CN101508909B - Selective hydrogenation desulfurization and highly-branched chain isomerous coupling modification method for faulty gasoline - Google Patents
Selective hydrogenation desulfurization and highly-branched chain isomerous coupling modification method for faulty gasoline Download PDFInfo
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- 239000003502 gasoline Substances 0.000 title claims abstract description 146
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 39
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 34
- 238000002715 modification method Methods 0.000 title claims abstract description 19
- 238000010168 coupling process Methods 0.000 title claims abstract description 18
- 230000008878 coupling Effects 0.000 title claims abstract description 16
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 16
- 230000023556 desulfurization Effects 0.000 title claims description 25
- 238000000034 method Methods 0.000 claims abstract description 78
- 150000001336 alkenes Chemical class 0.000 claims abstract description 58
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- 229910018575 Al—Ti Inorganic materials 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 21
- 239000002808 molecular sieve Substances 0.000 claims abstract description 21
- 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 21
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 20
- 150000001993 dienes Chemical class 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 80
- 239000002131 composite material Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 238000005520 cutting process Methods 0.000 claims description 8
- -1 alkyl silicate Chemical compound 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 150000003608 titanium Chemical class 0.000 claims description 5
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- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 159000000013 aluminium salts Chemical class 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 34
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 31
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 21
- 229910052717 sulfur Inorganic materials 0.000 abstract description 20
- 239000011593 sulfur Substances 0.000 abstract description 20
- 238000005516 engineering process Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 12
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 5
- 238000006317 isomerization reaction Methods 0.000 abstract description 5
- 238000004321 preservation Methods 0.000 abstract 1
- 150000003464 sulfur compounds Chemical class 0.000 abstract 1
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- 239000005864 Sulphur Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 18
- 229910021536 Zeolite Inorganic materials 0.000 description 17
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 17
- 239000010457 zeolite Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- 150000001335 aliphatic alkanes Chemical class 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 10
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- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 8
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- 238000012545 processing Methods 0.000 description 8
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- 229910052782 aluminium Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 6
- 238000010523 cascade reaction Methods 0.000 description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
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- 206010013786 Dry skin Diseases 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
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- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 238000005899 aromatization reaction Methods 0.000 description 2
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- 230000002779 inactivation Effects 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 229910001220 stainless steel Inorganic materials 0.000 description 2
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- 239000010936 titanium Substances 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- QYHKLBKLFBZGAI-UHFFFAOYSA-N boron magnesium Chemical compound [B].[Mg] QYHKLBKLFBZGAI-UHFFFAOYSA-N 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical class [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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Abstract
The invention relates to a coupling modification method of selective hydrodesulfurization and multibranched isomerization for poor gasoline, in particular to hydro-upgrading for FCC gasoline. In the method, the FCC gasoline is treated by using coupling of two-stage hydrogenation technology so that the FCC gasoline is firstly contacted with Al-Ti complex carrier catalyst having double functions of diene deprivation and high-selective hydrodesulfurization to deprive unstable diene and difficultly deprived sulfur compound in raw oil and then contacted with SAPO-11 molecular sieve catalyst having double functions of hydrocarbon multibranched isomerism and supplementary desulfuration to further realize desulfuration, olefin reducing and product octane number preservation. The method can obtain better hydro-upgrading effect particularly for medium-sulfur and high-olefin poor FCC gasoline, can reduce octane number loss of products and keep higher product liquid yield by producing more high-octane number multibranched isoparaffin while reducing the contents of olefin and sulfur.
Description
Technical field
The present invention relates to a kind of inferior patrol; Especially hydrogenation and modification of catalytic gasoline; Relate in particular to a kind of refining of petroleum field and be used for the selective hydrodesulfurization and the highly-branched chain isomerous coupling modification method of hydro carbons of the FCC gasoline inferior of catalytic cracking (FCC) gasoline, particularly moderate sulfur, high olefin.
Background technology
At present, high olefin(e) centent and sulphur content become the key issue that puzzlement world clean gasoline is produced in the catalytically cracked gasoline.Under the less situation of high-octane number component reformed gasoline and gasoline alkylate, for satisfying the clean gasoline standard-required of increasingly stringent, the hydro-upgrading of FCC gasoline just becomes one of gordian technique that clean fuel for vehicle produces.
Introduced with desulfurization that unifining-cracking/single side chain hydroisomerizing is the master among USP 5770047, the USP 5417697 etc., fallen olefin process.The main thought of these technologies be with full cut FCC gasoline be cut into gently, last running; The last running of FCC gasoline is after conventional Hydrobon catalyst deep desulfuration is handled; Alkene wherein all is converted into alkane; Products obtained therefrom is accomplished alkane cracking-hydroisomerizing reaction on the zeolite based catalysts that has proper sourness through screening then, reaches the purpose of improving and recovering octane value, is in harmonious proportion through the weight cut subsequently and obtains full fraction upgrading gasoline.According to the record of above-mentioned patent, the liquid yield of product of finally being in harmonious proportion is 94wt%, and gasoline research method octane value (RON) loss reaches about 2.0 units.
Much more more though the gasoline hydrogenation modifying method that above-mentioned patent provides can realize desulfurization, fall the purpose of alkene, olefin(e) centent is merely about 20v% and aromaticity content higher (about 30v%) in the raw oil that it was directed against, to be applicable to external gasoline component; The oil product of, aromaticity content lower (about 20v%) all higher for alkene and sulphur content; For example, use this technology to carry out upgrading, in desulfurating and reducing olefinic hydrocarbon to China FCC gasoline of olefin(e) centent about up to 40v%; A large amount of alkene are saturated by hydrogenation; Cause the loss of octane value to increase, so the modification technology of these public reported obviously is inapplicable.So just reason, to the singularity of Chinese FCC gasoline, exploring more scientific and reasonable method for modifying is the research focus of oil refining industry all the time.
