CN1282778A - Process for preparing hydrogen sulfide remover for liquid-state hydrocarbon and process for regenerating it - Google Patents
Process for preparing hydrogen sulfide remover for liquid-state hydrocarbon and process for regenerating it Download PDFInfo
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- CN1282778A CN1282778A CN 00121439 CN00121439A CN1282778A CN 1282778 A CN1282778 A CN 1282778A CN 00121439 CN00121439 CN 00121439 CN 00121439 A CN00121439 A CN 00121439A CN 1282778 A CN1282778 A CN 1282778A
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- hydrogen sulfide
- liquid hydrocarbon
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- sulfide remover
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Abstract
A hydrogen sulfide remover for liquid-state hydrocarbon is prepared through immersing activated carbon in soluble metal salt solution, reaction of the activated carbon adsorbed metal salt on alkali solution for adsorption, water washing until it becomes neutral, and drying. The content for metal in said remover is high than 15%. Its advantages are low use temp., and not causing polymerization of active unsaturated hydrocarbon.
Description
The present invention relates to a kind of preparation method of hydrogen sulfide remover and go up method again, this removes agent can remove hydrogen sulfide in the unsaturated liquid hydrocarbon, and avoids the unsaturated hydrocarbons polymerization.
In the liquid hydrocarbons such as liquefied gas, the petroleum naphtha that contains unsaturated hydrocarbons, gasoline, often contain a certain amount of hydrogen sulfide, hydrogen sulfide not only has toxicity, and also can produce corrosion to equipment, therefore it need be removed.
As the removal methods of hydrogen sulfide in the liquid state, have several, as utilizing sodium hydroxide solution in the gasoline pre-refining technology with the hydrogen sulfide stripping in the gasoline (Hou Xianglin chief editor, Chinese oil Refining Technologies, 82 pages, Sinopec press).This method operation is fairly simple, but this method is produced main pollution big (produce the catalytic cracking unit of 600,000 tons of FCC gasoline per year, the amount of the waste lye that pre-refining produced is about 1000 tons/a).
With cupric oxide or zinc oxide as main depriving hydrogen sulphide component, metal oxide with II B, III B, III A family is to be total to the depriving hydrogen sulphide component, the oxygen of preparation removes agent than copper system and Zinc oxide can be used for removing of liquid hydrocarbon hydrogen sulfide, announced with the cupric oxide to be the activated adsorption component as US 4224191, with the aluminum oxide is the agent that removes of preparing carriers, and this removes agent and the hydrogen sulfide in the liquid hydrocarbon can be removed fully about 82 ℃.US5177050 has announced with zinc oxide to be the adsorption activity component, is the hydrogen sulfide remover of carrier with the phosphide of aluminium, the hydrogen sulfide in the liquid hydrocarbon can be removed fully under being higher than 150 ℃ temperature.Because Zinc oxide and cupric oxide system remove the agent use temperature than higher, if contain active unsaturated component in the hydrocarbon, polymerization can take place at high temperature unsaturated component.
In addition, W09524962 has announced a kind of hydrogen sulfide stripping method of hydrocarbon, this method be with the ventilation breather composite particles as hydrogen sulfide remover, the hydrogen sulfide in can the liquid towards degree removes; It is lower that this removes the agent use temperature, relatively good to the removal effect of hydrogen sulfide, but the ventilation breather that this method adopted is a powdery, is difficult in the industrial operation realize.
The object of the present invention is to provide a kind of use temperature low, can not cause the preparation method and the renovation process of active unsaturated hydrocarbons polymeric hydrogen sulfide remover.
The agent that removes involved in the present invention is to be carrier with the activated carbon, hydrogen sulfide remover by precipitator method preparations (Precipitation), this removes agent and the hydrogen sulfide in the liquid hydrocarbon can be removed fully at normal temperatures, can not cause the polymerization of active unsaturated component in the liquid hydrocarbon.
