CN105176615B - A kind of liquefied gas fixed bed removal of mercaptans method - Google Patents
A kind of liquefied gas fixed bed removal of mercaptans method Download PDFInfo
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- CN105176615B CN105176615B CN201410246191.XA CN201410246191A CN105176615B CN 105176615 B CN105176615 B CN 105176615B CN 201410246191 A CN201410246191 A CN 201410246191A CN 105176615 B CN105176615 B CN 105176615B
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Abstract
The invention belongs to the purification manufacture fields of liquefied petroleum gas, are related to a kind of new method for removing thiol class substance in liquefied petroleum gas.Method includes the following steps: a) under conditions of complete alkali-free, pass through the effect of catalyst in fixed bed reactors by hydramine treated liquefied petroleum gas, make thiol class substance and alkene in liquefied petroleum gas that alkylated reaction occur, generates high boiling thioether substance；B) the liquefied petroleum gas outflow fixed bed reactors containing higher boiling thioether substance are separated into the high boiling component of the not liquefied petroleum gas components of sulfur-bearing and sulfur-bearing by the effect of rectifying into rectifying column, to achieve the purpose that liquefied gas refines.It is an advantage of the invention that safe and effective refining methd at low cost, of the invention, high-efficient, non-alkali liquor discharge, to having alkali treatment method, and absolutely not environmental pollution used by liquefied petroleum gas before enormously simplifying.
Description
Technical field
The invention belongs to the purification manufacture field of liquefied petroleum gas, it is related to thiol class substance in a kind of removing liquefied petroleum gas
Method, specifically, being a kind of to be evaporated in separation removal liquefied petroleum gas using thiol class substance alkylated reaction and subsequent fine
The process of thiol class substance.
Background technique
Oil plant can generate the liquefied petroleum gas of high added value in crude oil deep-processing process.It removes and contains in liquefied petroleum gas
Outside the acidic components such as hydrogen sulfide, carbon dioxide, carbon disulfide, also have containing some mercaptan, thioether, carbonyl sulfur, thiophene etc.
Machine sulfide.Mercaptan especially therein, since with stench and faintly acid, reactivity is also relatively strong, thus in certain condition
Under to metal generate corrosion and accelerated corrosion, swelling action is then generated to plastic containers.When what is isolated from liquefied petroleum gas
When propylene, butene component are as industrial chemicals, mercaptan therein also easily makes the catalyst inactivation in downstream process.In addition, mercaptan
It is the initiator, delivery agent and catalyst of hydrocarbon oxidation chain reaction, has the tendency that colloid, residue is promoted to generate, accelerate oil product
Plastic reaction is aoxidized, serious influence is brought on the stability of oil product.
Due to influence of the sulfide to its service performance in liquefied gas and to the pollution of environment, the sulphur of domestic and international liquefied gas contains
Amount sets stringent standard.With the enhancing of people's environmental consciousness, the requirement to the sulfur content in liquefied gas will increasingly
Strictly.Therefore, the research of desulfuration of liquefied gas technology also results in more and more concerns.Liquefied gas desulfurizing and refining system is usually wrapped
It includes depriving hydrogen sulphide and removal of mercaptans refines two parts.Currently, the hydrogen sulfide in liquefied gas can be effectively removed using hydramine law technology,
The technology comparative maturity, and removal of mercaptans purification techniques also in continuous development among.
Currently, liquid gas sweetening technology mainly has both at home and abroad:
(1) the Merox liquid liquid extracting-catalytic oxidation desulfurization alcohol technique of Uop Inc..Alkali cleaning is petroleum gas sweetening
Conventional method can convert mercaptans to sodium mercaptides using the chemical reaction between caustic alkali and mercaptan, and it is extracted from raw material
Into lye, to achieve the purpose that desulfurization.But generated a large amount of spent lyes will cause serious environmental pollution in alkali cleaning
And the wasting of resources.Uop Inc., the U.S. in 1958 is proposed Merox liquid liquid extracting-catalysis on the basis of caustic wash desulfuration alcohol technology
Air sweetening technique opens new era (US 2882224) of light-end products catalysis deodorization.
Merox process flow is as follows: liquefied gas carries out caustic prescrub first and removes a small amount of hydrogen sulfide retained after hydramine is washed,
It generates sodium mercaptides subsequently into extraction tower, mercaptan is reacted with the sodium hydroxide in the lye containing catalyst and is transferred to alkali phase
In, the agent lye containing sodium mercaptides after separating with liquefied gas enters oxidation regeneration tower, under the action of catalyst and air, sulphur
Sodium alkoxide is oxidized to disulphide, realizes the removing of mercaptan, while being recycled after agent alkali liquid regeneration, the liquefied gas warp after extracting
Up to liquefied refinery gas after sedimentation and washing removing lye and free moisture.
