CN1827564A - A kind of method that produces diesel oil by overlapping of C4 component containing butene - Google Patents
A kind of method that produces diesel oil by overlapping of C4 component containing butene Download PDFInfo
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- CN1827564A CN1827564A CN 200510008986 CN200510008986A CN1827564A CN 1827564 A CN1827564 A CN 1827564A CN 200510008986 CN200510008986 CN 200510008986 CN 200510008986 A CN200510008986 A CN 200510008986A CN 1827564 A CN1827564 A CN 1827564A
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- gasoline
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- butene
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 36
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 title claims abstract description 21
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000003502 gasoline Substances 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 239000000047 product Substances 0.000 claims abstract description 23
- 150000001336 alkenes Chemical class 0.000 claims abstract description 22
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract 2
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 17
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 12
- 239000010457 zeolite Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims 2
- 239000002131 composite material Substances 0.000 claims 2
- -1 butylene Chemical group 0.000 abstract description 13
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 30
- 239000000203 mixture Substances 0.000 description 25
- 238000002360 preparation method Methods 0.000 description 21
- 239000000843 powder Substances 0.000 description 20
- 239000002994 raw material Substances 0.000 description 20
- 239000004411 aluminium Substances 0.000 description 16
- 229910052782 aluminium Inorganic materials 0.000 description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 16
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 16
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 14
- 238000000465 moulding Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 239000012263 liquid product Substances 0.000 description 11
- 239000002685 polymerization catalyst Substances 0.000 description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 239000012530 fluid Substances 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- 229910021417 amorphous silicon Inorganic materials 0.000 description 9
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- LFLZOWIFJOBEPN-UHFFFAOYSA-N nitrate, nitrate Chemical compound O[N+]([O-])=O.O[N+]([O-])=O LFLZOWIFJOBEPN-UHFFFAOYSA-N 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 238000006384 oligomerization reaction Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 150000002815 nickel Chemical class 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052756 noble gas Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000004106 carminic acid Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- UMFCIIBZHQXRCJ-NSCUHMNNSA-N trans-anol Chemical compound C\C=C\C1=CC=C(O)C=C1 UMFCIIBZHQXRCJ-NSCUHMNNSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
C containing butylene4The method for producing diesel oil by component superposition comprises the step of firstly enabling the C4The components are subjected to a butene polymerization reaction, then a gasoline fraction and a diesel fraction in a polymerization reaction liquid product are separated, and then olefin in the gasoline fraction is subjected to a gasoline polymerization reaction. The method carries out two-stage superposition on the component C4, which not only can reduce the pressure of each step of reaction, but also can increase the yield of diesel oil in the superposed product.
Description
Technical field
The present invention is for a kind of by the C that contains butylene
4The method of the superimposed production diesel oil of component specifically, is a kind of method by the superimposed production diesel oil of butylene.
Background technology
Along with improving constantly of crude oil in China working ability and ethylene yield, catalytic cracking unit and steam cracking device be a large amount of liquefied gas of by-product all, and universal day by day along with civil natural gas in recent years, the liquefied gas market requirement of using that directly acts as a fuel is more and more littler.Therefore, a large amount of liquefied gas are badly in need of seeking new chemical utilization approach.
The butylene that contains a great deal of in the liquefied gas can be produced polymer gasoline and superimposed diesel oil through building-up reactions.Because olefin(e) centent height in the polymer gasoline, can not satisfy the use standard of present motor spirit, and superimposed diesel oil have advantages such as cetane value height, condensation point are low, can be used as the blend component of high-quality diesel oil, thereby brings favorable economic benefit to enterprise.
The catalyzer that alkene oligomerization technology is used in early days is homogeneous catalyst, and typical homogeneous catalyst is a nickel complex.The homogeneous catalytic reaction mild condition, reactive behavior and selectivity height are mainly used in and produce polymer gasoline and Chemicals, but reaction after product and catalyst separating difficulty, the solvent contamination environment that uses in the reaction, and process cost is higher, is now replaced by heterogeneous catalyst gradually.
