CN103232855A - Process of removing hydrogen sulfide in petroleum light hydrocarbon - Google Patents
Process of removing hydrogen sulfide in petroleum light hydrocarbon Download PDFInfo
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- CN103232855A CN103232855A CN2013101632131A CN201310163213A CN103232855A CN 103232855 A CN103232855 A CN 103232855A CN 2013101632131 A CN2013101632131 A CN 2013101632131A CN 201310163213 A CN201310163213 A CN 201310163213A CN 103232855 A CN103232855 A CN 103232855A
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- sodium hydroxide
- hydrogen sulfide
- hydroxide solution
- aqueous sodium
- lighter hydrocarbons
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Abstract
The invention discloses a process of removing hydrogen sulfide in petroleum light hydrocarbon and belongs to the refining process filed of petroleum light hydrocarbon in petroleum chemical enterprises. The process comprises the following steps of: feeding light hydrocarbon containing hydrogen sulfide and a sodium hydroxide aqueous solution to a mixer, entering a settling tank after sufficiently contacting and reacting; guiding out the refined light hydrocarbon form the top of the settling tank, guiding out alkali liquor from the bottom of the settling tank, and circulating to the mixer by pump; feeding the alkali liquor to an alkali liquor regenerating tank by adjusting a three-way valve at the outlet of sodium hydroxide alkali liquor when the concentration of the sodium hydroxide alkali liquor is consumed to a certain degree; uniformly mixing the alkali liquor with zinc oxide or zinc hydroxide in the regenerating tank in the certain proportion, filtering after the reaction, and returning the filtrate, i.e. regenerated alkali liquor to the mixer for further participating the reaction. The process not only can be used for overcoming inconvenience caused by stability of sodium sulphide, but also can be used for recycling the sodium hydroxide aqueous solution, and therefore, the process is simple and easy to implement, and capable of saving cost.
Description
Technical field
The present invention relates to a kind of process for refining to petrochemical enterprise PetroChina Company Limited. lighter hydrocarbons, relate in particular to a kind of process for refining that removes hydrogen sulfide in the oil lighter hydrocarbons.
Background technology
Contain a large amount of hydrogen sulfide in catalytic cracking liquefied gas in the petroleum chemical enterprise, the ethene cracking gas, in order to remove these hydrogen sulfide, often in the prior art adopt following technology: good certain density sodium hydroxide alkaline solution mixes will to need the material handled and configured in advance, the hydrogen sulfide that contains in its material and sodium hydroxide reaction, generate sodium sulphite and enter into alkali lye, thereby removed the hydrogen sulfide in the material, its reaction equation is: 2NaOH+H
2S=Na
2S+2H
2O.
The subject matter that exists in the above-mentioned prior art is: on the one hand, in the process that removes hydrogen sulfide with sodium hydroxide, can produce a large amount of waste soda residues, and containing a large amount of sodium sulphite in the waste soda residue, sodium sulphite is very unstable, can decompose to discharge a large amount of hydrogen sulfide contamination environment in processes such as storage, transportation; On the other hand, a large amount of unreacted sodium hydroxide can not get effective utilization, cause waste.Therefore, develop a kind of oil lighter hydrocarbons soda finishing technology, it is imperative to make alkali lye sodium hydroxide obtain recycle.
This shows that prior art awaits development and progress.
Summary of the invention
The present invention proposes a kind of technology that removes hydrogen sulfide in the oil lighter hydrocarbons in order to solve problems of the prior art, this technology had both overcome the problems such as instability that sodium sulphite produces in transportation, make the alkali lye sodium hydroxide solution obtain recycle again.
