CN102952567A - Method for producing gasoline by refinery dry gas - Google Patents
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Abstract
A method for producing gasoline by refinery dry gas comprises a reaction by contacting refinery dry gas with a catalyst under a hydrogen-free condition at 0.1-3.0 MPa and 200-400 DEG C, wherein the catalyst comprises 1.0-13.0 m% of VA-group element oxides, 0.1-5.0 m% of rare earth oxide, and 86-98.9 m% of a composite carrier; the composite carrier comprises 15-85 m% of ZSM-35, and 15-85 m% of a binder. The method can make effective use of ethylene in dry gas, and convert dry gas into a gasoline component with a high octane number and low olefin and benzene contents, and high-quality liquefied gas.
Description
Technical field
The present invention is a kind of method of utilizing oil refinery dry gas to produce gasoline, specifically, is that a kind of ZSM of utilization series zeolite is the method for catalyzer by ethene synthetic gasoline component.
Background technology
Oil refinery dry gas is mainly derived from the secondary processing process of crude oil, such as catalytic cracking, thermally splitting, delayed coking, hydrocracking etc.Wherein, catalytic cracked dry gas output is maximum, and productive rate is the highest.Contain the components such as hydrogen, ethene, ethane, propylene in the catalytic cracked dry gas, about 12～20 volume % of ethylene content do not burn owing to effectively utilize means, this part ethene to be arranged and act as a fuel into the gas pipe network.According to statistics, national catalyzed cracking processing ability was about 1,200 ten thousand ton/years in 2009, nearly 1,200,000 tons of total ethene potential content, and the ethene stock number is very considerable.If this part ethylene separation of oil refinery dry gas can be purified and effectively utilizes, will bring huge economic benefit.
At present, utilize method less to ethene resource in the oil refinery dry gas, feasible application mode mainly contains two kinds: the one, the ethene in the dry gas is concentrated, and then separate obtaining polymer grade ethylene, main method has separation by deep refrigeration, adsorption method of separation and membrane separation process etc.; The 2nd, directly use dry gas as raw material, utilize the direct and benzene reaction production ethylbenzene of ethene wherein, external main production has the ZSM-5 vapor phase process of ALKAR technique, Monsanto-Lummus technique and the Mobil company of American UOP company to produce ethylbenzene process.Front a kind of method separation investment is relatively large, energy consumption is high, causes the ethylene recovery cost high, and rear a kind of method needs relatively large benzene as raw material, and application seldom.
Along with the day by day minimizing of petroleum resources and the continuous increase of gasoline demand amount, utilize low-carbon alkene to produce gasoline fraction and become one of target of pursuing in recent years, mainly be to make low-carbon alkene that the series of complex reactions such as superimposed, hydrogen transference, aromizing, alkylation and isomerization occur at catalyzer, generate high-octane gasoline blending component.Although the research superimposed about ethene has been reported, utilize the catalyst research of the ethylene production gasoline fraction in the oil refinery dry gas seldom, mainly concentrate on the catalyzer of liquefied gas and naphtha aromtization.
" refining of petroleum and chemical industry " the 26th volume the 8th phase P59～63 disclose rare ethene and have been converted into the technology of iso-butylene and gasoline at ZSM-5 zeolite, and catalyzer is by ZSM-5 zeolite and binding agent Al
2O
3Form.
CN1011966B discloses and has a kind ofly produced the catalyst composition of aromatic hydrocarbons by aliphatic hydrocarbon, is comprised of phosphorous aluminum oxide, Ga and ZSM-5 zeolite, adopts this catalyzer can effectively reduce carbon deposit on the catalyzer, the life-span of extending catalyst.
CN98101358.9 discloses a kind of aromatizing catalyst for light hydrocarbon and preparation method thereof, contains Zn, mishmetal and HZSM-5 component in the catalyzer.This catalyzer is used for mixed C
4Aromatization, the catalyzer one way reaction life-span is about 300 hours, the aromatic hydrocarbons average yield is 47.9m%.
CN1651141A discloses a kind of aromatized catalyst and its preparation method and application, this catalyzer is comprised of 50～90% molecular sieve, 0～32% carrier and 4～20% binding agent, wherein molecular sieve is modified zsm-5 zeolite and Y zeolite, modifying element is zinc, phosphorus and rare earth metal, account for 0.01～20% of ZSM-5, Y zeolite accounts for 0.1～20% of catalyzer gross weight.
CN200610114158.7 discloses a kind of aromatizing catalyst for light hydrocarbon and preparation method thereof, this catalyzer comprises complex carrier and ZnO, rare earth oxide and the VA family element that the binding agent by the ZSM series zeolite of 20～70 quality % or MCM series zeolite and 30～80 quality % forms, and this catalyzer has higher aromatics yield and long work-ing life.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing oil refinery dry gas to produce gasoline, this method can effectively be utilized the ethene in the dry gas, makes it be converted into alkene and lower high octane gasoline component and the high-quality liquefied gas of benzene content.
