CN1350051A - Catalyst for modifying inferior gasoline to prepare clean gasoline and its prepn - Google Patents
Catalyst for modifying inferior gasoline to prepare clean gasoline and its prepn Download PDFInfo
- Publication number
- CN1350051A CN1350051A CN 01132487 CN01132487A CN1350051A CN 1350051 A CN1350051 A CN 1350051A CN 01132487 CN01132487 CN 01132487 CN 01132487 A CN01132487 A CN 01132487A CN 1350051 A CN1350051 A CN 1350051A
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- gasoline
- deionized water
- molecular sieve
- roastings
- Prior art date
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- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 18
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000002808 molecular sieve Substances 0.000 claims abstract description 12
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 7
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 4
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229910001994 rare earth metal nitrate Inorganic materials 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims 2
- 229910052723 transition metal Inorganic materials 0.000 claims 2
- 150000003624 transition metals Chemical class 0.000 claims 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 54
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 7
- 238000007233 catalytic pyrolysis Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000000197 pyrolysis Methods 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 238000004898 kneading Methods 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 25
- 150000001336 alkenes Chemical class 0.000 description 12
- 238000005303 weighing Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 239000005864 Sulphur Substances 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 241000080590 Niso Species 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- -1 desulfurization Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910000385 transition metal sulfate Inorganic materials 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The catalyst is formed from (wt%) 2.0-95.0% of small-grain ZSM-5 molecular sieve, 5.0-98.0% of inorganic oxide and 0.1-10.0% of rare earth metal oxide and filter metal oxide, in which the small-grain ZSM-5 molecular sieve can be synthesized according to the method described in applied Chinese patent No.99102700.0. Said ingredients are undergone the processes of mixing in a certain proportion, kneading, extruding, drying roasting, soaking, washing water water, drying and roasting to obtain the invented compound catalyst for improving low-grade gasolines of catalytically cracked gasoline, catalytic pyrolysis gasoline, thermal pyrolysis gasoline and coker gasoline. It can reduce their olefine, benzene and sulfur contents, and does not reduce octane value.
Description
Technical field the invention belongs to a kind of composite catalyst that modifying inferior gasoline to prepare clean gasoline uses and preparation method thereof that makes.
Background technology U.S. Pat P 4,997,543 have introduced a kind of MBR technology that reduces benzene content of Mobil company exploitation, and it adopts catalytic cracking (FCC) or coking tail gas (LPG) or light FCC raw gasline to carry out alkylated reaction to remove benzene with the benzene in the rich benzoline.This process using be the ZSM-5 catalyzer.
A kind of technology that reduces benzene content has been introduced by Uop Inc. in its patent USP 5,120,890, this process using is only handled the petroleum naphtha that contains benzene and two kinds of aromatic hydrocarbons of dimethylbenzene the method for raw material fractionation cutting, thereby can improve the transformation efficiency of aromatic hydrocarbons.This process using USY is a catalyzer.
A kind of method that reduces benzene content in the gasoline has also been introduced by Mobil company from another piece U.S. Pat P 5,336,820, it still adopts the ZSM-5 catalyzer, with the same C of rich benzoline
2-C
5Low-carbon alkene contacts on beds, makes benzene carry out alkylated reaction with low carbene, generates alkylbenzene to remove benzene.
U.S. Pat P 5,865, and 988 have also introduced a kind of low-quality gasoline upgrading technology of Mobil company exploitation.This process using two step method: at first with raw gasline by containing CoMo/Al
2O
3The bed of catalyzer is removed the sulfide hydrogenation, makes part alkene saturated simultaneously; Second step will generate previously reaction product by containing the bed of ZSM-5 catalyzer, with the octane value that recovers in hydrogenation process, to lose.Adopt this technology can reduce sulphur content and olefin(e) centent in the oil product greatly, increased aromaticity content simultaneously, and keep octane value not reduce.
