CN115678592A - Method for removing mercaptan in gasoline at lower temperature - Google Patents
Method for removing mercaptan in gasoline at lower temperature Download PDFInfo
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- CN115678592A CN115678592A CN202110873084.XA CN202110873084A CN115678592A CN 115678592 A CN115678592 A CN 115678592A CN 202110873084 A CN202110873084 A CN 202110873084A CN 115678592 A CN115678592 A CN 115678592A
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- mercaptan
- metal
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- gasoline
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- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000003463 adsorbent Substances 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 44
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical group [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 38
- 239000002808 molecular sieve Substances 0.000 claims abstract description 19
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 11
- 150000002739 metals Chemical class 0.000 claims abstract description 5
- 150000002697 manganese compounds Chemical class 0.000 claims description 27
- 239000012286 potassium permanganate Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 9
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- 238000002156 mixing Methods 0.000 claims description 8
- 239000012265 solid product Substances 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 229940099596 manganese sulfate Drugs 0.000 claims description 5
- 235000007079 manganese sulphate Nutrition 0.000 claims description 5
- 239000011702 manganese sulphate Substances 0.000 claims description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 5
- -1 mercaptan compound Chemical class 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- GIJGXNFNUUFEGH-UHFFFAOYSA-N Isopentyl mercaptan Chemical compound CC(C)CCS GIJGXNFNUUFEGH-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 19
- 239000011593 sulfur Substances 0.000 abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 abstract description 18
- 238000001179 sorption measurement Methods 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 5
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- 239000000126 substance Substances 0.000 abstract description 4
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- 238000000746 purification Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 238000006477 desulfuration reaction Methods 0.000 description 12
- 230000023556 desulfurization Effects 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- PNVJTZOFSHSLTO-UHFFFAOYSA-N Fenthion Chemical compound COP(=S)(OC)OC1=CC=C(SC)C(C)=C1 PNVJTZOFSHSLTO-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- WBYBBYXHPDBWJL-UHFFFAOYSA-N barium(2+);dioxido(oxo)manganese Chemical compound [Ba+2].[O-][Mn]([O-])=O WBYBBYXHPDBWJL-UHFFFAOYSA-N 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
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- 238000004939 coking Methods 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
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- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a method for removing mercaptan from gasoline at a lower temperature, which comprises the steps of contacting a mercaptan-removing adsorbent with a gasoline raw material containing mercaptan; the mercaptan removal adsorbent comprises a carrier and an active component, wherein the carrier is a manganese oxide molecular sieve, the active component comprises an oxide of a metal M, and the metal M is selected from one or more of metals in groups VIB, VIII, IB and IIB. The method adopts a manganese oxide molecular sieve, realizes the purification of sulfur-containing substances by combining the adsorption with the catalytic conversion by utilizing the special crystal structure of an active phase, can remove mercaptan in the gasoline at normal temperature or lower temperature, and can obtain the gasoline with ultra-low sulfur content on the premise of not losing octane number. The production method is convenient to operate, simple in process and beneficial to industrial popularization.
Description
Technical Field
The invention relates to the field of adsorption and impurity removal of industrial oil products, in particular to a method for removing mercaptan from gasoline at a lower temperature.
Background
With the rapid development of economy in China, the automobile holding capacity is continuously increased, the pollution degree of automobile exhaust to air is increasingly serious, and the quality of gasoline is highly valued in China as early as the beginning of the 21 st century. The cleaning of the FCC gasoline is mainly completed by relying on an FCC gasoline post-treatment technology, which mainly comprises a hydrodesulfurization technology, a hydrodesulphurization technology, an oxidation desulfurization technology, an extraction desulfurization technology, a biodegradation desulfurization technology and the like, and the hydrodesulfurization and the hydrodesulphurization technology are still mainstream technologies for cleaning the FCC gasoline at present or in a period of time in the future due to the maturity of the technologies. Hydrodesulfurization is a technological process for realizing the cleanness of FCC gasoline under the condition of hydrogen, and the current mainstream hydrodesulfurization technology adopts full-fraction FCC gasoline prehydrogenation, light and heavy fraction cutting and heavy gasoline selective hydrodesulfurization or modification technology. In the process, FCC gasoline firstly passes through a pre-hydrogenation unit, small molecular mercaptan and olefin in the gasoline are added to generate a macromolecular thioether sulfur-containing compound, and part of olefin in full-fraction FCC gasoline is saturated, so that the deactivation of a downstream main catalyst caused by polymerization and coking is reduced; then, the pre-hydrogenated product after mercaptan transfer is cut into light gasoline fraction with qualified sulfur content and heavy gasoline fraction with higher sulfur content by a cutting unit, the heavy gasoline fraction is directly subjected to hydrodesulfurization or modification, and finally a gasoline product with the sulfur content meeting the requirement is obtained by light/heavy gasoline blending.