The method of the deep desulfurization olefin hydrocarbon reduction of gasoline that provides among the CN145666A (Chinese patent 02121595.2); It is exactly These characteristics to Chinese FCC gasoline; To implement hydrogenation desulfurization and denitrogenation and the alkene heavy naphtha after saturated through Hydrobon catalyst; Utilization has the HZSM-5 base octane value recovering catalyst of enough acid functions; Realize the cracking of low octane rating alkane molecule and the isomerization reaction of alkane molecule, the last running that will implement upgrading then is mixed into final upgraded products may with the lighting end that cutting obtains.Introduction according to this patent; Because alkene is by hydrogenation is saturated fully in first section reaction; For the octane value that recovers product need improve the cracking ability of two sections catalyzer, its cost is that significantly reduction (being merely 86%), the tooling cost of product liquid yield significantly improves.
CN 1488722A (Chinese patent 0213311.1) discloses the similar FCC gasoline hydrogenation modifying process of a kind of and above-mentioned patent.Difference is the last running of FCC gasoline after conventional Hydrobon catalyst deep desulfuration, alkene all are converted into alkane, and the gained reaction effluent is normal paraffin cracking-single side chain hydroisomerizing reaction of on nanometer H β zeolite based catalysts, accomplishing.
The similarity of the modifying process of above two China patent all is to make through the isomerizing on the zeolite based catalysts of acid function of conventional hydrorefined heavy distillate; Realize normal paraffin cracking-single side chain hydroisomerizing; Because HZSM-5 zeolite and nanometer H β zeolite acidity are strong, the acid amount is bigger; Therefore cause cracking reaction comparatively serious, consequently suppressed single side chain isomerization reaction of alkane.
CN 1743425A (one Chinese patent application number 200410074058.7) discloses a kind of hydrogenation modifying process to China high olefin FCC gasoline.This method is under the effect of four kinds of difference in functionality catalyzer; Make full cut FCC gasoline through dialkene removal, alkene aromatization and replenishing three reactor drum upgradings of alkene fall and after; Desulfurization degree is 78%, the product olefin(e) centent is 30v%, product RON loss is 1.0 units, and the product liquid yield is about 98.5wt%.But this method is primarily aimed at low sulfur-bearing FCC gasoline; Under the prerequisite that reduces the RON loss as far as possible; Desulfurization degree is lower, the alkene range of decrease is little, and the products obtained therefrom quality also is difficult to satisfy state III and state IV clean gasoline standard, high-sulphur raw oil in obviously being not suitable for.
CN 1488724A (Chinese patent 02133130.8) discloses a kind of FCC gasoline hydrofinishing/aromizing process integration based on nano zeolite catalyst.Make full cut FCC gasoline after unifining is alkane with most of conversion of olefines, on nano zeolite catalyst, carry out alkane aromatization again; This patent is through adopting a kind of nano level hydrogen type molecular sieve catalyzer that comprises main group, magnesium-yttrium-transition metal and lanthanide rare MOX; Make that the upgraded products may desulfurization degree is high, the alkene range of decrease is big; But the product liquid yield that this method obtains is merely about 90wt%, and product RON loss is big (reaching 2.0～3.0 units), and the nano zeolite preparation is complicated, regenerability is not good; Cause the increase of technology cost, be difficult to adapt to suitability for industrialized production.
CN 1718688A (Chinese patent 200410020932.9) discloses a kind of FCC gasoline hydrogenation modifying method inferior.This patented process forms three reaction zones under the condition that hydrogen exists and temperature raises gradually, and full cut FCC gasoline is contacted with three kinds of catalyzer, adopts conventional Hydrobon catalyst (6h under high charging air speed earlier
-1) carry out the dialkene removal reaction, adopt nano zeolite catalyst under high temperature (415 ℃), to carry out aromizing, isomerization reaction then, adopt Co-Mo-K-P/Al at last
2O
3Catalyzer is at high temperature (415 ℃), high-speed (40h more
-1) under carry out selective desulfurization.The advantage of this method is that the alkene and the sulphur content of the product that obtains is all lower; But product RON loss is about 3.0 units; The product liquid yield is about 94wt%, and nano zeolite preparation is complicated, easy inactivation under the high temperature, regenerability are not good, in addition the also easy inactivation of the 3rd section desulfurization catalyst under high-speed very and high-temperature very; Influence the reaction stability of whole technology, increased the application difficulty of suitability for industrialized production.
CN 1597865A (Chinese patent 03133992.1) discloses a kind of inferior FCC gasoline hydrogenation modifying method similar with CN 1718688A thinking.This process method adopts conventional Hydrobon catalyst (6h under high charging air speed earlier
-1) carry out the dialkene removal reaction of full cut FCC gasoline, adopt Co-Mo-K-P/Al then
2O
3Catalyzer carries out selective desulfurization, adopts nano zeolite catalyst under high temperature (415 ℃), to carry out the alkene aromizing at last.The olefin(e) centent of product that this patented process obtains is lower; But product RON loss is about 1.0 units; The weak point of above-mentioned nano zeolite still exists, and product sulphur content higher (desulfurization degree only 75%), is difficult to satisfy state III and state IV clean gasoline standard.
CN 1769388A (Chinese patent 200410082704.4) discloses the hydrogenation modifying process of a kind of FCC of reduction gasoline sulfur and olefin(e) centent.The technology of this patent is to adopt conventional Hydrobon catalyst (6h under high charging air speed earlier
-1) carry out the dialkene removal reaction of full cut FCC gasoline; Carry out prefrationation then; Lighting end gasoline mainly carries out the alkene aromizing on nano zeolite catalyst; Last running gasoline carries out the selective hydrodesulfurization reaction successively on low-metal content aluminium oxide catalyst and high metal content aluminium oxide catalyst, can get full fraction upgrading gasoline after at last reacted weight gasoline being mixed.The alkene and the sulphur content of product that this patented process obtains are lower; But it is about 1.5 units that the whole machining process process still makes product RON loss; And the weak point of above-mentioned nano zeolite still exists, and needs four kinds of catalyzer and supporting complicated technology, has limited its industrial application.