Above-mentioned hydrogen sulfide remover prepares as follows:
Get and a certain amount ofly have the gac of certain particle size in metal salt solution, the volume ratio of gac and metal salt solution was less than 1: 2, metal salt solution can be the soluble copper salts solution, I B such as soluble Zn salts solution, II B, III A family soluble metal salts solution or its mixing solutions, stir under the room temperature and leach metal salt solution (stirring can be adopted any whipping appts) after 2～3 hours, add excessive 5%～100% the alkali lye that draws, alkali lye can be sodium carbonate solution, sodium hydrogen carbonate solution, solution of potassium carbonate, a kind of or its mixing solutions in the potassium bicarbonate solution, restir 2～3 hours, filter, be washed with distilled water to filtrate and be neutral, drying is 2～6 hours about 100 ℃.
Dried product is repeated to do twice as stated above, can obtain hydrogen sulfide remover, this removes, and the content of metal is greater than 15% in the agent, is preferably in more than 20%.
Zhi Bei hydrogen sulfide remover because the activated carbon that is adopted is the gac with high-specific surface area and flourishing pore structure, adopts the precipitator method during preparation as stated above; The metal-salt that generates distributes more even on activated carbon surface, therefore prepared as stated above hydrogen sulfide remover has reasonable hydrogen sulfide stripping performance, and this hydrogen sulfide remover can repeatedly be regenerated after adsorption of hydrogen sulfide reaches capacity, hydrogen sulfide remover after the regeneration still has certain hydrogen sulfide stripping performance, renovation process is as follows: get the hydrogen sulfide remover that adsorption of hydrogen sulfide reaches capacity and boiled in boiling water 20～30 minutes, remove liquid hydrocarbon adsorbed in the hydrogen sulfide remover, washing, filter, dry back (100～140 ℃ of drying temperatures, 4～6 hours time) load again as stated above can obtain the regenerated hydrogen sulfide remover.Hydrogen sulfide stripping method of the present invention, be to contain in the liquid hydrocarbon of hydrogen sulfide with respect to hydrogen sulfide content equivalent in the liquid hydrocarbon or excessive hydrogen sulfide remover adding, utilize any blending means, 0～80 ℃ of temperature of reaction, reaction is 2 hours under preferred 20～60 ℃ of conditions, the hydrogen sulfide in the gasoline can be removed fully.Liquid hydrocarbon feeds is the FCC catalytically cracked gasoline, in the gasoline unsaturated hydrocarbons content 40～60%, liquid hydrocarbon
Raw material also can be liquefied gas, contains petroleum naphtha of a large amount of unsaturated hydrocarbons or the like.
Embodiment 1
The copper-bath of getting 30 ml concns and be 1.2mol/L is in 50 milliliters Erlenmeyer flask, add the 10g granularity at 6～16 purpose apricot shell gacs, vibration absorption 4 hours, filter, get the gac that leaches in the 50ml Erlenmeyer flask, add the isocyatic sodium carbonate solution of 30ml, vibrated 4 hours, filter, be neutral with a large amount of distilled water washs to filtrate, then when 6 of 100 ℃ of dryings, to twice of the load again again of dried activated carbon, can obtain the copper salt kind hydrogen sulfide remover, this removes the CUCO that consists of of agent
3Cu (OH)
2, the content that removes metal in the agent is 23%.
Embodiment 2
Get 5g by the prepared hydrogen sulfide remover of the method for implementing 1 in the 1000ml Erlenmeyer flask, adding the 1000ml hydrogen sulfide content is the FCC gasoline (unsaturated hydrocarbons content is 40～60% in the gasoline) of 150ppm, reaction is after 2 hours down for 20 ℃ of agitation conditions, and detection exists less than hydrogen sulfide in the gasoline.
Embodiment 3
Get 5g by the prepared hydrogen sulfide remover of the method for embodiment 1 in the 1000ml Erlenmeyer flask, adding the 1000ml hydrogen sulfide content is the FCC gasoline (unsaturated hydrocarbons content is 40～60% in the gasoline) of 150ppm, reaction is after 2 hours down for 40 ℃ of agitation conditions, and detection exists less than hydrogen sulfide in the gasoline.
