CN103361113A - Process for producing high-octane gasoline by using raw material rich in carbon, four carbon, five carbon and six alkane - Google Patents
Process for producing high-octane gasoline by using raw material rich in carbon, four carbon, five carbon and six alkane Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 147
- 239000002994 raw material Substances 0.000 title claims abstract description 94
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 145
- 238000000034 method Methods 0.000 title claims description 70
- 230000008569 process Effects 0.000 title description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 150000001336 alkenes Chemical class 0.000 claims abstract description 51
- 239000001257 hydrogen Substances 0.000 claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 36
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 71
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 58
- 238000005899 aromatization reaction Methods 0.000 claims description 38
- 239000002808 molecular sieve Substances 0.000 claims description 36
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 34
- 229930195733 hydrocarbon Natural products 0.000 claims description 27
- 150000002430 hydrocarbons Chemical class 0.000 claims description 27
- 230000003197 catalytic effect Effects 0.000 claims description 26
- 239000004480 active ingredient Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 238000005336 cracking Methods 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 230000005496 eutectics Effects 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 230000006835 compression Effects 0.000 claims description 3
- 238000007906 compression Methods 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 9
- -1 benzene aromatic hydrocarbon Chemical class 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- 238000005516 engineering process Methods 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 15
- 239000004215 Carbon black (E152) Substances 0.000 description 12
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 12
- 229910021536 Zeolite Inorganic materials 0.000 description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000010457 zeolite Substances 0.000 description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000012188 paraffin wax Substances 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 206010013786 Dry skin Diseases 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
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- 238000000465 moulding Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
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- 230000000052 comparative effect Effects 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
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- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-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
- 229910002651 NO3 Inorganic materials 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- CAGZNTXUZUOERQ-UHFFFAOYSA-N [O-2].O.[Ce+3] Chemical compound [O-2].O.[Ce+3] CAGZNTXUZUOERQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical class [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
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- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
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- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A process for preparing the high-octane gasoline includes such steps as mixing the C-rich penta-carbon hexaalkane with hydrogen, dehydrogenating the alkane in the reactor containing dehydrogenating catalyst, separating the dehydrogenated product from non-condensable gas, mixing with the raw material rich in olefin, and aromatizing in the reactor containing aromatizing catalyst to obtain the low-benzene high-octane gasoline. The modified gasoline has high non-benzene aromatic hydrocarbon content, low benzene content and low olefin content.
Description
Technical field
The invention provides a kind of can be with refinery C four carbon five carbon six alkanes through catalytic dehydrogenation, the technique that mix the step production stop bracket gasoline such as aromizing with the raw material that is rich in alkene.
Background technology
Along with the develop rapidly of Chinese national economy, the continuous increase of automobile pollution, increasing to the demand of vehicle fuel gasoline.Simultaneously, also along with increasingly strict to gasoline quality standard of environmental requirement, the motor spirit quality standard is to low sulfur content, low olefin-content, low-steam pressure and high-octane future development.Market has very big demand to the volume increase premium-type gasoline with to low-sulfur, low olefin-content, high octane value gasoline blending component, and the technological development of this aspect also becomes the hot issue of domestic each research unit and enterprises pay attention.
Enter 12, propelling along with 2,000 ten thousand ton/years of oil refining of CNPC's Guangdong petrochemical industry, the 1000 ten thousand ton/years of oil refining in Kunming, Sichuan petrochemical industry Integrated Refinery And Petrochemical engineering, 800,000 ton/years of ethene of Fushun petrochemical industry, 1,200,000 ton/years of projects such as expansion of ethylene of Daqing petrochemical, the oil-refining capacity of CNPC and ethene production capacity also will further enlarge, the C of refinery's by-product
4/ C
5/ C
6Alkane (such as reforming topped oil, oil field light hydrocarbon, pentane wet goods), catalytic cracking C
4With cracking C
4The output of resource is also significantly increasing.C
4/ C
5/ C
6Alkane is not high because of itself octane value, can not directly as motor spirit, need further processing upgrading.C
4For the production of MTBE, alkylate oil, the polymerization single polymerization monomer, burn as domestic fuel by major part except partly for resource.And C
4Hydrocarbon and tops are not only cheap, and transportation cost is high, in the transportation loss large, concerning this refinery, belong to low-value product.
CN93102129 discloses inferior patrol catalytic reforming-aromatization method.Thick pressure gasoline is catalytic reforming under conditions of non-hydrogen at first, and then carries out aromizing at Zn-Al or Zn-AL～rare earth HZSM-5, and temperature is 480 ℃～650 ℃, and pressure is 0.05MPa～1.5MPa.The yield of final gasoline is 55m%～75m%.Because aromatized catalyst carbon distribution inactivation is very fast, general aromatized catalyst will be regenerated once in 15 days, therefore, need two aromatization reactor blocked operations.
Publication number a kind of method of gasoline hydrofinishing-aromizing that has been the CN1488724A patent disclosure.The catalytically cracked gasoline the first step is 220 ℃～300 ℃ in temperature, and pressure is 2.0MPa～10.0MPa, volume space velocity 2.0～10.0h
-1With hydrogen to oil volume ratio 200～800: under 1 the condition, hydrofining removes sulfide and the olefin(e) compound in the gasoline.Second step is 350 ℃～450 ℃ in temperature, and pressure is 1.5MPa～4.5MPa, volume space velocity 0.5～3.0h
-1With hydrogen to oil volume ratio 200～800: under 1 the condition.Adopt the hydrogen type molecular sieve of little grain fineness number, with light-hydrocarbon aromatized be aromatic hydrocarbons, to recover the explosion-proof exponential sum octane value of fs.Although this technology has reached the effect of desulfurating and reducing olefinic hydrocarbon, the explosion-proof index loss of octane number of gasoline is all about 2%, and the gasoline rate of loss is about 10%.