The method of utilizing oil refinery dry gas to produce gasoline provided by the invention, comprise and make oil refinery dry gas under conditions of non-hydrogen, under 0.1～3.0MPa, 200～400 ℃ condition, contact with catalyzer and react, described catalyzer comprises the VA family element oxide of 1.0～13.0 quality %, the rare earth oxide of 0.1～5.0 quality % and the complex carrier of 86～98.9 quality %, and described complex carrier comprises the ZSM-35 zeolite of 15～85 quality % and the binding agent of 15～85 quality %.
The inventive method uses ZSM-35 zeolite or ZSM-35 zeolite and ZSM-5 zeolite to be combined as the active ingredient of complex carrier, supported V A family element and rare earth oxide are made catalyzer again, use this catalyzer under suitable condition, can utilize ethylene production olefin(e) centent in the oil refinery dry gas to be lower than 5 quality %, benzene content is lower than the stop bracket gasoline blend component of 2.0 quality %, research octane number (RON) RON 〉=90, but be used for being in harmonious proportion its olefin(e) centent of catalytically cracked gasoline decrease.
Description of drawings
Fig. 1 is the inventive method schematic flow sheet.
Embodiment
The inventive method is the ethrel technology in a kind of new oil refinery dry gas, can make ethene in the oil refinery dry gas under the effect of catalyst system therefor of the present invention, the series reaction such as superimposed, hydrogen transference, aromizing, alkylation and isomerization occur under certain condition, generate high octane gasoline component and high-quality liquefied gas.The catalyzer that the present invention uses has preferably stability and regenerability, is 0.5h in the feed volume air speed
-1Reaction conditions under, single-pass reaction period can reach more than 1 month, and the approach of an effectively processing residue dry gas resource can be provided for the refinery.
The ZSM-35 zeolite can be contained in the complex carrier of the catalyzer that the present invention is used, also ZSM-35 zeolite and ZSM-5 zeolite can be contained.
Catalyzer of the present invention preferably includes the VA family element oxide of 1.0～7.0 quality %, the rare earth oxide of 0.1～2.0 quality % and the complex carrier of 91～98.9 quality %.
When only containing the ZSM-35 zeolite in the complex carrier, described complex carrier preferably includes the ZSM-35 zeolite of 35～85 quality % and the binding agent of 15～65 quality %.
When containing ZSM-35 zeolite and ZSM-5 zeolite in the complex carrier, described complex carrier comprises the ZSM-5 zeolite of 15～75 quality %, the ZSM-35 of 15～75 quality % and the binding agent of 10～70 quality %, preferably includes the ZSM-5 zeolite of 20～50 quality %, the ZSM-35 of 20～50 quality % and the binding agent of 20～50 quality %.
The described binding agent preferential oxidation of catalyzer of the present invention aluminium, more preferably gama-alumina.The preferred phosphorus of VA family element or antimony, the preferred mixed rare-earth oxide of rare earth oxide.Contain (in oxide compound) lanthanum 20～40 quality %, cerium 40～60 quality %, praseodymium 10～18 quality %, neodymium 2～10 quality % in the mishmetal.
The silica/alumina molar ratio of described ZSM-35 zeolite is 8～100, preferred 10～50, the silica/alumina molar ratio of ZSM-5 zeolite is 30～200, preferred 40～80.
Preferred 200～300 ℃ of the described temperature of reaction of the inventive method, the preferred 0.1～2.0MPa of pressure.The volume space velocity of dry gas is 0.1～8.0h during reaction
-1, preferred 0.2～2.0h
-1
The α value of described catalyzer complex carrier is 10～100, preferred 15～60.The measuring method of α value is write " Petrochemical Engineering Analysis method (RIPP experimental technique) " with reference to Yang Cuiding etc., and Science Press publishes, P255 " constant temperature method is measured the α value of an acidic catalyst ".
The preparation method of catalyzer of the present invention comprises the steps:
(1) Hydrogen ZSM-35 zeolite or Hydrogen ZSM-35 zeolite and Hydrogen ZSM-5 zeolite and hydrated aluminum oxide are mixed, extruded moulding, dry, roasting obtains complex carrier,
(2) with the complex carrier steam-treated,
(3) complex carrier after the hydrothermal treatment consists is flooded with the steeping fluid that contains VA group element compound and rare earth compound, then dry, roasting.
In the aforesaid method, (1) step is the preparation of complex carrier, the preferred pseudo-boehmite of described hydrated aluminum oxide.Preferably add peptizing agent during moulding with the powder kneading, the preferred nitric acid of peptizing agent or acetic acid.