Embodiment 4
Get 5g by the prepared hydrogen sulfide remover of the method for implementing 1 in the 1000ml Erlenmeyer flask, adding the 1000ml hydrogen sulfide content is the FCC gasoline (unsaturated hydrocarbons content is 40～60% in the gasoline) of 150ppm, reaction is after 2 hours down for 60 ℃ of agitation conditions, and detection exists less than hydrogen sulfide in the gasoline.
Embodiment 5
Get 5g by the prepared hydrogen sulfide remover of the method for embodiment 1 in the 1000ml Erlenmeyer flask, adding the 1000ml hydrogen sulfide content is the FCC gasoline (unsaturated hydrocarbons content is 40～60% in the gasoline) of 150ppm, 40 ℃ were fully reacted 2 hours down, the gasoline that repeats to add oil-containing hydrogen sulfide after the filtration reacts, when treating that the sulfur in gasoline hydrogen concentration does not change, it is saturated to think that hydrogen sulfide remover reaches absorption.
The hydrogen sulfide remover that adsorption of hydrogen sulfide reaches capacity is regenerated; Renovation process is as follows: put the hydrogen sulfide remover of absorption after reaching capacity in the beaker of 100ml, add 80ml distilled water, boil 20min, in 120 ℃ of dry 4h down, the method for pressing embodiment 1 then load again gets final product behind the filtration washing.
Hydrogen sulfide remover after the regeneration is carried out saturated adsorption test by described method, the postcure hydrogen that obtains regenerating takes off the saturated sulfur capacity of herding except that agent, using the same method to obtain regenerating 2 times, 3 times, 4 times the saturated sulfur capacity of hydrogen sulfide remover, and the result is as table.
| Regeneration times | Saturated sulfur capacity g sulphur/g hydrogen sulfide remover |
| ????0 | ????0．115 |
| ????1 | ????0．047 |
| ????2 | ????0．041 |
| ????3 | ????0．029 |
| ????4 | ????0．020 |
| Accumulative total | ????0．252 |
Embodiment 6
Get 5g by the hydrogen sulfide remover of the method for embodiment 5 regeneration 1 time in the Erlenmeyer flask of 1000ml, adding the 1000ml hydrogen sulfide content is the gasoline (unsaturated hydrocarbons content is 40～60% in the gasoline) of 150ppm, 40 ℃ reaction is after 2 hours down, and detection is less than the existence of hydrogen sulfide in the gasoline.
Embodiment 7
Get 5g by the hydrogen sulfide remover of the method for embodiment 5 regeneration 2 times in the Erlenmeyer flask of 1000ml, adding the 1000ml hydrogen sulfide content is the gasoline (unsaturated hydrocarbons content is 40～60% in the gasoline) of 150ppm, 40 ℃ reaction is after 2 hours down, and detection is less than the existence of hydrogen sulfide in the gasoline.
Embodiment 8
Get 5g by the hydrogen sulfide remover of the method for embodiment 5 regeneration 3 times in the Erlenmeyer flask of 1000ml, adding the 1000ml hydrogen sulfide content is the gasoline (unsaturated hydrocarbons content is 40～60% in the gasoline) of 150ppm, 40 ℃ reaction is after 2 hours down, and detection is less than the existence of hydrogen sulfide in the gasoline.
Embodiment 9
Get 5g by the hydrogen sulfide remover of the method for embodiment 5 regeneration 4 times in the Erlenmeyer flask of 1000ml, adding the 1000ml hydrogen sulfide content is the gasoline (unsaturated hydrocarbons content is 40～60% in the gasoline) of 150ppm, 40 ℃ reaction is after 2 hours down, and detection is less than the existence of hydrogen sulfide in the gasoline.
