CN105861030B - Gasoline alkylation desulfuration method based on modified heteropolyacid catalyst and products thereof - Google Patents
Gasoline alkylation desulfuration method based on modified heteropolyacid catalyst and products thereof Download PDFInfo
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- CN105861030B CN105861030B CN201510030421.3A CN201510030421A CN105861030B CN 105861030 B CN105861030 B CN 105861030B CN 201510030421 A CN201510030421 A CN 201510030421A CN 105861030 B CN105861030 B CN 105861030B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 49
- 230000029936 alkylation Effects 0.000 title claims abstract description 32
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 32
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical group [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims description 17
- 150000001336 alkenes Chemical class 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 238000007171 acid catalysis Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 229910020628 SiW12O40 Inorganic materials 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 37
- 239000000047 product Substances 0.000 description 22
- 230000023556 desulfurization Effects 0.000 description 19
- 239000000377 silicon dioxide Substances 0.000 description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- -1 60 seconds Chemical compound 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000001765 gas chromatography-flame photometric detection Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- UYDPQDSKEDUNKV-UHFFFAOYSA-N phosphanylidynetungsten Chemical compound [W]#P UYDPQDSKEDUNKV-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The present invention provides a kind of gasoline alkylation desulfuration method based on modified heteropolyacid catalyst, is contacted the described method includes gasoline and modified heteropolyacid catalyst is made at a temperature of inert atmosphere, 0.2 1.0Mpa, 50 150 DEG C；Wherein described catalyst is with gasoline according to weight ratio 1:(8 30), add；Wherein described modified heteropolyacid catalyst is amino silane modified heteropolyacid catalyst.The invention further relates to the gasoline products obtained by the method for the present invention, and the amino silane modified heteropolyacid catalyst used in the method for the present invention.
Description
Technical field
The present invention relates to a kind of gasoline alkylation desulfuration method based on modified heteropolyacid catalyst and its thus method obtains
The gasoline products obtained.
Technical background
At present, increasingly stringent with what is limited content of sulfur in gasoline, gasoline desulfurization technology is increasingly taken seriously.Work at present
Widely used in industry is gasoline hydrodesulfurizationmethod technology, although hydrodesulfurization technical matters is ripe, its cost of investment is high, operation
Equipment is expensive, hydrogen-consuming volume is big and deep desulfuration there are larger loss of octane number.Therefore, the exploitation of non-hydrodesulfurization new technology is got over
To be more valued by people, become the hot spot of current gasoline desulfurization technological development.Alkylation desulfurization of gasoline technology is included vapour
Oil is contacted with acidic catalyst, is made the alkene in Removal of Sulfur Compounds from Gasoline and gasoline that alkylated reaction occur, is produced height boiling
The alkylation sulfur-containing compound of point, then again cuts to sulfide in diesel oil distillate by distillation, so as to reduce gasoline fraction
In sulfur content.The technical operation condition relaxes, small investment, and hydrogen-free consumption, has the double effects of desulfurization and Olefin decrease.
For alkylating desulfurization technology, its process of the development and application of catalyst is vital.It is right at present
It can be divided into following 5 class from the source division for providing acid centre in alkylating and desulfurizing catalyst：(1) sulfonate resin class is catalyzed
Agent；(2) molecular sieve catalysts；(3) heteropoly acid (salt) class catalyst；(4) halogen metal class catalyst is loaded；(5) phosphorus is loaded
Acid catalyst.As a kind of in solid acid catalyst, heteropoly acid (salt) class catalyst be develop in recent years it is a kind of new solid
Body acid catalyst.Heteropoly acid is by being by the general name of condensation oxyacid prepared by different oxyacid condensations, oxyacid such as phosphorus tungsten
Acid, silico-tungstic acid, silicomolybdic acid etc..Heteropllyacids compound has superpower acidity, low temperature high activity and false liquid phase behavior, has acidity concurrently
And the advantages of oxidation susceptibility, compared to liquid acid catalyst, overcome the characteristics of corrosivity of liquid acid catalyst is with pollution environment.
Generally require catalyst that there is higher specific surface area in practical applications, but the reference area of heteropoly acid is smaller, generally about
10m2/ g is, it is necessary to be loaded on the carrier of high-specific surface area, generally use sulfonate resin, molecular sieve, silica, dioxy
Change titanium, activated carbon etc..