Mobil company is also at USP 5, developed another kind of low-quality gasoline upgrading technology in 041,028 patent, this process using is supported on Pt, Re on the USY, Ir etc. and is catalyzer, adopt this technology can reduce alkene and sulphur content significantly, improved aromaticity content simultaneously greatly.
Up to now, Shang Weijian has and adopts the small-grain ZSM-5 modified molecular sieve catalyst to be used for the technology of low-quality gasoline production clean gasoline, and can reduce the report that olefin(e) centent, benzene content, sulphur content, maintenance octane value do not reduce simultaneously.
The purpose of this invention is to provide a kind of gasoline aftertreatment catalyzer, the every index of the gasoline after this catalyst treatment can satisfy the requirement of GB GB17930-1999 fully, keeps octane value not reduce simultaneously.
Summary of the invention catalyzer provided by the invention is made up of rare-earth oxide and the filtering metal oxide of the ZSM-5 molecular sieve with small crystal grains of 2.0-95.0% (weight), 5.0-98.0% (weight) inorganic oxide, 0.1-10.0% (weight).So-called little crystal grain is meant that the size of ZSM-5 molecular sieve is less than 1 μ; Inorganic oxide is selected from TiO
2, SiO
2, ZrO
2, Al
2O
3, or mixture in them or mixture; Rare earth metal and transition metal oxide are selected from La
2O
3, NiO, SrO, MoO
3, Co
2O
3, Ce
2O
3, or mixture in them or mixture.
The Preparation of catalysts method, at first be that ZSM-5 molecular sieve with small crystal grains can be by number of patent application: 99102700.0 described methods are synthetic, and promptly adopting modulus is that 3.18 water glass is as the silicon source; With analytically pure Tai-Ace S 150 is the aluminium source; Water is deionized water; Sulfuric acid concentration is 98% (analytical pure); The organic amine template is 70% ethylamine solution (chemical pure) or chemical pure propylamine, n-Butyl Amine 99.
With synthetic ZSM-5 molecular sieve with small crystal grains and inorganic oxide by 1-10: 1 (weight ratio) mixed, and adds 0.1-3.0% (weight) binding agent sesbania powder, adds 1-10% (V/V) HNO
3The aqueous solution mixes and to pinch, to be squeezed into bar shaped (or cylinder or cloverleaf pattern) and be cut into particle.After the drying, 540 ℃ of roastings, more at normal temperatures and pressures, with catalyzer and aqueous ammonium nitrate solution, with 1: 3 dipping, with deionized water washing, drying, roasting obtained HZSM-5.
HZSM-5 is put into steam handle stove, at 350-700 ℃, with air speed 1-9hr
-1Feed the water vapor modification and handle, drop it off again in the aqueous solution of rare-earth metal nitrate, dipping exchange at room temperature 4 hours, clean oven dry, 540 ℃ of roastings then with deionized water, cooling, put into the transition metal sulfate aqueous solution again and flood, at room temperature, exchange 4 hours again, washing, drying, roasting obtains the used modified composite catalyst of the present invention.
Rare-earth oxide, transition metal oxide from their nitrate or vitriol or ammonium salt, through after the roasting, generate oxide compound usually.For example: La (NO
3)
36H
2O, Co (NO
3)
26H
2O, NiSO
47H
2O, (NH
4)
2Mo
4O
132H
2O etc.
The said clean gasoline of the present invention be meant through fall alkene behind the upgrading, fall benzene, desulfurization, gasoline that the maintenance octane value is constant.
The catalyzer that low-quality gasoline upgrading provided by the invention is used can be used for the upgrading of low-quality gasoline such as catalytic cracking (FCC) raw gasline, catalytic pyrolysis (DCC) raw gasline, pyrolysis gasoline, coker gasoline.Gasoline through after the catalyst treatment can reduce its alkene, benzene and sulphur content, satisfies the requirement of standard GB 17930-1999, keeps octane value not reduce simultaneously, is the catalyzer that a kind of more satisfactory low-quality gasoline upgrading is used.