Claims (9)
1. the preparation method of hydrogen sulfide remover in the liquid hydrocarbon.It is characterized in that: with I B, II B, III A family soluble metal salt solution impregnation gac, the volume ratio of gac and metal salt solution was less than 1: 2; After gac fully adsorbs metal salt solution, be adsorbed with the activated carbon of metal-salt again with excessive 5%～100% alkali lye, it is fully reacted, be washed with water to neutrality then, drying is 4～6 hours under 100 ℃～120 ℃ temperature,, can obtain the gac hydrogen sulfide remover of metal-containing salt, the content of metal in removing agent is greater than 15%.
2. the preparation method of hydrogen sulfide remover in a kind of liquid hydrocarbon according to claim 1. it is characterized in that: the soluble metal salts solution that is adopted is meant copper-bath, copper nitrate solution, venus crystals solution or its mixing solutions.
3. the preparation method of hydrogen sulfide remover in a kind of liquid hydrocarbon according to claim 1 is characterized in that: the alkali lye that is adopted is meant carbonate solution, sodium carbonate solution, sodium hydrogen carbonate solution, sal volatile, ammonium bicarbonate soln, potassium bicarbonate solution or its mixing solutions of solubility.
4. the preparation method of hydrogen sulfide remover in a kind of liquid hydrocarbon according to claim 1. it is characterized in that: the activated carbon grain particle size that is adopted is at 6～16 purpose apricot shell gac or cocoanut active charcoals.
5. the preparation method of hydrogen sulfide remover in a kind of liquid hydrocarbon according to claim 1. it is characterized in that: will contain in the liquid hydrocarbon of hydrogen sulfide with respect to hydrogen sulfide content equivalent in the liquid hydrocarbon or excessive hydrogen sulfide remover adding, under 0～80 ℃ temperature of reaction, utilize any mixing device to react 1～3 hour, can remove the hydrogen sulfide in the liquid hydrocarbon fully.
6. the preparation method of hydrogen sulfide remover in a kind of liquid hydrocarbon according to claim 5. it is characterized in that: hydrogen sulfide remover removes that the temperature of reaction of hydrogen sulfide is 20～60 ℃ in the liquid hydrocarbon.
7. the preparation method of hydrogen sulfide remover in a kind of liquid hydrocarbon according to claim 5. it is characterized in that: can utilize any mixing device to react 2 hours.
8. according to the preparation method of hydrogen sulfide remover in claim 1 and the 5 described a kind of liquid hydrocarbons. it is characterized in that: hydrogen sulfide remover removes in the liquid hydrocarbon that liquid hydrocarbon feeds is the FCC catalytically cracked gasoline in the hydrogen sulfide, contains petroleum naphtha, the liquefied gas of unsaturated hydrocarbons.
9. the preparation method of hydrogen sulfide remover in a kind of liquid hydrocarbon according to claim 1. it is characterized in that: put the hydrogen sulfide remover of absorption after reaching capacity in a container, adding distilled water boiled 20～30 minutes, filter the back in 120 ℃ dry 2～6 hours down, then by the method load again of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00121439 CN1132900C (en) | 2000-07-21 | 2000-07-21 | Process for preparing hydrogen sulfide remover for liquid-state hydrocarbon and process for regenerating it |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00121439 CN1132900C (en) | 2000-07-21 | 2000-07-21 | Process for preparing hydrogen sulfide remover for liquid-state hydrocarbon and process for regenerating it |
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|---|---|
| CN1282778A true CN1282778A (en) | 2001-02-07 |
| CN1132900C CN1132900C (en) | 2003-12-31 |