The heterogeneous catalyst of polymerization of low-carbon olefin is a solid acid catalyst, mainly comprises solid phosphate catalyst, and is the catalyzer of carrier, loaded metal active ingredient with crystalline silicate or with amorphous silicic aluminium.The easy argillization of solid phosphate catalyst, life-span are short and non-renewable, and the phosphate catalyst of inactivation causes environmental pollution easily, therefore, now use, research is more is back two kinds of catalyzer.
It is a kind of to contain C that EP0439865A1 provides
2～C
6The method of the hydrocarbon feed synthesizing liquid hydrocarbon of alkene, this method make described raw material under 150～295 ℃ by containing the reactor of crystallization carried catalyst, the residence time of granules of catalyst in reactor was at least 1 hour.Its described crystallization carrier comprises HZSM-5 and mordenite, and contains Ni.This patent adopts 10.3wt% Ni/ mordenite catalyst, is 1 hour at 215 ℃, 3.0MPa, weight time air speed
-1Condition under, be that raw material carried out the butylene building-up reactions 210 hours with the mixture that contains 50% butylene and 50% butane, 76% butylene changes under the normal temperature that comprises gasoline, diesel oil and lubricated wet goods and to be liquid hydrocarbon.
US4,551,438 disclose a kind of making contains C
6～C
9The catalyzer of high boiling point product is produced in the gasoline stocks oligomerisation of alkene.This catalyzer is an active ingredient with nickeliferous HZSM-5, HZSM-11, admixes a certain amount of aluminum oxide and makes, and under 177 ℃, the condition of 5.5MPa, C
6～C
9The conversion of olefines rate reaches 70%.After catalyzer is handled with the alkyl aluminum halide, the active raising, temperature of reaction drops to about 120 ℃.Described nickeliferous HZSM-5 adopts the ion exchange method preparation.
US4,542,251 disclosed liquid olefin oligomerizations use nickeliferous HZSM-5, HZSM-11 to be active ingredient, make C under 45～450 condition
2～C
20Olefin oligomerization.This catalyzer can make catalytic activity obviously improve after adding the Zn component.Make the Ni-Zn-HZSM-5 zeolite among the Zn-HZSM-5 as Ni is introduced, then reach same olefin conversion, and other reaction conditions is when identical, temperature of reaction can descend about 120 °F, and catalyst carbon deposit speed obviously reduces.
CN1046432C discloses a kind of butene oligomerization catalyzer, adopts aluminum oxide and X-amorphous silicic aluminium as complex carrier, the NiO of load 0～15 heavy %.Catalyzer was 110 ℃, 3.8MPa, weight time air speed 1.0 hours
-1Condition under carry out the mixed butene building-up reactions, butene conversion is 87.17%, C
8Olefine selective is 66.57%, C
12Olefine selective is 22.72%.This catalyzer is comparatively responsive to impurity such as water, sulfide, oxide compound, diolefine, after above-mentioned impurity contacts, and easy inactivation.
CN1442398A discloses a kind of by the olefin(e) centent of building-up reactions reduction olefine contained gasoline and the catalyzer of by-product diesel oil.It is the macropore complex carrier of 10～15 nanometers that this catalyzer uses mean pore size, makes catalyzer by load single nickel salt and stannic oxide, and its used complex carrier is made up of aluminum oxide and silicon-dioxide.Use this catalyzer, at 60～380 ℃, 0.5～6.0MPa, volume time air speed 0.5～5.0 hour
-1Reaction conditions under, can make the polymer gasoline olefin(e) centent descend 10～50 percentage points, the about 25 weight % of superimposed diesel yield.
CN1390917A discloses a kind of catalyzer of catalytic cracking of gasoline while reducing olefine.This catalyzer comprises two kinds of VIII family metal sulfates and γ-Al
2O
3Carrier, wherein main active ingredient is NiSO
4, secondary active ingredient is Fe
2(SO
4)
3Or CoSO
4At 150～200 ℃, 1.5～3.0MPa, volume time air speed is 0.5～2.0 hour
-1Condition under, olefin(e) centent is reduced to below the 35 volume %, simultaneously the diesel oil distillate of by-product 15～20 quality % greater than the olefins in FCC gasoline of 40 volume %.
