CN101927130B - Method for removing sulfur-containing compounds from oil by utilizing membrane process - Google Patents
Method for removing sulfur-containing compounds from oil by utilizing membrane process Download PDFInfo
- Publication number
- CN101927130B CN101927130B CN 200910020663 CN200910020663A CN101927130B CN 101927130 B CN101927130 B CN 101927130B CN 200910020663 CN200910020663 CN 200910020663 CN 200910020663 A CN200910020663 A CN 200910020663A CN 101927130 B CN101927130 B CN 101927130B
- Authority
- CN
- China
- Prior art keywords
- oil product
- sulfur
- film
- containing compound
- module
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000011593 sulfur Substances 0.000 title claims abstract description 86
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 86
- 239000012528 membrane Substances 0.000 title claims abstract description 84
- 150000001875 compounds Chemical class 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 47
- 230000008569 process Effects 0.000 title claims description 18
- 238000000926 separation method Methods 0.000 claims abstract description 41
- 239000012071 phase Substances 0.000 claims abstract description 12
- 229920001661 Chitosan Polymers 0.000 claims abstract description 6
- 239000012808 vapor phase Substances 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims description 77
- 239000000463 material Substances 0.000 claims description 27
- 230000015572 biosynthetic process Effects 0.000 claims description 24
- 238000003786 synthesis reaction Methods 0.000 claims description 24
- 238000006477 desulfuration reaction Methods 0.000 claims description 18
- 230000023556 desulfurization Effects 0.000 claims description 17
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000012466 permeate Substances 0.000 claims description 11
- 239000007791 liquid phase Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 229920002301 cellulose acetate Polymers 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 238000004523 catalytic cracking Methods 0.000 claims description 6
- 230000003009 desulfurizing effect Effects 0.000 claims description 6
- 230000008595 infiltration Effects 0.000 claims description 5
- 238000001764 infiltration Methods 0.000 claims description 5
- 230000003993 interaction Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical class OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000011229 interlayer Substances 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000035699 permeability Effects 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 238000004939 coking Methods 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 230000006196 deacetylation Effects 0.000 claims description 2
- 238000003381 deacetylation reaction Methods 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 230000008676 import Effects 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims 1
- 150000001243 acetic acids Chemical class 0.000 claims 1
- 238000009826 distribution Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 12
- 238000005373 pervaporation Methods 0.000 abstract description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 12
- 238000001704 evaporation Methods 0.000 description 9
- 239000005864 Sulphur Substances 0.000 description 8
- 229930192474 thiophene Natural products 0.000 description 8
- 238000000605 extraction Methods 0.000 description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 5
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 229920002239 polyacrylonitrile Polymers 0.000 description 4
- 229920002994 synthetic fiber Polymers 0.000 description 4
- 239000012209 synthetic fiber Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- -1 Polysiloxanes Polymers 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000009874 alkali refining Methods 0.000 description 2
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000008258 liquid foam Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- HUWSZNZAROKDRZ-RRLWZMAJSA-N (3r,4r)-3-azaniumyl-5-[[(2s,3r)-1-[(2s)-2,3-dicarboxypyrrolidin-1-yl]-3-methyl-1-oxopentan-2-yl]amino]-5-oxo-4-sulfanylpentane-1-sulfonate Chemical compound OS(=O)(=O)CC[C@@H](N)[C@@H](S)C(=O)N[C@@H]([C@H](C)CC)C(=O)N1CCC(C(O)=O)[C@H]1C(O)=O HUWSZNZAROKDRZ-RRLWZMAJSA-N 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 1
- 229920000914 Metallic fiber Polymers 0.000 description 1
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005008 domestic process Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000000409 membrane extraction Methods 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 150000003549 thiazolines Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a method for removing sulfur-containing compounds from oil by utilizing the membrane separation process, and belongs to the technical field of membrane separation. In the sulfur removing method, an organic/inorganic composite membrane formed by adsorbing high-hydrophilic chitosan on a high-hydrophilic synthesized hydrotalcite-like compound with a lamellar structure is taken as a pervaporation membrane separation module; the sulfur-containing compounds in an oil phase are concentrated on a side near the membrane module by utilizing the high affinity of the composite membrane to the sulfur-containing compounds in the oil, rapidly and selectively penetrate the membrane module by high concentration difference with a vapor phase side of the membrane module, and enter the vapor phase side of a penetrant so as to separate the sulfur-containing compounds from the oil. The adopted membrane separation module can adopt a one-stage, two-stage, three-stage or multistage combined membrane module system. The one-stage membrane module is adopted for removing sulfur, the residual sulfur content is 90 to 110 ppm and the sulfur removal rate is 93 to 96 percent; and the three-stage combined membrane module is adopted for removing sulfur, so the residual sulfur content is less than 15 ppm.