CN 1283761C (Chinese patent 200410060574.4) discloses a kind of inferior patrol hydrogenation modifying process.This technology is cut into lighting end and last running gasoline with full cut FCC gasoline earlier, then with last running gasoline at Co (Ni)-Mo/TiO
2Carry out hydrogenating desulfurization on the catalyzer, again at Co (Ni)-Mo (W)/ZSM-5-TiO
2Carry out aromizing on the catalyzer, at last reacted weight gasoline is mixed into full fraction upgrading gasoline.Olefin(e) centent according to product that this patented process obtains is lower, but the product sulphur content is difficult to satisfy and is not higher than 50 μ g.g in the state IV standards
-1Requirement; On the other hand; This method is to high sulfur-bearing oil; In order to improve the RON of final blending product; One of key of this patented process is that the last running gasoline after the hydrogenating desulfurization is carried out aromizing, but aromatic hydrocarbons is the precursor of coke, and higher aromatic hydrocarbons growing amount (product aromatic hydrocarbons is higher than more than the raw material 10v%) is stable totally unfavorable to catalyzer; Moreover the support of the catalyst in this patent technology requires with TiO
2Be main, this also makes the intensity of catalyzer significantly reduce, and is unfavorable for its LP steady running and regeneration.
In a word; Low grade oilses such as Chinese FCC gasoline to high sulfur-bearing and high olefin; A lot of researchs have been arranged at present; Though all realize desulfurating and reducing olefinic hydrocarbon at the upgrading of attempting through means of different, keep and improve simultaneously the octane value of oil product as far as possible, the list of also mentioning hydrogenation products props up chain isomerization to recovering the influence of octane value.Can see that these disclosed methods respectively have advantage and deficiency, majority is the gasoline to high sulfur content, does not especially all have the friendly hydro carbons of further concern for the environment highly-branched chain isomerous to improving the importance of FCC gasoline octane rating.Explore a kind of more rational modifying process; Select suitable function and active catalyzer, keeping octane value simultaneously, realize deep desulfuration and fall alkene; And solve problem such as the undesirable and tooling cost height of catalyst stability, be the target that the refining of petroleum field is pursued all the time.
Summary of the invention
Situation to prior art; The selective hydrodesulfurization and the highly-branched chain isomerous coupling hydro-upgrading method of hydro carbons that the purpose of this invention is to provide a kind of catalytically cracked gasoline; Coupling through the secondary hydrogenation reaction process; On the catalyzer of two kinds of difference in functionalitys, respectively the raw material oil product is realized that appropriate hydrogenation takes off diene and additional desulfurization-hydro carbons is highly-branched chain isomerous; Realize to FCC gasoline inferior deep desulfuration, fall alkene, recover octane value in, have very high liquid yield, become and be easy to industrialized hydrogenation modification method.
The invention provides a kind of selective hydrodesulfurization and the highly-branched chain isomerous coupling hydro-upgrading method of hydro carbons of catalytically cracked gasoline; This method comprises: adopt two-stage reaction that catalytically cracked gasoline is handled; In first section reaction; Make catalytically cracked gasoline contact hydrogenation reaction takes place, make the reaction effluent that obtains in second section reaction, contact further generation desulfurization, fall olefine reaction then with the highly-branched chain isomerous catalyzer of hydro carbons with taking off diene/catalyst for selectively hydrodesulfurizing; Wherein,
Take off the composition of diene/catalyst for selectively hydrodesulfurizing,, comprising: MoO in this catalyzer total mass
310-18%, CoO 2-5%, MgO 2-7% and B
2O
32-6%, surplus is the Al-Ti composite oxide carrier;
The composition of the highly-branched chain isomerous catalyzer of hydro carbons in this catalyzer total mass, comprising: MoO
33-8%, CoO 1-4%, NiO 1-5%, SAPO-11 molecular sieve 50-70%, surplus is the Al-Ti composite oxides.
Make straight chain hydrocarbon, especially alkene is realized two chain isomerisms even highly-branched chain isomerous, has very important environment protection significance for the octane value that improves inferior patrol.Hydrogenation modifying process provided by the invention has comprised the coupling of two-stage reaction process, has adopted the coupling of two kinds of character and function different catalyst and corresponding treatment process respectively, reaches the FCC gasoline upgrading effect of expection.At first have and remove high unsaturates in the FCC gasoline (mainly being diolefine etc.) on the dual-function catalyst that takes off diene and selective hydrodesulfurization and the suitable hydrogenation reaction takes place at first kind; Thereby realize the high-selective and hydrogenating desulfurization, and then make reaction effluent on another kind of catalyzer, further implement to replenish upgradings such as desulfurization and hydro carbons higly branched chain hydroisomerizing without separation.According to coupling technique of the present invention; FCC gasoline has removed diolefine after the contact reacts on first section catalyzer; Thereby avoid the polymerization of diolefine in subsequent disposal and the work-ing life that therefore influences two sections catalyzer, can solve the catalyst based problem that is difficult to remove steric hindrance sulfide in the oil product of two segment molecules sieve simultaneously; Moreover first section reacted elute do not contain diolefine and is main with thiophene, is more conducive to give full play to the highly-branched chain isomerous function of additional desulfurization-hydro carbons of second section catalyzer, thereby simplifies the required catalyst type of modifying process, reduce cost.Contrast experiment's result proves; Coupling technique of the present invention can make through the gasoline products after two sections processing and obtain than adopt the better deep desulfuration of other hydrogenation modification methods, falls the alkene effect, but also can improve the finished product octane value, significantly improve liquid yield.The inventive method is particularly useful for the FCC gasoline (poor quality) of high olefin and moderate sulfur content is carried out upgrading, realize to FCC gasoline inferior deep desulfuration, fall alkene, recover the effect of octane value.
For reaching better upgrading effect,, can control and adjust the condition of each stage of reaction based on the character and the reaction characteristics of concrete catalyst.When adopting hydrogenation modification method of the present invention that catalytically cracked gasoline is carried out hydro-upgrading, can control catalytically cracked gasoline and be: reaction pressure 1-3MPa, liquid volume air speed 3-6h at the reaction conditions of first section reaction zone
-1, temperature of reaction 200-300 ℃, hydrogen to oil volume ratio 200-500; The elute of first section reaction at the reaction conditions of second section reaction zone is: reaction pressure 1-3MPa, liquid volume air speed 1-4h
-1, temperature of reaction 250-350 ℃, hydrogen to oil volume ratio 200-500.