Technical scheme of the present invention comprises:
A kind of technology that removes hydrogen sulfide in the oil lighter hydrocarbons, described oil lighter hydrocarbons are ethene cracking gas or catalytic cracking liquefied gas, described technology may further comprise the steps:
The lighter hydrocarbons that a will contain hydrogen sulfide mix in mixing tank with aqueous sodium hydroxide solution, abundant contact reacts, and wherein the initial concentration of aqueous sodium hydroxide solution is 10～20%, the outlet conduit along mixing tank enters in the slurry tank then;
B will remove the later lighter hydrocarbons of hydrogen sulfide and discharge from the exit on slurry tank top, and described aqueous sodium hydroxide solution is extracted out by pump, is recycled in the mixing tank;
C treats that aqueous sodium hydroxide solution recycles 8～10h, getting aqueous sodium hydroxide solution at the exit end of slurry tank detects, when if the concentration of aqueous sodium hydroxide solution is reduced to 5～9 ﹪, regulate T-valve, the waste lye of extracting out is fed be equipped with in the regenerating tank of zinc oxide, stir fully and mix, after question response is complete, filter, obtain filtrate and filter residue, filtrate is returned in the mixing tank, repeats circulate successively above-mentioned steps a, b, c.
Waste lye among the described step c is the mixture of aqueous sodium hydroxide solution and sodium sulphite.
Preferably, described step c zinc oxide according to waste lye in the equimolar amount of sodium sulphite add.
Described step c zinc oxide available hydrogen zinc oxide replaces.
Preferably, the concentration of aqueous sodium hydroxide solution is reduced to 50% of naoh concentration among the step a among the described step c, just the concentration of sodium hydroxide solution is reduced to a half of original sodium hydroxide (naoh concentration among the step a) among the step c, regulate T-valve, the waste lye of extracting out is fed in the regenerating tank that zinc oxide is housed regenerate.
The useful technique effect that the present invention is obtained:
The present invention proposes a kind of technology that removes hydrogen sulfide in the oil lighter hydrocarbons, the lighter hydrocarbons that this technology at first will contain hydrogen sulfide mix in mixing tank with aqueous sodium hydroxide solution, abundant contact reacts, and the outlet conduit along mixing tank enters in the slurry tank then; Discharge from the exit on slurry tank top removing the later lighter hydrocarbons of hydrogen sulfide, described aqueous sodium hydroxide solution is extracted out by pump, is recycled in the mixing tank; Aqueous sodium hydroxide solution concentration in the slurry tank is detected, when treating that naoh concentration is reduced to a certain degree, regulate T-valve, the waste lye of extracting out in the slurry tank with pump arrives regenerating tank; Waste lye and zinc oxide or zinc hydroxide mixed according to certain in regenerating tank is even, after reacting completely, filter, obtain filtrate and filter residue, filtrate is aqueous sodium hydroxide solution, and filter residue is zinc sulphide, and filtrate is returned in the mixing tank.This technology is on the basis of conventional process hydrogen sulfide, utilized zinc oxide or the zinc hydroxide in the regenerating tank, zinc oxide or zinc hydroxide can with have instable sodium sulphite and react, make it be converted into the aqueous sodium hydroxide solution with utility value, this technology had both overcome many inconveniences that the unstable of sodium sulphite is brought to a certain extent, make aqueous sodium hydroxide solution obtain recycle again, this is simple for process, the saving cost.
Description of drawings
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described in further detail:
Fig. 1 is the process flow sheet of the embodiment of the invention.
Embodiment
The invention provides a kind of technology that removes hydrogen sulfide in the oil lighter hydrocarbons, clearer, clear and definite in order to make purpose of the present invention, technical scheme and advantage, below with reference to specific embodiment, the present invention is described in more detail.
Material that this invention is handled is the oil lighter hydrocarbons, and it is ethene cracking gas or catalytic cracking liquefied gas, contains the hydrogen sulfide that is dissolved in aqueous sodium hydroxide solution and other gas that is insoluble to aqueous sodium hydroxide solution in these oil lighter hydrocarbons.