The evaluation index that reaction result adopts is: olefin(e) centent (V/V) :≤35%;
Aromaticity content (V/V) :≤40%;
The content of benzene (V/V) :≤2.5%;
The content of sulphur :≤800ppm
Embodiment
Embodiment 1
Weigh in the balance and get 100g by number of patent application 99102700.0 described method synthetic ZSM-5 molecular sieve with small crystal grains, 30gAl
2O
3The HNO that adds 1-10% (V/V) after powder and 0.1-5% (weight) sesbania powder mixes
3The aqueous solution mixes and pinches back extruded moulding in banded extruder, after drying 540 ℃ of roasting.Catalyzer that roasting is good and 0.4NNH
4NO
3The aqueous solution is at normal temperatures and pressures to flood 1hr at 1: 3 by the sieve liquor ratio, outwells exchange liquid, repeats above operation, uses the deionization washing with volume then, and dry back is 540 ℃ of roastings, HZSM-5.
Embodiment 2
Take by weighing 2.79g La (NO with analytical balance
3)
36H
2O adds the 60mL deionized water dissolving; Take by weighing NiSO
47H
2O3.95g adds the 60mL deionized water dissolving; To place steam to handle stove by the HZSM-5 that embodiment 1 makes and use steam-treated for inherent 550-600 ℃; Take by weighing the catalyzer 35g that handles through steam, impouring La (NO
3)
3In the aqueous solution, at room temperature static exchange 4hr outwells exchange liquid, cleans with deionized water, and the oven dry back is in 540 ℃ of roastings in retort furnace in baking oven; Product of roasting is cooled off back impouring NiSO slightly
4In the aqueous solution, at room temperature static exchange 4hr outwells exchange liquid, cleans with deionized water, and the oven dry back is in 540 ℃ of roastings in baking oven.The catalyzer cooling that roasting is good is placed in the drying basin standby.
Embodiment 3
Take by weighing 0.267g La (NO with analytical balance
3)
36H
2O adds the 20mL deionized water dissolving; Take by weighing 0.377gNiSO
47H
2O adds the 20mL deionized water dissolving; To place steam to handle stove by the HZSM-5 that embodiment 1 makes and use steam-treated for inherent 550-600 ℃; Take by weighing the catalyzer 10g that handles through steam, impouring La (NO
3)
3In the aqueous solution, at room temperature static exchange 4hr outwells exchange liquid, cleans with deionized water, and the oven dry back is in 540 ℃ of roastings in retort furnace in baking oven; Product of roasting is cooled off back impouring NiSO slightly
4In the aqueous solution, at room temperature static exchange 4hr outwells exchange liquid, cleans with deionized water, and the oven dry back is in 540 ℃ of roastings in baking oven.The catalyzer cooling that roasting is good is placed in the drying basin standby.
Embodiment 4
Take by weighing 2.67g La (NO with analytical balance
3)
36H
2O adds the 40mL deionized water dissolving; Take by weighing 3.7652gNiSO
47H
2O adds the 40mL deionized water dissolving; To place steam to handle stove by the HZSM-5 that embodiment 1 makes and use steam-treated for inherent 550-600 ℃; Take by weighing the catalyzer 20g that handles through steam, impouring La (NO
3)
3In the aqueous solution, at room temperature static exchange 4hr outwells exchange liquid, cleans with deionized water, and the oven dry back is in 540 ℃ of roastings in retort furnace in baking oven; Product of roasting is cooled off back impouring NiSO slightly
4In the aqueous solution, at room temperature static exchange 4hr outwells exchange liquid, cleans with deionized water, and the oven dry back is in 540 ℃ of roastings in baking oven.The catalyzer cooling that roasting is good is placed in the drying basin standby.
