CN106540517A - The new chemical absorption process of mercaptan in a kind of removing gas - Google Patents
The new chemical absorption process of mercaptan in a kind of removing gas Download PDFInfo
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- CN106540517A CN106540517A CN201510596992.3A CN201510596992A CN106540517A CN 106540517 A CN106540517 A CN 106540517A CN 201510596992 A CN201510596992 A CN 201510596992A CN 106540517 A CN106540517 A CN 106540517A
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Abstract
The invention belongs to the refined manufacture field of industrial gases, is related to a kind of new chemical absorption process of thiol class substance in removing industrial gases.Including：（1）Industrial gases raw material is introduced from absorption tower bottom, with the solution counter current contacting of olefin-containing, the alkene in thiol class substance solution in gas reacts, and gas enters separator by Jing condensations after producing at the top of absorption tower, obtains final product purified gas after the solution for separating entrainment；（2）React into regenerator after the solution heat exchange for absorbing thiol class substance, the thiol class substance Jing overhead condensations for discharging enter separator, and isolated solution is back in regenerator.It is an advantage of the invention that the absorbent solution for adopting is non-alkaline solution, can alkaline consumption be big in the current industrial gases removal of mercaptans field of effectively solving and the problems such as difficult salkali waste.
Description
Technical field
The invention belongs to the refined manufacture field of industrial gases, is related to a kind of new chemical absorption process of thiol class substance in removing gas, specifically, using non-alkaline solution to the chemical absorbing of mercaptan in gas and the flow process for regenerating to realize Mercaptan removal in gas.
Background technology
Often contain a certain amount of thiol class substance in the industrial gases such as natural gas, synthesis gas, refinery gas.Although the content of mercaptan is very low, there is many harm：（1）Foul smelling abnormal smells from the patient, can pollute environment and human body is damaged；（2）In faintly acid, reactivity is stronger, produces corrosion and accelerated corrosion to metal under certain condition, then produces swelling action to plastic containers；（3）Catalyst poisoning inactivation in downstream process is made easily；（4）It is initiator, delivery agent and the catalyst of hydrocarbon oxidation chain reaction, has the trend for promoting colloid, residue to generate, serious impact is brought to the stability of hydro carbons.
Due to impact of the mercaptan in industrial gases to its performance and the pollution to environment, various laws and regulations set strict standard to the sulfur content in industrial gases.With the enhancing of people's environmental consciousness, the requirement to the sulfur content in industrial gases will be more and more stricter.Therefore, the research of industrial gases mercaptan removal technique also result in increasing concern.
Caustic extraction-catalytic oxidation is the most widely used method of thiol class substance that industrially removes at present.Uop Inc. of the U.S. is in patent US Pat 2882224 within 1958, it is proposed Merox caustic extractions-oxidation regeneration doctor process, new era of catalysis deodorize is opened, the method is applied widely, removing capacity is big, is worldwide obtained for and is widely applied.But, the method there is also difficult spent lye, catalyst easy in inactivation, carry the problems such as serious, desulfurization degree is unstable secretly.Form and the regularity of distribution of patent CN101705108 according to sulfur-containing compound in liquid hydrocarbon, in traditional liquid hydrocarbon extraction and oxidation sweetening process, the techniques such as agent deoxidation with extractant is separated and is circulated to the mixed intensified regeneration of the circulating solvent function intensified, three-phase of enforcement, regenerated catalyst by adopting, reinforcing Mercaptan removal depth is realized, carbonyl sulfide removal rate is improved, is reduced or avoided in extracting while forming the technique effects such as disulphide, energy-saving and emission-reduction, so that liquid hydrocarbon can deep desulfuration, the bed drain purge of original technique is greatly reduced.
Merichem companies report fiber liquid film mercaptan removal technique in patent US Pat3977829, using the interfacial surface tension of alkali liquor and metallic fiber it is larger the characteristics of, alkali liquor microdroplet is become attached to into the liquid film on metallic fiber surface, the extraction of non-hydrocarbon impurities on liquid film realizing alkali liquor to liquefied gas, the mass transfer area of alkali liquor and liquefied gas is considerably increased, reaction rate is improve.Therefore, the technology is just progressively replacing Merox caustic extractions-oxidation regeneration technique.At present, the technology has been achieved with production domesticization, and patent CN202808743 discloses a kind of catalytic liquefied petroleum gas deep desulfuration alcohol device, in extraction unit, pending liquefied gas eventually passes washing process and transfers out device by one-level, two grades, three-level fiber liquid film equipment.In alkali liquid regeneration unit, the separation of disulphide in regeneration alkali liquor is realized using two-stage fiber liquid film equipment, such that it is able to reach high mercaptan removal efficiency and high disulphide separation efficiency.