Publication number be CN1580199A patent disclosure a kind of technique by etherificate and aromatization reformulated gasoline.This technology is cut into gasoline first weight two portions, contains 1～20% carbon four, 60～80% carbon five, no more than 20% carbon in the light constituent more than six, carbon six following components no more than 30% in the restructuring minute.Alkene in the light constituent and alcohols carry out etherification reaction, and restructuring minute is advanced reactor with hydrogen and carried out aromatization, and then with the component blending, octane value that can Effective Raise gasoline.
EP256604A2 discloses a kind of C
5～C
7The isomerized method of straight-chain paraffin is containing C
5～C
7Raw material be divided into two cuts of weight, lighting end enters isomerization reactor from a segmentation after mixing with hydrogen, the middle part from isomerization reactor after last running mixes with hydrogen enters reaction, reactor upper end temperature of reaction is low, lower end temperature of reaction height.The catalyzer that this method is used is the catalyzer that contains mordenite or y-type zeolite.
CN200410004475 discloses a kind of C
5, C
6Isomerized method.The method is with the raw material rectifying separation, with C
5Light constituent and C
6Restructuring divides respectively aromizing under different processing condition.
CN1073198A discloses a kind of dehydroaromatizationof dual-function catalyst preparation method who utilizes macropore L alkali type zeolite and a kind of butter binding agent mixing moulding.The active ingredient of this catalyzer is precious metals pt.US4104320, US4435283, US4458075, US4619906, EP184451A, US4780223 and CN86107521A introduce the Pt-L zeolite to introduce Ba, sylvite, basic metal and come modification L zeolite, to overcome this weakness of less stable in the dehydroaromatizationof of alkane reaction.
CN101993320A discloses a kind of method of producing light aromatics, comprises with mixed c 4 and C
9+ heavy arene is raw material, under conditions of non-hydrogen with aromatized catalyst 400～600 ℃ of abundant contact reactss.The method can also reduce the dry gas yield except can raising light aromatics yield by a relatively large margin, the approach of cost-effective processing residue lighter hydrocarbons and heavy arene resource is provided for the refinery.
CN101747933A discloses a kind of petroleum naphtha and light-hydrocarbon aromatized method for modifying, comprises petroleum naphtha and C
3～C
5Lighter hydrocarbons in the presence of hydrogen-containing gas, contact with aromatized catalyst and carry out the aromatization modification reaction, described upgrading temperature of reaction is that the volume ratio of 250～600 ℃, hydrogen and petroleum naphtha is 20～400.
CN101538184 discloses a kind of method for aromatizing light hydrocarbons, comprises C
3～C
12Hydro carbons under 250～650 ℃, the condition of 0.1～4.0MPa, produce aromatic hydrocarbons and liquefied gas with the aromatized catalyst contact reacts, described aromatized catalyst comprises complex carrier and the following component of content in catalyzer: ZnO 0.5～5.0 quality %; Rare earth oxide 0.1～5.0 quality %; VA family element 1.0～7.0 quality %.Described complex carrier comprises the ZSM series zeolite of 20～50 quality % and the binding agent of 50～80 quality %.This method is applicable to carry out with the reaction-renovation process of moving-bed.
CN101429452 provides a kind of catalytically cracked gasoline and C
4Mixing raw material contacts with catalyzer on aromatization reactor and carries out the method that aromatization is produced stop bracket gasoline, catalytically cracked gasoline and C
4Olefin enters fixed bed or simulation moving-bed aromatization reactor that molecular sieve catalyst is housed, contacts with aromatized catalyst, carry out the alkene aromatization, its reaction conditions: 250～340 ℃ of temperature of reaction, pressure 0.5～3.0MPa, weight space velocity are 0.5～10h
-1, C
4The mass ratio of alkene and catalytically cracked gasoline is 90: 10～2: 98; The carrier molecule sieve active ingredient of catalyzer is one or more in rare earth element, VIB, the group VIII element, and active ingredient weight is 0.01～10% of carrier; Can significantly reduce the feed gasoline olefin(e) centent, the Effective Raise octane value reaches the purpose of producing clean gasoline with high octane.
As mentioned above, the modification technology of existing carbon four carbon five carbon six alkane, by isomerization, aromizing, etherificate be combined with aromizing, hydrogenating desulfurization is combined with aromizing etc., and technology realizes.Isomerization technique produces a large amount of diluted acids, serious environment pollution owing to adopt hydrofluoric acid and the vitriol oil to make catalyzer.Because the direct technology of aromatization temperature of reaction of carbon four carbon five carbon six alkane is high, yield of gasoline is low, and the aromatized catalyst life-span is short.No matter and hydrogenating desulfurization is combined with aromatization technology or etherification technology is combined with aromatization technology, the just loss of octane value in remedying hydrogenation, etherification procedure of aromatization technology.
Think C more than contriver's process
4/ C
5/ C
6In the alkane transformation of the way technology, mainly undertaken by isomerization of paraffins and aromizing, but owing to severe reaction conditions, liquid are received the lower economic benefit that had a strong impact on.The alkene octane value is high than alkane in the gasoline, but poor stability, and environmental protection standard is more and more stricter to its requirement, and is low but alkene is compared the alkane reaction temperature in the reactions such as polymerization, cyclisation, alkylation, aromizing.Aromatization mainly by cracking, oligomerisation, dehydrogenation, cyclisation, alkylation, take off that many reactions steps such as alkyl realize.In the alkene aromatization, temperature of reaction is hanged down the generation that well suppresses cracking, dehydrogenation when guaranteeing olefin conversion, take off the reactions such as alkyl, will significantly lower C
1～C
4Deng the lower carbon number hydrocarbons growing amount, improve gasoline yield.Provide after the dehydrogenation of relatively high olefin(e) centent after intermediate product and the aromizing high-carbon five above liquid to receive and aromatics yield is technology emphasis of the present invention.
