CN1594506A - Catalyst for modifying catalytic gasoline to clean gasoline and its preparation process - Google Patents
Catalyst for modifying catalytic gasoline to clean gasoline and its preparation process Download PDFInfo
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- CN1594506A CN1594506A CN 200410020454 CN200410020454A CN1594506A CN 1594506 A CN1594506 A CN 1594506A CN 200410020454 CN200410020454 CN 200410020454 CN 200410020454 A CN200410020454 A CN 200410020454A CN 1594506 A CN1594506 A CN 1594506A
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- catalyzer
- gasoline
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- molecular sieve
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Abstract
The invention discloses a catalyst for modifying catalytic gasoline to clean gasoline and its preparation process, wherein the catalyst comprises nano HZSM-5 molecular sieve, inorganic oxide, mixed rare earth metallic oxide and zinc, gallium oxide. The preparing process comprises making nano HZSM-5 molecular sieve, catalyst heat treatment, impregnating interchange, drying, and sintering.
Description
Technical field
The invention belongs to a kind of combination modified composite catalyst that makes the reduction of catalytic gasoline upgrading alkene, sulphur and benzene content system clean gasoline and preparation method thereof.
Background technology
U.S. Pat P 4,997, and 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 reduce benzene content 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, thereby can be improved aromatics conversion rate the method for stock oil fractionation cutting.This process using USY is a catalyzer.
U.S. Pat P 5,336, and 820 another kinds of having introduced the exploitation of Mobil company reduce the method for benzene content in the gasoline, and still adopting ZSM-5 is catalyzer, with the same C of rich benzoline
2-C
5Low-carbon alkene contacts at beds, makes benzene and low-carbon alkene carry out alkylated reaction and generates alkylaromatic hydrocarbon and remove benzene.
U.S. Pat P 5,865, and 988 have introduced a kind of low-quality gasoline upgrading technology of Mobil company exploitation.This process using two step method is carried out upgrading to gasoline, at first with raw gasline by containing Co-Mo/Al
2O
3The bed of catalyzer, hydrogenation and removing sulfide makes part alkene saturated simultaneously; Then with the reaction product that generates previously by containing the bed of ZSM-5 catalyzer, to recover the saturated and loss of octane number that causes of in hydrogenation process alkene.This technology can reduce sulphur content and the olefin(e) centent in the gasoline significantly, increases aromaticity content, thereby keeps octane value not reduce.
A kind of low-quality gasoline upgrading technology has also been introduced at USP 5,041 by Mobil company in 028 patent, the USY that this process using supports Pt, Re, Ir etc. is a catalyzer, and this technology aromaticity content when reducing alkene and sulphur content significantly obviously increases.
A kind of method of modifying inferior gasoline to prepare clean gasoline is introduced by commercial catalysts institute of Dalian University of Technology in ZL 01132487.2, it is catalyzer less than the small-grain ZSM-5 modified molecular screen of 1 μ that this method adopts particle.Gasoline can significantly reduce alkene, benzene and the sulphur content of gasoline after this art breading, and octane value does not reduce.
The present invention is on the basis of Chinese patent ZL 01132487.2, the catalyzer that provides a kind of new whole-distillate gasoline aftertreatment to use.
Summary of the invention
The catalyzer that technical scheme of the present invention provides is that nanometer HZSM-5 molecular sieve, the weight percentage of 65.0-80.0% is that 18.0-30.0% inorganic oxide, weight percentage are that the based metallic oxides with mixed rare earth of 0.1-10.0% and zinc or gallium oxide that weight percentage is 0.1-10.0% are formed by weight percentage.
The grain size of nanometer HZSM-5 molecular sieve is less than 100nm; Inorganic oxide is Al
2O
3Contain La in the based metallic oxides with mixed rare earth
2O
3, Ce
2O
3, Pr
6O
11, Nd
2O
3And Sm
2O
3Zinc, gallium oxide are nitrate or the vitriol ZnO, the Ga that generate through roasting that is selected from them
2O
3Or their mixture.
Preparation of catalysts method: at first press CN 1,240,193 described method synthesis of nano NaZSM-5 molecular sieves, promptly adopting modulus is that 3.18 water glass is as the silicon source, with analytical pure sulfuric acid aluminium is the aluminium source, water is deionized water, and analytically pure sulfuric acid concentration is 98%, and the organic amine template is chemical pure 70% ethylamine solution or chemical pure propylamine or n-Butyl Amine 99.