It is many on the supported method of heteropoly acid at present, such as：Infusion process, absorption method, coprecipitation, sol-gel process
Deng different carriers uses different solid support methods, because the selection of solid support method will directly influence heteropoly acid and carrier table
The immobilized fastness in face, and then influence the catalytic activity height and service life of catalyst.
CN1078096 discloses a kind of catalyst of loading silicon dioxide with heteropoly acid, wherein using particle diameter as the super of 1-100nm
Fine silica is carrier, loads 5-80wt% heteropoly acids.Certain density heteropoly acid solution is prepared first, by itself and titanium dioxide
Silicon mixes, and fully mediates and forms uniform colloidal sol, then dry, roasts, that is, the heteropolyacid catalyst loaded.Though the invention
So heteropoly acid is preferably loaded on silica supports, but still without solve heteropoly acid in subsequent reactions easy solution-off it is scarce
Point, causes the performance of gasoline products to be insufficient to.
Therefore, it is still necessary to the new catalyst for alkylation desulfurization of gasoline is developed, it is excellent to be obtained based on the catalyst
Gasoline products.
The content of the invention
The present invention provides a kind of gasoline alkylation desulfuration method based on modified heteropolyacid catalyst, the described method includes：
Gasoline and modified heteropolyacid catalyst is set to be contacted at a temperature of inert atmosphere, 0.2-1.0Mpa, 50-150 DEG C；
Wherein described catalyst is with gasoline according to weight ratio 1:(8-30), preferably 1:(10-25), more preferably 1:(12-20)
Add；
Wherein described modified heteropolyacid catalyst is amino silane modified heteropolyacid catalyst, it makes by the following method
It is standby：
(a) heteropoly acid and amino silane are dissolved in solvent respectively and form solution A and solution B, then by solution A and solution B
Solution C is mixed to form, is heated to reflux；Wherein heteropoly acid has below general formula (I)：
H3[XY12O40] (I)
Wherein variable is each defined as follows：
X is P, Si, Fe or Co, and preferably X is P, Si；
Y is W, Mo or V, and preferably Y is W, Mo；
(b) inorganic carrier is added in solution C, then stirs, filters, washing, is dry, roasting, obtain modified heteropoly acid
Catalyst；
Gross weight meter wherein based on modified heteropolyacid catalyst, the amount of the heteropoly acid is 10-60 weight %, preferably
15-55 weight %, more preferably 20-45 weight %.
Another aspect, the present invention also provides the gasoline products by foregoing gasoline alkylation desulfuration method acquisition.
Another further aspect, the present invention also provides the modification heteropoly acid catalysis in the gasoline alkylation desulfuration method for the present invention
Agent；The modified heteropolyacid catalyst, is prepared by the following method：
(a) heteropoly acid and amino silane are dissolved in solvent respectively and form solution A and solution B, then by solution A and solution B
Solution C is mixed to form, is heated to reflux；Wherein heteropoly acid has below general formula (I)：
H3[XY12O40] (I)
Wherein variable is each defined as follows：
X is P, Si, Fe or Co, and preferably X is P, Si；
Y is W, Mo or V, and preferably Y is W, Mo；
(b) inorganic carrier is added in solution C, then stirs, filters, washing, is dry, roasting, obtain modified heteropoly acid
Catalyst；
Gross weight meter wherein based on modified heteropolyacid catalyst, the amount of the heteropoly acid is 10-60 weight %, preferably
15-55 weight %, more preferably 20-45 weight %.
Used in the gasoline alkylation desulfuration method of the present invention based on through amino silane modified heteropolyacid catalyst,
Fabulous anti-solution-off performance and excellent desulfurization effect are shown, thus the method for the present invention obtains sulfur content and is less than 50ppm
Gasoline products.
Brief description of the drawings
Fig. 1 is the GC-SCD spectrograms before and after FCC gasoline desulfurization.