(2) the fiber liquid film mercaptan removal technique of Merichem chemical company exploitation.The fiber liquid of Merichem company exploitation
Film mercaptan removal technique (US Pat3977829, US Pat 3992156), the interfacial surface tension using lye and metallic fiber is larger
The characteristics of, lye droplet is become attached to the liquid film on metallic fiber surface, realizes lye to nonhydrocarbon in liquefied gas on liquid film
The extraction of impurity considerably increases the mass transfer area of lye and liquefied gas, improves reaction rate.
(3) Merox fixed bed catalytic oxidation technology.In order to reduce the dosage of liquid base, activity and the longevity of catalyst are improved
Life, Merox liquid liquid doctor process is transformed in Uop Inc., develops Merox fixed-bed catalytic doctor process.It should
Technique is divided into two kinds according to whether needing liquid base: one is catalyst is loaded on porous carrier, filling catalyst is fixed
Bed, then bed is soaked with alkaline solution, so that feedstock oil is passed through bed together with air, mercaptan oxidation reaction is directly being catalyzed
It is carried out on the agent surface of solids, used porous carrier includes active carbon (US 2988500, US 4913802), clay or oxidation
Object etc. (US 4290913, US 4337147)；It is another then be that metal complex is loaded to (US on solid base carrier
5286372) bifunctional catalyst, is become, mercaptan is direct oxidation into disulphide, recycles solvent extraction or distillation
Mode separates it from raw material, which does not need additional liquid base.
The country has also carried out relevant research, Sinopec collection similar to the Merox fixed-bed catalytic desulfurization technology of UOP
Group naphthology research institute also disclose porous carrier and solid base load phthalocyanine cobalt catalyst patent (CN1200958,
CN1200957, CN1200956, CN1978058, CN1986056, CN1986059).In addition, Beijing trimerization environmental friendly material has
Limit company also developed alkali-free catalytic oxidation desulfurization technology (CN01134688, CN1687327, CN1330132, CN1347966,
CN1702157, CN1687320, CN101590361, CN101590408, CN101591213, CN1706549, CN1935377),
Disulphide is converted mercaptans in fixed bed reactors using metal oxide, then again with the mode of distillation by it from original
It is separated in material.
(4) absorption method.Hydrocarbon molecules and thiol molecule due to form and configuration on difference so that molecular polarity and other
Property is different, and absorption removal of mercaptans is exactly to carry out removal of mercaptans to the mercaptan compound in light-end products using this principle.
CN101747931, CN101885981, CN1324686, CN1067828, CN1069673, CN1081424, CN1706921,
CN1793289 reports the preparation method of a variety of absorption method doctor process and adsorbent.Absorption method mercaptan removal technique in spite of
Certain industrial application, but the limitation of sorbent suspension adsorption capacity are only applicable to the lower raw material of sulfur content.
Currently, industrially the wide liquid gas sweetening method of application is mainly Merox liquid liquid extracting-catalysis oxidation work
Skill and Merichem fiber liquid film mercaptan removal technique, still, both techniques can all generate a large amount of salkali waste in operation
Liquid, and the problems such as separated there are the disulphide after catalyst easy in inactivation, oxidation with lye difficulty.Merox fixed bed catalytic oxidation
Although technology can be to avoid the use of liquid base, there is also some problems, industrial applications for the stability of current solid catalyst
It is less.
Merox liquid liquid extracting-catalytic oxidation technique, Merichem fiber liquid film doctor process and Merox fixed bed is urged
Change oxidation technology and be all based on identical thinking: being translated into disulphide using the oxidation reaction of mercaptan, then utilizes two
Sulfide is separated with difference of the liquefied petroleum gas in solubility or boiling point.The present invention is considered as other reactions of mercaptan
Path changes the properties such as the solubility of sulfide or boiling point in liquefied petroleum gas, and it is an object of the present invention to provide a kind of liquefied petroleum qi exhaustion
The new process of mercaptan.
Summary of the invention
The purpose of the present invention is to propose to a kind of refinery's liquefied gas fixed bed mercaptan removal techniques.
Liquefied gas fixed bed removal of mercaptans method of the present invention mainly includes following two step: (1) removing sulphur by hydramine method
Liquefied petroleum gas after changing hydrogen, into fixed bed reactors, the catalyst in certain temperature, pressure and fixed bed reactors
Under effect, thiol class substance and olefin compound in liquefied petroleum gas is made to react, generates high boiling thioether substance；
(2) liquefied petroleum gas after reacting flows out fixed bed reactors, since high boiling thioether substance is located at liquefied petroleum gas
Except boiling range, rectifying column can be used to separate high boiling thioether substance from liquefied petroleum gas, rectifying tower top extraction
Purified liquefied gas product, rectifying tower reactor extraction is rich in the product of thioether substance, to achieve the purpose that desulfurization.