Summary of the invention
The object of the present invention is to provide a kind ofly with refinery's low octane rating, low value-added carbon four carbon five carbon six alkane that are rich in, mix the technique of aromizing production high octane gasoline component through catalytic dehydrogenation, with the raw material that is rich in alkene.
The present invention relates to a kind of usefulness be rich in carbon four carbon five carbon six paraffinic feedstock, be rich in the method for the raw material production gasoline of alkene, the present invention is characterised in that the raw material that will be rich in first carbon four carbon five carbon six alkane, mixes being fed through dehydrogenation reactor and contacting with dehydrogenation catalyst and carry out catalytic dehydrogenating reaction such as reforming topped oil, oil field light hydrocarbon, pentane wet goods and hydrogen.The catalytic dehydrogenation product is through the noncondensable gas tripping device, isolate behind the noncondensable gas with after the raw material that is rich in alkene, hydrogen mix, entering aromatization reactor contacts with aromatized catalyst and carries out aromatization, reacted product can be divided into dry gas, liquefied gas, gasoline component and diesel component by separating.
The raw material that is rich in carbon four carbon five carbon six alkane among the present invention refers to the in process of production hydro carbons take carbon four carbon five carbon six alkane as main ingredient of institute's by-product of refinery, carbon four carbon five carbon six hydro carbons that reclaim such as tops, coking light naphthar, oil field light hydrocarbon, pentane oil and other device etc., the content of general paraffinic hydrocarbons is preferably 95% more than 90%.The boiling range of raw material 95% preferably below 60 ℃, can be the same raw material below 70 ℃, also can be that different material mixes.Below all be weight percentage.
The raw material that is rich in alkene of indication refers to that alkene content is more than 35% among the present invention, be preferably in more than 45%, the boiling range of raw material 95% in 75 ℃, preferably at 65 ℃ with interior hydro carbons, such as carbon behind the ether four, catalytically cracked C four, cracking c_4, catalytic light gasoline etc.
The raw material that is rich in alkene among the present invention is 0.01: 1～100: 1 with the mass ratio that is rich in carbon four carbon five carbon six alkane.
Enter the mass ratio of hydrogen in the dehydrogenation reactor and the raw material that is rich in carbon four carbon five carbon six alkane among the present invention and enter that the mass ratio of hydrogen and hydro carbons is 0.01: 1 in the aromatization reactor～1: 1, be preferably 0.1: 1～0.5: 1.
Be not particularly limited dehydrogenation catalyst among the present invention, be rich in carbon four carbon five carbon six paraffinic feedstocks after entering the catalytic dehydrogenating reaction device after the preheating, olefin(e) centent preferably is not less than 35% in the catalytic dehydrogenation product.Dehydrogenation catalyst preferably is comprised of carrier and active ingredient, and catalyzer is preferably take high-temperature inorganic oxide as carrier, as being TiO
2, Al
2O
3, SiO
2, one or several the mixing among the ZnO, also can be molecular sieve or molecular sieve and the mixing of above several high-temperature inorganic oxides.Contain preferably that at least a metal is active ingredient in VIB, VIII, IA, the IIA family, as being Na, Zn, Rb, Cs, Mg, Sr, Ba, Pt, Mo, Cl, F, Br etc., preferably Pt, Cl, Mo, Cr; The content of active ingredient is 0.1%～20% of catalyst weight.It can also be the compound multi-metal-oxide catalyst that above-mentioned active ingredient obtains with co-precipitation; Molecular sieve can be one or more in ZSM-5, ZSM-11, ZSM-12, ZSM-35, MCM-22, Y type, the aluminium silicophosphate molecular sieve equimolecular sieve, and two or more molecular sieve can be composite molecular screen or eutectic molecular sieve.The shape of catalyzer can be bead, also can be bar shaped.The per-cent that the present invention does not specify is % by weight.
The reaction conditions of catalytic dehydrogenating reaction is preferably among the present invention: 480～700 ℃, and pressure 0.01～3MPa, the liquid volume air speed is 0.1～10h
-1The air speed that the present invention does not specify is the liquid volume air speed.
Be not particularly limited aromatized catalyst among the present invention, catalyzer preferably contains molecular sieve and one or more active ingredients.Molecular sieve specifically can be the molecular sieve of the mesopores such as ZSM-5, ZSM-11, ZSM-12, ZSM-35, MCM-22, Y type, aluminium silicophosphate molecular sieve, mesoporous and micropore, can be one or more in the molecular sieve, two or more molecular sieve can be composite molecular screen or eutectic molecular sieve.Large pore molecular sieve also is not suitable for aromatization of the present invention, and this is that the characteristics of raw material cause, the dehydrogenation intermediate product receive through liquid behind this catalytic unit and aromatics yield very undesirable.Aromatized catalyst can contain high-temperature inorganic oxide and molecular sieve, one or more active ingredients, and wherein high-temperature inorganic oxide can be TiO
2, Al
2O
3, SiO
2, one or several the mixing among the ZnO.The active ingredient that supports can be in rare earth element, IIIB, VIB, VIIB, VIII, the IIB family element one or several, as being La, Pr, Nd, Zn, Cr, Mo, Mn, W, Co, Ni, Pt etc., preferably La, Pr, Ni, Co, Cr; The active ingredient weight that supports is 0.01～8%.Catalyst shape can be bead, also can be strip.