Embodiment
The present invention provides a kind of gasoline alkylation desulfuration method based on modified heteropolyacid catalyst, the method bag
Include：Gasoline and modified heteropolyacid catalyst is set to be contacted at a temperature of inert atmosphere, 0.2-1.0Mpa, 50-150 DEG C；
Wherein described catalyst is with gasoline according to weight ratio 1:(8-30), preferably 1:(10-25), more preferably 1:(12-20)
Add；
Wherein described modified heteropolyacid catalyst is amino silane modified heteropolyacid catalyst, it makes by the following method
It is standby：
(a) heteropoly acid and amino silane are dissolved in solvent respectively and form solution A and solution B, then by solution A and solution B
Solution C is mixed to form, is heated to reflux；Wherein heteropoly acid has below general formula (I)：
H3[XY12O40] (I)
Wherein variable is each defined as follows：
X is P, Si, Fe or Co, and preferably X is P, Si；
Y is W, Mo or V, and preferably Y is W, Mo；
(b) inorganic carrier is added in solution C, then stirs, filters, washing, is dry, roasting, obtain modified heteropoly acid
Catalyst；
Gross weight meter wherein based on modified heteropolyacid catalyst, the amount of the heteropoly acid is 10-60 weight %, preferably
15-55 weight %, more preferably 20-45 weight %.
Another aspect, the present invention also provides the gasoline products by foregoing gasoline alkylation desulfuration method acquisition.
Another further aspect, the present invention also provides the modification heteropoly acid catalysis in the gasoline alkylation desulfuration method for the present invention
Agent；The modified heteropolyacid catalyst, is prepared by the following method：
(a) heteropoly acid and amino silane are dissolved in solvent respectively and form solution A and solution B, then by solution A and solution B
Solution C is mixed to form, is heated to reflux；Wherein heteropoly acid has below general formula (I)：
H3[XY12O40] (I)
Wherein variable is each defined as follows：
X is P, Si, Fe or Co, and preferably X is P, Si；
Y is W, Mo or V, and preferably Y is W, Mo；
(b) inorganic carrier is added in solution C, then stirs, filters, washing, is dry, roasting, obtain modified heteropoly acid
Catalyst；
Gross weight meter wherein based on modified heteropolyacid catalyst, the amount of the heteropoly acid is 10-60 weight %, preferably
15-55 weight %, more preferably 20-45 weight %.
Used in the gasoline alkylation desulfuration method of the present invention based on through amino silane modified heteropolyacid catalyst,
Fabulous anti-solution-off performance and excellent desulfurization effect are shown, thus the method for the present invention obtains the gasoline production of low sulfur content
Product.It is not intended to stick to any theory, now thinking that this effect is derived from is included with amino silane modified catalyst preparation and application
Process.
In the present specification, following preferred feature is suitable for gasoline alkylation desulfuration method, product and its modified heteropoly acid
Catalyst.
The present invention gasoline alkylation desulfuration method can in a continuous manner or batch process carry out.
In a preferred embodiment of the invention, gasoline alkylation desulfuration method of the invention with batch process into
OK；Wherein described gasoline and modified heteropolyacid catalyst contact in a kettle, and reactor temperature is down to room temperature after reaction,
Catalyst is isolated, obtains gasoline products.
In a preferred embodiment of the invention, the gasoline alkylation desulfuration method is carried out as follows：
1) gasoline and modified heteropolyacid catalyst are added and mixes and kept under an inert atmosphere in reaction kettle；
2) pressure is risen into 0.2-1.0Mpa, temperature rises at 50-150 DEG C, reacted；
3) reactor temperature is down to room temperature, isolates catalyst, obtain gasoline products.
In a preferred embodiment of the invention, gasoline and modified heteropolyacid catalyst are added in reaction kettle and mixed
And keep under an inert atmosphere, nitrogen can be selected in inert atmosphere, such as is purged 30-300 seconds with nitrogen, such as 60 seconds, and keeps anti-
It is normal pressure to answer in kettle.
In a preferred embodiment of the invention, in gasoline alkylation desulfuration method of the invention, pressure is risen to
0.2-1.0Mpa, preferably 0.4-0.8Mpa, such as 0.5Mpa；Temperature rises to 50-150 DEG C, preferably 70-105 DEG C, such as 90 DEG C,
Reacted at least more than 30 minutes, such as 30-120 minutes, such as 60 minutes；
In a preferred embodiment of the invention, in gasoline alkylation desulfuration method of the invention, by reaction kettle
Temperature is down to room temperature, isolates catalyst, obtains gasoline products；The catalyst isolated can be recycled for multiple times, such as 10-20
It is secondary.In one embodiment of the invention, catalyst circulation of the invention 10 times still has excellent desulfurization effect and does not have
It is found the solution-off phenomenon of catalyst.