With nanometer NaZSM-5 molecular sieve and the inorganic oxide Al of crystal grain less than 100nm
2O
3By weight 1-10: 1 mixes, and adding weight percentage is the binding agent sesbania powder of 0.1-5.0%, and adds volume ratio 1-10%HNO
3Aqueous solution is even, mixes and pinches, and is squeezed into bar shaped, garden cylindricality or cloverleaf pattern, is cut into a material, after the drying, 540 ℃ of roastings; Again at normal temperatures, it is put into aqueous ammonium nitrate solution, with 1: 3-10 dipping 1-6 hour, use deionized water wash, drying, roasting makes nanometer HZSM-5 catalyzer.
Catalyzer is put into the hydrothermal treatment consists stove, at 350-700 ℃, with air speed 1-9h
-1Feeding concentration is that the modification of 0.05-4.0mol/L ammonia vapor is handled; Again successively or be put into together in the consoluet norium carbonate solution with its, at room temperature, incipient impregnation exchange 2-24h, oven dry 540 ℃ of roastings, is put into after the cooling in the nitrate or sulfate solution of zinc or gallium metal again, at room temperature, incipient impregnation exchange 2-24h, oven dry makes the combination modified composite catalyst 540 ℃ of roastings.
Based metallic oxides with mixed rare earth, zinc or gallium metal oxide compound are selected from their nitrate, vitriol or carbonate, and the oxide compound that generates after roasting is as RE
2(CO)
36H
2O, Zn (NO
3)
26H
2O, Ga
2(SO
4)
318H
2O etc.
The catalyzer that modifying inferior gasoline to prepare clean gasoline provided by the invention is used can be used for the upgrading of low-quality gasoline such as catalytic cracking (FCC) gasoline, catalytic pyrolysis (DCC) gasoline.Gasoline through after the catalyst treatment can reduce its alkene, benzene and sulphur content in a large number, and the octane value of gasoline does not reduce or slightly improves simultaneously, is a kind of more satisfactory and cheap modifying inferior gasoline to prepare clean gasoline catalyzer.
The evaluation index that reaction result adopts is: olefin(e) centent (V/V) :≤20%
Aromaticity content (V/V) :≤40%
Benzene content (V/V) :≤2.5%
Sulphur content :≤200ppm
Embodiment
Embodiment 1
Take by weighing 200g by patent CN 1,240,193 described method synthetic nanometer NaZSM-5 molecular sieves, 50g Al
2O
3After mixing, the binding agent sesbania powder of powder and 0.1-5.0% (weight) adds 1-10% (V/V) HNO
3The aqueous solution mixes and to pinch back extrusion in banded extruder and become cylindrical, after 120 ℃ of dried overnight 540 ℃ of roastings.Catalyzer that roasting is good and the NH of 0.4N
4NO
3The aqueous solution is 1 by the sieve liquor ratio: 3-10 floods 1-6h at normal temperatures, outwells exchange liquid, repeats above operation, and the deionized water wash of using equal volume then is up to neutrality, and dry back obtains nanometer ZHSM-5 540 ℃ of roastings.Nanometer HZSM-5 76.9%, Al
2O
323.1%.
Embodiment 2
Take by weighing 2.84g norium carbonate, add the HNO of 10ml 40% (V/V)
3After the dissolving, add the 40ml deionized water again; Take by weighing Zn (NO
3)
26H
2O 1.46g adds the 80ml deionized water dissolving; To place by the nanometer HZSM-5 that embodiment 1 makes in the hydrothermal treatment consists stove constant temperature zone, handle for the 0.05-4.0mol/L ammonia vapor with concentration at 500-550 ℃; Take by weighing the catalyzer 38g that handles through ammonia vapor, in the impouring norium carbonate solution, the 4h of incipient impregnation exchange at room temperature, the oven dry back is in 540 ℃ of roastings in retort furnace in baking oven; Product of roasting is cooled off back impouring Zn (NO slightly
3)
2In the aqueous solution, dipping exchange 4h at room temperature, in baking oven behind the evaporate to dryness in 540 ℃ of roastings.Standby with being positioned in the moisture eliminator after the cooling of the catalyzer after the roasting.Mishmetal 3.03%, ZnO 0.9%, and nanometer HZSM-5 73.87%, Al
2O
322.20%.