Description
Technical field:
The invention belongs to the membrane separation technique field, specifically a kind of method of utilizing the film pervasion evaporation process to remove sulfur-containing compound in the oil product.
Background technology:
Can produce a large amount of SO after the sulfur-containing compound burning in the gasoline
2Gas enters it in atmosphere and can cause environmental pollution, serious harm existent environment of people and healthy; Also be the main cause that nature forms acid rain, in order to reduce this harm, people develop various new technologies to remove the sulphur in the gasoline; Chemical refining at present commonly used both at home and abroad, catalytic hydrogenation, catalysis absorption, solvent extraction, biological desulfurizing technology, wherein chemical refining is traditional method, and two kinds of acid treating and alkali refinings are arranged; Because the acid-alkali refining method is bad for organic sulfur-containing thing removal effect, and is easy to generate liquid foam entrainment, even serious emulsification problem; Isolated acid sludge or alkaline residue deal with difficulty in the process, and the oil product loss is bigger; Hydrofinishing need be carried out under high-temperature and high-pressure conditions, and the equipment investment expense is high, also receives the restriction of hydrogen source in addition.Merox alkali extraction process removes the mercaptan in the gasoline; Oxidable recovery sulphur and part alkali lye; But existence is used for the catalyst of oxidation sulfur-containing compound to be taken place to assemble and lose activity easily; The isomer of oxidation mercaptan is difficulty comparatively, and the disulphide of generation is prone to bring in the oil product, contains toxic catalyst in the discharging waste liquid.Mericat
TMThe sulfur-containing compound that the metallic fiber membrane technology is used for removing gasoline can reach more than 90%; But because this technology adopts the direct way of contact of the aqueous solution of oil and alkali; Also there are liquid foam entrainment and dulling problem; This method is very high to the cleanliness factor requirement of each medium, and every kind of medium all must filter through filter, and equipment cleaning is also quite difficult.
In recent years; Give great concern to C5, C6 hydrocarbon isomerization production high octane gasoline component both at home and abroad; But the sulfur-bearing light naphthar can not be as the raw material of isoversion; Adopt membrane separation technique to reduce the content of the mercaptan in the naphtha, can substitute expensive hydrotreatment technology, can promote the extensive use of isomerization technique.In addition, C
3, C
4Raw material-light-end products the depickling of the isoversion of component and production methyl tertiary butyl ether(MTBE), desulfurization etc. can adopt membrane separation technique to realize.
At present, the domestic method of taking membrane separation technique to remove the sulfur-containing compound in the oil product mainly adopts infiltration--extraction, infiltration--evaporation technique.
" membrane science with technology " discloses people such as the Chen Cui of Tsing-Hua University celestial being and adopted PDMS film infiltration-evaporation to remove contained thiophenic sulfur in the gasoline simulation component normal octane.
" membrane science and technology " discloses people such as Li Jiding and utilized dimethyl silicone polymer (PDMS)/polyacrylonitrile (PAN) composite membrane as infiltration--and evaporating film removes armaticity sulfur-containing compound thiophene and the alkylated substituted thiazoline fen in the gasoline.
Chinese patent 200610090982.4 discloses the method that the infiltration-extraction of a kind of high-hydrophilic cellulosic polymer film removes sulfur-containing compound in the petroleum oil product.The polymer film module separates oil product and sulfur-containing compound extract in the film both sides; Sulfur-containing compound in the oil product penetrates the opposite side that perforated membrane arrives film from oil product one side of film template, and reacts on the interface in the extract molecule; Product rapidly from interfacial diffusion to extraction liquids mutually in; The extract that flows is taken away product, and Membrane Extraction has high selectivity to the sulfur-containing compound in the oil product, and this exactly high selectivity makes sulfur-containing compound be able to extraction and removes; Basically do not exert an influence for hydrocarbon compound, but receive the optionally limitation of extract sulfur-containing compound.