The catalyzer that the present invention adopted all comprises the Al-Ti composite oxides; Promptly; The catalyzer that diene and selective hydrodesulfurization are taken off in first section realization is that to utilize the Al-Ti composite oxides be carrier loaded product after the active ingredient; Second section realize to be replenished desulfurization and the highly-branched chain isomerous catalyzer of hydro carbons then is to be carrier with the matrix material behind growth in situ SAPO-11 molecular sieve on the Al-Ti composite oxides, load active component and processing.Particularly, the weight of said Al-Ti composite oxides consists of: Al
2O
370-95%, TiO
25-30%.
Said Al-Ti composite oxides are fractional precipitation aluminium salt and titanium salt and process, and obtain precipitation of alumina through pH value swing method earlier, and then make titanium salt generation precipitin reaction through regulator solution pH value to alkalescence.For example; The preparation of Al-Ti composite oxide carrier can be according to following method: under continuous violent stirring; With appropriate bases precipitation agent (alkali precipitation agent volumetric usage first be about aluminum salt solution total amount 15%～30%); Commonly used can be sodium hydroxide solution, also can be to mix ammonia solution (NH for example
3H
2O and NH
4HCO
3Mixed solution, mol ratio is 2-10: 1), add simultaneously with aluminum salt solution and stream; This appropriate bases precipitant solution is used up the back and is continued to add aluminum salt solution, and (for example pH 2-4) stops to add aluminum salt solution under proper acidic pH value, and stirring adds the alkali precipitation agent solution after for some time (5-30 minute) again; Under suitable alkaline pH value (for example pH 7.5-9.5), stop to add precipitation agent; Restir for some time (5-30 minute), swing the pH value so repeatedly and repeatedly (be generally 2-5 time), obtain precipitation of alumina; Aluminum salt solution is used up the back after suitable alkaline pH (for example 8.0-9.5) stirs for some time (5-30 minute), adds titanium salt solution, keeps solution to be alkalescence; Reinforced finish, after the precipitin reaction fully, continue to stir for some time (5-30 minute), through cooling, filter, the making beating washing, filtration cakes torrefaction, fragmentation after the washing are sieved, make the Al-Ti composite powder.In the preparation of these composite oxides, aluminum salt solution can be salts solutions such as aluminum nitrate, aluminum chloride, Tai-Ace S 150, and titanium salt solution can be Titanium Nitrate, titanium chloride, titanium sulfate salts solution etc.Can adopt the moulding in banded extruder of conventional forming method, after drying, roasting, process required support of the catalyst again.
First section used diene/catalyst for selectively hydrodesulfurizing that takes off of reaction is the catalyzer that Al-Ti composite oxide carrier step impregnation Mg, B and Mo, Co obtain.
According to hydrogenation modification method of the present invention, adopt in the catalyzer in second section reaction zone, preferably control the SiO of SAPO-11 molecular sieve
2/ Al
2O
3Mol ratio is 0.1-2.0: 1, and P
2O
5/ Al
2O
3Mol ratio is 0.5-2.5: 1, and use organosilicon source and the pure identical organic alcohol that generates with this organosilicon source hydrolysis in this molecular sieve synthetic.Preferably, the organosilicon source of the used molecular sieve of this catalyzer is an alkyl silicate, and alkyl is selected from C
2-C
8, it is C that said organic alcohol then is selected from carbon chain lengths
2-C
8Alcohol.Than conventional SAPO-11 zeolite, the present invention utilizes organic pure adding can regulate and control silicon source hydrolysis degree to enlarge the SAPO-11 molecular sieve bore diameter, thus the further highly-branched chain isomerous performance of regulatory molecule sieve.Particularly, said organosilicon source can be selected from long-chain organosilicon sources such as tetraethoxy, the positive third silicic acid propyl ester, butyl silicate, positive silicic acid pentyl ester or the positive own ester of silicic acid, then corresponding ethanol, propyl alcohol, propyl carbinol, Pentyl alcohol or the n-hexyl alcohol of being selected from of organic alcohol.Other raw material of synthetic SAPO-11 is all selected according to routine techniques; Can be according to the organosilicon source: aluminium source: phosphorus source: template: the mole of organic alcohol: water=0.1-2.0: 1: 0.5-2.5: 0.7-2.0: 0.1-40: 20-60 be recently confirmed the feed ratio of raw material; But for reaching the purpose of modulation molecular sieve bore diameter; The template of using during said SAPO-11 molecular sieve is synthetic is preferably the mixture of di-n-propylamine and long-chain organic amine; The mol ratio of the two is 3-10: 1, and this long-chain organic amine to be selected from carbon chain lengths be C
4-C
8Alkyl diamine, said long-chain organic amine for example can be for one of Di-n-Butyl Amine, two n-amylamines, two normal hexyl Amines etc., to be more conducive to further regulatory molecule sieve aperture structure to adapt to the highly-branched chain isomerous requirement of hydro carbons.
Above-mentioned on the Al-Ti mixture implementation procedure of growth in situ SAPO-11 molecular sieve can be: phosphorus source (for example phosphoric acid), aluminium source (for example pseudo-boehmite) and deionized water are mixed; Stir (for example 20-40 ℃ or room temperature; 1.0-2.0 hour) mix and process mixed sols; In this mixed sols, add organosilicon source and organic pure mixed solution then; Mix (for example 2.0-3.0 hour), the thorough mixing thing with Al-Ti mixture and template adds wherein again, continues to stir up to forming even colloid; Then reaction product is packed into to have in the teflon-lined stainless steel still and implement crystallization; Crystallization temperature 150-200 ℃; Crystallization time 8-60 hour; Crystallization is separated solid product after accomplishing with mother liquor, after washing to neutrality, dry (for example in 110-120 ℃ of air drying or oven dry), obtain support of the catalyst.
Utilize above-mentioned carrier, adopt conventional pickling process behind load Mo, Co and Ni on the carrier, promptly to process second section catalyzer of the present invention.In the preparation of this support of the catalyst the Al-Ti mixture is introduced in the SAPO-11 synthesis mother liquid, the SAPO-11 that crystallization is formed is dispersed on the Al-Ti mixture, helps fully contacting with reactant; In the SAPO-11 building-up process, introduce and the corresponding organic alcohol of alkyl silicate (silicon source); For example, positive silicic acid propyl ester and n-propyl alcohol are shared, can effectively suppress organosilicon hydrolyzation; Thereby improve the aperture of SAPO-11, significantly improve its highly-branched chain isomerous reactivity worth hydro carbons.