Embodiment 5
Take by weighing the 7.20g molybdenum acid ammonia with analytical balance, add the 300mL deionized water dissolving; Take by weighing the 8.85g Xiao Suangu, be dissolved in molybdenum acid ammonia solution; Weigh in the balance and get 100g, put into the aforementioned solution for preparing, under 70 ℃ of temperature, stir and spend the night, dry, ZSM-5 molecular sieve and the 30g Al after the oven dry by number of patent application 99102700.0 described method synthetic ZSM-5 molecular sieve with small crystal grains
2O
3After mixing, powder and an amount of sesbania powder add an amount of 10% (V/V) HNO
3The aqueous solution mixes and to pinch back extruded moulding in extrusion, after drying in retort furnace in 540 ℃ of roastings.The catalyzer cooling that roasting is good is placed in the drying basin standby.
Embodiment 6
The application of present embodiment explanation catalyzer aspect processing low-quality catalytic pyrolysis (DCC) gasoline.Dress 2g catalyzer in reaction tubes.Hydrogen flowing quantity measures with mass flowmeter; Reaction raw materials---thick catalytic pyrolysis (DCC) gasoline is squeezed in the pipe with pump, and enters reaction zone after hydrogen mixes and reacts on beds.Flow out reaction product bottom from knockout drum after gas-liquid separation, tail gas emptying after the spinner-type flowmeter metering.Live catalyst and regenerated catalyst are at 390 ℃ of temperature of reaction, reaction pressure 16atm, air speed 6hr
-1, reaction result and contrast situation under hydrogen-oil ratio 1200 (V/V) reaction conditions in the 300hr see Table 1,2,3 respectively.
Table 1 live catalyst changeed character in 300 hours
| Reaction times (hour) | Benzene % (V/V) | Alkene % (V/V) | Aromatic hydrocarbons % (V/V) | Stable hydrocarbon % (V/V) | ???RON |
| ????6 | ?????1.86 | ?????28.5 | ?????37.7 | ????33.8 | ???98.37 |
| ????12 | ?????1.76 | ?????26.4 | ?????39.4 | ????34.2 | ???99.19 |
| ????18 | ?????1.77 | ?????28.2 | ?????36.0 | ????35.8 | ???99.53 |
| ????24 | ?????1.68 | ?????26.3 | ?????39.4 | ????34.3 | ???98.33 |
| ????30 | ?????1.64 | ?????27.1 | ?????37.9 | ????35.0 | ???98.58 |
| ????36 | ?????1.59 | ?????28.4 | ?????36.2 | ????35.4 | ???98.36 |
| ????42 | ?????1.57 | ?????28.1 | ?????35.6 | ????36.3 | ???97.67 |
| ????48 | ?????1.57 | ?????28.6 | ?????35.6 | ????35.8 | ???97.91 |
| ????54 | ?????1.49 | ?????28.3 | ?????36.6 | ????35.1 | ???97.59 |
| ????60 | ?????1.39 | ?????28.9 | ?????31.2 | ????38.9 | ???97.10 |
| ????66 | ?????1.58 | ?????29.3 | ?????33.0 | ????37.7 | ???97.85 |
| ????72 | ?????1.59 | ?????28.6 | ?????35.9 | ????35.5 | ???97.77 |
| ????78 | ?????1.57 | ?????28.6 | ?????39.4 | ????33.8 | ???97.32 |
| ????84 | ?????1.66 | ?????29.5 | ?????34.6 | ????35.9 | ???97.54 |
| ????90 | ?????1.60 | ?????28.4 | ?????36.3 | ????35.3 | ???97.00 |
| ????96 | ?????1.53 | ?????27.3 | ?????39.4 | ????33.3 | ???97.42 |