In order to reduce the consumption of liquid base, activity and the life-span of catalyst are improved, and Uop Inc. is transformed to Merox liquid liquid doctor processes, develops fixed bed catalytic oxidation technique.Patent US 2988500 and US5286372 individually disclose the technique that its porous carrier and solid base load phthalocyanine cobalt catalyst removal of mercaptans.The country has been also carried out the research of correlation, CN1200958, CN1200957, CN1200956, CN1978058, CN1986056, CN1986059, CN01134688, CN1687327, CN1330132, CN1347966, CN1702157, CN1687320, CN101590361, CN101590408, CN101591213, CN1706549, CN1935377 also report similar technique.
Absorption method is another kind of method for removing Biogenic thiols in industrial gases.Mercaptan in absorption method removing hydro carbons is the mercaptan compound in light-end products to be removed using the polarity difference between hydrocarbon molecules and thiol molecule.Conventional mercaptan adsorbent has molecular sieve, activated carbon and metal-oxide etc..Patent CN101747931, CN101885981, CN1324686, CN1067828, CN1069673, CN1081424, CN1706921, CN1793289 report the preparation method of various absorption method doctor processes and adsorbent.
Solution absorption method is the traditional method for industrially removing sulfide in gas, whether chemical reaction there is according to absorption process, Physical Absorption method and chemical absorption method can be divided into,, using Physical Absorption solvents such as methanol, polyalcohol ethers, the latter is using chemical absorption solvents such as hydramine for the former.In order to improve the removal of mercaptans efficiency of solution absorption method, new solvent is constantly found out.Patent CN101998985 reports a kind of Mercaptan removal agent, and it is ROOCN=NCOOR to contain a kind of formula in the scavenger2Disubstituted azodiformate, the scavenger is to remove the mercaptan in hydrocarbon, faster than traditional Mercaptan removal agent.Patent CN101227964 provides a kind of method of the gas stream for producing depleted of hydrogen sulphide and depleted of mercaptans, in Mercaptan removal area, gas stream and comprising CuSO4Wash water solution contact, generate Cu- alkylsulphide products, so as to by Mercaptan removal, the concentration of mercaptan is less than 10ppmv in gas stream after process.
At present, industrially it is mainly Merox liquid liquid extracting-catalytic oxidation techniques and Merichem fiber liquid film mercaptan removal techniques using wide removal of mercaptans method, but, both techniques can all produce spent lye in operation, have certain harm to environment.It is an object of the present invention to a kind of new chemical absorbent solution without basic component is developed, to remove the thiol class substance in industrial gases.
The content of the invention
The new chemical absorption process of mercaptan in the removing gas of present invention exploitation, mainly including following two steps：（1）Industrial gases raw material is introduced from absorption tower bottom, contact with the solvent counter current of the top-down olefin-containing of tower top, thiol class substance in gas is through diffusing in solution, and react with the olefin compound in solution in the presence of catalyst, gas enters separator by Jing condensations after producing at the top of absorption tower, obtains final product purified gas after the solution for separating entrainment；（2）Regenerator is entered after the solution heat exchange for absorbing thiol class substance, in regenerator, the product in solution occurs backward reaction, and the thiol class substance Jing overhead condensations for discharging enter separator, and isolated solution is back in regenerator.Solution Jing after regeneration cools Posterior circle into absorption tower.
In the method that the present invention is provided, involved thiol class substance mainly includes one or more of methanthiol, ethyl mercaptan, propanethiol etc..
Involved olefin compound is C3~C10One or more of alkene, preferred C4~C8Alkene, the mass content of alkene can be 0.01% ~ 100%, preferably 5% ~ 30%；
Involved solvent can select C3~C12Alkane, cycloalkane, one or more in aromatic hydrocarbons.
In the method that the present invention is provided, the catalyst used in absorption tower includes but is not limited to liquid acid catalyst, solid acid catalyst, ionic liquid acid catalyst etc..
The operating condition on absorption tower is：30～150 DEG C of temperature, preferably 50～120 DEG C；0.1～8 MPa of pressure, preferably 0.5～5 MPa；Gas liquid ratio 50～1000, preferably 200～600.