In a preferred embodiment of the invention, wherein the catalyst and gasoline are according to weight ratio 1:(8-30),
It is preferred that 1:(10-25), more preferably 1:(12-20) is added.
In a preferred embodiment of the invention, prepare in catalyst, the inorganic carrier with heteropoly acid solution
Before contact, acidifying, washing and drying are first passed through.It is preferred that with dilute hydrochloric acid, dust technology, dilute sulfuric acid, acetic acid diluted or its any mix
When thing processing 0.2-2 is small, then it is washed with deionized 1-2 times, then in 90-110 DEG C of drying.The purpose of this processing is clearly
Wash inorganic carrier.Acid concentration 0.1-0.2mol/L, preferably 0.1-0.15mol/L.It will preferably be acidified, wash and dried inorganic
Carrier is added in step (a), by heteropoly acid and inorganic carrier according to weight ratio 1:(1.5-9) is added, and stirring 1-12h, filter, wash
Wash, dry 1-6h, 200-380 DEG C of roastings 1-6h of 60 DEG C of vacuum, that is, obtain carried heteropoly acid catalyst.
In one embodiment of the invention, in the modified heteropolyacid catalyst, amino silane and heteropoly acid rub
Your ratio is 0.01-1:1, preferably 0.01-0.2:1, more preferably 0.05-0.1:1.
In the present invention, solvent used is alcohols, preferably ethers, alcohols, such as second in the step of preparing catalyst (a)
Alcohol.The solvent of solution A and the solvent of solution B can be the same or different, as long as both can form homogeneous solution；It is preferred that make
With identical solvent.
In the present invention, the concentration of solution A is 0.01-0.1mol/L, preferably 0.03- in the step of preparing catalyst (a)
0.1mol/L；The concentration of solution B is the preferred 0.03-0.1mol/L of 0.01-0.1mol/L.The concentration of solution A and the concentration of solution B
It can be the same or different, as long as the molar ratio for ensuring wherein amino silane and heteropoly acid is 1:10-10:1, preferably 1:5-5:
1, more preferably 1:2.5-2.5:1.
In one embodiment of the invention, the heteropoly acid of logical formula (I) is added in alcoholic solvent, it obtains concentration and is
0.01-0.1mol/L, then again with the alcoholic solution for the amino silane that concentration 0.01-0.1mol/L is wherein added dropwise, both rub
You are than being 1:10-10:1, it is heated to reflux 1-12h.
In one embodiment of the invention, wherein the heteropoly acid is preferably H3SiW12O40And/or H3PW12O40。
In one embodiment of the invention, amino silane has with lower structure：(Z1-O)3-Si-Z2-NH2, wherein Z1
For C1-C3Straight chained alkyl, Z2For C1-C6Straight chained alkyl, preferably C1-C4Straight chained alkyl, more preferably C1-C3Straight chained alkyl；In the present invention
Embodiment in, the amino silane is preferably aminopropyl triethoxysilane and/or aminopropyl trimethoxysilane.
In a preferred embodiment of the invention, inorganic carrier for silica, aluminium oxide, activated carbon, magnesia,
Titanium oxide, zirconium oxide, zeolite, molecular sieve, carbon fiber or natural clay or its mixture.It may further be preferable that inorganic carrier
For silica, or at least 90 weight %, preferably at least 95 weight %, the more preferably at least silica of 98 weight % with it is following
The mixture of material：Aluminium oxide, activated carbon, magnesia, titanium oxide, zirconium oxide, zeolite, molecular sieve, carbon fiber or natural clay.
Silica preferably has mesoporous, more preferably aperture 10-30nm, specific surface area 100-600m2/ g, preferably 100-300m2/g.Nothing
The average pore size of airborne body is measured according to DIN66134-1998 methods；Specific surface area utilizes BET method according to DIN66131-1993
Measure.
In the present invention, dry under preferred vacuum in the step of preparing catalyst (b), drying temperature is less than 60 DEG C, preferably
40-60℃；200-380 DEG C of calcination temperature, preferably 200-300 DEG C.