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| CN 00121439 Expired - Fee Related CN1132900C (en) | 2000-07-21 | 2000-07-21 | Process for preparing hydrogen sulfide remover for liquid-state hydrocarbon and process for regenerating it |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329485C (en) * | 2002-04-26 | 2007-08-01 | 英国石油国际有限公司 | Method and apparatus for improving the oxidative thermal stability of distillate fuel |
| CN100341617C (en) * | 2002-04-30 | 2007-10-10 | 中国人民解放军63971部队 | Chromium-free normal-temperature efficient purifying adsorbent for removing H2S or SO2 and preparing method thereof |
| CN101049550B (en) * | 2006-04-04 | 2010-04-07 | 中国石油大学(华东) | Solid base adsorption agent for treating processes of deacidification in use for liquid matter in esters of organic acid |
| CN101857807A (en) * | 2009-04-08 | 2010-10-13 | 中国石油天然气股份有限公司 | Method for refining liquid hydrocarbon |
| CN102091526A (en) * | 2009-12-09 | 2011-06-15 | 北京三聚环保新材料股份有限公司 | Normal-temperature desulfurizer and preparation method thereof |
| CN103145534A (en) * | 2013-03-26 | 2013-06-12 | 南开大学 | Method for deeply removing sulfides in gasoline additive, namely methyl tert-butyl ether |
| US10301524B2 (en) | 2017-10-04 | 2019-05-28 | King Fahd University Of Petroleum And Minerals | Method of drilling a substerranean geological formation with a drilling fluid composition comprising copper nitrate |
-
2000
- 2000-07-21 CN CN 00121439 patent/CN1132900C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329485C (en) * | 2002-04-26 | 2007-08-01 | 英国石油国际有限公司 | Method and apparatus for improving the oxidative thermal stability of distillate fuel |
| CN100341617C (en) * | 2002-04-30 | 2007-10-10 | 中国人民解放军63971部队 | Chromium-free normal-temperature efficient purifying adsorbent for removing H2S or SO2 and preparing method thereof |
| CN101049550B (en) * | 2006-04-04 | 2010-04-07 | 中国石油大学(华东) | Solid base adsorption agent for treating processes of deacidification in use for liquid matter in esters of organic acid |
| CN101857807A (en) * | 2009-04-08 | 2010-10-13 | 中国石油天然气股份有限公司 | Method for refining liquid hydrocarbon |
| CN102091526A (en) * | 2009-12-09 | 2011-06-15 | 北京三聚环保新材料股份有限公司 | Normal-temperature desulfurizer and preparation method thereof |
| CN102091526B (en) * | 2009-12-09 | 2014-05-28 | 北京三聚环保新材料股份有限公司 | Normal-temperature desulfurizer and preparation method thereof |
| CN103145534A (en) * | 2013-03-26 | 2013-06-12 | 南开大学 | Method for deeply removing sulfides in gasoline additive, namely methyl tert-butyl ether |
| US10301524B2 (en) | 2017-10-04 | 2019-05-28 | King Fahd University Of Petroleum And Minerals | Method of drilling a substerranean geological formation with a drilling fluid composition comprising copper nitrate |
| US10479919B2 (en) * | 2017-10-04 | 2019-11-19 | King Fahd University Of Petroleum And Minerals | Method for drilling a hydrogen sulfide-containing formation |
| US10501676B2 (en) * | 2017-10-04 | 2019-12-10 | King Fadh University Of Petroleum And Minerals | Method for drilling a wellbore with a weighted hydrogen sulfide scavenger fluid |
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| Publication number | Publication date |
|---|---|
| CN1132900C (en) | 2003-12-31 |
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Owner name: PETROLDUM UNIV. (BEIJING); CHINA PETROLEUM & CHEMI Free format text: FORMER NAME OR ADDRESS: PETROLDUM UNIV. (BEIJING); WUHAN PETRO-CHEMICAL PLANT, CHINA PETRO-CHEMICALCORP. |
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Address after: Beijing Changping Reservoir Road zip code: 102200 Co-patentee after: Sinopec Corp. Patentee after: Petroleum University (Beijing) Address before: Beijing Changping Reservoir Road zip code: 102200 Co-patentee before: Wuhan Petro-Chemical Plant of China Petro-Chemical Corp. Patentee before: Petroleum University (Beijing) |
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Granted publication date: 20031231 Termination date: 20120721 |