Owing to receive the restriction of permeable membrane material itself and application technology; Existing membrane separation technique sulfur method is all not ideal enough; The difficulty that particularly removes thiophene sulfocompounds is bigger, and existing sulfur method can't make the sulfur content in the gasoline be reduced to the level less than 120ppm.
Summary of the invention:
Utilize the film pervasion evaporation isolation technics to remove the method for sulfur-containing compound in the gasoline in order to obtain the higher desulfuration effect, to the invention provides.The film pervasion evaporation isolation technics is an efficient mass transfer process; The vapour phase of oil phase and pervaporation thing is in the both sides of film module respectively in the separation process, and having a large amount of fine apertures in the film module is that penetrant rapid permeability to be separated provides huge mass transfer area through film module arrival vapour phase one side.Compare with film infiltration-extraction, saved a large amount of extracts, technology is simple, and mode is various, and energy consumption is low, and separative efficiency is high, and process conditions are easy to control.
The invention provides a kind of technical scheme of utilizing film infiltration-evaporation method to remove sulfur-containing compound in the oil product.
Oil product desulfurization method of the present invention is: adopt the high-hydrophilic shitosan is adsorbed on the compound permeable membrane film of organic/inorganic that forms on the strongly hydrophilic synthesis hydrotalcite-like material particle surface with layer structure major function module as the film separation module; Utilize permeable membrane that the sulfur-containing compound in the oil product is had strong affinity interaction; Make that sulfur-containing compound is enriched near film module one side in the oil phase; Rely on the high concentration difference that exists with film module vapour phase one side, optionally see through film module fast, get into penetrant vapor phase one side; Thereby oil product is separated with sulfur-containing compound, reach the purpose of desulfurization.
The above-mentioned film module that is used for the film separation can be the combination of flat sheet membrane, tubular membrane and multistage flat sheet membrane, the combination of multi-level tubular film.
According to desulfurization quality needs, can adopt the single stage membrane template way to carry out, also can adopt secondary, three grades or multistage combined films template way to carry out.
The sweetening process of single-stage permeable membrane module is shown in accompanying drawing 1:
The raw material oil product is sent into film separation mask oil product liquid phase one side, the opposite side of film from the oil product import under higher pressure; It is sulfur-rich compounds penetrant vapor phase one side; Keep vacuum or lower pressure, because compound membrane permeable substance, makes near the sulfur-containing compound enrichment near film module in the oil product to the strong affinity interaction of polar organic compound; Under the promotion of film both sides steam pressure difference; Infiltration is gone from membrane permeate one sidesway with steam condition through film, and the oil product after the desulfurization reclaims from the oil product outlet.
The main technique condition of single-stage permeable membrane module desulfurization is following:
Pending oil product feed pressure (1～3.3) * 10
5Pa
Pending oil product flow 115～125L/min.
Membrane permeate one side vacuum (7.5～8) * 10
3Pa
25～30 ℃ of penetrant steam condensation temperatures
Desulfurized effect: residual sulphur content 90～110ppm sulfur removal rate 93～96%.
The sweetening process of three grades of composite permeable membranes modules is shown in accompanying drawing 2:
The raw material oil product at first gets into first order film module liquid phase oil product one side; Penetrant one side of film keeps vacuum or lower pressure; Sulfur-containing compound in the oil product is under the promotion of film both sides steam pressure difference, and infiltration is gone from membrane permeate one sidesway with steam condition through film.
Get into liquid phase oil product one side of second level film separation mask again through the oil product of the low sulfur content of first grade desulfurizing, repeat the separation process of the sulfur-containing compound of first order template, the sulfur content in the liquid phase oil product is further reduced.
Through the oil product of secondary desulfurization, get into liquid oil product one side of third level film separation mask in succession again, again sulfur-containing compound is wherein carried out permeability and separation one time, obtain the super-low sulfur oil product in liquid phase oil product one side at last.
The main technique condition of three grades of permeable membrane modules desulfurization is following:
Pending oil product feed pressure (1～3.3) * 10
5Pa
Pending oil product flow 115～125L/min.
Membrane permeate one side vacuum (1～12) * 10
3Pa
25～30 ℃ of penetrant steam condensation temperatures
Desulfurized effect: residual sulphur content＜15ppm
In order to obtain excellent desulfurized effect, selecting performance excellent permeation film is key problem in technology.
The inventor has succeeded in developing a kind of shitosan/synthetic hydrotalcite composite permeable membrane on the basis of the existing permeable membrane of analysis and research.