Hydrodesulfurization is a recognized environment-friendly desulfurization process, but the catalytic cracking gasoline has more loss after hydrogenation and is poorer in economical efficiency. Various domestic research institutions reduce octane number loss through hydroisomerization and aromatization processes, but still lose part of the octane number. If the hydrodesulfurization and the adsorption desulfurization are organically combined, and sulfide (mainly mercaptan) of the hydrogenated gasoline is removed by adsorption desulfurization, a more ideal process route is formed, and the method has important significance on environmental protection and refinery economic benefit in China.
The patent US 5730860 adopts a solid aluminum-based selective adsorbent modified by an inorganic promoter in an offline adsorption tower, the adsorbent is in countercurrent contact with gasoline to adsorb and remove sulfur-containing compounds therein, the desulfurization rate reaches 90%, and the deactivated adsorbent is activated and regenerated in a hydrogen atmosphere and is circulated to the adsorption tower for continuous use, which is typical physical adsorption. However, the desulfurizing agent is used at a high temperature. Therefore, the development of the adsorbent which is simple to prepare, high in desulfurization precision and capable of removing mercaptan in gasoline at a lower temperature has great practical significance.
Disclosure of Invention
The invention aims to provide a non-hydrogenation method for removing mercaptan in gasoline at a lower temperature, which specifically comprises the following contents for realizing the aim:
the invention provides a method for removing mercaptan from gasoline at a lower temperature, which comprises the steps of contacting a mercaptan-removing adsorbent with a gasoline raw material containing mercaptan; the mercaptan removal adsorbent comprises a carrier and an active component, wherein the carrier is a manganese oxide molecular sieve, the active component comprises an oxide of a metal M, and the metal M is selected from one or more of metals in VIB, VIII, IB and IIB groups.
The method adopts a manganese oxide molecular sieve, realizes the purification of sulfur-containing substances by utilizing the special crystal structure of an active phase and combining the adsorption with the catalytic conversion, can remove mercaptan in the gasoline at normal temperature or lower temperature, and can obtain the gasoline with ultra-low sulfur content on the premise of not losing octane number. Especially when the active metal is Cu, the active metal and the manganese oxide molecular sieve are doped to form a new structure, so that mercaptan sulfur in the gasoline can be removed with high precision. The mercaptan removal adsorbent used in the invention has the advantages of low cost, high desulfurization precision, high conversion per pass, convenient operation of the production method, simple process and contribution to industrial popularization.
Detailed Description
The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
In the present invention, the mercaptan content in gasoline is generally expressed by the mass content of sulfur element in mercaptan sulfur, and ppm is generally used as a unit of measurement.
The invention provides a method for removing mercaptan from gasoline at a lower temperature, which comprises the steps of contacting a mercaptan-removing adsorbent with a gasoline raw material containing mercaptan; the mercaptan removal adsorbent comprises a carrier and an active component, wherein the carrier is a manganese oxide molecular sieve, the active component comprises an oxide of a metal M, the metal M is one or more selected from VIB, VIII, IB and IIB metals, preferably, the metal M is at least one IB metal and/or at least one IIB metal; most preferably a metal IB.
According to the invention, the source of the mercaptan-containing gasoline raw material is not particularly limited, the sulfur-containing compound is generally one or more selected from the group consisting of n-butyl mercaptan, methyl mercaptan, ethyl mercaptan, propyl mercaptan and 3-methyl-1-butyl mercaptan, and the content of mercaptan sulfur is not particularly limited, and preferably the content of mercaptan is 10 to 1000ppm by mass of elemental sulfur based on the mass of the mercaptan-containing gasoline raw material.