The reaction conditions of aromatization is preferably among the present invention: 260～600 ℃, pressure 0.5～5.0MPa, volume space velocity are 0.1～10h
-1
Naphthene content and should be less than 10%, preferably less than 5% in the raw material.Such substances content surpasses 10% raw material, and to be not suitable for reason of the present invention be that the conversion of such raw material aromizing unit after dehydrogenation is limited, affects the quality of gasoline component among the present invention.
The flow process of petroleum naphtha etc. 95% more than 75 ℃ not within raw material range of the present invention, because the C of aromizing product after the overweight component dehydrogenation
5More than and aromatics yield, also greatly shorten simultaneously work-ing life of aromatized catalyst, can increase cost of the present invention undoubtedly.
Olefin(e) centent in the dehydrogenation product and be rich in olefin(e) centent in the olefin feedstock generally greater than 35%, more preferably greater than 45%.Olefin(e) centent is crossed the low aromaticity content that will cause in the aromizing unit product and is crossed low and C
5Liquid is received not high, will affect the economic performance of technique of the present invention.
In addition, for variation and the realization mass transfer that adapts to pressure between technique dehydrogenation unit of the present invention and the aromizing unit, should between two districts, add the tripping device of noncondensable gas, such as flash tank, absorption/Analytic Tower, refrigerating unit and compression set etc.
The catalytic dehydrogenating reaction device, the aromatization reactor that relate among the present invention are fixed-bed reactor, can be that a reactor uses separately, intermittently realize by two processes of reaction-catalyst regeneration, also can in parallel use of two or more reactors carry out cyclical operation, can also divide a plurality of reactors in parallel and series combination use.Catalyzer in one or several reactor is because the serious inactivation of carbon distribution by switching material import and export, recycles the continuous operation of realization response, regeneration system rapidly after the decaying catalyst regeneration.
Method of the present invention can be more specifically: make first the raw material and the hydrogen that are rich in carbon four carbon five carbon six alkane be blended in 480～600 ℃, pressure 0.01～3.0MPa, volume space velocity are 0.1～10h
-1Under carry out catalytic dehydrogenating reaction, so that then olefin(e) centent mixes with the raw material that is rich in alkene, hydrogen behind the dehydrogenation product process noncondensable gas tripping device, again at 260～560 ℃ more than 45% in the dehydrogenation product, pressure 0.5～5.0MPa, volume space velocity are 0.1～8h
-1Under carry out aromizing so that the liquid product yield is more than 43% in the aromizing product, the high octane gasoline component yield is more than 40%.
Aromizing, dehydrogenation etherificate dual-function catalyst technology are different respectively for utilize aromizing after technology such as the first etherificate, the weight component of the present invention and existing carbon four carbon five carbon six alkane, because aromizing after this technology employing mixes with the dehydrogenation of raw material elder generation, with the raw material that is rich in alkene, independently dehydrogenation unit can guarantee higher olefins yield, receives with the aromatics yield and the carbon five above liquid that improve the aromizing unit.Aromizing unit process temperature is lower, has well suppressed the generation of dry gas and propane, diesel component, has improved the yield of gasoline component.
Description of drawings
Fig. 1 is for using process flow diagram of the present invention.
Among the figure: 1-catalytic dehydrogenating reaction device, 2-aromatization reactor, 3-separation system, 4-noncondensable gas tripping device.
The hydro carbons that uses the raw material that is rich in alkene that method of the present invention can produce the refinery and tops, oil field light hydrocarbon, pentane wet goods to be rich in carbon four carbon five carbon six alkane, itself can not to use as gasoline, upgrading is gasoline component and the diesel component of low olefin-content, high non-benzene aromaticity content, has well improved the added value of raw material.
Embodiment
Below by embodiment in detail the present invention is described in detail.Table 1～table 6 is adopted raw material properties by embodiment, and table 7 is the character of reaction product.Wherein raw material A is the circulating water plant of Dushanzi Refinery reforming topped oil, raw material B is circulating water plant of Dushanzi Refinery hydrocracking light naphthar, raw material C is circulating water plant of Dushanzi Refinery aromatic hydrocarbons pentane oil, raw material D is Lanzhou Petrochemical Company catalysis workshop mixed c 4, raw material E is that Daqing Refinery company one heavily urges mixed c 4, and raw material F is Lanzhou Petrochemical ethylene plant petroleum naphtha.
Embodiment all adopts as shown in Figure 1 technique, and reactor all adopts the 200ml fixed bed reactor.The tripping device of noncondensable gas is flash tank, and embodiment 1～3 is for catalytic dehydrogenating reaction device and aromatization reactor are single reactor periodical operation, and among the embodiment 4～6, catalytic dehydrogenating reaction device and aromatization reactor are two reactor parallel circulatings and use.Analytic sample is the instantaneous sample of reaction after 10 hours.
Embodiment 1
Dehydrogenation catalyst adopts the Hai Tai HTPB-DH of company dehydrogenation catalyst, wherein with Al
2O
3For carrier take Pt and Cl as active ingredient, wherein the mass content of Pt is 1%, the chlorine mass content is 2%, specific surface area is 200m
2/ g, pore volume 0.5ml/g, diameter are 1.59mm, bulk density 0.6g/cm
3
Aromatized catalyst adopts the method for CN1586721A catalyzer Preparation Example 3 and adds active ingredient Ni, its concrete preparation process is as follows: adopt Hydrothermal Synthesis to go out grain fineness number less than the former powder of the supersiliceous zeolite of 500nm, 110 ℃ lower dry 3 hours, 550 ℃ of dryings 24 hours.Then according to the Ni (NO of the drying of 80g zeolite 20g aluminum oxide butt and 3.66g
3)
2The powder hand mix is even, uses rare nitric acid kneading of 10% again, then with behind the twin screw extruder extruded moulding 110 ℃ lower dry 3 hours, afterwards 550 ℃ of constant temperature 3 hours.Then with 0.6mol/L, the liquid-solid volume ratio of exchange be 10, each 1 hour swap time, exchange 5 times, liquid is changed in the centre.Exchange use deionized water wash after finishing, and 110 ℃ lower dry 3 hours, at 550 ℃ of lower constant temperature after 5 hours, the cooling use.