| ????102 | ?????1.51 | ?????27.6 | ?????38.7 | ????33.6 | ???97.36 |
| ????108 | ?????1.50 | ?????26.6 | ?????39.9 | ????33.5 | ???96.51 |
| ????114 | ?????1.53 | ?????27.5 | ?????38.2 | ????34.3 | ???97.83 |
| ????120 | ?????1.52 | ?????27.4 | ?????39.7 | ????32.9 | ???96.78 |
| ????126 | ?????1.52 | ?????28.7 | ?????37.1 | ????34.2 | ???96.56 |
| ????132 | ?????1.54 | ?????28.1 | ?????37.8 | ????34.1 | ???96.88 |
| ????138 | ?????1.46 | ?????29.9 | ?????36.9 | ????33.2 | ???99.98 |
| ????144 | ?????1.55 | ?????29.8 | ?????34.9 | ????35.3 | ???96.81 |
| ????150 | ????1.34 | ????31.1 | ????35.4 | ????33.5 | ????95.45 |
| ????156 | ????1.42 | ????28.6 | ????37.2 | ????34.2 | ????96.52 |
| ????162 | ????1.55 | ????30.7 | ????33.1 | ????36.3 | ????96.51 |
| ????168 | ????1.44 | ????29.1 | ????36.9 | ????34.0 | ????96.21 |
| ????174 | ????1.39 | ????27.3 | ????39.7 | ????33.0 | ????95.77 |
| ????180 | ????1.39 | ????26.7 | ????39.9 | ????33.4 | ????94.92 |
| ????186 | ????1.45 | ????29.1 | ????37.2 | ????33.8 | ????95.44 |
| ????192 | ????1.51 | ????30.3 | ????35.7 | ????34.0 | ????95.55 |
| ????198 | ????1.44 | ????28.0 | ????39.2 | ????32.8 | ????95.49 |
| ????204 | ????1.38 | ????29.2 | ????37.9 | ????32.9 | ????95.60 |
| ????210 | ????1.45 | ????28.3 | ????36.1 | ????35.6 | ????95.41 |
| ????216 | ????1.47 | ????29.3 | ????33.9 | ????36.8 | ????95.76 |
| ????222 | ????1.62 | ????31.2 | ????31.9 | ????36.9 | ????95.44 |
| ????228 | ????1.49 | ????28.5 | ????35.7 | ????35.8 | ????95.15 |
| ????234 | ????1.32 | ????27.4 | ????39.0 | ????33.6 | ????94.51 |
| ????240 | ????1.46 | ????30.2 | ????33.7 | ????36.1 | ????95.83 |
| ????246 | ????1.52 | ????30.6 | ????32.9 | ????36.5 | ????94.98 |
| ????252 | ????1.55 | ????30.4 | ????32.1 | ????37.5 | ????94.98 |
| ????258 | ????1.38 | ????28.6 | ????35.4 | ????34.0 | ????95.49 |
| ????264 | ????1.46 | ????29.3 | ????35.0 | ????35.7 | ????95.13 |
| ????270 | ????1.72 | ????33.2 | ????31.6 | ????35.2 | ????93.95 |
| ????276 | ????1.62 | ????30.4 | ????35.8 | ????34.2 | ????93.53 |
| ????282 | ????1.38 | ????30.7 | ????35.2 | ????34.1 | ????94.63 |
| ????288 | ????0.83 | ????30.5 | ????30.2 | ????39.3 | ????94.12 |
| ????294 | ????0.85 | ????28.9 | ????33.1 | ????38.0 | ????92.33 |
| ????300 | ????1.03 | ????34.7 | ????27.3 | ????38.0 | ????92.23 |
Table 2 regenerated catalyst reactivity worth
| Reaction times (hour) | Benzene % (V/V) | Alkene % (V/V) | Aromatic hydrocarbons % (V/V) | Stable hydrocarbon % (V/V) | ??RON |
| ????10 | ????2.19 | ????20.0 | ????47.8 | ????32.2 | ??100.50 |
| ????20 | ????1.64 | ????19.6 | ????47.8 | ????32.5 | ??98.96 |
| ????30 | ????1.49 | ????22.0 | ????42.5 | ????35.5 | ??98.29 |
| ????40 | ????1.45 | ????25.7 | ????35.3 | ????38.8 | ??97.38 |
| ????50 | ????1.47 | ????23.5 | ????43.2 | ????33.2 | ??93.07 |
| ????60 | ????1.25 | ????22.3 | ????40.6 | ????37.0 | ??94.80 |
| ????70 | ????1.33 | ????26.6 | ????34.9 | ????38.5 | ??95.51 |