According to the usual phraseology of catalyst field, active ingredient on carrier that the present invention is mentioned and the catalyzer (element) content is all in its corresponding oxide.
Hydrogenation modification method of the present invention especially can obtain hydro-upgrading effect preferably to the catalytically cracked gasoline inferior of moderate sulfur, high olefin content, and for example: sulphur content is 300-600 μ g.g
-1, olefin(e) centent is the gasoline of 40-45v%.In the concrete upgrading process,, can be directed against full cut FCC gasoline according to oil property; Also can be to the heavy distillate after the cut cutting; That is, said pending catalytically cracked gasoline is the heavy distillate of catalytic gasoline of whole fraction after 50-90 ℃ of cutting, at this moment; This method also comprise with the product after the two-stage reaction upgrading is handled with cut after benzoline mix, obtain clean gasoline.
Compared with prior art, coupling hydro-upgrading technology of the present invention has following characteristics:
(1) can be 300-600 μ g.g with sulphur content
-1, olefin(e) centent is up to 40v%, for example is processed as sulphur content≤50 μ g.g for the FCC gasoline of 40-45v%
-1,≤1.0 units of olefin(e) centent≤25v%, gasoline research method octane value (RON) loss premium, and product liquid yield>=99wt%.
(2) in the process that gasoline stocks is handled, can take direct charging of full cut FCC gasoline or heavy FCC gasoline feeding according to different oil properties, operating procedure is flexible, wide adaptability, can adopt serial operation, does not need separating device in the treating processes.
(3) the FCC gasoline of desire being handled inferior; At first realize taking off diene and high-selective and hydrogenating desulfurization through the selected catalyzer of first section reaction zone; Gelationus generates in the subsequent reactions process, prolong life of catalyst thereby greatly reduce, and reduces the desulfurization burden in second-stage reaction district simultaneously; Second section reaction zone adopted contains the SAPO-11 molecular sieve based catalyst, have hydro carbons highly-branched chain isomerous-to replenish desulfurization difunctional, help realizing FCC gasoline deep desulfuration, fall alkene, improve the effect of product octane value.Compare with aromatized catalyst, employed catalyzer coke content in treating processes is very low in the coupling hydro-upgrading method provided by the present invention, and stability is high; Compare with cracking-single side chain heterogeneous catalyst, employed catalyzer liquid in treating processes is received height in the coupling hydro-upgrading method provided by the present invention, the octane value recovering ability is strong.
(4) hydrogenation modification method of the present invention is particularly useful for the FCC gasoline upgrading inferior of moderate sulfur, high olefin content; Can be when significantly reducing its alkene and sulphur content; Improve its octane value and keep the high product liquid yield; Therefore than external gasoline hydrogenation modifying method, coupling hydro-upgrading method of the present invention is more suitable for the FCC gasoline component of China is handled.
Embodiment
Through embodiment hydrogenation modification method provided by the invention is further explained below, but therefore do not limited the present invention.
Embodiment 1
The catalyzer that present embodiment is used for the processing of FCC gasoline upgrading comprises:
First section is taken off diene-high-selective and hydrogenating desulfurization catalyst, in this total catalyst weight: 5wt%CoO-14wt%MoO
3-5wt%MgO-4wt%B
2O
3/ 65wt%Al
2O
3-7wt%TiO
2Second section contains the SAPO-11 molecular sieve based catalyst, in this total catalyst weight: 1wt%CoO-6wt%MoO
3-3wt%NiO/64wt%SAPO-11-22wt%Al
2O
3-4wt%TiO
2
The concrete preparation process of first section catalyzer is following:
Take by weighing 631.83g Al (NO
3)
39H
2O adds the 819.7ml deionized water, stirs and makes it whole dissolvings, is called A
1Solution;
Take by weighing 31.30g Ti (SO
4)
2, adding the 357.7ml deionized water, vigorous stirring makes it whole dissolvings, is called T
1Solution;
Configuration 1000ml mixes ammonia solution (NH
3H
2O and NH
4HCO
3Mol ratio be 8: 1) as the alkali precipitation agent, measure this alkali precipitation agent of 180mL under violent stirring and A
1Solution and stream add, and control pH value after this mixed ammonia solution adding finishes, continues to add A about 9.0
1Solution to pH value is 4.0, stops to add A this moment
1Solution continues to stir 10 minutes; Adding mixed ammonia solution to pH value again is 9.0, stops to add mixed ammonia solution this moment, continues to stir 10 minutes, swings the pH value so repeatedly 3 times; A
1After solution is used up, when 9.0 left and right sides, add T with mixing ammonia solution control pH value
1Solution makes the titanium deposition fully, continues to stir suction filtration after 15 minutes, with the NH of 0.6mol/L
4HCO
3Solution making beating washing 2 times, use deionized water wash twice again, then, filter cake is put into 120 ℃ of dry 24h of baking oven, make 300 purpose Al-Ti composite oxide powers, 100 grams after broken, the screening.
Take by weighing 70 gram above-mentioned Al-Ti composite powders (moisture 25wt%) and 1.6 gram sesbania powder; Its ground and mixed is even, and adding 5mL mass concentration is 65% salpeter solution, fully mixes and pinches back extruded moulding in banded extruder; After 120 ℃ of dryings, 520 ℃ of roastings, process first section support of the catalyst.
40 gram said catalyst carrier impregnated in the mixed steeping fluid of 35mL magnesium nitrate and boric acid,, contain 2.78 gram MgO and 2.22 gram B in this steeping fluid in oxide compound
2O
3, ageing was at room temperature handled 5 hours then, again 120 ℃ of dryings 3 hours and 520 ℃ of roastings 4 hours;
Preparation 32mL contains 2.78 gram CoO and 7.78 gram MoO under the Heating temperature about 70-80 ℃
3(content of each active ingredient is in oxide form; And the active ingredient in the unrestricted mixed solution exists with oxide form) the mixed liquid of Xiao Suangu and ammonium molybdate; And to add the 3.3mL mass concentration be 17% ammoniacal liquor, and fully vibration is dissolved fully until solid and processed steeping fluid; Then the above-mentioned support of the catalyst that contains magnesium boron impregnated in this steeping fluid, room temperature ageing 5 hours after 5 hours, is processed catalyst I-A through 120 ℃ of drying treatment 3 hours and 520 ℃ of calcination process.