CN1245203A discloses a kind of olefine contained gasoline through the superimposed catalyzer of producing diesel oil distillate, and this catalyzer is made up of the metal component that is selected from Ag, Ba, V and Mo, amorphous silicic aluminium and aluminum oxide.With the gasoline that contains alkene 85 quality % is raw material, is 0.71 hour at 250 ℃, 3.0MPa, raw materials quality time air speed
-1Condition under, with the catalyzer contact reacts that contains Ag 0.466 weight % after 4 hours, the liquid hydrocarbon yield of boiling range more than 200 ℃ is 54 heavy % in the reactant.
In sum, existing most of alkene oligomerization technologies and catalyzer are suitable for producing polymer gasoline; With regard to producing superimposed diesel oil, all there is the lower or more high deficiency of reaction pressure of yield.
Summary of the invention
The purpose of this invention is to provide a kind of by the C that contains butylene
4The method of the superimposed production diesel oil of component, this method can obtain higher diesel yield under lower reaction pressure.
Provided by the invention by the C that contains butylene
4The method of the superimposed production diesel oil of component comprises making described C earlier
4Component is carried out the butylene building-up reactions, separates gasoline fraction and diesel oil distillate in the building-up reactions product liquid then, makes the alkene in the described gasoline fraction carry out the gasoline building-up reactions again.
The inventive method makes C by the superimposed method of secondary
4Butylene in the component carries out superimposed earlier, gasoline fraction in the building-up reactions product liquid is separated with diesel oil distillate again, makes the alkene in the gasoline fraction further superimposed to generate more diesel component then.C
4Component is superimposed through secondary, and the pressure of per step reaction is reduced, and also can increase the diesel yield in total superimposed product.
Description of drawings
Fig. 1 is the comparatively preferred a kind of schematic flow sheet of the inventive method.
Embodiment
The inventive method makes C earlier
4Butylene in the component carries out building-up reactions and generates diesel oil under the certain reaction condition, unreacted gaseous fraction in the butylene building-up reactions product is discharged system, and gasoline fraction in the separation of liquid products and diesel oil distillate, make the alkene in the gasoline fraction further superimposed under than the demulcent condition again to generate more diesel oil distillate.
The condition of described butylene building-up reactions is 300～450 ℃, 0.5～2.0MPa, and the superimposed reaction conditions of gasoline is 180～280 ℃, 1.0～2.0MPa.
Raw material C during the butylene building-up reactions
4Preferred 1～5 hour of the mass space velocity that component contacts with the butylene polymerization catalyst
-1Preferred 0.7～2.0 hour of the mass space velocity that the feed gasoline cut contacts with the gasoline polymerization catalyst during gasoline building-up reactions
-1
Described butylene polymerization catalyst comprises the HZSM-5 zeolite of NiO, 40～80 quality % of 1～20 quality % and the aluminum oxide of 10～50 quality %.The SiO of HZSM-5 zeolite wherein
2/ Al
2O
3Mol ratio preferred 90～320.
Described gasoline polymerization catalyst comprises the amorphous silicic aluminium of NiO, 45～82 quality % of 1～12 quality % and the aluminum oxide of 10～50 quality %.The SiO of amorphous silicic aluminium wherein
2/ Al
2O
3Mol ratio preferred 6～10.
The preparation method of butylene polymerization catalyst provided by the invention comprises HZSM-5 zeolite and aluminum oxide powder mixing, adds less water, also can add peptizing agent, fully kneads to even as rare nitric acid, and extruded moulding obtains carrier after drying, the roasting then.With described carrier 450～650 ℃ with steam treatment 2～10 hours, the consumption of water vapour is 10～30 times of carrier quality.Use the solution impregnation of water soluble nickel salt then, dipping temperature is 60～90 ℃, Gu steeping fluid/than being 1～3: 1.With solid drying, in 400～550 ℃ of roastings, preferred noble gas is a nitrogen in noble gas behind the dipping.