| ????80 | ????1.25 | ????26.1 | ????34.7 | ????39.2 | ??95.34 |
| ????90 | ????1.13 | ????23.2 | ????40.7 | ????35.4 | ??93.07 |
| ????100 | ????1.26 | ????25.6 | ????37.1 | ????37.4 | ??94.38 |
| ????110 | ????1.19 | ????27.6 | ????33.5 | ????39.1 | ??94.29 |
| ????120 | ????1.11 | ????27.6 | ????34.2 | ????38.2 | ??94.30 |
| ????130 | ????1.10 | ????26.4 | ????34.4 | ????39.1 | ??91.47 |
| ????140 | ????1.25 | ????27.6 | ????33.4 | ????39.0 | ??92.43 |
| ????150 | ????1.55 | ????31.0 | ????30.8 | ????38.1 | ??91.84 |
| ????160 | ????1.18 | ????27.6 | ????32.7 | ????39.5 | ??91.67 |
| ????170 | ????1.19 | ????29.0 | ????31.5 | ????39.4 | ??92.59 |
| ????180 | ????1.17 | ????28.7 | ????32.8 | ????38.4 | ??92.60 |
| ????190 | ????1.26 | ????30.5 | ????29.3 | ????40.1 | ??92.70 |
| ????200 | ????1.13 | ????28.3 | ????33.7 | ????38.0 | ??91.57 |
| ????210 | ????1.19 | ????29.0 | ????31.5 | ????39.3 | ??92.59 |
| ????220 | ????1.17 | ????28.7 | ????32.8 | ????38.4 | ??92.60 |
| ????230 | ????1.26 | ????30.5 | ????29.3 | ????40.1 | ??92.70 |
| ????240 | ????1.13 | ????28.3 | ????33.7 | ????38.0 | ??91.57 |
| ????250 | ????1.34 | ????32.7 | ????28.3 | ????38.9 | ??91.65 |
| ????260 | ????1.26 | ????30.2 | ????32.9 | ????36.8 | ??91.01 |
| ????270 | ????1.26 | ????30.5 | ????34.4 | ????35.9 | ??92.50 |
| ????280 | ????1.34 | ????30.6 | ????31.6 | ????37.5 | ??91.23 |
| ????290 | ????1.35 | ????32.1 | ????30.9 | ????36.9 | ??92.30 |
| ????300 | ????1.42 | ????33.2 | ????29.2 | ????37.5 | ??91.96 |
| ????310 | ????1.46 | ????33.8 | ????27.2 | ????38.9 | ??91.27 |
| ????320 | ????1.49 | ????34.5 | ????28.0 | ????37.8 | ??91.89 |
| ????330 | ????1.43 | ????32.4 | ????31.2 | ????36.4 | ??91.26 |
| ????340 | ????1.43 | ????33.9 | ????28.9 | ????37.2 | ??91.19 |
| ????350 | ????1.55 | ????33.8 | ????30.1 | ????36.0 | ??92.14 |
| ????360 | ????1.56 | ????32.0 | ????31.6 | ????36.3 | ??91.86 |
| ????370 | ????1.41 | ????31.7 | ????34.8 | ????33.5 | ??92.06 |
| ????380 | ????1.61 | ????34.2 | ????30.5 | ????35.7 | ??92.85 |
300 hours internal reaction average results of table 3 live catalyst and regenerated catalyst and raw material contrast
| Catalyst type | Product is formed | Evaluation index | ||||||
| Alkene (V/V%) | Aromatic hydrocarbons (V/V%) | Benzene | Organon RON | Alkene (V/V%) | Aromatic hydrocarbons (V/V%) | Benzene | ??RON | |
| Live catalyst | ????28.9 | ????36.0 | ??1.49 | ??96.34 | ????≤35 | ????≤40 | ?≤2.5 | ??≥91.9 |
| Regenerated catalyst | ????29.5 | ????34.9 | ??1.37 | ??93.56 | ????≤35 | ????≤40 | ?≤2.5 | ??≥91.9 |
| Raw material | ????64.7 | ????15.9 | ??3.0 | ??91.9 | ????≤35 | ????≤40 | ?≤2.5 | ??91.9 |
Embodiment 7