The concrete preparation process of second section catalyzer is following:
According to the chemical constitution that feeds intake (mol ratio) of SAPO-11 molecular sieve, PE (n-propyl alcohol): DBA (Di-n-Butyl Amine): DPA (di-n-propylamine): Al
2O
3: P
2O
5: SiO
2: H
2O=5: 0.2: 1: 1: 1: 0.4: 50; Earlier phosphoric acid, pseudo-boehmite and deionized water are mixed; Stir about made it evenly become mixed sols in 1.0 hours, in this mixed sols, added an amount of positive silicic acid propyl ester and n-propyl alcohol mixed solution then, mixed 2.0 hours; Again the Al-Ti composite powder of formula ratio and the thorough mixing thing of di-n-propylamine and Di-n-Butyl Amine are added wherein, continue to stir up to forming even colloid; Then reaction product being packed into has in the teflon-lined stainless steel still, takes out 185 ℃ of following crystallization 24 hours, cooling, filters, and obtains the SAPO-11 zeolite product of in-situ crystallization on the Al-Ti mixture after 120 ℃ of oven dry.In this zeolite product, SAPO-11 molecular sieve weight content is 71.1wt%, Al
2O
3Be 24.4wt%, TiO
2Be 4.5wt%.
Take by weighing 90 grams above-mentioned on the Al-Ti mixture SAPO-11 molecular sieve and the 2.5 gram sesbania powder of in-situ crystallization; Ground and mixed is even; Adding 6mL mass concentration is 65% salpeter solution; Fully mix and pinch back extruded moulding in banded extruder, after 120 ℃ of dryings, 520 ℃ of roastings, process second section support of the catalyst of moulding.
Preparation 60mL contains 5.0 gram MoO
3Ammonium molybdate solution, and to add the 5.8mL mass concentration be 17% ammoniacal liquor, fully vibration is dissolved fully until solid and is processed steeping fluid; Second section support of the catalyst with the above-mentioned moulding of 75 grams impregnated in this steeping fluid then, and room temperature ageing 5 hours was through 120 ℃ of drying treatment 3 hours and 500 ℃ of calcination process 4 hours; Catalysts containing molybdenum after this roasting impregnated in Xiao Suangu and the nickelous nitrate that 60mL contains 0.83 gram CoO and 2.5 gram NiO mix in the liquid, ageing is 5 hours under the room temperature, after 120 ℃ of dryings 3 hours and 500 ℃ of roastings 4 are little, processes catalyst I I-A.
Oil product upgrading and catalyst reaction performance test carry out on the device of two reactors in series, and the specification of each reactor drum is 100ml, and first section catalyzer of the above-mentioned 25mL of first reactor charge dilutes with porcelain sand with 2: 1 volume ratios; Second section catalyzer of second above-mentioned 50mL of reactor charge dilutes with porcelain sand with 1: 1 volume ratio.
Pending raw material oil product is full cut FCC gasoline 1, and its character is referring to table 1.
Airtight qualified after, at first carry out the prevulcanized of catalyzer.Vulcanized oil is a straight-run spirit, and vulcanizing agent is CS
2, concentration is 3.0wt%; Sulfide stress is 2.0MPa, vulcanizes 1 hour down at 150 ℃, under 230 ℃, 290 ℃ and 320 ℃, vulcanizes respectively 6 hours; One anti-volume space velocity of vulcanized oil is 3.0h
-1, hydrogen to oil volume ratio is 300.After sulfuration finishes, switch to 50% full cut FCC gasoline 1+50% straight-run spirit and replaced 5 hours, then reaction pressure is kept 2.0MPa, it is 4.0h that first section temperature of reaction reduced to 220 ℃, volume space velocity
-1, it is 2.0h that second section temperature of reaction reduced to 280 ℃, volume space velocity
-1, get into 100% full cut FCC gasoline 1 reaction after 400 hours, sampling analysis.
Upgrading reactor product character is seen table 2.
Embodiment 2
Present embodiment and embodiment 1 difference are full cut FCC gasoline 1 is cut into light, heavy FCC gasoline at 65 ℃; Their character is referring to table 1; Heavy FCC gasoline carries out the two-stage hydrogenation upgrading as reaction raw materials to be handled, and catalyzer is identical with embodiment 1, and the agent of raw material oil product (last running) process two-stage catalytic is reacted successively; Heavy petrol reactor product after upgrading is handled then mixes with light gasoline fraction, obtains low-sulfur, low alkene clean gasoline.
Wherein, 1 two sections cascade reaction conditions of heavy FCC gasoline are: pressure is 1.5MPa, and hydrogen to oil volume ratio is that 400, the first sections temperature of reaction are that 240 ℃, volume space velocity are 3.0h
-1, second section temperature of reaction is that 300 ℃, volume space velocity are 1.5h
-1
Upgrading reactor product character is seen table 2.
Embodiment 3
Present embodiment and embodiment 1 difference are that raw oil is changed to full cut FCC gasoline 2 from full cut FCC gasoline 1, and oil property is referring to table 1.
The full condition of cut FCC gasoline 2 in two sections cascade reactions is: pressure is 1.8MPa, and hydrogen to oil volume ratio is that 500, the first sections temperature of reaction are that 230 ℃, volume space velocity are 4.0h
-1, second section temperature of reaction is that 290 ℃, volume space velocity are 2.0h
-1
Upgrading reactor product character is seen table 2.
Embodiment 4
Present embodiment and embodiment 1 difference are full cut FCC gasoline 1 is changed to full cut FCC gasoline 2; And being cut into light, heavy FCC gasoline at 55 ℃, their character will weigh FCC gasoline and carry out the reaction of two-stage hydrogenation upgrading as reaction raw materials referring to table 1; The catalyzer of two-stage reaction is identical with embodiment 1; The agent of raw material oil product (heavy naphtha) process two-stage catalytic is reacted successively, and the reactor product with this heavy naphtha mixes with light gasoline fraction then, obtains low-sulfur, low alkene clean gasoline.