In the method that the present invention is provided, the catalyst used in regenerator includes but is not limited to liquid acid catalyst, solid acid catalyst, ionic liquid acid catalyst etc..
The operating condition of regenerator is：100～300 DEG C of temperature, preferably 120～200 DEG C；Pressure is normal pressure.
The method that the present invention is provided, the absorbent solution for adopting is non-alkaline solution, liquid base is not used completely, can alkaline consumption be big in the current industrial gases removal of mercaptans field Merox liquid liquid extracting-catalytic oxidation technique of effectively solving and Merichem fiber liquid film techniques and the problems such as difficult salkali waste.
Description of the drawings
Simplification of flowsheet schematic diagrams of the Fig. 1 for present invention method.
In figure, 1- feed gas heaters, 2- absorption towers, 3- purification Gas Coolers, 4- purge gas separators, 5- regenerators, 6- regeneration Gas Coolers, 7- regeneration gas separating devices, 8- solution circulation pumps, 9- solution coolers, 10- heat exchangers, 11- reboilers.
Specific embodiment
With reference to specific embodiments and the drawings, the invention will be further described.
Following examples technical process is referring to accompanying drawing 1.
Embodiment 1
This example demonstrates that containing the effect of the solution removal methanthiol of iso-amylene used in the present invention.
The method of the present embodiment has steps of：
Unstripped gas containing methanthiol 860ppm（Remaining is N2, stagnation pressure 1.0MPa）After preheated device is preheated to 60 DEG C, introduced by absorption tower tower reactor.The quality of solution is consisted of：2-methyl-1-butene alkene：1%；2- methyl-2-butenes：9%；Normal octane：90%, solution temperature is controlled at 60 DEG C, is introduced from absorption tower tower top by pump.In absorption tower in addition to equipped with filler, the catalyst bag for having loaded macropore sulfuric acid resin is also intervally distributed with.The unstripped gas and solution counter current contacting on filler and catalyst, the methanthiol in unstripped gas are absorbed by solution, and chemical reaction occurs with the iso-amylene in solution in the presence of macropore sulfuric acid resin.Unstripped gas after purification is by absorption tower overhead extraction, and sampling is analyzed, and analysis result shows, the methanthiol in purified gas is 5ppm, has reached estimated removal effect.
Embodiment 2
This example demonstrates that in the present invention solution that regenerator is obtained to embodiment 1 regeneration effect.
The method of the present embodiment has steps of：
The solution that methanthiol is absorbed in embodiment 1 is placed in regenerator, solution is heated using the reboiler of regeneration tower reactor, regenerator is equipped with hydrogen type molecular sieve, at a temperature of 150 DEG C or so, in solution, methanthiol is inversely carried out with the reaction of iso-amylene, methanthiol is discharged from solution, and is sailed against the current along regenerator, is drawn from regeneration overhead.Regenerator atmospheric operation.Solution after regeneration is produced by tower reactor, and sampling is analyzed, and analysis result shows, the sulfur content after regeneration in solution is 268ppm, has reached estimated regeneration effect.
Embodiment 3
This example demonstrates that containing C used in the present invention6The effect of the solution removal ethyl mercaptan of alkene.
The method of the present embodiment has steps of：
Unstripped gas containing ethyl mercaptan 730ppm（Remaining is N2, stagnation pressure 1.3MPa）After preheated device is preheated to 60 DEG C, introduced by absorption tower tower reactor.The quality of solution is consisted of：2,3- dimethyl -1-butylene：5%；2,3- dimethyl -2-butylene：10%；Normal octane 80%；Acidic ionic liquid catalysts 5%, solution temperature are controlled at 60 DEG C, are introduced from absorption tower tower top by pump.The unstripped gas and solution counter current contacting on filler, the ethyl mercaptan in unstripped gas by solution absorb, and in the presence of acidic ion liquid with solution in C6There is chemical reaction in alkene.Unstripped gas after purification is by absorption tower overhead extraction, and sampling is analyzed, and analysis result shows, the ethyl mercaptan content in purified gas is 8ppm, has reached estimated removal effect.
Embodiment 4
This example demonstrates that in the present invention solution that regenerator is obtained to embodiment 3 regeneration effect.