The raw material that is rich in carbon four carbon five carbon six alkane adopts raw material A, enters that hydrogen is 0.25: 1 with the mass ratio that is rich in the raw material of carbon four carbon five carbon six alkane in the dehydrogenation reactor, at 480 ℃ of temperature of reaction, volume space velocity 0.1h
-1, catalytic dehydrogenation under the condition of reaction pressure 0.01MPa, reaction obtains that olefin(e) centent is 37.1% in the dehydrogenation product.Enter that the mass ratio of hydrogen and hydro carbons is 0.25: 1 in the aromatization reactor, the raw material that is rich in alkene adopts raw material D, and raw material D is 0.01: 1 with the ratio that is rich in carbon four carbon five carbon six paraffinic feedstocks.The reaction conditions of aromizing is: 340 ℃ of temperature of reaction, volume space velocity 0.8h
-1, reaction pressure 1.8MPa, acquired results is listed in table 7.
Embodiment 2
The load 10%MoO that dehydrogenation catalyst adopts fine chemistry industry key lab of Xinjiang University to provide
3γ-Al
2O
3Catalyzer, its preparation process are to take by weighing a certain amount of (NH
4)
6Mo
7O
244H
2Dipping γ-Al after O is dissolved in the hot water
2O
3, stirring is evaporated to dried, and 120 ℃ of lower dry 10h at last at 550 ℃ of lower roasting 4h, make catalyzer.
Aromatized catalyst adopts that Dalian University of Technology provides contains chromium ZSM-5 zeolite molecular sieve catalyst, and its carrier is Al
3O
2, wherein chromium content is 4%, ZSM-5 zeolite molecular sieve content 25%, profile are the cylindrical bars of the long 3mm of diameter 1.5mm, bulk density 0.65g/ml, specific surface area 340m
2/ g, pore volume are 0.25ml/g.
The raw material that is rich in carbon four carbon five carbon six alkane adopts raw material B, changes to enter that hydrogen is 0.1: 1 with the mass ratio that is rich in the raw material of carbon four carbon five carbon six alkane in the dehydrogenation reactor, and the processing condition of catalytic dehydrogenation are 700 ℃ of temperature of reaction, volume space velocity 1.0h
-1, reaction pressure 0.15MPa, reaction obtains that olefin(e) centent is 51.6% in the dehydrogenation product.Change and to enter that the mass ratio of hydrogen and hydro carbons is 0.1: 1 in the aromatization reactor, the raw material that is rich in alkene adopts raw material D, and raw material D and the ratio that is rich in carbon four carbon five carbon six paraffinic feedstocks are 0.3: 1.The processing condition that change aromizing are 380 ℃ of temperature of reaction, volume space velocity 0.1h
-1, reaction pressure 2.2MPa.Experimental results is listed in table 7.
Dehydrogenation catalyst adopts the method preparation of embodiment 1 among the patent CN101618319.2.24 gram calcium oxide and 3.1 gram polyoxyethylene glycol are dissolved in the 120ml deionized water, 240 ℃ of hydrothermal treatment consists 24 hours, 600 ℃ of calcinations are after 5 hours, it is mixed with an amount of dehydrated alcohol and 7.2 gram chromium nitrates, 6 gram aluminium sesquioxides, grind after dry 12 hours evenly, for subsequent use after 3 hours 550 ℃ of lower calcinations.
Aromatized catalyst adopts the prosperous grand chemical industry OCTC-02 of the company limited aromatization of gas catalyzer in Zibo.Its main component is the cobalt of 40%ZSM-5 molecular sieve and 6%, and all the other are Al
2O
3Its profile is the cylindrical bars of the long 3mm of diameter 2.5mm, bulk density 0.70g/ml, and ultimate compression strength is 90N/cm.
The raw material that is rich in carbon four carbon five carbon six alkane adopts raw material C, changes that to enter hydrogen and the mass ratio that is rich in the raw material of carbon four carbon five carbon six alkane in the dehydrogenation reactor be that the reaction conditions of catalytic dehydrogenation in 0.5: 1 is 570 ℃ of temperature of reaction, volume space velocity 3.0h
-1, reaction pressure 1.7MPa, reaction obtains that olefin(e) centent is 54.9% in the dehydrogenation product.Change and to enter that the mass ratio of hydrogen and hydro carbons is 0.5: 1 in the aromatization reactor, the raw material that is rich in alkene adopts raw material D, and raw material D and the ratio that is rich in carbon four carbon five carbon six paraffinic feedstocks are 25: 1.The reaction conditions that changes aromizing is: 600 ℃ of temperature of reaction, volume space velocity 5h
-1, reaction pressure 2.8MPa.Acquired results is listed in table 7.
Embodiment 4
Dehydrogenation catalyst adopts the method preparation of embodiment 4 among the CN101940922A.Its concrete steps are: take by weighing first the chromic oxide of 117.5 grams, be dissolved in the deionized water and fully stir, being mixed with weight concentration is 47% chromic oxide solution.Be 3.86% Alkitrate in the configuration weight concentration.Then with 55.0 gram pseudo-boehmites, 2.2 gram wilkinites, the chromic oxide solution for preparing with 7.59 grams fully mixes, and mediates, is extruded into bead.And then 120 ℃ lower dry 3 hours, and then 500 ℃ of constant temperature 3 hours, 620 ℃ of constant temperature 2 hours, at last 760 ℃ of roastings 4 hours under 20% water and 80% air.Get again chromic oxide solution 11.39 gram for preparing, will join burned sample dipping 20 minutes, 120 ℃ of dryings 3 hours, 550 ℃ of constant temperature calcinings 5 hours.Get again the Alkitrate dipping for preparing, 120 ℃ of dryings 3 hours, for subsequent use 620 ℃ of constant temperature calcinings 6 hours.