According to the invention, the contacting condition is a normal sweetening condition or a milder condition than the normal condition, such as non-hydrogen, normal pressure, normal temperature to 100 ℃, and the mass ratio of the mercaptan compound to the sweetening adsorbent is 0.1-20: 1. the lower temperature of the invention is relative to the temperature required by the prior art for removing mercaptan in gasoline, such as the normal temperature of 100 ℃. The normal temperature of the invention refers to the environmental temperature which does not need to be heated, and is generally 13-35 ℃, that is, the temperature range of the contact condition of the invention can be 15-100 ℃, 20-100 ℃ and the like according to the difference of the environmental temperature. In order to achieve better mercaptan removal effect, the mass ratio of the mercaptan-containing gasoline raw material to the mercaptan removal adsorbent is 1-200: 1.
the location where the sweetening adsorbent is contacted with the mercaptan-containing gasoline according to the present invention is not particularly limited, and may be various types of reactors known to those skilled in the art, preferably a fixed bed reactor, so that the mercaptan-containing gasoline is continuously passed through. In the contact process, the contact efficiency can be increased through various conventional modes, and the adsorption reaction effect is improved.
The carrier in the sweetening adsorbent is a manganese oxide molecular sieve, and the active component is an oxide of metal M. The manganese oxide molecular sieve can be selected from one or more of birnessite, bussel ore, birnessite, barium manganite, kalium manganite and manganite, and the metal M is selected from one or more of copper, iron, zinc, titanium, tungsten and zirconium. The content of each component in the sweetening adsorbent in the invention is preferably as follows based on the dry weight of the sweetening adsorbent: the content of the carrier is 80-99.5 wt%, and the content of the active component is 0.5-20 wt% calculated by metal oxide.
The specific surface area and pore volume of the mercaptan removal adsorbent of the present invention are not particularly limited, and the specific surface area may be generally 50 to 300m 2 Per g, pore volume can be 0.2-1.2cm 3 /g。
The mercaptan removal adsorbent used in the invention is not particularly limited in source, can be a commercial reagent, and can also be prepared by raw materials, so long as the composition and the content meet the corresponding requirements of the invention. In order to better realize the method, the invention provides two preparation methods for obtaining the mercaptan removal adsorbent, namely a doping method and a loading method, which are respectively described as follows:
the method a is a doping method, which is to mix a reduced manganese compound with a salt of a metal M and then mix the reduced manganese compound with an oxidized manganese compound for hydrothermal reaction so as to avoid the salt of the metal M and the oxidized manganese compound from forming an undesired complex compound to change the crystal structure, and mainly comprises the following steps:
(a-1) dissolving a reduced manganese compound and a salt of a metal M in water to obtain a mixed solution;
(a-2) mixing an oxidation state manganese compound with the mixed solution in the step (a-1), carrying out hydrothermal reaction, and collecting a precipitate;
(a-3) drying and roasting the precipitate obtained in the step (a-2) to obtain the mercaptan removal adsorbent.
The manganese compounds in the oxidized and reduced form are relative terms in the present invention; the manganese compound in an oxidized state is generally referred to as containing relatively high valence manganese (e.g., mn) 7+ 、Mn 6+ Etc.), reduced manganese compounds generally refer to compounds containing relatively low levels of manganese (e.g., mn) 2+ Etc.). For example, the oxidized manganese compound is selected from one or more of potassium permanganate, potassium permanganate and sodium permanganate, the salt of the metal M is respectively and independently selected from one or more of nitrate, sulfate, hydrochloride and carbonate of the metal M, and the reduced manganese compound is selected from one or more of manganese sulfate, manganese nitrate, manganese acetate and manganese chloride; preferably, the molar ratio of the manganese compound in the oxidized state, the manganese compound in the reduced state and the salt of the metal M is (0.2 to 3): 1: (0.01-1).
And (3) washing the precipitate obtained in the step (a-2) according to needs, wherein the washing refers to washing the collected solid product by using deionized water until the washing liquid is neutral (for example, the pH value is 6.5-7.5).
The drying and calcination in the step (a-3) are conventional operations in the art, and the relevant conditions are not particularly limited, for example, the temperature of the drying in the step (a-3) is 80 to 350 ℃, preferably 100 to 300 ℃, and the time is 1 to 24 hours, preferably 2 to 12 hours; the roasting temperature is 200-900 ℃, preferably 250-800 ℃ and the time is 0.5-12 h, preferably 2-6 h. The calcination may be carried out in an air atmosphere or in an inert gas atmosphere, preferably N 2 The reaction is carried out in an atmosphere.
In order to further improve the performance of the mercaptan removal adsorbent, between the step (a-2) and the step (a-2), the method also comprises the step of adding acid into the mixed solution, and adjusting the pH value of the mixed solution to 0.2-3; the acid may be inorganic acid such as nitric acid, hydrochloric acid, sulfuric acid, etc., or organic acid such as acetic acid, etc. for achieving the above purpose.