Wherein, the condition of heavy FCC gasoline 2 in two sections cascade reactions is: pressure is 1.6MPa, and hydrogen to oil volume ratio is that 400, the first sections temperature of reaction are that 245 ℃, volume space velocity are 3.0h
-1, second section temperature of reaction is that 310 ℃, volume space velocity are 1.5h
-1
Upgrading reactor product character is seen table 2.
Embodiment 5
Present embodiment and embodiment 1 difference are that first section catalyzer is I-B:3wt%CoO-12wt%MoO
3-7wt%MgO-6wt%B
2O
3/ 62wt%Al
2O
3-10wt%TiO
2, second section catalyzer is II-B:2wt%CoO-8wt%MoO
3-4wt%NiO/60wt%SAPO-11-20wt%Al
2O
3-6wt%TiO
2Pending oil product is full cut FCC gasoline 1, and the technology of the Preparation of catalysts process and the hydro-upgrading of pending FCC oil product is identical with embodiment 1.
Upgrading reactor product character is seen table 3.
Embodiment 6
Present embodiment and embodiment 5 differences are full cut FCC gasoline 1 is cut into light, heavy FCC gasoline at 65 ℃; React successively as reaction raw materials (pending raw material oil product) and above-mentioned two-stage catalytic agent with heavy FCC gasoline; Reactor product with this heavy naphtha mixes with light gasoline fraction then, obtains low-sulfur, low alkene clean gasoline.
Wherein, 1 two sections cascade reaction conditions of heavy FCC gasoline are: pressure is 1.5MPa, and hydrogen to oil volume ratio is that 400, the first sections temperature of reaction are that 240 ℃, volume space velocity are 3.0h
-1, second section temperature of reaction is that 300 ℃, volume space velocity are 1.5h
-1
Upgrading reactor product character is seen table 3.
Embodiment 7
Present embodiment and embodiment 5 differences are that raw oil is changed to full cut FCC gasoline 2 from full cut FCC gasoline 1.
Complete 2 two sections cascade reaction conditions of cut FCC gasoline are: pressure is 1.8MPa, and hydrogen to oil volume ratio is that 500, the first sections temperature of reaction are that 230 ℃, volume space velocity are 4.0h
-1, second section temperature of reaction is that 290 ℃, volume space velocity are 2.0h
-1
Upgrading reactor product character is seen table 3.
Embodiment 8
Present embodiment and embodiment 5 differences are full cut FCC gasoline 1 is changed to full cut FCC gasoline 2; And be cut into light, heavy FCC gasoline at 55 ℃; To weigh FCC gasoline and carry out the reaction of two-stage hydrogenation upgrading as reaction raw materials, the catalyzer of two-stage reaction is identical with embodiment 1, and the agent of raw material oil product (heavy naphtha) process two-stage catalytic is reacted successively; Reactor product with this heavy naphtha mixes with light gasoline fraction then, obtains low-sulfur, low alkene clean gasoline.
Wherein, 2 two sections cascade reaction conditions of heavy FCC gasoline are: pressure is 1.6MPa, and hydrogen to oil volume ratio is that 400, the first sections temperature of reaction are that 245 ℃, volume space velocity are 3.0h
-1, second section temperature of reaction is that 310 ℃, volume space velocity are 1.5h
-1
Upgrading reactor product character is seen table 3.
Table 1 raw oil character
Table 2 embodiment 1～4 gasoline upgrading effect
Table 3 embodiment 5～8 gasoline upgrading effects
Can be known by table 2 and 3, be 389 μ g.g to sulphur content
-1, olefin(e) centent is the full cut FCC of moderate sulfur, the high olefin gasoline of 40.8v%, hydrogenation modification method of the present invention can make the product sulphur content be reduced to 35-40 μ g.g
-1, olefin(e) centent is reduced to 20-22v%, and liquid yield is 99.8m%, and highly-branched chain isomerous alkane increases about 8v%, and about 0.9 unit of product RON loss, the product boiling range is identical with raw oil, and quality product meets the total sulfur≤50 μ g.g of state IV clean gasoline requirement
-1, alkene≤25v% standard, show that this method has wide in range application prospect.Adopting the heavy FCC gasoline after 65 ℃ of cuttings is that raw material is processed, and can make sulphur content by 580 μ g.g
-1Be reduced to 17-20 μ g.g
-1, olefin(e) centent is reduced to 5-7v% by 36v%, and highly-branched chain isomerous alkane increases 14-16v%, and RON slightly reduces to about 88.8 by 89.0 of heavy FCC gasoline; Full cut product sulphur content after the weight distillation gasoline is in harmonious proportion is 24 μ g.g
-1, olefin(e) centent is 21v%; Product RON only is lower than 0.1-0.3 unit of full feedstock oil; Liquid yield is up to 99.8m%, and quality product meets state IV clean gasoline standard, shows that fully this method all has good hydro-upgrading effect to different fractions FCC gasoline.
To sulphur content is 590 μ g.g
-1, olefin(e) centent is the full cut FCC of another kind of moderate sulfur, the high olefin gasoline of 39.5v%, this method can make the product sulphur content be reduced to 40-47 μ g.g
-1, olefin(e) centent is reduced to 21v%, and liquid yield is 99.7m%, and highly-branched chain isomerous alkane increases about 9v%, and product RON loses 0.8-1.0 unit, and the product boiling range is identical with raw oil, and quality product meets state IV clean gasoline standard.Adopting the heavy FCC gasoline after 55 ℃ of cuttings is that raw material is processed, and can make sulphur content by 774 μ g.g
-1Be reduced to 8-11 μ g.g
-1, olefin(e) centent is reduced to 7v% by 34v%, and highly-branched chain isomerous alkane increases 16-18v%, and product RON is basic identical with heavy FCC gasoline stocks; Full cut product sulphur content after the weight distillation gasoline is in harmonious proportion is 41-44 μ g.g
-1, olefin(e) centent is 21v%; Product RON only is lower than 0.2 unit of full feedstock oil; Liquid yield is 99.9m%, and quality product meets state IV clean gasoline standard, shows that this method all has good hydro-upgrading effect to different moderate sulfur, high olefin FCC gasoline.