The raw material of the permeable membrane that the present invention adopted comprises shitosan, synthesis hydrotalcite-like material, butanedial and synthetic fibers; The composite film that shitosan and synthesis hydrotalcite-like material form has adsorptive concentration oil product Semi-polarity sulfur-containing compound and controls it and in film, permeate diffusion process, is main function module; Butanedial is a cross-linked material, and synthetic cellulose is the supporting layer of membrane material;
The parts by weight of each raw material components consumption of permeable membrane are: 2～10 parts of shitosans, 70～80 parts of synthesis hydrotalcite-like materials, 0.2～0.9 part of butanedial, 17.8～19.1 parts of synthetic fibers.
Wherein, the shitosan of being selected for use is that deacetylation is 75-85%, and molecular weight is the low molecular shitosan of 8000-15000;
The framework material synthesis hydrotalcite-like material of being selected for use is to use MgCl
26H
2O, AlCl
36H
2O and FeCl
36H
2O is a raw material, presses (0.5～0.9): (3～1): the representative molecular formula of the synthetic preparation of the mol ratio of (1～3) is Fe
0.87Mg
2.60[Al (OH)
10.2Cl
0.6] the stratiform houghite compound of hexagonal laminated crystalline particle.Particle diameter is distributed in 60～202nm, the average thickness 30～40nm of laminated crystalline, and interlamellar spacing 0.70～0.83nm, interlayer channel height are 0.30～0.7nm, specific area 1200～1820m
2/ g, point of zero electric charge 10.35～11.25, isoelectric point 11.2～12.1.It has the houghite crystal structure X-ray analysis proof: its characteristic angle of diffraction 2 θ be respectively 10.2 (°); 22.5 (°); 34.6 (°); 59.8 (°); Characteristic peak d value is respectively 0.776nm; 0.387nm; 0.258nm; 0.232nm.
The preparation method of the shitosan/synthetic hydrotalcite composite permeable membrane that is adopted in the oil product desulfurization method according to the invention is following: the shitosan of 2～10 weight portions is dissolved in the 3wt% aqueous acetic acid; Under constantly stirring, add the synthesis hydrotalcite-like material fine powder of 70～80 weight portions, stirred 2 hours; At room temperature add the 25wt% butanedial solution of 0.8～3.6 weight portion, make shitosan generation cross-linking reaction, obtain the synthesis hydrotalcite-like material suspension that the surface scribbles crosslinked chitosan film; 15% synthetic fibers cellulose solution is coated on the glass substrate surface,, obtains the support membrane of 15-32 μ m 100 ℃ of oven dry down; Suspension with the shitosan/synthesis hydrotalcite-like material for preparing is spin-coated on the synthetic fibers supporting film again; 60 ℃ of oven dry down; Obtain the film that total film thickness is 25-62um, strip down, be the osmotic evaporating and separating membrane that this sulfur method adopts from glass substrate surface.
The present invention be used for the chitosan molecule of the composite membrane of desulfurizing oil can intercalation to the interlayer of houghite; Film surface and interlayer passage have strong affinity ability to hydrone and polar organic compound; So-called strongly hydrophilic is its strong affinity to hydrone or polar organic compound; This strong affinity interaction is derived from a large amount of hydroxyl that contains in the chitosan molecule and the hydrogen-oxygen group in amide groups and the synthesis hydrotalcite-like material structure; This strongly hydrophilic composite membrane has strong affinity interaction to the polarity sulfur-containing compound in the gasoline; Help it the concentrating of film module near zone, the synthesis hydrotalcite-like material in the film module is a kind of inorganic material with certain rigidity layer structure, has very big specific area.System has very big mass transfer interface and high mass-transfer efficiency, and this film module has high mechanical strength and long useful life.Because chitosan molecule is on the surface that is distributed in synthesis hydrotalcite-like material of molecular level in the permeable membrane; Be cross-linked into network structure with the butanedial reaction again; Free volume is big, makes film have high permeation flux, and sulfur-containing compound is had strong selective permeation ability.
The composite membrane permeation flux that the present invention is used for desulfurizing oil is 120～136kg/m
2H, separation are 56.3～62.2.