The method b is a loading method, firstly preparing the manganese oxide molecular sieve from the oxidation state manganese compound and the reduction state manganese compound, and then loading the salt of the metal M thereon, and specifically comprises the following steps:
(b-1) carrying out hydrothermal reaction on an aqueous solution containing an oxidized manganese compound and a reduced manganese compound, collecting a solid product, and carrying out first drying and first roasting to obtain a manganese oxide molecular sieve;
(b-2) loading the salt of the metal M on the manganese oxide molecular sieve, and performing second drying and second roasting to obtain the mercaptan removal adsorbent.
Wherein the selection and content of the oxidized manganese compound, the reduced manganese compound and the salt of the metal M can be referred to method a, and preferably comprises the step of adding an acid to an aqueous solution before the hydrothermal reaction is carried out, the pH value of the aqueous solution is adjusted to 0.2-3, and the selection of the type of the acid can also be referred to method a.
The method provided by the invention can be used for directly and well removing the sulfur-containing compounds in the gasoline containing the thiol at room temperature or lower temperature, the mercaptan removal adsorbent is low in cost, high in desulfurization precision and high in one-way conversion rate, and the desulfurization method is convenient in process, simple to operate and beneficial to industrial popularization.
The present invention is further illustrated by the following specific examples, which describe preferred embodiments, but which are not to be construed as limiting the invention, and any person skilled in the art may, by applying the above teachings, modify the equivalent embodiments equally.
Reagents, instruments and tests
Unless otherwise specified, all reagents used in the invention are analytically pure, and all reagents are commercially available.
The model of the XRD diffractometer adopted by the invention is an XRD-6000X-ray powder diffractometer (Shimadzu Japan), and the XRD test conditions are as follows: cu target, K α ray (wavelength λ =0.154 nm), tube voltage 40kV, tube current 200mA, scanning speed 10 ° (2 θ)/min.
The content of the active ingredient was measured by X-ray fluorescence spectroscopy RIPP 132-90 (petrochemical analysis (RIPP test method), yangchini, kangying, wu Wenhui ed., first 9 months of 1990 by scientific Press, p. 371-379).
H used in the invention 2 The S analyzer was a German SICK GMS810 hydrogen sulfide analyzer.
Preparation of comparative example 1
Dissolving 3.17g of potassium permanganate in 40.55g of deionized water, heating and stirring to dissolve the potassium permanganate to form a potassium permanganate solution, then mixing the potassium permanganate solution with 5.78g of 50 wt% manganese sulfate solution, adding 6ml of nitric acid to adjust the pH value of the solution to 1.0, stirring uniformly, and reacting for 24 hours at 130 ℃. The resulting brown precipitate was filtered and washed several times with deionized water until the pH of the washing solution =7, and then the solid product was dried at 120 ℃ overnight, followed by calcination at 400 ℃ for 4h in an air atmosphere to obtain a demercaptan adsorbent D1: OMS-2-Hydro.
Preparation example 1
Dissolving 3.17g of potassium permanganate in 40.55g of deionized water, heating and stirring to dissolve the potassium permanganate to form a potassium permanganate solution, then mixing 5.78g of 50 wt% manganese sulfate solution and 1.22g of copper nitrate, uniformly stirring, mixing the two solutions, adding 6ml of nitric acid to adjust the pH value of the solution to 1.0, uniformly stirring, and reacting at 130 ℃ for 24 hours. The generated brown precipitate is filtered and washed by deionized water for multiple times until the pH of the washing liquid is =7, and then the solid product is dried at 120 ℃ overnight and roasted at 400 ℃ for 4h to prepare the mercaptan removal adsorbent A1:3% of CuO-OMS-2.
Preparation example 2
A sweetening adsorbent A2 was prepared by the same procedure as in preparation example 1, except that the reaction temperature was varied, the reaction was carried out at 190 ℃ and the A2 composition was 3% by weight of CuO-OMS-2-190.
Preparation example 3
Dissolving 3.17g of potassium permanganate in 40.55g of deionized water, heating and stirring to dissolve the potassium permanganate to form a potassium permanganate solution, then mixing 5.78g of 50 wt% manganese sulfate solution and 1.56g of ferric nitrate, stirring uniformly, mixing the two solutions, adding 6ml of nitric acid to adjust the pH value of the solution to 1.0, stirring uniformly, and reacting at 130 ℃ for 24 hours. Filtering the generated brown precipitate, washing the precipitate with deionized water for multiple times until the pH value of the washing solution is =And 7, drying the solid product at 120 ℃ overnight and roasting the dried solid product at 500 ℃ for 4 hours to obtain a mercaptan removal adsorbent A3:10% of Fe 2 O 3 -OMS-2。
Preparation example 4
Using the sweetening adsorbent D1 prepared in preparation comparative example 1 as a carrier, zinc nitrate was supported on an OMS-2 carrier by a supporting method, and after drying the solid product at 120 ℃ overnight and calcining at 500 ℃ in air for 4 hours, a sweetening adsorbent A4 was prepared: 10% ZnO/OMS-2.