Described gasoline polymerization catalyst preparation method comprises that sesbania powder dosage is 0.5～2.0 quality % of amorphous silicic aluminium and aluminum oxide powder total mass with amorphous silicic aluminium, aluminum oxide powder and a small amount of sesbania powder thorough mixing.Water soluble nickel salt is mixed with solution with diluted acid and water, make that acid concentration is 0.1～0.5 quality % in the solution, press liquid/solid volume than 1.0～1.2 with this solution and the amorphous silicic aluminium of a small amount of sesbania powder of above-mentioned adding and the mixture of aluminum oxide again: 1 mixed is even, be heated with stirring at 80～95 ℃ then and be thick thing, extruded moulding then, dry, roasting.
In the described method, water soluble nickel salt is selected from nickelous nitrate, nickelous carbonate, nickelous oxalate or nickelous acetate, preferred nickelous nitrate.
In the inventive method, generate diesel oil, preferably superimposed product of gasoline and the superimposed product of butylene are mixed laggard promoting the circulation of qi liquid and separate, then gasoline fraction in the liquid is separated with diesel oil distillate, again gasoline fraction is carried out building-up reactions for making the more gasoline alkene oligomerization.Like this, unreacted gasoline olefin can mix with the gasoline fraction of the superimposed generation of butylene in the gasoline building-up reactions, carries out the gasoline building-up reactions again, to increase utilization ratio of raw materials.
In the inventive method, C
4Component can be liquefied gas, catalytic cracking C-4-fraction, ethylene unit C-4-fraction, and MTBE device carbon four is taken out excess etc., preferred liquefied gas.Described C
4Preferred 20～100 quality % of the content of butylene, more preferably 40～100 quality % in the component.The gasoline fraction of the superimposed generation of butylene is formed comparatively complicated, and the C that is mainly of building-up reactions takes place
5～C
12Alkene.Carry out gasoline when superimposed, require that total olefin content is 35～100 quality % in the gasoline, preferred 45～85 quality %.
Below in conjunction with Fig. 1 the inventive method is described.Among Fig. 1, contain the C of butylene
4Component is pumped into interchanger 2 preheatings through surge tank 1 usefulness, enters butylene superposition reactor 3 and/or reactor 4 then, contacts with the butylene polymerization catalyst of heat to carry out butylene building-up reactions generation diesel oil and gasoline component.With butylene building-up reactions product through interchanger 5 by being pumped into branch flow container 6, the gaseous fraction that is rich in butane is discharged by pipeline 8, can be used as motor liquified gas; Liquid ingredient is discharged by minute flow container 6 bottoms and is entered separation column 7 separation gasoline fraction and diesel oil distillates.The gasoline fraction of telling enters gasoline basin 9 by the top, gasoline component is discharged by gasoline basin 9 bottom line 13, through entering gasoline superposition reactor 11 and/or 12 after interchanger 2 heat exchange, gasoline polymerization catalyst contact reacts with heat, reaction product is discharged by reactor bottom, behind interchanger 5,, isolate gasoline fraction and diesel oil distillate by being pumped into branch flow container 6 and separation column 7.Isolated gasoline fraction enters product jar 9, and diesel oil distillate enters diesel storing 10 through after the heat exchange.
In the above-mentioned reaction process, the superimposed and superimposed reactor of gasoline of butylene all can be one or more, if during two reactors, then building-up reactions and catalyst regeneration can hocket in two reactors respectively.Decaying catalyst can be by slowly being warming up to 500～600 ℃ of coke burning regenerations at air.Catalyzer after the regeneration promptly can be recycled after removing the non-hydrocarbons impurity that adsorbs on it with air or other gas.
Further describe the present invention below by example, but the present invention is not limited to this.