In the present invention, heteropoly acid and inorganic carrier are according to weight ratio 1 in the step of preparing catalyst (b):(1.5-9),
It is preferred that 1:(2-7), more preferably 1:(4-5) is added.
In the present invention, the gasoline can be that the end point of distillation is less than 210 DEG C, more than sulfur content 100ppm, alkene mass content
The gasoline of 30-60%.Wherein described catalyst is 1 according to weight ratio with gasoline:(8-30), preferably 1:(10-25) more preferably 1:
(12-20) is added.
Present invention also offers gasoline products made from foregoing gasoline alkylation desulfuration method, it meets that national standard will
Ask.
The sulfur content of the gasoline products is less than 50ppm, preferably shorter than 30ppm, more preferably less than 10ppm, alkene quality
Content is in 25-55%.The present invention also provides the gasoline alkylation desulfuration method for being used for the present invention prepared by mode as described above
In modification heteropolyacid catalyst.
In the present invention, such as illustrate without other, then all operations carry out under room temperature, condition of normal pressure.
In the present invention, unless otherwise stated, otherwise all contents according to weight meter.
In the present invention, material used is known substance, commercially available or synthesized by known method.
In the present invention, equipment therefor or equipment are conventional equipment or equipment known to the field, commercially available.
The present invention is described in further detail by the following examples.
Embodiment 1：Prepare carried heteropoly acid catalyst
(1) by silica (average pore size：15nm, specific surface area are：203m2/ g) add in 0.1mol/L hydrochloric acid and soak
1h, then deionized water wash 2 times after 100 DEG C it is dry 1.5 it is small when；
(2) by H3PW12O40.3H2O (0.1mol) is added in alcohol solvent, and the solution A that concentration is 0.1mol/L is made,
Then in the ethanol solution B for -3 Ethoxysilane of 3- aminopropyls (0.1mol) that concentration 0.1mol/L is wherein added dropwise, heating
Flow back 6h；
(3) silica by step (1) acidifying washing is added in the mixture that step (2) obtains, by heteropoly acid and two
Siliconoxide mass is than 1:5 add silica, and stirring 12h, filtering, deionized water wash 2 times, dry 3h, 200 at 60 DEG C of vacuum
DEG C roasting 3h, that is, obtain carried heteropoly acid catalyst.
Embodiment 2：Prepare carried heteropoly acid catalyst
(1) by silica (average pore size：15nm, specific surface area are：203m2/ g) add in 0.1mol/L hydrochloric acid and soak
1h, then deionized water wash 1 time after 110 DEG C it is dry 1 it is small when；
(2) by H3SiW12O40.3H2O (0.1mol) is added in alcohol solvent, and the solution that concentration is 0.05mol/L is made
A, then in the ethanol solution B for -3 Ethoxysilane of 3- aminopropyls (0.1mol) that concentration 0.05mol/L is wherein added dropwise, adds
Heat reflux 12h；
(3) silica by step (1) acidifying washing is added in step (2), by heteropoly acid and silica quality ratio
2:3 add silica, stirring 12h, filtering, deionized water wash 2 times, the dry 6h of 60 DEG C of vacuum, 350 DEG C roast 2h, to obtain the final product
To carried heteropoly acid catalyst.
Comparative example 1
Carried heteropoly acid catalyst：Heteropoly acid is without amino modified
(1) by silica (average pore size：15nm, specific surface area are：203m2/ g) add in 0.1mol/L hydrochloric acid and soak
1h, then deionized water wash 2 times after 100 DEG C it is dry 1.5 it is small when；
(2) by H3PW12O40.3H2O (0.1mol) is added in alcohol solvent, and the solution A that concentration is 0.1mol/L is made；
(3) silica by step (1) acidifying washing is added in the solution in step (2), by heteropoly acid and titanium dioxide
Silicon mass ratio 1:5 add silica, and stirring 12h, filtering, deionized water wash 2 times, dry 3h, 200 DEG C of roastings at 60 DEG C of vacuum
3h is burnt, that is, obtains comparative catalyst.