As shown in Figure 1, be used for removing the equipment of oil lighter hydrocarbons hydrogen sulfide, comprise mixing tank 1, slurry tank 2 and regenerating tank 4, the exit end place of regenerating tank 4 is connected with and has filter 5, the pipeline of recycle pump 6, mixing tank 1 comprises two entrance ends and an exit end, two entrance ends are respectively import one, import two, import one is used for the feeding of oil lighter hydrocarbons (ethene cracking gas or catalytic cracking liquefied gas), import two is used for the feeding of alkali lye circulation feeding or regenerating tank 4 sodium hydroxide alkaline solutions, the exit end of mixing tank 1 feeds in the slurry tank 2 through outlet conduit, slurry tank 2 has two exit end, be respectively outlet one, outlet two, outlet one is for removing the relief outlet of the later lighter hydrocarbons of hydrogen sulfide, the exit end of outlet two is connected with pipeline, this pipeline is provided with valve, this valve place is provided with two pipelines, the aqueous sodium hydroxide solution of pipeline control by valve in can extraction slurry tank 2 wherein, another pipe connection has pump 3, the other end of pump 3 is connected with the pipeline that has T-valve 7, T-valve 7 is used for the flow direction of control aqueous sodium hydroxide solution, when normally going into operation the situation of alkali liquid regeneration described below (just except), regulate T-valve 7, make alkali lye enter mixing tank by T-valve and recycle; When alkali liquid regeneration (when just the concentration of outlet two place's aqueous sodium hydroxide solutions of slurry tank is reduced to 5～9 ﹪), regulate T-valve 7, alkali lye is fed in the regenerating tank, the exit end of regenerating tank 4 is through the import two of filter, recycle pump, feeding mixing tank.
Embodiment 1:
A kind of technology that removes hydrogen sulfide in the oil lighter hydrocarbons, this technology may further comprise the steps:
Step 1: in mixing tank, feed the aqueous sodium hydroxide solution of 10 ﹪, the oil lighter hydrocarbons are fed in the mixing tank fast and with the abundant contact reacts of aqueous sodium hydroxide solution, the outlet conduit along mixing tank enters in the slurry tank then;
Step 2: remove the later lighter hydrocarbons of hydrogen sulfide in the slurry tank then from outlet one discharge on slurry tank top, aqueous sodium hydroxide solution is extracted out, is recycled in the mixing tank by pump, when treating aqueous sodium hydroxide solution circulation 8h, getting aqueous sodium hydroxide solution at the outlet conduit valve place of slurry tank detects, when if the concentration of aqueous sodium hydroxide solution is reduced to 5 ﹪, regulate T-valve the waste lye in the slurry tank is retracted to regenerating tank, this waste lye is the mixture of sodium hydroxide and sodium sulphite;
Step 3: waste lye (mixture of sodium hydroxide and the sodium sulphite) feeding of extracting out is equipped with in the regenerating tank of zinc oxide, zinc oxide according to waste lye in the equimolar amount of sodium sulphite add, stir fully and mix, after question response is complete, filter, obtain filtrate and filter residue, filtrate is the aqueous solution of sodium hydroxide, filtrate feeds the mixing tanks from the import two of mixing tank, and then repeating step a, b, c; A, b, c; Circulation repeats successively.
Embodiment 2:
A kind of technology that removes hydrogen sulfide in the oil lighter hydrocarbons, this technology may further comprise the steps:
Step 1: in mixing tank, feed the aqueous sodium hydroxide solution of 15 ﹪, the oil lighter hydrocarbons are fed in the mixing tank fast and with the abundant contact reacts of aqueous sodium hydroxide solution, the outlet conduit along mixing tank enters in the slurry tank then;
Step 2: remove the later lighter hydrocarbons of hydrogen sulfide in the slurry tank then from outlet one discharge on slurry tank top, aqueous sodium hydroxide solution is extracted out, is recycled in the mixing tank by pump, when treating that aqueous sodium hydroxide solution recycles 9h, getting aqueous sodium hydroxide solution at the outlet conduit valve place of slurry tank detects, when if the concentration of aqueous sodium hydroxide solution is reduced to 7 ﹪, regulate T-valve the waste lye in the slurry tank is retracted to regenerating tank, this waste lye is the mixture of sodium hydroxide and sodium sulphite;
Step 3: waste lye (mixture of sodium hydroxide and the sodium sulphite) feeding of extracting out is equipped with in the regenerating tank of zinc oxide, zinc oxide according to waste lye in the equimolar amount of sodium sulphite add, stir fully and mix, after question response is complete, filter, obtain filtrate and filter residue, filtrate is the aqueous solution of sodium hydroxide, filtrate feeds the mixing tanks from the import two of mixing tank, and then repeating step a, b, c; A, b, c; Circulation repeats successively.