Embodiment 3
Take by weighing 0.36g norium carbonate, add the HNO of 10ml 10% (V/V)
3After the dissolving, add the 10ml deionized water again; Take by weighing 0.74g Zn (NO
3)
26H
2O adds the 20ml deionized water dissolving; To place by the nanometer HZSM-5 that embodiment 1 makes in the hydrothermal treatment consists stove constant temperature zone, handle for the 0.05-4.0mol/L ammonia vapor with concentration at 500-550 ℃; Take by weighing the catalyzer 10g that handles through ammonia vapor, in the impouring norium carbonate solution, the 4h of incipient impregnation exchange at room temperature, the oven dry back is in 540 ℃ of roastings in retort furnace in baking oven; Product of roasting is cooled off back impouring Zn (NO slightly
3)
2In the aqueous solution, dipping exchange 4h at room temperature, in baking oven behind the evaporate to dryness in 54O ℃ of roasting.Standby with being positioned in the moisture eliminator after the cooling of the catalyzer after the roasting.Nanometer HZSM-5 74.2%, Al
2O
322.3%, mishmetal 1.51%, ZnO 2.03%.
Embodiment 4
Take by weighing 2.92g norium carbonate, add the HNO of 30ml 10% (V/V)
3After the dissolving, add the 30ml deionized water again; Take by weighing Zn (NO
3)
26H
2O 3.46g adds the 60ml deionized water dissolving; To place by the nanometer HZSM-5 that embodiment 1 makes in the hydrothermal treatment consists stove constant temperature zone, handle for the 0.05-4.0mol/L ammonia vapor with concentration at 500-550 ℃; Take by weighing the catalyzer 30g that handles through ammonia vapor, in the impouring norium carbonate solution, the 4h of incipient impregnation exchange at room temperature, the oven dry back is in 540 ℃ of roastings in retort furnace in baking oven; Product of roasting is cooled off back impouring Zn (NO slightly
3)
2In the aqueous solution, dipping exchange 4h at room temperature, in baking oven behind the evaporate to dryness in 540 ℃ of roastings.Standby with being positioned in the moisture eliminator after the cooling of the catalyzer after the roasting.Mishmetal 4.09%, ZnO 3.16%, and nanometer HZSM-5 71.36%, Al
2O
321.3%.
Embodiment 5
Take by weighing 2.84g norium carbonate, add the HNO of 40ml 10% (V/V)
3After the dissolving, add the 40ml deionized water again; Take by weighing Ga
2(SO
4)
318H
2O 3.15g adds the 80ml deionized water dissolving; To place by the nanometer HZSM-5 that embodiment 1 makes in the hydrothermal treatment consists stove constant temperature zone, handle for the 0.05-4.0mol/L ammonia vapor with concentration at 500-550 ℃; Take by weighing the catalyzer 40g that handles through ammonia vapor, in the impouring norium carbonate solution, the 4h of incipient impregnation exchange at room temperature, the oven dry back is in 540 ℃ of roastings in retort furnace in baking oven; Product of roasting is cooled off back impouring Ga slightly
2(SO
4)
3In the aqueous solution, dipping exchange 4h at room temperature, in baking oven behind the evaporate to dryness in 540 ℃ of roastings.Standby with being positioned in the moisture eliminator after the cooling of the catalyzer after the roasting.Mishmetal 2.98%, Ga
2O
31.96%, nanometer HZSM-5 71.10%, Al
2O
321.96%.
Embodiment 6
Take by weighing 2.44g norium carbonate, add the HNO of 20ml 10% (V/V)
3After the dissolving, add the 20ml deionized water again; Take by weighing Ga
2(SO
4)
318H
2O 0.80g adds the 40ml deionized water dissolving; To place by the nanometer HZSM-5 that embodiment 1 makes in the hydrothermal treatment consists stove constant temperature zone, handle for the 0.05-4.0mol/L ammonia vapor with concentration at 500-550 ℃; Take by weighing the catalyzer 20g that handles through ammonia vapor, in the impouring norium carbonate solution, the 4h of incipient impregnation exchange at room temperature, the oven dry back is in 540 ℃ of roastings in retort furnace in baking oven; Product of roasting is cooled off back impouring Ga slightly
2(SO
4)
3In the aqueous solution, dipping exchange 4h at room temperature, in baking oven behind the evaporate to dryness in 540 ℃ of roastings.Standby with being positioned in the moisture eliminator after the cooling of the catalyzer after the roasting.Mishmetal 6.04%, Ga
2O
30.99%, nanometer HZSM-5 73.49%, Al
2O
321.48%.