In method provided by the invention, related thiol class substance mainly includes methyl mercaptan, ethyl mercaptan, propanethiol etc.
It is one or more；Related olefin compound mainly include 2- metering system, 2-methyl-1-butene alkene, 2- methyl-2-butene,
1- butylene, cis-2-butene, Trans-2-butene, propylene etc. it is one or more.
In method provided by the invention, the catalyst of alkylated reaction specifically includes that acid resin catalyst, solid phosphoric acid
Catalyst, acid molecular sieve catalyst, solid super acid catalyst etc..
The condition of alkylated reaction are as follows: 30~300 DEG C of temperature, preferably 50~150 DEG C；Pressure 0.5~3 MPa, preferably 1~
2 MPa；LHSV is 0.1~100 h-1, preferably 1~10 h-1。。
In method provided by the invention, the condition of rectifying are as follows: reflux ratio 1.5~5 mol/mol, preferably 2.5~3.5
mol/mol；Overhead extraction/charge ratio 0.7~0.9, preferably 0.75~0.85；0.5~3MPa of operating pressure, preferably 1~2
MPa。
Method provided by the invention has that reaction condition is mild, process flow is simple using fixed bed alkylating desulfurization technique
The advantages that list, small, environmentally protective investment, it can effectively solve current desulfuration of liquefied gas field Merox liquid liquid extracting-catalysis oxidation work
The problems such as alkaline consumption is big in skill, salkali waste is difficult and catalyst easy in inactivation.
Detailed description of the invention
Fig. 1 is the simplification of flowsheet of the embodiment of the present invention.
In figure, 1- reactor 2- rectifying column 3- heat exchanger 4- condenser.
Specific embodiment
The invention will be further described with attached drawing combined with specific embodiments below.
Embodiment 1
This example demonstrates that acid resin catalyst is catalyzed the alkylated reaction of methyl mercaptan and 2- metering system in the present invention
Effect.
The method of the present embodiment has follow steps:
It weighs 30ml acid resin catalyst to be fitted into fixed-bed tube reactor, with N2Bed is purged, heating is opened and rises
Temperature to stabilization after 80 DEG C stops N after twenty minutes2Purging.By prepared simulation liquefied gas (quality composition: propane 45.21%, fourth
Alkane 50.12%, 2- metering system 4.62%, methyl mercaptan 0.05%) it is passed through in fixed bed reactors, the quality of control simulation liquefied gas
Flow velocity (LHSV) are as follows: 5 h-1, pressure 1.5MPa.Raw material after collecting reaction is to carry out rectifying cutting, while sampling carries out gas
Phase chromatography FPD analysis is 95.3% by the conversion ratio that chromatogram can obtain methyl mercaptan.
Embodiment 2
This example demonstrates that the cutting effect for the alkylated reaction product that rectifying obtains embodiment 1 in the present invention.
The method of the present embodiment has follow steps:
The alkylated reaction product that embodiment 2 obtains is passed through laboratory room small-sized stainless steel rectifying column, loads θ in rectifying column
Ring filler, is equivalent to 8 pieces of theoretical plates, and feed entrance point is located among tower at the 4th block of plate.Control tower top pressure is 1.5MPa, reflux
Than for 3 mol/mol, overhead extraction/charge ratio is 0.8, the liquefied gas product after overhead extraction cutting, sampling carries out microcoulomb
Instrument analysis, the sulfur content of the liquefied gas product after can obtaining rectifying cutting are 3.3ppm.
Embodiment 3
This example demonstrates that acidic molecular sieve resin catalyst is catalyzed the alkane of ethyl mercaptan and 2- methyl-2-butene in the present invention
Glycosylation reaction effect.
The method of the present embodiment has follow steps:
It weighs 5g acid molecular sieve catalyst to be fitted into fixed-bed tube reactor, with N2Bed is purged, heating is opened and rises
Temperature to stabilization after 100 DEG C stops N after twenty minutes2Purging.By prepared simulation liquefied gas (quality composition: propane 40.03%, fourth
Alkane 53.53%, 2- methyl-2-butene 6.40%, ethyl mercaptan 0.04%) it is passed through in fixed bed reactors, the matter of control simulation liquefied gas
Measuring flow velocity (LHSV) is 10 h-1, pressure 1.0MPa.Raw material after collecting reaction samples progress to carry out rectifying cutting
Gas-chromatography FPD analysis is 94.7% by the conversion ratio that chromatogram can obtain ethyl mercaptan.