Embodiment 3:
A kind of technology that removes hydrogen sulfide in the oil lighter hydrocarbons, this technology may further comprise the steps:
Step 1: in mixing tank, feed the aqueous sodium hydroxide solution of 20 ﹪, the oil lighter hydrocarbons are fed in the mixing tank fast and with the abundant contact reacts of aqueous sodium hydroxide solution, the outlet conduit along mixing tank enters in the slurry tank then;
Step 2: remove the later lighter hydrocarbons of hydrogen sulfide in the slurry tank then from outlet one discharge on slurry tank top, alkali lye is extracted out by pump and is recycled in the mixing tank, when treating that aqueous sodium hydroxide solution recycles 10h, getting aqueous sodium hydroxide solution at the outlet conduit valve place of slurry tank detects, when if the concentration of aqueous sodium hydroxide solution is reduced to 9 ﹪, regulate T-valve the waste lye in the slurry tank is retracted to regenerating tank, this waste lye is the mixture of sodium hydroxide and sodium sulphite;
Step 3: waste lye (mixture of sodium hydroxide and the sodium sulphite) feeding of extracting out is equipped with in the regenerating tank of zinc oxide, zinc oxide according to waste lye in the equimolar amount of sodium sulphite add, stir fully and mix, after question response is complete, filter, obtain filtrate and filter residue, filtrate is the aqueous solution of sodium hydroxide, filtrate feeds the mixing tanks from the import two of mixing tank, and then repeating step a, b, c; A, b, c; Circulation repeats successively.
Above-mentioned three embodiment, the zinc oxide that adopts in the step 3 also available hydrogen zinc oxide replace.
Should be understood that; above-mentioned description at embodiment is comparatively detailed; can not therefore think the restriction to scope of patent protection of the present invention; those of ordinary skill in the art is under enlightenment of the present invention; do not breaking away under the scope situation that claim of the present invention protects; can also make various deformation such as replacement, simple combination, the scope of asking for protection of the present invention should be as the criterion with claims.
Claims (5)
1. technology that removes hydrogen sulfide in the oil lighter hydrocarbons, described oil lighter hydrocarbons are ethene cracking gas or catalytic cracking liquefied gas, it is characterized in that described technology may further comprise the steps:
The lighter hydrocarbons that a contains hydrogen sulfide mix in mixing tank with aqueous sodium hydroxide solution, abundant contact reacts, and wherein the initial concentration of aqueous sodium hydroxide solution is 10～20%, the outlet conduit along mixing tank enters in the slurry tank then;
After b step a finishes, discharge from the exit on slurry tank top removing the later lighter hydrocarbons of hydrogen sulfide, described aqueous sodium hydroxide solution is extracted out by pump, is recycled in the mixing tank;
C treats that aqueous sodium hydroxide solution recycles 8～10h, getting aqueous sodium hydroxide solution at the exit end of slurry tank detects, when if the concentration of aqueous sodium hydroxide solution is reduced to 5～9 ﹪, regulate T-valve, the waste lye of extracting out is fed be equipped with in the regenerating tank of zinc oxide, stir fully and mix, after question response is complete, filter, obtain filtrate and filter residue, filtrate is returned in the mixing tank, repeats circulate successively above-mentioned steps a, b, c.
2. a kind of technology that removes hydrogen sulfide in the oil lighter hydrocarbons according to claim 1, it is characterized in that: the waste lye among the described step c is the mixture of aqueous sodium hydroxide solution and sodium sulphite.
3. a kind of technology that removes hydrogen sulfide in the oil lighter hydrocarbons according to claim 2 is characterized in that: described step c zinc oxide according to waste lye in the equimolar amount of sodium sulphite add.