The application of present embodiment explanation catalyzer aspect processing low-quality catalytic pyrolysis (FCC) gasoline.Dress 2g catalyzer in reaction tubes.Hydrogen flowing quantity measures with mass flowmeter; Reaction raw materials---thick catalytic pyrolysis (FCC) gasoline is squeezed in the pipe with pump, and enters reaction zone after hydrogen mixes and reacts on beds.Flow out reaction product bottom from knockout drum after gas-liquid separation, tail gas emptying after the spinner-type flowmeter metering.Live catalyst and regenerated catalyst are at 400 ℃ of temperature of reaction, reaction pressure 20atm, air speed 3hr
-1, the reaction result under hydrogen-oil ratio 70 (V/V) reaction conditions in the 5hr sees Table 4:
Table 4 FCC gasoline changes before and after handling
| Test item | Raw material | Reaction product | GB | Experimental technique |
| Alkene (V/V%) | ????72.6 | ????26.9 | ????≤35 | ??GB/T11132 |
| Aromatic hydrocarbons (V/V%) | ????12.0 | ????35.8 | ????≤40 | ??GB/T11132 |
| Alkane (V/V%) | ????24.7 | ????37.3 | ??GB/T11132 | |
| Benzene | ????2.4 | ????0.90 | ????≤2.5 | Chromatography |
| ????RON | ????89.1 | ????96.8 | Chromatography is calculated |
Embodiment 8
Present embodiment illustrates the application of this catalyzer aspect the low-quality gasoline of processing high-sulfur.Adopting sulphur content is raw material up to the raw gasline of 2537ppm.Dress 2g catalyzer in reaction tubes.Hydrogen flowing quantity measures with mass flowmeter; The reaction raw materials raw gasline is squeezed in the pipe with pump, and enters reaction zone after hydrogen mixes and reacts on beds.Flow out reaction product bottom from knockout drum after gas-liquid separation, tail gas emptying after the spinner-type flowmeter metering.Live catalyst and regenerated catalyst are at 390 ℃ of reactions, reaction pressure 16atm, air speed 6hr
-1, the reaction result under hydrogen-oil ratio 600 (V/V) reaction conditions sees Table 5:
The desulfurization performance of table 5 catalyzer is investigated
| Reaction times | ??8 | ??16 | ??24 | ??32 | ??40 | ??48 | ??56 |
| Sulphur content, ppm | ??190 | ??192 | ??191 | ??189 | ??192 | ??206 | ??217 |
| Decreasing ratio, % | ??92.5 | ??92.4 | ??92.5 | ??92.5 | ??92.4 | ??91.9 | ??91.4 |
Claims (7)
1, a kind of catalyzer that is used for modifying inferior gasoline to prepare clean gasoline is characterized in that this catalyzer is made up of rare-earth oxide and the filtering metal oxide of the ZSM-5 molecular sieve with small crystal grains of 2.0-95.0% (weight), 5.0-98.0% (weight) inorganic oxide, 0.1-10.0% (weight).
2, according to the described catalyzer of claim 1, the granular size that it is characterized in that ZSM-5 molecular sieve with small crystal grains is less than 1 μ.
3,, it is characterized in that inorganic oxide is TiO according to the described catalyzer of claim 1
2, SiO
2, ZrO
2, Al
2O
3, or mixture in them or mixture.
4,, it is characterized in that rare-earth oxide is selected from La according to the described catalyzer of claim 1
2O
3, Ce
2O
3, or their based metallic oxides with mixed rare earth, transition metal oxide is selected from NiO, MoO
3, Co
2O
3, or the mixture in them.