To investigate the solution-off performance of catalyst of the present invention, tested as follows：
Application Example 1
Catalyst prepared by 15g embodiments 1, adds in the reaction kettle that volume is 0.6 liter, according to gasoline/catalyst matter
Ratio 15 is measured, adds FCC gasoline (cycle oil, sulfur content 700ppm；45 weight % of olefin(e) centent) 225g, it is passed through nitrogen
(micro-positive pressure) purges about 1min, is then shut off valve, boosts to 0.5Mpa, be warming up to 90 DEG C, starts to count after reaching predetermined temperature
When, react after 1h and stop, reaction kettle being inserted room temperature is cooled down in cold water rapidly；Kettle is driven, retention of drawing oil sample carries out GC-SCD
(gas-chromatography-sulfur chemiluminescence detection instrument) is analyzed and ICP (inductively coupled plasma spectrum generator) analyses.
Catalyst filtration in reaction kettle is gone out, above-mentioned experiment is repeated after dry, is repeated 9 times altogether, the oil sample after each reaction
Retain and carry out GC-SCD analyses and icp analysis.
Using 1 catalyst of the embodiment of the present invention to the GC-SCD analysis results before and after FCC gasoline desulfurization as shown in Figure 1,
Its desulfurization degree is 93wt%.To the oil product icp analysis after desulfurization, the W elements in heteropoly acid are not detected, illustrate described urge
The non-solution-off of agent.Olefin(e) centent in gasoline, is measured using gas chromatography, and olefin(e) centent is 41wt% in its 1 product.It is real
Test that the result is shown in table 1 below.
Application Example 2
The process of test example 1 is repeated, difference is：Catalyst prepared by 15g embodiments 2, according to gasoline/
Catalyst quality adds reaction kettle than 12.Experimental result see the table below 1.
Application Example 3
The process of test example 1 is repeated, difference is：Catalyst prepared by 15g comparative examples 1, according to
Gasoline/catalyst quality adds reaction kettles than 15, and repeats above-mentioned experiment 1 time.Experimental result see the table below 1.
The performance comparison of 1 catalyst of the embodiment of the present invention of table and comparative example catalyst
| Embodiment 1 | Embodiment 2 | Comparative example 1 | |
| 1 desulfurization degree | 93wt% | 97wt% | 89wt% |
| 2 desulfurization degrees | 93wt% | 97wt% | 85wt% |
| 3 desulfurization degrees | 93wt% | 97wt% | 80wt% |
| 4 desulfurization degrees | 93wt% | 97wt% | 68wt% |
| Olefin(e) centent in 1 product | 41wt% | 40wt% | 43wt% |
| Olefin(e) centent in 2 products | 41wt% | 40wt% | 44wt% |
| Olefin(e) centent in 3 products | 41wt% | 40wt% | 44wt% |
| Olefin(e) centent in 4 products | 41wt% | 40wt% | 44wt% |
| 1 solution-off | Do not detect | Do not detect | Detection |
| 2 solution-off | Do not detect | Do not detect | Detection |
| 3 solution-off | Do not detect | Do not detect | Detection |
| 4 solution-off | Do not detect | Do not detect | Detection |
| 5 solution-off | Do not detect | Do not detect | —— |
| 6 solution-off | Do not detect | Do not detect | —— |
| 7 solution-off | Do not detect | Do not detect | —— |
| 8 solution-off | Do not detect | Do not detect | —— |
| 9 solution-off | Do not detect | Do not detect | —— |
| 10 solution-off | Do not detect | Do not detect | —— |
In table 1, icp analysis is carried out to each oil sample, W the or Mo elements in heteropoly acid is not detected, illustrates used catalyst not
Solution-off, is expressed as " not detecting "；If detecting W the or Mo elements in heteropoly acid, illustrate used catalyst solution-off, be expressed as " inspection
Go out ".Wherein " desulfurization degree " refers to the weight ratio of total sulfur content in the sulfur content removed in gasoline and gasoline, " alkene in product
Content " refers to the olefin(e) centent in gasoline products.
As can be seen from the above table, catalyst of the invention is amino modified by being carried out to heteropoly acid, with being adopted in contrast experiment
The catalyst prepared with conventional loading processes is compared, and has strong anti-solution-off and more preferable desulfurization effect.