When carrying out building-up reactions in the example, raw material and gas-phase product are used HP 5890-II gas chromatograph (FID, Al respectively
2O
3-PLOT chromatographic column) analyze, liquid product is analyzed with HP 5890-II gas chromatograph (FID, PANOL chromatographic column), and the boiling range of polymer gasoline and diesel oil adopts the simulation distil method to determine 173 ℃ of diesel oil initial boiling points.
Example 1
Following examples preparation butylene polymerization catalyst.
(1) preparation carrier
Get 15 gram SiO
2/ Al
2O
3Mol ratio is that 90 HZSM-5 zeolite and 5 gram aluminum oxide powders mix, adds 12 gram deionized waters and mixes and pinches, and extruded moulding then, 4 hours, 540 ℃ roastings of 120 ℃ of dryings made carrier in 4 hours.With carrier 450 ℃ with steam treatment 8 hours, the water vapour consumption is 20 times of carrier quality.Pulverizing is 0.6～0.9 millimeter a particle then.
(2) preparation catalyzer
Get carrier granule 20 grams that (1) step makes, add by 16.0 gram nickelous nitrate [Ni (NO
3)
26H
2O] and the steeping fluid of 40 ml deionized water preparations in, 60 ℃ of dippings 3 hours, 120 ℃ of dryings 4 hours, roasting is 8 hours in 550 ℃ of nitrogen, makes catalyst A, its composition sees Table 1.
Example 2
Method by 1 (1) step of example prepares carrier, and different is with 10 gram SiO
2/ Al
2O
3Mol ratio is that 180 HZSM-5 zeolite and 10 gram aluminum oxide powders mix, and extruded moulding then makes carrier after dry, the roasting, again with carrier 520 ℃ with steam treatment 6 hours, be ground into particle then.
Method by example 1 (2) step prepares catalyzer, and different is that the used nickelous nitrate of preparation steeping fluid is 8 grams, 80 ℃ with steeping fluid impregnated carrier 4 hours, make catalyst B after dry, the roasting, its composition sees Table 1.
Example 3
Method by 1 (1) step of example prepares carrier, and different is with 13 gram SiO
2/ Al
2O
3Mol ratio is that 320 HZSM-5 zeolite and 7 gram aluminum oxide powders mix, and extruded moulding then makes carrier after dry, the roasting, again with carrier 540 ℃ with steam treatment 6 hours, be ground into particle then.
Method by example 1 (2) step prepares catalyzer, and different is that the used nickelous nitrate of preparation steeping fluid is 2.4 grams, 90 ℃ with steeping fluid impregnated carrier 3 hours, after the drying, 450 ℃ of roastings made catalyzer C in 5 hours, its composition sees Table 1.
Example 4
Method by 1 (1) step of example prepares carrier, and different is with 11 gram SiO
2/ Al
2O
3Mol ratio is that 200 HZSM-5 zeolite and 9 gram aluminum oxide powders mix, and extruded moulding then makes carrier after dry, the roasting, again with carrier 580 ℃ with steam treatment 6 hours, be ground into particle then.
Method by example 1 (2) step prepares catalyzer, and different is that the used nickelous nitrate of preparation steeping fluid is 4.8 grams, 70 ℃ with steeping fluid impregnated carrier 5 hours, after the drying, 400 ℃ of roastings made catalyzer D in 8 hours, its composition sees Table 1.
Example 5
Method by 1 (1) step of example prepares carrier, and different is with 14 gram SiO
2/ Al
2O
3Mol ratio is that 120 HZSM-5 zeolite and 6 gram aluminum oxide powders mix, and extruded moulding then makes carrier after dry, the roasting, again with carrier 650 ℃ with steam treatment 6 hours, be ground into particle then.
Method by example 1 (2) step prepares catalyzer, and different is that the used nickelous nitrate of preparation steeping fluid is 12 grams, 90 ℃ with steeping fluid impregnated carrier 3 hours, after the drying, 450 ℃ of roastings made catalyzer E in 6 hours, its composition sees Table 1.
Example 6～11
Following example carries out the butylene building-up reactions, and investigates the reactivity worth of butylene polymerization catalyst under the differential responses condition.