4. a kind of technology that removes hydrogen sulfide in the oil lighter hydrocarbons according to claim 3 is characterized in that: described step c zinc oxide available hydrogen zinc oxide replacement.
5. according to claim 3 or 4 described a kind of technologies that remove hydrogen sulfide in the oil lighter hydrocarbons, it is characterized in that: the concentration of aqueous sodium hydroxide solution is reduced to 50% of naoh concentration among the step a among the described step c.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103805225A (en) * | 2013-10-18 | 2014-05-21 | 中国石油化工股份有限公司 | Method for degassing liquefied petroleum gas waste alkaline residues |
| CN113908683A (en) * | 2021-12-14 | 2022-01-11 | 东营联合石化有限责任公司 | Liquefied petroleum gas desulphurization device |
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| US20040175307A1 (en) * | 2001-12-20 | 2004-09-09 | Luigi Laricchia | Apparatus and process for extracting sulfur compounds from a hydrocarbon stream |
| CN101319150A (en) * | 2007-06-07 | 2008-12-10 | 中国石油化工股份有限公司 | Hot-soda washing desulfurization method |
| CN102757809A (en) * | 2012-08-03 | 2012-10-31 | 宁波中一石化科技有限公司 | Mercaptan removal and lye regeneration device and method for gasoline light fractions |
| CN102815815A (en) * | 2011-06-10 | 2012-12-12 | 中国石油天然气股份有限公司 | Method for processing acid gas alkali-wash waste liquor |
-
2013
- 2013-05-07 CN CN2013101632131A patent/CN103232855A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040175307A1 (en) * | 2001-12-20 | 2004-09-09 | Luigi Laricchia | Apparatus and process for extracting sulfur compounds from a hydrocarbon stream |
| CN101319150A (en) * | 2007-06-07 | 2008-12-10 | 中国石油化工股份有限公司 | Hot-soda washing desulfurization method |
| CN102815815A (en) * | 2011-06-10 | 2012-12-12 | 中国石油天然气股份有限公司 | Method for processing acid gas alkali-wash waste liquor |
| CN102757809A (en) * | 2012-08-03 | 2012-10-31 | 宁波中一石化科技有限公司 | Mercaptan removal and lye regeneration device and method for gasoline light fractions |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103805225A (en) * | 2013-10-18 | 2014-05-21 | 中国石油化工股份有限公司 | Method for degassing liquefied petroleum gas waste alkaline residues |
| CN103805225B (en) * | 2013-10-18 | 2016-08-24 | 中国石油化工股份有限公司青岛安全工程研究院 | Liquefied petroleum gas waste soda residue degassing method |
| CN113908683A (en) * | 2021-12-14 | 2022-01-11 | 东营联合石化有限责任公司 | Liquefied petroleum gas desulphurization device |
| CN113908683B (en) * | 2021-12-14 | 2022-03-11 | 东营联合石化有限责任公司 | Liquefied petroleum gas desulphurization device |
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Owner name: CHINA NATIONAL OFFSHORE OIL AND GAS DEVELOPMENT AN Effective date: 20140306 Owner name: CHINA MARINE PETROLEUM GENERAL CO. Free format text: FORMER OWNER: CHINA NATIONAL OFFSHORE CORPORATION (QINGDAO) HEAVY OIL PROCESSING ENGINEERING TECHNOLOGY RESEARCH CETER CO., LTD. Effective date: 20140306 |
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Effective date of registration: 20140306 Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant after: China National Offshore Oil Corporation Applicant after: China National Offshore Oil and Gas Development and Utilization Co., Ltd. Applicant after: CNOOC ( Qingdao) Heavy Oil Processing Engineering Technology Research Center Co.,Ltd. Address before: 266500 No. 575 Qianshan North Road, Qingdao economic and Technological Development Zone, Shandong, China Applicant before: CNOOC ( Qingdao) Heavy Oil Processing Engineering Technology Research Center Co.,Ltd. |
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Application publication date: 20130807 |