Preparation example 5
The same procedure as in preparation example 1 was conducted except that sodium tungstate was used as the active metal salt, and that the composition of the thus-obtained sweetening adsorbent A5 was 2% 3 -OMS-2。
Preparation of comparative example 2
Preparation of 10% MnO-10% CuO/Al by the impregnation method 2 O 3 Selecting manganese nitrate and copper nitrate to impregnate the alumina support, preparing 10% MnO-10% The CuO/Al 2 O 3 Mercaptan removal adsorbent D2.
XRD analysis is carried out on the sweetening adsorbents obtained in the preparation examples and the preparation comparative examples, and both D1 and A1-A5 only show characteristic peaks of OMS-2, which shows that the sweetening adsorbents have an OMS-2 molecular sieve structure and active metals are uniformly doped; d2 did not show the characteristic OMS-2 peak.
Examples
Weighing 0.5g of sweetening adsorbent, placing the sweetening adsorbent in a 100mL reaction kettle, adding 50g of gasoline raw material containing mercaptan into the reaction kettle, stirring at normal temperature and normal pressure for 1h, centrifugally separating the sweetening adsorbent from the gasoline, and analyzing the content of the mercaptan in the gasoline fraction. The properties of the mercaptan-containing gasoline feedstock are shown in Table 1, and the properties of the mercaptan-removing adsorbent and the evaluation thereof are shown in Table 2.
TABLE 1
| Density, kg/m 3 | 722 |
| Mercaptan sulfur,. Mu.g/g | 31 |
| Total sulfur,. Mu.g/g | 36 |
| Octane RON | 93 |
TABLE 2
* The desulfurization rate refers to the total sulfur removal rate.
The data in the table show that the sweetening adsorbent provided by the invention can remove the mercaptan in the gasoline at a lower temperature, and the octane number of the raw material gasoline is not lost when the doped sweetening adsorbent or the supported sweetening adsorbent is used in the adsorption and desulphurization reaction, and the desulphurization precision of the adsorbent is obviously higher than that of the contrast agent 1, wherein the adsorbent with copper as an active metal has the highest desulphurization efficiency.
According to the physicochemical properties of the manganese oxide molecular sieve, the chemical adsorption of the special crystal structure of the manganese oxide molecular sieve to mercaptan in gasoline is fully utilized, the removal can be realized at normal temperature and normal pressure, the problems of high energy consumption, octane number loss and the like caused by high-temperature hydrogenation removal or high-temperature adsorption removal are avoided, and meanwhile, the preparation method of the adsorbent is simple, has good repeatability and is beneficial to industrial popularization.
According to the physicochemical properties of the manganese oxide molecular sieve, the chemical adsorption of the special crystal structure of the manganese oxide molecular sieve to hydrogen sulfide and carbonyl sulfide is fully utilized, the hydrogen sulfide and carbonyl sulfide can be removed in one step at normal temperature and normal pressure, especially when the active metal is IB group metal, the mercaptan removal effect is better, the problems of high energy consumption and the like caused by high-temperature hydrogenation removal or high-temperature adsorption removal are avoided, and meanwhile, the preparation method of the mercaptan removal adsorbent is simple, has good repeatability and is beneficial to industrial popularization.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
In addition, any combination of the various embodiments of the present invention can be made, and the same should be considered as the disclosure of the present invention as long as the idea of the present invention is not violated.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it should be understood that various changes and modifications can be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for removing mercaptan from gasoline at a lower temperature comprises the steps of contacting a mercaptan-removing adsorbent with a gasoline raw material containing mercaptan; the mercaptan removal adsorbent comprises a carrier and an active component, wherein the carrier is a manganese oxide molecular sieve, the active component comprises an oxide of a metal M, and the metal M is selected from one or more of metals in groups VIB, VIII, IB and IIB.