Filling 10 gram catalyzer in the stainless steel reactor (80mm * 20mm) of the small-sized reaction unit of continuous flow fixed bed.Liquefied gas (raw material I or II) is pumped into reactor through surge tank with metering to be contacted with hot catalyzer and reacts, product enters the branch flow container, gas-phase product is told by the top and through the wet flow indicator metering, liquid product is told by the bottom and measured with electronic scale.Liquid product yield is that benchmark calculates with butene content in the raw material.Each example is raw materials used, catalyzer and reaction conditions and the results are shown in Table 2, and raw material is formed and seen Table 3.
As shown in Table 2, catalyzer of the present invention is under lower reaction pressure, and butene conversion, liquid product yield and diesel oil content are all higher.In addition, example 8 and 11 illustrates that also the raw material that catalyzer of the present invention is suitable for is wider, not only the higher liquefied gas of butene content is had higher diesel yield, and the lower liquefied gas of butene content is also had higher diesel yield.
Example 12
Below preparation is used for the superimposed catalyzer of gasoline fraction.
(1) gets 14 gram SiO
2/ Al
2O
3Mol ratio is that 10 amorphous silicon aluminium powder, 6 gram aluminium oxide powders and 0.3 gram sesbania powder thorough mixing are even.
(2) with 0.8 gram nickelous nitrate [Ni (NO
3)
26H
2O] be dissolved in the dilute nitric acid solution, be made into the aqueous solution of nickelous nitrate-nitric acid, concentration of nitric acid is 0.1 quality % in this solution.The mixture that nickelous nitrate-aqueous nitric acid and (1) step of preparation is prepared mixes and stirs, and liquid/solid volume ratio is 1.1.90 ℃ are heated with stirring to mixture and become thick.With the mixture of viscous form extruded moulding, 120 ℃ of dryings 4 hours, 540 ℃ of roastings 4 hours are ground into 0.6～0.9 millimeter particle, make catalyzer F, and its composition sees Table 4.
Example 13
Method by example 12 prepares catalyzer, and that different is the SiO of used amorphous silicon aluminium of (1) step
2/ Al
2O
3Mol ratio is 8, adds 2.4 gram nickelous nitrates when (2) go on foot the aqueous solution of preparing nickelous nitrate-nitric acid, and concentration of nitric acid is 0.2 quality % in the solution of preparation.Maturing temperature behind the extruded moulding is 500 ℃, and the catalyzer that makes is G, and its composition sees Table 4.
Example 14
Method by example 12 prepares catalyzer, and that different is the SiO of used amorphous silicon aluminium of (1) step
2/ Al
2O
3Mol ratio is 6, adds 4.8 gram nickelous nitrates when (2) go on foot the aqueous solution of preparing nickelous nitrate-nitric acid, and concentration of nitric acid is 0.4 quality % in the solution of preparation.Maturing temperature behind the extruded moulding is 450 ℃, and the catalyzer that makes is H, and its composition sees Table 4.
Example 15
Method by example 12 prepares catalyzer, and that different is the SiO of used amorphous silicon aluminium of (1) step
2/ Al
2O
3Mol ratio is 9, adds 8.1 gram nickelous nitrates when (2) go on foot the aqueous solution of preparing nickelous nitrate-nitric acid, and concentration of nitric acid is 0.3 quality % in the solution of preparation.Maturing temperature behind the extruded moulding is 540 ℃, and the catalyzer that makes is I, and its composition sees Table 4.
Example 16
Method by example 12 prepares catalyzer, and that different is the SiO of used amorphous silicon aluminium of (1) step
2/ Al
2O
3Mol ratio is 7, adds 2.4 gram nickelous nitrates when (2) go on foot the aqueous solution of preparing nickelous nitrate-nitric acid, and concentration of nitric acid is 0.45 quality % in the solution of preparation.Maturing temperature behind the extruded moulding is 520 ℃, and the catalyzer that makes is J, and its composition sees Table 4.