Aromatized catalyst adopts the method for CN1586721A catalyzer Preparation Example 3 also to add active ingredient Pr, and its concrete preparation process is as follows: adopt Hydrothermal Synthesis to go out the ZSM-11 zeolite powder, 110 ℃ lower dry 3 hours, 550 ℃ of dryings 24 hours.Then according to the Pr (NO of the drying of 70g zeolite 30g aluminum oxide butt and 7g
3)
2The powder hand mix is even, uses rare nitric acid kneading of 10% again, then with behind the twin screw extruder extruded moulding 110 ℃ lower dry 3 hours, afterwards 550 ℃ of constant temperature 3 hours.Then with 1mol/L, the liquid-solid volume ratio of exchange be 5, each 2 hours swap times, exchange 3 times, liquid is changed in the centre.Exchange use deionized water wash after finishing, and 110 ℃ lower dry 3 hours, at 550 ℃ of lower constant temperature after 5 hours, the cooling use.
The raw material that is rich in carbon four carbon five carbon six alkane adopts raw material A, changes that to enter hydrogen and the mass ratio that is rich in the raw material of carbon four carbon five carbon six alkane in the dehydrogenation reactor be that the reaction conditions of catalytic dehydrogenation in 0.3: 1 is 600 ℃ of temperature of reaction, volume space velocity 5.0h
-1, reaction pressure 1.1MPa, reaction obtains that olefin(e) centent is 64.0% in the dehydrogenation product.Change and to enter that the mass ratio of hydrogen and hydro carbons is 0.3: 1 in the aromatization reactor, the raw material that is rich in alkene adopts raw material E, and raw material E and the ratio that is rich in carbon four carbon five carbon six paraffinic feedstocks are 60: 1.The reaction conditions that changes aromizing is: 260 ℃ of temperature of reaction, volume space velocity 8h
-1, reaction pressure 4.1MPa.Acquired results is listed in table 7.
Embodiment 5
Dehydrogenation catalyst adopts the method preparation of embodiment 9 among the patent CN96121452.X.Take by weighing 17 gram Cr (NO
3)
3.9H
2O, 1.1 gram Cu (NO
3)
23H
2O, 80.8 gram Al (NO
3)
3.9H
2O uses the coprecipitation method Kaolinite Preparation of Catalyst, and precipitation agent is selected 10% KOH (or NaOH) solution, nitrate is dissolved in the distilled water, add while stirring precipitation agent, make it be completed into gel, and the pH value is 8.5～9, aging 3 hours, filter, under 110 ℃, dry 20 hours, 650 ℃ of roastings 7 hours, for subsequent use behind crushing and screening.
The preparation method of catalyzer C1 among the embodiment 1 among the aromatized catalyst employing patent CN101898150A.Concrete steps are as follows: get 100 gram SiO
2/ Al
2O
3The molecule mol ratio is 65 HZSM-5 molecular sieve, is 6.32 mg/ml phosphoric acid solutions dipping 8 hours with 100 ml concns first, and 110 ℃ of dryings are the LaCl of 3.04 mg/ml with 100 ml concns again after 4 hours
3.
6H
2O solution impregnation 8 hours, so that the content of La in catalyzer is 8wt%, then 110 ℃ of dryings are 4 hours, 550 ℃ of roastings 4 hours are for subsequent use.
The raw material that is rich in carbon four carbon five carbon six alkane adopts raw material B, changes to enter that hydrogen is 0.15: 1 with the mass ratio that is rich in the raw material of carbon four carbon five carbon six alkane in the dehydrogenation reactor, and the reaction conditions of catalytic dehydrogenation is 650 ℃ of temperature of reaction, volume space velocity 8.0h
-1, reaction pressure 2.4MPa, reaction obtains that olefin(e) centent is 35.6% in the dehydrogenation product.Change and to enter that the mass ratio of hydrogen and hydro carbons is 0.15: 1 in the aromatization reactor, the raw material that is rich in alkene adopts raw material E, and raw material E and the ratio that is rich in carbon four carbon five carbon six paraffinic feedstocks are 100: 1.The reaction conditions that changes aromizing is: 400 ℃ of temperature of reaction, volume space velocity 1.5h
-1, reaction pressure 5.0MPa.Acquired results is listed in table 7.
Embodiment 6
Dehydrogenation catalyst adopts the step Kaolinite Preparation of Catalyst that catalyzer prepares among the embodiment 1 among the patent CN101623633A.At first the former powder of ZSM-5 molecular sieve is at the SnCl of carrier at 0.16M
22H
2In the O solution in 80 ℃ of dipping 10hr, so that the charge capacity of the Sn in the catalyzer reaches 4wt%, and then 120 ℃ of lower dry 6hr.Dried sample is roasting 4hr under 550 ℃ of air atmosphere.Powder after the roasting is at the H of 0.03M
2PtCl
66H
2At 80 ℃ of lower dipping 4hr, make and finally make the catalyzer that Pt content is 20wt% in the O solution, then at 120 ℃ of lower dry 6hr, at 550 ℃ of lower roasting 4hr.For subsequent use at 550 ℃ of hydrogen reducing 12hr afterwards.