Embodiment 7
The application of present embodiment explanation catalyzer aspect processing high olefin content catalytic cracking (FCC) gasoline.Catalyzer makes by embodiment 2.The 2g catalyzer of in reaction tubes, packing into.Control and metering with mass flowmeter at hydrogen flowing quantity; Reaction raw materials-catalytic cracking (FCC) gasoline is squeezed into digital display metering pump, and enters beds after hydrogen mixes and reacts.Reaction product is after gas-liquid separation, and product liquid is discharged from the separating tank lower curtate, gaseous product emptying after the spinner-type flowmeter metering.Catalyzer is at 370 ℃ of temperature, pressure 3.0MPa, air speed 3.0h
-1See Table 1 and table 2 with reaction result in the 108h under the reaction conditions of hydrogen-oil ratio 600 (V/V) and with raw material contrast situation.
108 hours reaction result of table 1 catalyzer
Product gasoline is formed and octane value
Reaction times
Alkene aromatic hydrocarbons stable hydrocarbon benzene
(hour)
RON
％(V/V)??％(V/V)??％(V/V)??％(V/V)
12??????????8.10?????36.40????55.50????2.01????99.3
24??????????9.85?????35.50????54.65????1.72????98.6
36??????????10.24????34.76????55.00????1.68????99.0
48??????????10.76????33.87????55.37????1.63????97.1
60??????????10.14????34.66????55.20????1.71????96.7
72??????????11.45????33.22????55.33????1.66????96.5
84??????????12.20????32.33????55.47????1.58????96.5
96??????????12.60????32.05????55.33????1.49????96.4
108?????????12.85????31.76????55.39????1.52????96.0
300 hours internal reaction average results of table 2 catalyzer and raw material contrast
| Project | Product is formed | Evaluation index | |||||||
| Alkene % (V/V) | Aromatic hydrocarbons % (V/V) | Benzene % (V/V) | Sulphur % (V/V) | ??RON | Alkene % (V/V) | Aromatic hydrocarbons % (V/V) | Benzene % (V/V) | ???RON | |
| Feed gasoline | ??49.6 | ??11.4 | ??2.84 | ??0.02 | ??89.4 | ??≤20 | ??≤40 | ??≤2.5 | ??≥90 |
| Reformulated gasoline | ??17.3 | ??33.4 | ??1.67 | ??0.01 | ??92.0 | ??≤20 | ??≤40 | ??≤2.5 | ??≥90 |
Embodiment 8
Present embodiment illustrates the application of catalyzer aspect processing high olefin content catalytic cracking (FCC) gasoline that makes by embodiment 5.The 2g catalyzer of in reaction tubes, packing into.Hydrogen flowing quantity is controlled and metering with mass flowmeter; Reaction raw materials-catalytic cracking (FCC) gasoline is squeezed into digital display metering pump, and enters beds after hydrogen mixes and reacts.Reaction product is after gas-liquid separation, and product liquid is discharged from the separating tank lower curtate, gaseous product emptying after the spinner-type flowmeter metering.Catalyzer is at 370 ℃ of temperature, pressure 3.0MPa, air speed 3.0h
-1See Table 3 with the reaction result in the 14h under the reaction conditions of hydrogen-oil ratio 600 (V/V).