Example 17
Get 10 gram SiO
2/ Al
2O
3Mol ratio is that 6 amorphous silicon aluminium powder, 10 gram aluminium oxide powders and 0.2 gram sesbania powder thorough mixing are even.Method by example 12 (2) step prepares catalyzer then, adds 2.4 gram nickelous nitrates during the aqueous solution of different is preparation nickelous nitrate-nitric acid, and concentration of nitric acid is 0.2 quality % in the solution of preparation.Maturing temperature behind the extruded moulding is 500 ℃, and the catalyzer that makes is K, and its composition sees Table 4.
Example 18
Get 16 gram SiO
2/ Al
2O
3Mol ratio is that 6 amorphous silicon aluminium powder, 4 gram aluminium oxide powders and 0.2 gram sesbania powder thorough mixing are even.Method by example 12 (2) step prepares catalyzer then, adds 2.4 gram nickelous nitrates during the aqueous solution of different is preparation nickelous nitrate-nitric acid, and concentration of nitric acid is 0.2 quality % in the solution of preparation.Maturing temperature behind the extruded moulding is 500 ℃, and the catalyzer that makes is L, and its composition sees Table 4.
Example 19～25
Following example carries out the gasoline building-up reactions, and investigates the reactivity worth of gasoline polymerization catalyst under the differential responses condition.
In the stainless steel reactor (80mm * 20mm) of the small-sized reaction unit of continuous flow fixed bed, load 10 gram catalyzer respectively.The polymer gasoline raw material is pumped into reactor through surge tank with metering contact and react with the catalyzer of heat, gas-phase product is discharged by the top and the process wet flow indicator measures, and liquid product measures by the bottom discharge and with electronic scale.Liquid product yield is that benchmark calculates with the raw material that enters reactor.Used polymer gasoline is formed and is seen Table 5, each example catalyst system therefor, reaction conditions and the results are shown in Table 6.
Example 26
Filling 10 gram catalyst B in the stainless steel reactor (80mm * 20mm) of the small-sized reaction unit of continuous flow fixed bed.It is 2.0 hours at 350 ℃, 1.0MPa, mass space velocity that liquefied gas raw material II shown in the table 3 is pumped into reactor and hot catalyzer through surge tank with metering
-1Condition under contact carry out the butylene building-up reactions, reaction product enters the branch flow container, gas-phase product is discharged by the top and through the wet flow indicator metering, liquid product is discharged by the bottom and measured with electronic scale.Butene conversion is 82.7 quality % in the reaction, and liquid product yield 83.7 quality % wherein contain diesel oil 33 quality %, and liquid product yield is that benchmark calculates with butene content in the raw material.Will be from product liquid isolated gasoline fraction be pumped into metering in the stainless steel reactor (80mm * 20mm) of loading 10 gram catalyzer G, be 1.0 hours at 180 ℃, 2.0MPa, mass space velocity
-1Condition under carry out the gasoline building-up reactions, reaction product enters the branch flow container, gas-phase product is told by the top and through wet flow indicator metering, liquid product is told by the bottom and measured with electronic scale.The diesel yield that generates in the gasoline building-up reactions is 46 quality %, is that benchmark calculates with the gasoline stocks that enters reactor.
Through behind the above-mentioned secondary building-up reactions, be that the diesel oil distillate one way total recovery that benchmark calculates is 62.2 quality % with butene content in the raw material.