The method of the present embodiment has steps of：
The solution that ethyl mercaptan is absorbed in embodiment 3 is placed in regenerator, solution is heated using the reboiler of regeneration tower reactor, at a temperature of 150 DEG C or so, ethyl mercaptan and C in solution6The reaction of alkene is inversely carried out, and ethyl mercaptan is discharged from solution, and is sailed against the current along regenerator, is drawn from regeneration overhead.Solution after regeneration is produced by tower reactor, and sampling is analyzed, and analysis result shows, the sulfur content after regeneration in solution is 343ppm, has reached estimated regeneration effect.
Claims (10)
1. it is a kind of removing gas in mercaptan new chemical absorption process, it is characterised in that comprise the following steps：（1）Industrial gases raw material is introduced from absorption tower bottom, contact with the solvent counter current of the top-down olefin-containing of tower top, thiol class substance in gas is through diffusing in solution, and react with the olefin compound in solution in the presence of catalyst, gas enters separator by Jing condensations after producing at the top of absorption tower, obtains final product purified gas after the solution for separating entrainment；（2）Regenerator is entered after the solution heat exchange for absorbing thiol class substance, in regenerator, there is backward reaction in the product in solution, the thiol class substance Jing overhead condensations for discharging enter separator, isolated solution is back in regenerator, and the solution Jing after regeneration cools Posterior circle into absorption tower.
2. method according to claim 1, it is characterised in that：Step（1）Described in thiol class substance include methanthiol, ethyl mercaptan, one or more of propanethiol.
3. method according to claim 1, it is characterised in that：Step（1）Described in olefin compound include C3~C10One or more of alkene, the mass content 0.01% ~ 100% of alkene.
4. method according to claim 3, it is characterised in that：Step（1）Described in olefin compound include C4~C8One or more of alkene, the mass content 5% ~ 30% of alkene.
5. method according to claim 1, it is characterised in that：Step（1）Described in solvent select C3~C12Alkane, cycloalkane, one or more in aromatic hydrocarbons.
6. method according to claim 1, it is characterised in that：Step（1）Middle absorption tower and step（2）The catalyst used by middle regenerator includes liquid acid catalyst, solid acid catalyst, ionic liquid acid catalyst.
7. method according to claim 1, it is characterised in that：Step（1）The operating condition on middle absorption tower is：30～150 DEG C of temperature；0.1～8 MPa of pressure；Gas liquid ratio 50～1000.
8. method according to claim 7, it is characterised in that：Step（1）The operating condition on middle absorption tower is：50～120 DEG C of temperature；0.5～5 MPa of pressure；Gas liquid ratio 200～600.
9. method according to claim 1, it is characterised in that：Step（2）The operating condition of middle regenerator is：100～300 DEG C of temperature, pressure are normal pressure or vacuum.
10. method according to claim 9, it is characterised in that：Step（2）The operating condition of middle regenerator is：120～200 DEG C of temperature, pressure are normal pressure or vacuum.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120152119A1 (en) * | 2010-12-17 | 2012-06-21 | Battelle Memorial Institute | System and process for capture of h2s from gaseous process streams and process for regeneration of the capture agent |
| CN103768913A (en) * | 2012-10-22 | 2014-05-07 | 中国石油化工股份有限公司 | Method for removing hydrogen sulfide and mercaptan |
| CN103861423A (en) * | 2012-12-12 | 2014-06-18 | 中国石油化工股份有限公司 | Renewable absorption liquid for removing RSH and COS in acidic fluid |
| CN104511244A (en) * | 2013-10-08 | 2015-04-15 | 中国石油化工股份有限公司 | Method for removing mercaptan from gas-phase hydrocarbon through alkylation reaction |
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- 2015-09-18 CN CN201510596992.3A patent/CN106540517A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120152119A1 (en) * | 2010-12-17 | 2012-06-21 | Battelle Memorial Institute | System and process for capture of h2s from gaseous process streams and process for regeneration of the capture agent |
| CN103768913A (en) * | 2012-10-22 | 2014-05-07 | 中国石油化工股份有限公司 | Method for removing hydrogen sulfide and mercaptan |
| CN103861423A (en) * | 2012-12-12 | 2014-06-18 | 中国石油化工股份有限公司 | Renewable absorption liquid for removing RSH and COS in acidic fluid |
| CN104511244A (en) * | 2013-10-08 | 2015-04-15 | 中国石油化工股份有限公司 | Method for removing mercaptan from gas-phase hydrocarbon through alkylation reaction |
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Application publication date: 20170329 |