Aromatized catalyst adopts the method preparation of aromatized catalyst preparation among the embodiment 1 among the patent CN98101358.9.Concrete preparation process is: with 10gHZSM-5 and Al
2O
3Than being to pour the Zn (NH that concentration is 54 mg/ml in 65: 35 the carrier
3)
4(NO
3)
212 milliliters of the aqueous solution flooded 2 hours.Then use twice, 120 ℃ of drying of deionized water rinsing 6 hours.Then use 8 milliliters of chloride containing mishmetal (industrial goods, packet header, Inner Mongol industrial produces, wherein lanthanum trioxide 31%, oxygen cerium oxide 51%, Praseodymium trioxide 14%, Neodymium trioxide 4%) the aqueous solution at room temperature flooded two hours, 110 ℃ of dryings 16 hours, 540 ℃ of roastings are after 6 hours, 540 ℃ of steam treatment 2 hours.Make rare earth oxide content 0.34wt% in the catalyzer, zinc content 2.1wt%
The raw material that is rich in carbon four carbon five carbon six alkane adopts raw material C, changes that to enter hydrogen and the mass ratio that is rich in the raw material of carbon four carbon five carbon six alkane in the dehydrogenation reactor be that the reaction conditions of catalytic dehydrogenation in 0.5: 1 is 550 ℃ of temperature of reaction, volume space velocity 10.0h
-1, reaction pressure 3.0MPa, reaction obtains that olefin(e) centent is 44.7% in the dehydrogenation product.Change and to enter that the mass ratio of hydrogen and hydro carbons is 0.5: 1 in the aromatization reactor, be rich in the raw material employing raw material E of alkene, the ratio of raw material E and carbon four carbon five carbon six raw materials is 1: 1.The reaction conditions of aromizing is 560 ℃ of temperature of reaction, volume space velocity 3.5h
-1, reaction pressure 0.5MPa.Acquired results is listed in table 7.
Comparative Examples 1:
Repeat embodiment 1, change in its technological process dehydrogenation unit and do not use, raw material A and D are directly carried out aromizing, product separation.Products therefrom character is listed in table 7.
Comparative Examples 2:
Repeat embodiment 1, feed change A is raw material F, and products therefrom character is listed in table 7.
Table 1 raw material A forms (W%)
| Component | Naphthenic hydrocarbon | Branched paraffin | Straight-chain paraffin | Alkene | Aromatic hydrocarbons |
| C 4 | 3.19 | 5.20 | |||
| C 5 | 14.85 | 15.88 | 9.11 | 0.03 | |
| C 6 | 4.19 | 41.20 | 3.93 | 1.90 | |
| C 7 | 0.05 | 0.09 | 0.06 | ||
| C 8 | 0.16 |
Table 2 raw material B forms (W%)
| Component | Naphthenic hydrocarbon | Branched paraffin | Straight-chain paraffin | Alkene | Aromatic hydrocarbons |
| C 4 | 5.81 | 8.82 | |||
| C 5 | 0.92 | 50.87 | 14.47 | ||
| C 6 | 1.75 | 15.47 | 1.38 | 0.11 | |
| C 7 | 0.12 | 0.22 | 0.01 | ||
| C 8 | 0.05 |
Table 3 raw material C forms (W%)
| Component | Naphthenic hydrocarbon | Branched paraffin | Straight-chain paraffin | Alkene | Aromatic hydrocarbons |
| C 4 | 0.24 | 11.73 | 0.07 | ||
| C 5 | 0.32 | 53.16 | 32.36 | 0.86 |
Table 4 raw material D forms (W%)
| Component | ω％ | Component | ω％ |
| Propane | 0.04 | Iso-butylene | 17.11 |
| Propylene | 0.01 | Cis-butene-2 | 12.51 |
| Trimethylmethane | 29.50 | Iso-pentane | 0.66 |
| Normal butane | 9.16 | 1,3-butadiene | 0.09 |
| Trans-butene-2 | 17.51 | The 2-methyl-2-butene | 0.01 |
| 1-butylene | 13.39 | The 1-amylene | 0.01 |
Table 5 raw material E forms
| Component | ω％ | Component | ω％ |
| Propane | 0.00 | Iso-butylene | 12.45 |
| Propylene | 0.00 | Cis-butene-2 | 12.79 |
| Trimethylmethane | 34.29 | Iso-pentane | 0.06 |
| Normal butane | 10.38 | 1,3-butadiene | 0.07 |
| Trans-butene-2 | 17.33 | The 2-methyl-2-butene | 0.02 |
| 1-butylene | 12.63 | The 1-amylene | 0.04 |
The composition of table 6 raw material F
| Component | Naphthenic hydrocarbon | Branched paraffin | Straight-chain paraffin | Alkene | Aromatic hydrocarbons |
| C 4 | 1.40 | 3.61 | 0.03 | ||
| C 5 | 1.01 | 4.07 | 5.24 | 0.15 | |
| C 6 | 4.91 | 6.86 | 5.96 | 0.29 | 2.57 |
| C 7 | 10.16 | 5.45 | 5.41 | 0.32 | 2.06 |
| C 8 | 9.21 | 5.54 | 4.48 | 0.28 | 2.28 |
| C 9 | 1.18 | 8.38 | 2.63 | 0.13 | 1.29 |
| C 10 | 0.93 | 2.63 | 1.37 | 0.09 |
Reaction effect after the six alkane catalytic dehydrogenations of table 7 carbon four carbon five carbon, the aromizing
Claims (29)
1. technique with the raw material production gasoline that is rich in carbon four carbon five carbon six alkane, the raw material that it is characterized in that will being rich in first carbon four carbon five carbon six alkane and hydrogen are mixed and are fed through dehydrogenation reactor and contact with dehydrogenation catalyst and carry out catalytic dehydrogenating reaction; The catalytic dehydrogenation product is through the noncondensable gas tripping device, isolates behind the noncondensable gas with after the raw material that is rich in alkene, hydrogen mix, and enters aromatization reactor and contacts with aromatized catalyst and carry out aromatization; Reacted product is divided into dry gas, liquefied gas, gasoline component and diesel component by separating.