Before and after handling, table 3 FCC gasoline forms and the octane value variation
| Interventions Requested | Raw material | Reaction product | Standard | The method of inspection |
| Alkene % (V/V) | ????49.6 | ????8.80 | ????≤20 | ??GB/T?11132 |
| Aromatic hydrocarbons % (V/V) | ????11.4 | ????37.2 | ????≤40 | ??GB/T?11132 |
| Alkane % (V/V) | ????39.0 | ????54.0 | ??GB/T?11132 | |
| Benzene % (V/V) | ????2.84 | ????1.69 | ????≤2.5 | Chromatography |
| RON | ????90.0 | ????96.8 | ????95 | Chromatography |
Claims (6)
1, a kind of catalyzer that is used for reducing catalytic gasoline alkene, sulphur and benzene content system clean gasoline is characterized in that this catalyzer is that nanometer HZSM-5 molecular sieve, the weight percentage of 65.0-80.0% is that 18.0-30.0% inorganic oxide, weight percentage are that the based metallic oxides with mixed rare earth of 0.1-10.0% and zinc or gallium oxide that weight percentage is 0.1-10.0% are formed by weight percentage.
2, according to the described catalyzer of claim 1, the grain size that it is characterized in that nanometer HZSM-5 molecular sieve is less than 100nm.
3,, it is characterized in that inorganic oxide is Al according to the described catalyzer of claim 1
2O
3
4,, it is characterized in that containing in the based metallic oxides with mixed rare earth La according to the described catalyzer of claim 1
2O
3, Ce
2O
3, Pr
6O
11, Nd
2O
3And Sm
2O
3
5,, it is characterized in that zinc, gallium oxide are nitrate or the vitriol ZnO, the Ga that generate through roasting that is selected from them according to the described catalyzer of claim 1
2O
3Or their mixture.
6, a kind of according to the described Preparation of catalysts method of claim 1, it is characterized in that present method at first is with nanometer NaZSM-5 molecular sieve and the inorganic oxide Al of crystal grain less than 100nm
2O
3By weight 1-10: 1 mixes, and adding weight percentage is the binding agent sesbania powder of 0.1-5.0%, and adds volume ratio 1-10%HNO
3Aqueous solution is even, mixes and pinches, and is squeezed into bar shaped, garden cylindricality or cloverleaf pattern, is cut into a material, after the drying, 540 ℃ of roastings; Again at normal temperatures, it is put into aqueous ammonium nitrate solution, with 1: 3-10 dipping 1-6 hour, use deionized water wash, drying, roasting makes nanometer HZSM-5 catalyzer; Then, catalyzer is put into the hydrothermal treatment consists stove, at 350-700 ℃, with air speed 1-9h
-1Feeding concentration is that the modification of 0.05-4.0mol/L ammonia vapor is handled; Again successively or be put into together in the consoluet norium carbonate solution with its, at room temperature, dipping exchange 2-24h, oven dry 540 ℃ of roastings, is put into after the cooling in the nitrate or sulfate solution of zinc or gallium metal again, at room temperature, incipient impregnation exchange 2-24h, oven dry makes the combination modified composite catalyst 540 ℃ of roastings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410020454 CN1594506A (en) | 2004-04-23 | 2004-04-23 | Catalyst for modifying catalytic gasoline to clean gasoline and its preparation process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410020454 CN1594506A (en) | 2004-04-23 | 2004-04-23 | Catalyst for modifying catalytic gasoline to clean gasoline and its preparation process |
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| Publication Number | Publication Date |
|---|---|
| CN1594506A true CN1594506A (en) | 2005-03-16 |
Family
ID=34663222
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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|---|---|
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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 |
| CN101559380B (en) * | 2009-06-03 | 2011-02-02 | 中国科学院大连化学物理研究所 | Catalyst used for producing BTX aromatics and clean gasoline by using catalytic gasoline and preparation |
| CN101584991B (en) * | 2008-05-23 | 2011-05-04 | 中国石油化工股份有限公司 | Catalyst for olefin catalytic cracking to produce propylene and ethylene and application thereof |
| CN103055928A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing arene via direct methanol conversion and preparation method thereof |
-
2004
- 2004-04-23 CN CN 200410020454 patent/CN1594506A/en active Pending
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 |
| CN101584991B (en) * | 2008-05-23 | 2011-05-04 | 中国石油化工股份有限公司 | Catalyst for olefin catalytic cracking to produce propylene and ethylene and application thereof |
| CN101559380B (en) * | 2009-06-03 | 2011-02-02 | 中国科学院大连化学物理研究所 | Catalyst used for producing BTX aromatics and clean gasoline by using catalytic gasoline and preparation |
| CN103055928A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing arene via direct methanol conversion and preparation method thereof |
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