Composite membrane separating property and prior art that the present invention is used for the film separation contrast as follows:
| Composite membrane | Liquid mixture | Temperature | Permeation flux kg/m 2·h | Separation | Documents |
| Shitosan/synthesis hydrotalcite-like material | Naphtha/thiophene sulfocompounds | 25 | 120 | 56.3 | The embodiment of the invention 1 |
| Shitosan/synthesis hydrotalcite-like material) | Catalysis light oil/thiophene | 28 | 136 | 62.2 | The embodiment of the invention 3 |
| Polysiloxanes (PDMS)/polyacrylonitrile (PAN) | Normal octane/ |
30 | 0.37 | 5.2 | 〔1〕 |
| Shitosan (CA)/beta cyclodextrin (β-CD) | D-type tryptophan/mixture of enantiomers | 25 | 0.388 | 2.33 | 〔2〕 |
| Polysiloxanes (PDMS)/pottery | Ethanol/ |
60 | 12.95 | 6.25 | 〔3〕 |
| Polysiloxanes (PDMS)/Ni 2+The Y zeolite | Gasoline/sulfur-containing |
40 | 3.26 | 4.84 | 〔4〕 |
Documents:
(1), Zhao Changwei, Li Jiding etc., " membrane science and technology " 2006,26 (5), 72
〔2〕、H.D.Wang，L.Y.Chu，et.al，《J.of?Membrane?Sci》2007，297，262
〔3〕、X.L.Fenjuan，W.Wang，et.al，《J.of?Membrane?Sci》2008，311，23
〔4〕、B.Li，D.XU，et.al，《J.of?Membrane?Sci》2008，322，293
Pervaporation according to the invention separates sulfur method, can be used for the separation of the contained multiple sulfur-containing compound in all kinds of oil products.Described raw material oil product can be light naphtha, catalytic cracking light petrol, catalytic cracking heavy gasoline and/or coking liquefied hydrocarbon mixture.Said sulfur-containing compound can be thio-alcohol, hydrogen sulfide, thioether class and/or thiophene-type sulfide.
Description of drawings:
Fig. 1 is for using single-stage permeable membrane desulfurization sketch map
Fig. 2 is for using three grades of permeable membrane desulfurization sketch mapes
Fig. 3 is-the synthesis hydrotalcite-like material X-ray diffractogram
Wherein 003 peak d value is 0.776nm among Fig. 3
006 peak d value is 0.387nm
009 peak d value is 0.258nm
015 peak d value is 0.232nm
The specific embodiment:
Embodiment 1. single-stage permeable membrane sweetening processes
Pending feedstock oil is from the coker light oil cut, and sulfur-containing compound is mainly thiophene, benzothiophene, and its sulfur content is 1590ppm..The single-stage permeable membrane module that adopts 2 weight portion shitosans, 80 weight portion synthesis hydrotalcite-like materials, 0.2 weight portion butanedial and 17.8 weight portion cellulose acetates to process.With pending feedstock oil 3.3 * 10
5Under the Pa pressure, in the volume flow entering film separation system with 120 liters/min, film module is the single-stage flat sheet membrane, template thickness 62 μ m, and the vacuum pressure of film module penetrant vapour phase one side remains on 7.5 * 10
3Under the Pa, the rich sulphur penetrant steam in the film system condenses with 26 ℃ quencher.Product oil sulfur-bearing is 110ppm after the gained desulfurization.The sulfur-containing compound removal efficiency is 93.25%.
Embodiment 2. single-stage permeable membrane sweetening processes
Pending feedstock oil comes the catalytic cracking light naphtha, and sulfur-containing compound is mainly thio-alcohol and thiophene, and its sulfur content is 1590ppm..The single-stage permeable membrane module that adopts 6 weight portion shitosans, 74 weight portion synthesis hydrotalcite-like materials, 0.5 weight portion butanedial and 19.5 weight portion cellulose acetates to process.Under normal pressure, in the volume flow entering film separation system with 115 liters/min, film module is the single-stage flat sheet membrane with pending feedstock oil, template thickness 56 μ m, and the vacuum pressure of film module penetrant vapour phase one side remains on 8 * 10
3Under the Pa, the rich sulphur penetrant steam in the film system condenses with 28 ℃ quencher.Product oil sulfur-bearing is 90ppm after the gained desulfurization.The sulfur-containing compound removal efficiency is 95.7%.