(2) step is for to carry out steam-treated to complex carrier, to regulate the α value of complex carrier.The temperature of steam-treated is 450～700 ℃, preferred 500～600 ℃, preferred 0.5～8.0 hour for the treatment of time, more preferably 2～6 hours.The standard of adjusting is to make complex carrier be 10～100, be preferably 15～60 through the acid cracked activity α value after the steam-treated.
(3) step is to introduce VA family's element and rare earth in complex carrier, the preferred phosphorus of described VA group element compound or antimony, and the soluble compound preferably phosphoric acid of phosphorus, the water-soluble cpds of antimony are its nitrate or acetate.The preferred mixed rare earth compound of described rare earth compound, mishmetal can be introduced complex carrier by the method for dipping or ion-exchange with muriate or nitrate form, or adds when the shaping of catalyst with the form of oxide compound.Dipping temperature is 20～100 ℃, preferred 25～85 ℃.
In the aforesaid method, the drying temperature of complex carrier and dipping rear catalyst is 80～140 ℃, preferred 90～120 ℃, and be 5～30 hours, preferred 8～24 hours time of drying, and maturing temperature is 500～650 ℃, preferred 550～600 ℃, roasting time is 1～10 hour, preferred 3～5 hours.(2) high-temperature water vapor in step is processed and also can be carried out before or after shaping of catalyst.
The inventive method is applicable to contain the reaction that the oil refinery dry gas of ethene is produced high octane value gasoline blending component.Described oil refinery dry gas mainly comprises catalytic cracked dry gas, catalytic pyrolysis dry gas, coking dry gas etc., and ethylene content is 5～50 quality %, preferred 10～30 quality % in the dry gas.The reaction raw materials oil refinery dry gas need not to give refining, can adopt the simple process flow of single reactor, saves facility investment.Be suitable for the multiple reaction units such as fixed bed, moving-bed, fluidized-bed.The high octane gasoline component of producing both can directly be dispatched from the factory as No. 90 gasoline, also can be used for the catalytically cracked gasoline of mediation high olefin content, to reduce the olefin(e) centent of catalytically cracked gasoline.
Behind the catalyst deactivation of the present invention, but by the regeneration Reusability.Catalyst regeneration adopts oxygen containing rare gas element to carry out, and wherein oxygen level is 0.5～5.0 volume %, the rare gas element preferred nitrogen.Suitable regeneration temperature is 400～500 ℃, and pressure is 0.1～3.0MPa, and gas/agent volume ratio is 250～1000.
Below in conjunction with description of drawings the present invention.Among Fig. 1, the raw material oil refinery dry gas is by volume pump 1 output, through interchanger 4, with reactor 3 reaction product heat exchange out, enter process furnace 2, be heated to temperature of reaction, entering from top to bottom reactor 3 contacts with catalyzer, under the effect of catalyzer, react, generate stop bracket gasoline, simultaneously by-product part liquefied gas and unreacted dry gas, reacted product, enters flash tank 5 and is separated into gas-liquid two-phase by overcooling through interchanger 4 and raw material heat exchange, the tank deck rich gas enters absorption and desorption tower 6 through after the compressor compresses, fuel gas enters stabilizer tower 7 middle parts by overhead line 9 discharge systems after the isolated liquid mixing of materials at bottom of tower and flash tank 5 bottoms, in stabilizer tower 7 liquefied gas is separated with high octane gasoline component, liquefied gas is discharged by overhead line 10, the part gasoline component of extracting out at the bottom of stabilizer tower 7 towers is with pumped back absorption and desorption tower 6, as absorption agent, rest part by pipeline 8 carrying devices as gasoline product.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
Prepare catalyst system therefor of the present invention.
(1) preparation carrier
Getting 130 gram silica/alumina molar ratio is 15 HZSM-35 zeolite powder (production of the molecular sieve of founding the factory factory), (German Sasol company produces 70 gram pseudo-boehmite powder, alumina content 75 quality %), adding 100g concentration is the aqueous nitric acid peptization of 1.0 quality %, mediate extrusion, 110 ℃ of dryings 8 hours, pelletizing, 550 ℃ of roastings 4 hours complex carrier.
(2) steam-treated
The complex carrier of step (1) preparation is packed in the tubular reactor, be warming up to 550 ℃ under the 0.1MPa in airflow, passed into steam-treated 4 hours, its α value is 35.