Claims (11)
1. a kind of gasoline alkylation desulfuration method based on modified heteropolyacid catalyst, the described method includes making, gasoline and modification are miscellaneous
More acid catalysts contact at a temperature of inert atmosphere, 0.2-1.0Mpa, 50-150 DEG C；
Wherein described catalyst is with gasoline according to weight ratio 1:(8-30) is added；
Wherein described modified heteropolyacid catalyst is amino silane modified heteropolyacid catalyst, it is prepared by the following method：
(a) heteropoly acid and amino silane are dissolved in solvent respectively and form solution A and solution B, then mix solution A with solution B
Solution C is formed, is heated to reflux；Wherein heteropoly acid has below general formula (I)：
H3[XY12O40] (I)
Wherein variable is each defined as follows：
X is P, Si, Fe or Co；
Y is W, Mo or V；
(b) inorganic carrier is added in solution C, then stirs, filters, washing, is dry, roasting, obtain modified heteropoly acid catalysis
Agent；
Gross weight meter wherein based on modified heteropolyacid catalyst, the amount of the heteropoly acid is 10-60 weight %.
2. the gasoline alkylation desulfuration method described in claim 1, wherein the gasoline and modified heteropolyacid catalyst are reacting
Contacted in kettle, reactor temperature is down to room temperature after reaction, isolate catalyst, obtain gasoline products.
3. the gasoline alkylation desulfuration method described in claim 1, wherein the inorganic carrier is contacting it with heteropoly acid solution
Before, first pass through acidifying, washing and drying.
4. the gasoline alkylation desulfuration method of claim 1, wherein in the modified heteropolyacid catalyst, amino silane with it is miscellaneous more
The molar ratio of acid is 0.01-1:1.
5. in the gasoline alkylation desulfuration method of claim 1, wherein catalyst preparation step (a) solvent used be alcohols,
Ethers, the solvent of solution A and the solvent of solution B can be the same or different.
6. the gasoline alkylation desulfuration method described in one of claim 1-5, wherein the heteropoly acid is H3SiW12O40And/or
H3PW12O40。
7. the gasoline alkylation desulfuration method described in one of claim 1-5, wherein the ammonia in the modified heteropolyacid catalyst
Base silane has with lower structure：(Z1-O)3-Si-Z2-NH2, wherein Z1For C1-C3Straight chained alkyl, Z2For C1-C6Straight chained alkyl.
8. the gasoline alkylation desulfuration method of one of claim 1-5, wherein the gasoline is less than 210 DEG C for the end point of distillation, sulphur contains
Amount is more than 100ppm, the gasoline of alkene mass content 30-60%.
A kind of 9. gasoline products made from gasoline alkylation desulfuration method with any one of claim 1-8.
10. the gasoline products of claim 9, the sulfur content of the gasoline products is less than 50ppm.
11. a kind of heteropolyacid catalyst, is prepared by the following method：
(a) heteropoly acid and amino silane are dissolved in solvent respectively and form solution A and solution B, then mix solution A with solution B
Solution C is formed, is heated to reflux；Wherein heteropoly acid has below general formula (I)：
H3[XY12O40] (I)
Wherein variable is each defined as follows：
X is P, Si, Fe or Co；
Y is W, Mo or V；
(b) inorganic carrier is added in solution C, then stirs, filters, washing, is dry, roasting, obtain modified heteropoly acid catalysis
Agent；
Gross weight meter wherein based on modified heteropolyacid catalyst, the amount of the heteropoly acid is 10-60 weight %.
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| CN1233532A (en) * | 1998-03-10 | 1999-11-03 | 英国石油化学品有限公司 | Catalyst and use thereof |
| CN102079993A (en) * | 2010-12-31 | 2011-06-01 | 无锡蓝星石油化工有限责任公司 | Catalytic gasoline alkylation desulfuration method and device |
| CN102294270A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Catalyst applied to preparation of sec-butyl acetate by directly esterifying acetic acid and butylene |
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| WO1994021583A1 (en) * | 1993-03-13 | 1994-09-29 | Solvay Interox Limited | Oxidation of alcohols |
| CN1233532A (en) * | 1998-03-10 | 1999-11-03 | 英国石油化学品有限公司 | Catalyst and use thereof |
| CN102294270A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Catalyst applied to preparation of sec-butyl acetate by directly esterifying acetic acid and butylene |
| CN102079993A (en) * | 2010-12-31 | 2011-06-01 | 无锡蓝星石油化工有限责任公司 | Catalytic gasoline alkylation desulfuration method and device |
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