbon forming
| Numbering | Additive | Concentration, g/100mL | Sulfur capacity, Wt% | |
| CH 3SH | (CH 3) 2S 2 | |||
| 19 | Na 2SiO 3 Na 2CO 3 Cu(NO 3) 2 | 1 5 15 | 6.0 | 2.2 |
| 20 | Na 2SiO 3 NaOH Cu(AC) 2 | 2 5 15 | 6.8 | 2.5 |
The Sulfur capacity of the activated carbon desulphurization agent that table 4 dipping slaine of the same race activates under different temperatures
Claims (3)
1. a refined active carbon desulfurizer that removes mercaptan and thioether is characterized in that being made up of oxide or the salt of load Na, Cu, Si on absorbent charcoal carrier and the carrier, and its content is counted 0.25%～1.00%SiO of carrier active carbon weight with oxide
2, 2.10%～7.85%Na
2O, 4.38%～12.30%CuO, active carbon are bar shaped, sphere or amorphous, rate of wear＜10%, crush strength＞30N/cm, specific surface 500～1500m
2/ g, water absorption rate 0.4～1.0mL/g.
2. the preparation method of the described refined active carbon desulfurizer of claim 1, it is characterized in that water soluble compound with described element is that nitrate or sulfate, silicate, carbonate, chloride, acylate, hydroxide add before active carbon forming, or divide and soak or soak altogether active carbon more than 2 hours, dry down in room temperature～120 ℃ then, in 150～300 ℃ of blanket of nitrogen, activate more than 4 hours maceration extract compound concentration 0.5～40g/100mL at last.
3. the preparation method of refined active carbon desulfurizer as claimed in claim 2, the water soluble compound that it is characterized in that used Na, Cu, Si is Na
2SiO
3, NaNO
3, Na
2CO
3, NaOH, Cu (AC)
2, CuCl
2, Cu (NO
3)
2, CuSO
4
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00114588 CN1095393C (en) | 2000-05-24 | 2000-05-24 | Refined active carbon desulfurizer for eliminating mercaptan and thioether and its prepn. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00114588 CN1095393C (en) | 2000-05-24 | 2000-05-24 | Refined active carbon desulfurizer for eliminating mercaptan and thioether and its prepn. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1324686A CN1324686A (en) | 2001-12-05 |
| CN1095393C true CN1095393C (en) | 2002-12-04 |
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100415344C (en) * | 2004-05-28 | 2008-09-03 | 长春东狮科贸实业有限公司 | Active carbon desulfurizing agent and application thereof |
| CN100446852C (en) * | 2006-04-07 | 2008-12-31 | 大连普瑞特化工科技有限公司 | Desulfurizer with high sulfur capacity for eliminating sulfur alcohol, sulphide and hydrogen sulfide through catalytic oxidation, and preparation |
Families Citing this family (8)
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|---|---|---|---|---|
| CN1313201C (en) * | 2004-10-29 | 2007-05-02 | 中国石油化工股份有限公司 | Supported type active carbon and its preparation method |
| CN100406113C (en) * | 2005-10-26 | 2008-07-30 | 中国石油化工股份有限公司 | Preparation method of carried active carbon |
| CN101418229B (en) * | 2008-11-14 | 2013-01-02 | 中国石油化工集团公司 | Mercaptans removal apparatus for light oil and mercaptans removal method thereof |
| CN102115685B (en) * | 2011-01-06 | 2013-10-02 | 克拉玛依金叶化工有限责任公司 | Method for finely removing hydrogen sulfide from natural gas at normal temperature |
| CN102172512A (en) * | 2011-03-22 | 2011-09-07 | 翟常忠 | Desulphurizer capable of removing smelly impurities such as thiophene, mercaptan, thioether and hydrogen sulphide by catalytic oxidation and preparation method and application of desulphurizer |
| CN104437366A (en) * | 2014-11-13 | 2015-03-25 | 安徽凤凰滤清器股份有限公司 | Uneasily-disintegrated mixed active carbon desulfurizing agent and preparation method thereof |
| CN112642396B (en) * | 2019-10-11 | 2022-05-03 | 中国石油化工股份有限公司 | Modified activated carbon and composite material as well as preparation method and application thereof |
| CN114433012B (en) * | 2020-11-06 | 2023-06-02 | 中国石油化工股份有限公司 | Forming method of molecular sieve adsorbent, molecular sieve adsorbent prepared by forming method and application of molecular sieve adsorbent |
-
2000
- 2000-05-24 CN CN 00114588 patent/CN1095393C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100415344C (en) * | 2004-05-28 | 2008-09-03 | 长春东狮科贸实业有限公司 | Active carbon desulfurizing agent and application thereof |
| CN100446852C (en) * | 2006-04-07 | 2008-12-31 | 大连普瑞特化工科技有限公司 | Desulfurizer with high sulfur capacity for eliminating sulfur alcohol, sulphide and hydrogen sulfide through catalytic oxidation, and preparation |
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| Publication number | Publication date |
|---|---|
| CN1324686A (en) | 2001-12-05 |
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Address after: No. 30 Guan Shan Road, Hongshan District, Hubei, Wuhan Patentee after: Huashuo Technology Co., Ltd. Address before: No. 30 Guan Shan Road, Hongshan District, Hubei, Wuhan Patentee before: Hubei Research Institute of Chemistry |
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