Can find out from above experimental result; Utilize processing of taking off the highly-branched chain isomerous coupling modification technology of diene/selective hydrodesulfurization and additional desulfurization/hydro carbons of the present invention; The sulphur content of FCC gasoline products significantly reduces, high-octane highly-branched chain isomerous alkane content significantly increases (increase rate can reach about 10v%), thereby the RON loss of upgraded products may is reduced most possibly.
In addition; Result by table 1-3 also can know; The present invention takes oil product cutting one to take off diene/selective hydrodesulfurization one and replenishes the corresponding processing scheme that the highly-branched chain isomerous processing scheme of desulfurization/hydro carbons is superior to the full distillate oil article, and it is relevant that this contains a large amount of high octane olefins with lighting end, last running contains most of sulphur compound.Take the processing scheme of the full cut FCC gasoline of cutting earlier, can keep high-octane benzoline, and the heavy distillate of the high sulfur-bearing of processing treatment, thereby the octane value of having guaranteed weight mediation product is kept and high sweetening effectiveness.
Claims (8)
1. catalytic gasoline selective hydrodesulfurizationmodification and the highly-branched chain isomerous coupling hydro-upgrading method of alkene; This method comprises: adopt two-stage reaction that catalytically cracked gasoline is handled; In first section reaction; Make pending catalytically cracked gasoline contact the generation hydrogenation reaction with taking off diene/catalyst for selectively hydrodesulfurizing, generation replenishes desulfurization, falls olefine reaction to make the reaction effluent that obtains in second section reaction, contact further with the highly-branched chain isomerous catalyzer of hydro carbons then; Wherein,
Take off the composition of diene/catalyst for selectively hydrodesulfurizing,, comprising: MoO in this catalyzer total mass
310-18%, CoO 2-5%, MgO 2-7% and B
2O
32-6%, surplus is the Al-Ti composite oxide carrier;
The composition of the highly-branched chain isomerous catalyzer of hydro carbons in this catalyzer total mass, comprising: MoO
33-8%, CoO 1-4%, NiO 1-5%, SAPO-11 molecular sieve 50-70%, surplus is the Al-Ti composite oxides;
The SiO of said SAPO-11 molecular sieve
2/ Al
2O
3Mol ratio is 0.1-2.0: 1, and P
2O
5/ Al
2O
3Mol ratio is 0.5-2.5: 1, and use organosilicon source and the pure identical organic alcohol that generates with this organosilicon source hydrolysis in this molecular sieve synthetic;
The template of using during said SAPO-11 molecular sieve is synthetic is the mixture of di-n-propylamine and long-chain organic amine, and the mol ratio of the two is 3-10: 1, and this long-chain organic amine to be selected from carbon chain lengths be C
4-C
8Alkyl diamine.
2. hydrogenation modification method according to claim 1, wherein, the reaction conditions of said catalytically cracked gasoline in first section reaction is: reaction pressure 1-3MPa, liquid volume air speed 3-6h
-1, temperature of reaction 200-300 ℃, hydrogen to oil volume ratio 200-500.
3. hydrogenation modification method according to claim 1, wherein, the reaction conditions of the elute of first section reaction in second section reaction is: reaction pressure 1-3MPa, liquid volume air speed 1-4h
-1, temperature of reaction 250-350 ℃, hydrogen to oil volume ratio 200-500.
4. hydrogenation modification method according to claim 1, wherein, the weight of Al-Ti composite oxides consists of: Al
2O
370-95%, TiO
25-30%.
5. hydrogenation modification method according to claim 1, wherein, the carrier of second section highly-branched chain isomerous catalyzer of the used hydro carbons of reaction is the product that growth in situ SAPO-11 molecular sieve obtains on the Al-Ti composite oxides.
6. according to claim 1 or 4 described hydrogenation modification methods, wherein, said Al-Ti composite oxides are the product of aluminium salt and titanium salt fractional precipitation.
7. hydrogenation modification method according to claim 1, wherein, said organosilicon source is an alkyl silicate, wherein alkyl is selected from C
2-C
8, it is C that said organic alcohol then is selected from carbon chain lengths
2-C
8Alcohol.
8. hydrogenation modification method according to claim 1, said pending catalytically cracked gasoline is a catalytic gasoline of whole fraction; Perhaps be the heavy distillate of catalytic gasoline of whole fraction after 50～90 ℃ of cuttings, this moment this method also comprise with the heavy distillate product after handling through second section reaction upgrading with cut after benzoline mix, obtain clean gasoline.
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| CN103396832A (en) * | 2013-06-24 | 2013-11-20 | 大连理工大学 | Modification method for full-range catalytic cracking gasoline |
| CN107151563B (en) * | 2016-03-04 | 2019-09-17 | 中国石油大学(北京) | Couple the clean gasoline production method of ultra-deep desulfurization and the conversion of alkene high-octane rating |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5399258A (en) * | 1991-08-15 | 1995-03-21 | Mobil Oil Corporation | Hydrocarbon upgrading process |
| US6231754B1 (en) * | 1996-02-02 | 2001-05-15 | Exxon Research And Engineering Company | High temperature naphtha desulfurization using a low metal and partially deactivated catalyst |
| US6641714B2 (en) * | 2000-07-21 | 2003-11-04 | Exxonmobil Research And Engineering Company | Hydrocarbon upgrading process |
| CN101245260A (en) * | 2008-02-20 | 2008-08-20 | 宋金文 | Method for producing ultra-low-sulfur oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5399258A (en) * | 1991-08-15 | 1995-03-21 | Mobil Oil Corporation | Hydrocarbon upgrading process |
| US6231754B1 (en) * | 1996-02-02 | 2001-05-15 | Exxon Research And Engineering Company | High temperature naphtha desulfurization using a low metal and partially deactivated catalyst |
| US6641714B2 (en) * | 2000-07-21 | 2003-11-04 | Exxonmobil Research And Engineering Company | Hydrocarbon upgrading process |
| CN101245260A (en) * | 2008-02-20 | 2008-08-20 | 宋金文 | Method for producing ultra-low-sulfur oil |
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