3. 3 grades of combined films modules of embodiment infiltration-evaporation sweetening process
Pending feedstock oil is the catalytic cracking light naphtha, and sulfur-containing compound is mainly thio-alcohol, thiophene-based, and its sulfur content is 1925ppm.Adopt 10 weight portion shitosans, 70 weight portion synthesis hydrotalcite-like materials, 0.9 weight portion butanedial and 19.1 weight portion cellulose acetates to process a grade combined films, template thickness 36 μ m, desulfurizer are three grades of permeable membrane modular systems.With pending feedstock oil 1.1 * 10
5Under the Pa, flow 125L/min gets into first order film template high sulfur content one side down, and membrane permeate one side keeps the vacuum of 11.9kPa.The penetrant vapour phase is with 26 ℃ quencher condensation.After one-level film permeability and separation, the sulfur content of poor sulphur penetrant is reduced to 425ppm, then 1.1 * 10
5Pa, flow 125L/min get into down second level film template than low sulfur content oil one side.The vacuum that keeps 6.6kPa in penetrant one side.Penetrant steam is with 26 ℃ quencher condensation.After second level film separated, the sulfur content of poor sulphur penetrant was reduced to 109ppm.And then entering third level lamina membranacea separation entering pressure is 2.1 * 10
5Pa, flow 95L/min penetrant one side keeps the vacuum of 1.3kPa, and penetrant steam is with 26 ℃ quencher condensation.After third level lamina membranacea separated, the sulfur content of product gasoline was less than 15ppm.
Claims (7)
1. method of utilizing the film separation process to remove sulfur-containing compound in the oil product; It is characterized in that adopting the high-hydrophilic shitosan is adsorbed on the compound permeable membrane of organic/inorganic that forms on the strongly hydrophilic synthesis hydrotalcite-like material particle surface with layer structure major function module as the film separation module; Utilize permeable membrane that the sulfur-containing compound in the oil product is had strong affinity interaction; Make that sulfur-containing compound is enriched near film module one side in the oil phase, rely on the high concentration difference that exists with film module vapour phase one side, optionally see through film module fast; Get into permeable membrane vapor phase one side, thereby oil product is separated with sulfur-containing compound; Said compound permeable membrane is processed by shitosan, synthesis hydrotalcite-like material, butanedial and cellulose acetate; The parts by weight of each amounts of components are: 2～10 parts of shitosans; 70～80 parts of synthesis hydrotalcite-like materials, 0.2～0.9 part of butanedial, 17.8～19.1 parts of cellulose acetates; The preparation method of compound permeable membrane is: shitosan is dissolved in the 3 wt% aqueous acetic acids, under constantly stirring, adds the synthesis hydrotalcite-like material fine powder, stirred 2 hours; At room temperature add 25wt% butanedial solution, make shitosan generation cross-linking reaction, obtain the synthesis hydrotalcite-like material suspension that the surface scribbles crosslinked chitosan film; Cellulose acetate solution with 15% is coated on the glass substrate surface, 100 ℃ of oven dry down, obtains the support membrane of 15-32 μ m; Suspension with the shitosan/synthesis hydrotalcite-like material for preparing is spin-coated on the cellulose acetate support membrane again, and 60 ℃ of oven dry down obtain the film that total film thickness is 25-62 μ m, strip down from glass substrate surface, are the compound permeable membrane that is adopted.
2. the method for utilizing the film separation process to remove sulfur-containing compound in the oil product as claimed in claim 1 is characterized in that the process conditions of desulfurizing oil process are following:
Raw material oil product feed pressure (1～3.3) * 10
5Pa
Raw material oil product flow 115～125L/min
Membrane permeate one side vacuum (1～12) * 10
3Pa
25～30 ℃ of penetrant steam condensation temperatures.
3. the method for utilizing the film separation process to remove sulfur-containing compound in the oil product as claimed in claim 1 is characterized in that described film separation module adopts one-level, secondary or three grades of combined films modular systems.
4. the method for utilizing the film separation process to remove sulfur-containing compound in the oil product as claimed in claim 3 is characterized in that one-level module infiltration sweetening process is:
Pending oil product is sent into film separation module oil product liquid phase one side, the opposite side of film from the oil product import under pressure; Be sulfur-rich compounds penetrant vapor phase one side, keep vacuum or lower pressure, the sulfur-containing compound in the oil product is under the strong affinity effect of compound permeable membrane; Near film module one lateral enrichment, under the promotion of film both sides steam pressure difference, film is passed through in infiltration in oil phase; Go from membrane permeate one sidesway with steam condition, the oil product after the desulfurization reclaims from the oil product outlet;
The main technique condition of one-level permeable membrane module desulfurization is following:
Pending oil product feed pressure (1～3.3) * 10
5Pa
Pending oil product flow 115～125L/min
Membrane permeate one side vacuum (7.5～8) * 10
3Pa
25～30 ℃ of penetrant steam condensation temperatures.