Table 1
| Instance number | The catalyzer numbering | HZSM-5 zeolite SiO 2/Al 2O 3Mol ratio | Catalyzer is formed, quality % | ||
| NiO | HZSM-5 | Aluminum oxide | |||
| 1 | A | 90 | 20 | 62 | 18 |
| 2 | B | 180 | 10 | 45 | 45 |
| 3 | C | 320 | 3 | 63 | 34 |
| 4 | D | 200 | 6 | 52 | 42 |
| 5 | E | 120 | 15 | 60 | 25 |
Table 2
| Instance number | The catalyzer numbering | Reaction raw materials | Reaction conditions | Reaction result | ||||
| Temperature, ℃ | Pressure, MPa | Mass space velocity, hour -1 | Butene conversion, quality % | Liquid is received, quality % | Diesel oil content in the product liquid, quality % | |||
| 6 | A | I | 350 | 1.0 | 1.0 | 76.2 | 76.5 | 26.6 |
| 7 | B | I | 400 | 0.5 | 7.0 | 82.0 | 84.2 | 22.0 |
| 8 | C | I | 350 | 1.0 | 2.0 | 80.0 | 87.5 | 30.0 |
| 9 | D | I | 300 | 2.0 | 2.0 | 70.0 | 76.2 | 28.0 |
| 10 | E | I | 450 | 1.5 | 5.0 | 80.8 | 86.5 | 28.0 |
| 11 | C | II | 350 | 1.0 | 2.0 | 82.7 | 83.7 | 33.0 |
Table 3
| Raw material | Hydrocarbon composition, mol% | Foreign matter content, μ g/g | |||||||||
| i-C 0 4 | n-C 0 4 | C ＝x-1 | c-C ＝ 4-2 | i-C ＝ 4 | t-C ＝ 4-2 | C 3 | ∑C ＝ 4 | Diene | S | Alkali N | |
| I II | 40.81 - | 11.24 3.08 | 14.46 3.89 | 14.54 32.72 | 0.47 0.18 | 12.04 59.59 | 6.33 - | 41.51 96.38 | 5000 1000 | 10 8 | 5 5 |
Table 4
| Instance number | The catalyzer numbering | Amorphous silicon aluminium SiO 2/Al 2O 3Mol ratio | Catalyzer is formed, quality % | ||
| NiO | Amorphous silicon aluminium | Aluminum oxide | |||
| 12 | | 10 | 1.0 | 69.3 | 29.7 |
| 13 | | 8 | 2.9 | 67.9 | 29.2 |
| 14 | H | 6 | 6.0 | 65.8 | 28.2 |
| 15 | I | 9 | 10.0 | 63.0 | 27.0 |
| 16 | | 7 | 2.9 | 67.9 | 29.2 |
| 17 | K | 6 | 6.0 | 47.0 | 47.0 |
| 18 | L | 6 | 6.0 | 75.3 | 18.7 |
Table 5
| Form quality % | Boiling range, ℃ | Diesel oil content, quality % | Impurity, μ g/g | |||||
| Alkane | Alkene | Naphthenic hydrocarbon | Aromatic hydrocarbons | Fore-running/do | H 2O | S | Alkali N | |
| 23.92 | 61.89 | 8.32 | 5.83 | 170/204 | 6～9 | 200 | 10 | 5 |
Table 6
| Instance number | The catalyzer numbering | Reaction conditions | Reaction result | |||
| Temperature, ℃ | Pressure, MPa | The raw materials quality air speed, hour -1 | Liquid is received, quality % | Diesel yield, quality % | ||
| 19 | F | 210 | 1.0 | 3.0 | 95 | 32 |
| 20 | G | 180 | 2.0 | 1.0 | 98 | 46 |
| 21 | H | 250 | 1.0 | 0.7 | 93 | 36 |
| 22 | I | 280 | 1.5 | 2.0 | 93 | 38 |
| 23 | G | 220 | 2.0 | 2.0 | 95 | 42 |
| 24 | K | 250 | 1.0 | 0.7 | 92 | 31 |
| 25 | L | 250 | 1.0 | 0.7 | 90 | 29 |
Claims (10)
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Cited By (7)
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| CN101875851A (en) * | 2009-04-30 | 2010-11-03 | 中国石油化工股份有限公司 | A non-hydrogenation upgrading method of liquefied gas fraction |
| CN102060647A (en) * | 2010-12-03 | 2011-05-18 | 中国石油天然气股份有限公司 | A method for selective hydrogenation of carbon distillates |
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| US4777316A (en) * | 1987-11-10 | 1988-10-11 | Mobil Oil Corporation | Manufacture of distillate hydrocarbons from light olefins in staged reactors |
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