5, Preparation of catalysts method according to claim 1, it is characterized in that this method is with ZSM-5 molecular sieve with small crystal grains and inorganic oxide less than 1 μ, press 1-10: 1 (weight ratio) mixed, and adds the binding agent sesbania powder of 0.1-3.0% (weight), adds 1-10% (V/V) HNO
3The aqueous solution mixes and pinches, is squeezed into bar shaped or cylinder or cloverleaf pattern, is cut into particle, after the drying, and 540 ℃ of roastings; Again at normal temperatures and pressures, it is put into aqueous ammonium nitrate solution with 1: 3 dipping, with deionized water washing, oven dry, roasting.Make the HZSM-5 catalyzer; Carry out steam then and handle modification, more successively or be put into together in the aqueous solution of the nitrate of rare earth metal and transition metal or vitriol, flood exchange, clean with deionized water, oven dry 540 ℃ of roastings, makes modified composite catalyst.
6,, it is characterized in that it is that catalyzer HZSM-5 with forming is put into and handles in the stove, at 350-700 ℃, with air speed 1-9hr that the steam modification is handled according to the described Preparation of catalysts method of claim 5
-1Feed steam-treated.
7, according to the described Preparation of catalysts method of claim 5, the catalyzer that it is characterized in that flooding modification and be forming is put into earlier in the aqueous solution of rare-earth metal nitrate, at room temperature, dipping exchange 4 hours is with deionized water washing, oven dry, 540 ℃ of roastings, cooling is put in the sulfate solution of transition metal, at room temperature again, dipping exchange 4 hours, clean with deionized water, oven dry, 540 ℃ of roastings make modified composite catalyst.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011324872A CN1151234C (en) | 2001-10-30 | 2001-10-30 | Catalyst for modifying inferior gasoline to prepare clean gasoline and its prepn |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011324872A CN1151234C (en) | 2001-10-30 | 2001-10-30 | Catalyst for modifying inferior gasoline to prepare clean gasoline and its prepn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1350051A true CN1350051A (en) | 2002-05-22 |
| CN1151234C CN1151234C (en) | 2004-05-26 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100384535C (en) * | 2004-07-09 | 2008-04-30 | 大连理工大学 | Modified nanometer ZSM-5 molecular sieve catalyst, preparation method and application thereof |
| US7485595B2 (en) | 2003-05-30 | 2009-02-03 | China Petroleum & Chemical Corporation | Molecular sieve-containing catalyst for cracking hydrocarbons and a method for preparing the same |
| CN109385305A (en) * | 2017-08-09 | 2019-02-26 | 中国石油化工股份有限公司 | A method of low-sulphur oil is produced by sulfur-bearing straight-run naphtha |
| CN112973772A (en) * | 2019-12-17 | 2021-06-18 | 中国石油天然气股份有限公司 | Gasoline aromatization isomerization catalyst and preparation method thereof |
-
2001
- 2001-10-30 CN CNB011324872A patent/CN1151234C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7485595B2 (en) | 2003-05-30 | 2009-02-03 | China Petroleum & Chemical Corporation | Molecular sieve-containing catalyst for cracking hydrocarbons and a method for preparing the same |
| CN100384535C (en) * | 2004-07-09 | 2008-04-30 | 大连理工大学 | Modified nanometer ZSM-5 molecular sieve catalyst, preparation method and application thereof |
| CN109385305A (en) * | 2017-08-09 | 2019-02-26 | 中国石油化工股份有限公司 | A method of low-sulphur oil is produced by sulfur-bearing straight-run naphtha |
| CN109385305B (en) * | 2017-08-09 | 2022-08-09 | 中国石油化工股份有限公司 | Method for producing low-sulfur gasoline from sulfur-containing straight-run naphtha |
| CN112973772A (en) * | 2019-12-17 | 2021-06-18 | 中国石油天然气股份有限公司 | Gasoline aromatization isomerization catalyst and preparation method thereof |
| CN112973772B (en) * | 2019-12-17 | 2023-08-22 | 中国石油天然气股份有限公司 | Gasoline aromatization isomerization catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1151234C (en) | 2004-05-26 |
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