5. the method for utilizing the film separation process to remove sulfur-containing compound in the oil product as claimed in claim 3 is characterized in that the sweetening process of three grades of combined films modules is:
Pending oil product at first gets into first order film separation module liquid phase oil product one side; Penetrant one side of film keeps vacuum or lower pressure; Sulfur-containing compound in the oil product is under the promotion of film both sides steam pressure difference, and infiltration is gone from membrane permeate one sidesway with steam condition through film;
Liquid phase oil product one side through the oil product of the low sulfur content of first grade desulfurizing gets into second level film separation module again repeats the separation process of the sulfur-containing compound of first order module, and the sulfur content in the liquid phase oil product is further reduced;
Through the oil product of secondary desulfurization, get into liquid oil product one side of third level film separation module in succession again, again sulfur-containing compound is wherein carried out permeability and separation one time, obtain the super-low sulfur oil product in liquid phase oil product one side at last;
The main technique condition of three grades of combined films modules desulfurization is following:
Pending oil product feed pressure (1～3.3) * 10
5Pa
Pending oil product flow 115～125L/min
Membrane permeate one side vacuum (1～12) * 10
3Pa
25～30 ℃ of penetrant steam condensation temperatures.
6. the method for utilizing the film separation process to remove sulfur-containing compound in the oil product as claimed in claim 1; The shitosan of being selected for use in the compound permeable membrane that it is characterized in that being adopted is that deacetylation is 75-85%, and molecular weight is the low molecular shitosan of 8000-15000; The synthesis hydrotalcite-like material of being selected for use is the houghite compound of laminated crystalline, particle diameter distribution 60～202nm, laminated crystalline average thickness 30～40nm, interlamellar spacing 0.70～0.83nm, interlayer channel height 0.30～0.7nm, specific area 1200～1820m
2/ g, point of zero electric charge 10.35～11.25, isoelectric point 11.2～12.1.
7. the method for utilizing the film separation process to remove sulfur-containing compound in the oil product as claimed in claim 1 is characterized in that can be used for the separation of multiple sulfur-containing compound contained in all kinds of oil products; Described oil product is light naphtha, catalytic cracking light petrol, catalytic cracking heavy gasoline and/or coking liquefied hydrocarbon mixture; Said sulfur-containing compound is thio-alcohol, hydrogen sulfide, thioether class and/or thiophene-type sulfide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910020663 CN101927130B (en) | 2009-04-16 | 2009-04-16 | Method for removing sulfur-containing compounds from oil by utilizing membrane process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910020663 CN101927130B (en) | 2009-04-16 | 2009-04-16 | Method for removing sulfur-containing compounds from oil by utilizing membrane process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101927130A CN101927130A (en) | 2010-12-29 |
| CN101927130B true CN101927130B (en) | 2012-11-28 |
Family
ID=43366717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910020663 Active CN101927130B (en) | 2009-04-16 | 2009-04-16 | Method for removing sulfur-containing compounds from oil by utilizing membrane process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101927130B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011079647A1 (en) * | 2011-07-22 | 2013-01-24 | Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH | Membrane module for organophilic pervaporation |
| CN104629097B (en) * | 2013-11-13 | 2017-02-08 | 中国科学院海洋研究所 | Carboxymethyl chitosan-hydrotalcite nanocomposite hydrogel film and preparation method thereof |
| FR3045403B1 (en) * | 2015-12-18 | 2022-02-11 | Electricite De France | MEMBRANE REGENERATION SYSTEM OF AN ACID GAS CAPTURE SOLVENT |
| CN110496637B (en) * | 2018-05-17 | 2021-10-19 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation |
| CN108913196A (en) * | 2018-08-08 | 2018-11-30 | 盐城市锦瑞石油机械有限公司 | A kind of intelligence oil desulfurization equipment |