2. technique according to claim 1 is characterized in that being rich in the boiling range of raw material 95 % by weight of carbon four carbon five carbon six alkane below 70 ℃.
3. technique according to claim 2 is characterized in that being rich in the boiling range of raw material 95 % by weight of carbon four carbon five carbon six alkane below 60 ℃.
4. technique according to claim 1 is characterized in that being rich in the raw material paraffinicity of carbon four carbon five carbon six alkane more than 90 % by weight.
5. technique according to claim 4 is characterized in that being rich in the raw material paraffinicity of carbon four carbon five carbon six alkane more than 95 % by weight.
6. technique according to claim 1, it is characterized in that the catalytic dehydrogenating reaction condition is: 480～700 ℃, pressure 0.01～3MPa, volume space velocity are 0.1～10h
-1, entering hydrogen in the dehydrogenation reactor is 0.01: 1～1: 1 with the mass ratio that is rich in the raw material of carbon four carbon five carbon six alkane.
7. technique according to claim 1 is characterized in that the raw material that is rich in alkene refers to olefin(e) centent carbon four, catalytically cracked C four and/or cracking c_4 behind the light FCC gasoline more than 35%, ether.
8. technique according to claim 7 is characterized in that the raw material that is rich in alkene refers to olefin(e) centent carbon four, catalytically cracked C four and/or cracking c_4 behind the light FCC gasoline more than 45%, ether.
9. technique according to claim 1 is characterized in that the mass ratio that is rich in the raw material of alkene and is rich in the raw material of carbon four carbon five carbon six alkane is 0.01: 1～100: 1.
10. technique according to claim 6 is characterized in that entering that hydrogen is 0.1: 1～0.5: 1 with the mass ratio that is rich in the raw material of carbon four carbon five carbon six alkane in the dehydrogenation reactor.
11. technique according to claim 1 is characterized in that the aromatization condition is: 260～600 ℃, pressure 0.5～5.0MPa, volume space velocity are 0.1～10h
-1, enter that the mass ratio of hydrogen and hydro carbons is 0.01: 1～1: 1 in the aromatization reactor.
12. technique according to claim 11 is characterized in that entering that the mass ratio of hydrogen and hydro carbons is 0.1: 1～0.5: 1 in the aromatization reactor.
13. technique according to claim 1 is characterized in that catalytic dehydrogenating reaction device and aromatization reactor are fixed-bed reactor, is respectively the in parallel or series connection of a reactor or a plurality of reactor.
14. technique according to claim 1 is characterized in that the tripping device with noncondensable gas is connected between catalytic dehydrogenating reaction device and the aromatization reactor.
15. technique according to claim 1 is characterized in that tripping device comprises flash tank, absorption/Analytic Tower, refrigerating unit and/or compression set.
16. technique according to claim 1 is characterized in that dehydrogenation catalyst is comprised of carrier and active ingredient, active ingredient contains in VIB, VIII, IA, the IIA element at least a, and the content of active ingredient is 0.1%～20% of catalyst weight.
17. technique according to claim 1 is characterized in that dehydrogenation catalyst is the multi-metal-oxide catalyst that coprecipitation method makes, active metal component contains in VIIB, VIII, IA, the IIA family at least a.
18. technique according to claim 16, the carrier that it is characterized in that dehydrogenation catalyst is TiO
2, Al
2O
3, SiO
2, one or several the mixture among the ZnO.
19. technique according to claim 16, the carrier that it is characterized in that dehydrogenation catalyst is the mixture of molecular sieve or molecular sieve and high-temperature inorganic oxide.
20. technique according to claim 16 is characterized in that active ingredient is one or several among Na, Zn, Rb, Cs, Mg, Sr, Pt, Ba, Re, Mn, Cl, F, the Br.
21. technique according to claim 19, it is characterized in that molecular sieve is one or more in ZSM-5, ZSM-11, ZSM-12, ZSM-35, MCM-22, Y type, the aluminium silicophosphate molecular sieve, two or more molecular sieve is composite molecular screen or eutectic molecular sieve.
22. technique according to claim 1 is characterized in that aromatized catalyst contains molecular sieve and one or more active ingredients, active ingredient weight is 0.01～8%.
23. technique according to claim 1 is characterized in that aromatized catalyst contains high-temperature inorganic oxide and molecular sieve supported one or more active ingredients.
24. technique according to claim 23 is characterized in that high-temperature inorganic oxide is TiO in the aromatized catalyst
2, Al
2O
3, SiO
2, one or several the mixture among the ZnO.
25. according to claim 22 or 23 described techniques, it is characterized in that the molecular sieve in the aromatized catalyst is micropore, mesoporous or/and the mixing of one or several in the mesoporous molecular sieve.
26. technique according to claim 25, it is characterized in that molecular sieve in the aromatized catalyst is one or more in ZSM-5, ZSM-11, ZSM-12, ZSM-35, MCM-22, Y type, the aluminium silicophosphate molecular sieve, two or more molecular sieve is composite molecular screen or eutectic molecular sieve.
27. according to claim 22 or 23 described techniques, it is characterized in that active ingredient in the aromatized catalyst is one or several in rare earth element, IIIB, VIB, VIIB, VIII, the IIB family element.
28. technique according to claim 27 is characterized in that active ingredient in the aromatized catalyst is one or more among La, Pr, Nd, Zn, Cr, Mo, Mn, W, Co, Ni, the Pt.
29. technique according to claim 28 is characterized in that active ingredient in the aromatized catalyst is one or more among La, Pr, Ni, Co, the Cr.
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