2. The process according to claim 1, wherein the mercaptan compound in the mercaptan-containing gasoline raw material is selected from one or more of n-butylmercaptan, methyl mercaptan, ethyl mercaptan, propyl mercaptan and 3-methyl-1-butylmercaptan, and the mercaptan content in the mercaptan-containing gasoline raw material is 10 to 1000ppm by mass based on the mass of the mercaptan element.
3. The method of claim 1, wherein the contacting conditions comprise: the temperature is normal temperature to 100 ℃, the pressure is normal pressure, the mass ratio of the mercaptan-containing gasoline raw material to the mercaptan removal adsorbent is 1-200: 1.
4. a process as claimed in claim 1, wherein the carrier is present in an amount of 80 to 99.5% by weight, based on the dry weight of the sweetening adsorbent, and the active component is present in an amount of 0.5 to 20% by weight, based on the metal oxide.
5. The method of claim 1, wherein the manganese oxide molecular sieve is selected from one or more of birnessite, buchner, birnessite, bartonite, kalmanesite, and calciumusite, and the metal M is selected from one or more of copper, iron, zinc, titanium, tungsten, and zirconium; preferably, the metal M is at least one metal IB and/or at least one group IIB metal, more preferably a group IB metal.
6. The method of claim 1, wherein the mercaptan removal adsorbent is prepared by method a or method b,
the method a comprises the following steps:
(a-1) dissolving a reduced manganese compound and a salt of a metal M in water to obtain a mixed solution;
(a-2) mixing an oxidation state manganese compound with the mixed solution in the step (a-1), carrying out hydrothermal reaction, and collecting a precipitate;
(a-3) drying and roasting the precipitate obtained in the step (a-2) to obtain the mercaptan removal adsorbent;
the method b comprises the following steps:
(b-1) carrying out hydrothermal reaction on an aqueous solution containing an oxidized manganese compound and a reduced manganese compound, collecting a solid product, and carrying out first drying and first roasting to obtain a manganese oxide molecular sieve;
(b-2) loading the salt of the metal M on the manganese oxide molecular sieve, and performing second drying and second roasting to obtain the mercaptan removal adsorbent.
7. The method of claim 6, wherein in method a and method b, the oxidized manganese compounds are respectively and independently selected from one or more of potassium permanganate, potassium permanganate and sodium permanganate, the salts of the metal M are respectively and independently selected from one or more of nitrate, sulfate, hydrochloride and carbonate of the metal M, and the reduced manganese compounds are respectively and independently selected from one or more of manganese sulfate, manganese nitrate, manganese acetate and manganese chloride;
preferably, the molar ratio of the oxidized manganese compound, the reduced manganese compound and the salt of the metal M is (0.2 to 3): 1: (0.01-1).
8. The method according to claim 6, wherein in the step (a-3) of the method a, the drying temperature is 80-350 ℃ and the time is 1-24 h, the roasting temperature is 200-900 ℃ and the time is 0.5-12 h; in the method b, the temperature of the first drying is 80-350 ℃, the time is 1-24 h, the temperature of the first roasting is 200-900 ℃, the time is 0.5-12 h, the temperature of the second drying is 80-350 ℃, the time is 1-24 h, and the temperature of the second roasting is 200-900 ℃, and the time is 0.5-12 h.
9. The method according to claim 6, wherein between the step (a-2) and the step (a-2), the method further comprises the step of adding an acid to the mixed solution, and adjusting the pH value of the mixed solution to 0.2-3.
10. The method according to claim 6, wherein the hydrothermal reaction of the method b further comprises a step of adding an acid to the aqueous solution to adjust the pH of the aqueous solution to 0.2 to 3.
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| US20160175806A1 (en) * | 2014-12-17 | 2016-06-23 | University Of Connecticut | Adsorptive desulfurization |
| CN112691651A (en) * | 2020-12-22 | 2021-04-23 | 沈阳三聚凯特催化剂有限公司 | Preparation method of desulfurizer, desulfurizer and application |
| CN112791721A (en) * | 2019-10-28 | 2021-05-14 | 中国石油化工股份有限公司 | Supported catalyst precursor, supported catalyst, preparation method and activation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160175806A1 (en) * | 2014-12-17 | 2016-06-23 | University Of Connecticut | Adsorptive desulfurization |
| CN112791721A (en) * | 2019-10-28 | 2021-05-14 | 中国石油化工股份有限公司 | Supported catalyst precursor, supported catalyst, preparation method and activation method |
| CN112691651A (en) * | 2020-12-22 | 2021-04-23 | 沈阳三聚凯特催化剂有限公司 | Preparation method of desulfurizer, desulfurizer and application |
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