Embodiment 4
This example demonstrates that the cutting effect for the alkylated reaction product that rectifying obtains embodiment 3 in the present invention.
The method of the present embodiment has follow steps:
The alkylated reaction product that embodiment 3 obtains is passed through laboratory room small-sized stainless steel rectifying column, loads θ in rectifying column
Ring filler, is equivalent to 8 pieces of theoretical plates, and feed entrance point is located among tower at the 4th block of plate.Control tower top pressure is 1MPa, reflux ratio
For 3 mol/mol, overhead extraction/charge ratio is 0.8, and the liquefied gas product after overhead extraction cutting, sampling carries out microcoulomb instrument
Analysis, the sulfur content of the liquefied gas product after can obtaining rectifying cutting are 2.8ppm.
Claims (4)
1. a kind of liquefied gas fixed bed removal of mercaptans method, it is characterized in that the following steps are included: (1) removes the liquefaction stone after hydrogen sulfide
Oil gas in fixed bed reactors under the action of catalyst, makes thiol class substance therein that alkylated reaction occur, used
Catalyst includes: acid resin catalyst, solid phosphoric acid catalyst, acid molecular sieve catalyst, solid super acid catalyst；
(2) liquefied petroleum gas after reacting flows into rectifying column from fixed bed reactors, will using the method for rectifying using the difference of boiling point
Sulfide after alkylated reaction is removed from liquefied petroleum gas；The reaction condition of fixed bed reaction in the step (1) are as follows: temperature
30~300 DEG C of degree, pressure 0.5~3 MPa, LHSV are 0.1~100 h-1；The condition of rectifying in the step (2) are as follows: reflux
Than 1.5~5mol/mol, overhead extraction/charge ratio 0.7~0.9,0.5~3MPa of operating pressure.
2. liquefied gas fixed bed removal of mercaptans method according to claim 1, it is characterised in that: sulphur as described in step (1)
Alcohols material include methyl mercaptan, ethyl mercaptan, propanethiol it is one or more.
3. liquefied gas fixed bed removal of mercaptans method according to claim 1, it is characterised in that: fixed bed is anti-in step (1)
The reaction condition answered are as follows: 50~150 DEG C of temperature；1~2 MPa of pressure；LHSV is 1~10 h-1。
4. liquefied gas fixed bed removal of mercaptans method according to claim 1, it is characterised in that: the item of rectifying in step (2)
Part are as follows: 2.5~3.5 mol/mol of reflux ratio；Overhead extraction/charge ratio 0.75~0.85；1~2 MPa of operating pressure.
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| CN106731578B (en) * | 2017-01-05 | 2023-08-25 | 延安家安能源科技有限公司 | Continuous desulfurization production system and desulfurization process thereof |
| CN109722271B (en) * | 2017-10-31 | 2020-12-04 | 中国石油化工股份有限公司 | Method for reducing mercaptan content of light oil product |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1583970A (en) * | 2003-08-20 | 2005-02-23 | 中国石油化工股份有限公司 | Desulfurizing method for distillate |
| CN102149793A (en) * | 2008-09-09 | 2011-08-10 | 鲁姆斯科技公司 | Thioetherification processes for the removal of mercaptans from gas streams |
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| US6231752B1 (en) * | 1999-09-17 | 2001-05-15 | Catalytic Distillation Technologies | Process for the removal of mercaptans |
| CN100363473C (en) * | 2005-05-30 | 2008-01-23 | 北京三聚环保新材料有限公司 | Method for converting alkyl sulfhydrate contained in liquefied petroleum gas |
| WO2008127952A1 (en) * | 2007-04-13 | 2008-10-23 | Shell Oil Company | A process for removing sulfur from a fuel gas stream |
| US8119848B2 (en) * | 2008-10-01 | 2012-02-21 | Catalytic Distillation Technologies | Preparation of alkylation feed |
| CN103965984B (en) * | 2013-02-04 | 2015-09-23 | 中国石油大学(北京) | A kind of method of liquefied petroleum gas (LPG) catalytic desulfurization alcohol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1583970A (en) * | 2003-08-20 | 2005-02-23 | 中国石油化工股份有限公司 | Desulfurizing method for distillate |
| CN102149793A (en) * | 2008-09-09 | 2011-08-10 | 鲁姆斯科技公司 | Thioetherification processes for the removal of mercaptans from gas streams |
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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: China Petroleum & Chemical Corp. Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: China Petroleum & Chemical Corp. Patentee before: Nanhua Group Research Institute |
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