| CN112755793B (en) * | 2020-12-31 | 2022-05-24 | 浙江工业大学 | Hydrophobic modified black talc-based composite pervaporation membrane and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7041212B2 (en) * | 2001-02-16 | 2006-05-09 | W.R. Grace & Co. - Conn. | Membrane separation for sulfur reduction |
| CN1974729A (en) * | 2006-11-23 | 2007-06-06 | 中国石油化工股份有限公司 | Prepn process of membrane material for desulfurizing FCC gasoline |
| CN101100613A (en) * | 2006-07-06 | 2008-01-09 | 中国科学院大连化学物理研究所 | Oil product desulfurization method |
-
2009
- 2009-04-16 CN CN 200910020663 patent/CN101927130B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7041212B2 (en) * | 2001-02-16 | 2006-05-09 | W.R. Grace & Co. - Conn. | Membrane separation for sulfur reduction |
| CN101100613A (en) * | 2006-07-06 | 2008-01-09 | 中国科学院大连化学物理研究所 | Oil product desulfurization method |
| CN1974729A (en) * | 2006-11-23 | 2007-06-06 | 中国石油化工股份有限公司 | Prepn process of membrane material for desulfurizing FCC gasoline |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101927130A (en) | 2010-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101927130B (en) | Method for removing sulfur-containing compounds from oil by utilizing membrane process | |
| CN101927132B (en) | Chitosan/ synthetic hydrotalcite composite permeable membrane, preparation method and application thereof | |
| Saha et al. | Review on recent advances in adsorptive desulfurization | |
| Wang et al. | MCM-41@ ZIF-8/PDMS hybrid membranes with micro-and nanoscaled hierarchical structure for alcohol permselective pervaporation | |
| KR101452081B1 (en) | High permeance polyimide membranes for air separation | |
| JP5750109B2 (en) | Method for improving the selectivity of polybenzoxazole membranes | |
| CN102448591A (en) | Polymer membranes prepared from aromatic polyimide membranes by thermal treating and UV crosslinking | |
| CN102448592A (en) | Polymer membranes derived from aromatic polyimide membranes | |
| KR20130137238A (en) | Polyimide gas separation membranes | |
| CN102448593A (en) | High performance cross-linked polybenzoxazole and polybenzothiazole polymer membranes | |
| JP5124158B2 (en) | Methane concentration apparatus and method | |
| Lin et al. | A high ZIF-8 loading PVA mixed matrix membrane on alumina hollow fiber with enhanced ethanol dehydration | |
| WO2010032474A1 (en) | Method for producing alcohol, method for producing hydrogen or synthetic gas using the method for producing alcohol, and alcohol | |
| Hosseini et al. | Progress in high performance membrane materials and processes for biogas production, upgrading and conversion | |
| Li et al. | A graphene oxide membrane with self‐regulated nanochannels for the exceptionally stable bio‐oil dehydration | |
| WO2017003661A1 (en) | Cross-linked mixed matrix membranes by in-situ polymerization | |
| Sajjad et al. | Development of novel hydrophilic ionic liquid membranes for the recovery of biobutanol through pervaporation | |
| Bolto et al. | New generation vapour permeation membranes | |
| RU2726354C1 (en) | Highly elastic polymer membranes for separation process | |
| Lee et al. | Zeolite adsorbents for the separation of n-butyric acid from fermentation broths via adsorption | |
| Zhang et al. | Chitosan/polyvinylpyrrolidone‐silica hybrid membranes for pervaporation separation of methanol/ethylene glycol azeotrope | |
| CN102716683B (en) | A kind of pervaporation hybrid membrane and uses thereof | |
| CN101100613A (en) | Oil product desulfurization method | |
| Lin et al. | Y type zeolites/PI membranes for sulfur-free hydrogen source and for fuel cell applications | |
| JP2001038159A (en) | Separation membrane for organic liquid mixture |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160310 Address after: North Qilihe Road, Licheng District, Shandong city of Ji'nan Province, No. 2 250100 Patentee after: SHANDONG TAIDE NEW ENERGY Co.,Ltd. Address before: Xinluo Avenue high tech Zone of Ji'nan City, Shandong province 250100 No. 786 Room 201 Patentee before: JINAN DEVELOPMENT ZONE XINGHUO SCIENCE AND TECHNOLOGY Research Institute |
|
| PP01 | Preservation of patent right |
Effective date of registration: 20191017 Granted publication date: 20121128 |
|
| PP01 | Preservation of patent right | ||
| PD01 | Discharge of preservation of patent |
Date of cancellation: 20221017 Granted publication date: 20121128 |
|
| PD01 | Discharge of preservation of patent | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20230207 Granted publication date: 20121128 |
|
| PP01 | Preservation of patent right |