(3) Kaolinite Preparation of Catalyst
Get the complex carrier after 100 grams (2) go on foot the steam-treated for preparing, be the phosphoric acid solution dipping 1 hour of 100mg/ml with 50ml concentration, be the chlorination mishmetal aqueous solution (Inner Mongol Baotou rare earth industrial production of 10mg/ml again with 100ml concentration, wherein contain lanthanum trioxide 14.6 quality %, cerium oxide 24.0 quality %, Praseodymium trioxide 6.6 quality %, Neodymium trioxide 1.9 quality %, x-ray fluorescence method is analyzed) flooded 2 hours at 80 ℃, collect solids in 120 ℃ of dryings 8 hours, 550 ℃ of roastings 4 hours, the composition that makes catalyst A sees Table 1.
Example 2
The used double zeolite catalyst of preparation the present invention.
(1) preparation carrier
Getting 65 gram silica/alumina molar ratio is 56 HZSM-5 zeolite powder, 65 gram silica/alumina molar ratio are 15 HZSM-35 zeolite powder, 70 gram pseudo-boehmite powder, adding 100g concentration is the aqueous nitric acid peptization of 1.0 quality %, mediate extrusion, 110 ℃ of dryings 8 hours, pelletizing, 550 ℃ of roastings 4 hours complex carrier.
(2) steam-treated
The complex carrier of (1) step preparation is packed in the tubular reactor, in airflow, is warming up to 550 ℃ under the 0.1MPa, pass into steam-treated 4 hours complex carrier, its α value is 31.
(3) Kaolinite Preparation of Catalyst
Get complex carrier 100 grams of (2) step after steam-treated, be the phosphoric acid solution dipping 1 hour of 100mg/ml with 50ml concentration, again with 100ml concentration be 10mg/ml the chlorination mishmetal aqueous solution in 80 ℃ the dipping 2 hours, collect solids in 120 ℃ of dryings 8 hours, 550 ℃ of roastings 4 hours, the composition that makes catalyst B sees Table 1.
Example 3
Press the method Kaolinite Preparation of Catalyst of example 2, different is (1) step gets 92.8 gram silica/alumina molar ratio are 56 HZSM-5 zeolite powder, 37.2 gram silica/alumina molar ratio are 15 HZSM-35 zeolite powder and 70 gram pseudo-boehmite powder mixings, adding 100g concentration is the aqueous nitric acid peptization of 1.0 quality %, make complex carrier through extrusion, drying, roasting, its α value is 29 after steam-treated.Then the carrier after the steam-treated is introduced phosphorus and mishmetal by the method in (3) step, the composition of the catalyzer C that makes sees Table 1.
Example 4
Press the method Kaolinite Preparation of Catalyst of example 2, different is (1) step gets 65 gram silica/alumina molar ratio are 56 HZSM-5 zeolite powder, 65 gram silica/alumina molar ratio are 15 HZSM-35 zeolite powder and 70 gram pseudo-boehmite powder, adding 100g concentration is the aqueous nitric acid peptization of 1.0 quality %, make complex carrier through extrusion, drying, roasting, its α value is 31 after steam-treated.Then the carrier after the steam-treated is introduced modified component by the method in (3) step, different is with 50ml concentration is the nitric acid antimony solution impregnating carrier 1 hour of 40mg/ml, be the chlorination mishmetal aqueous solution dipping 2 hours of 10mg/ml with 100ml concentration again, the composition of the catalyzer D that makes sees Table 1.
Table 1
Example 5～6
10 milliliters of (7 gram) catalyst A of filling are carried out conversion of ethylene reaction evaluating in the oil refinery dry gas in 10 milliliters of continuous flow reactor of fixed bed.Use two kinds to form different raw materials, its composition sees Table 2.Raw materials usedly send into reactor through volume pump and react, the control reaction conditions is: feed volume air speed 1.0h
-1, temperature of reaction is that 280 ℃, pressure are 0.3MPa.Reaction product enters watercooler, is separated into gas-liquid two-phase, measures respectively and carries out compositional analysis, and the different dry gas reaction results that form see Table 3.
By table 3 result as can be known, the raw material of two kinds of differing ethylene contents all can be produced gasoline, and all more than 95 quality %, the stable gasoline productive rate reaches more than the 15 quality % conversion of ethylene.
Table 2
| Component, quality % | Dry gas raw material 1 | Dry gas |
| Hydrogen | 2.51 | 3.62 |
| Methane | 17.70 | 28.91 |
| Ethane | 6.99 | 25.26 |
| Ethene | 21.74 | 32.01 |
| Propane | 1.28 | 3.95 |
| Propylene | 5.30 | 6.25 |
| Butane | 2.25 | - |
| Butylene | 5.44 | - |
| Carbonic acid gas | 9.61 | - |
| Nitrogen | 27.18 | - |
Table 3
| Project | Example 5 | Example 6 |
| Reaction raw materials | Raw material 1 | |
| Conversion of ethylene, quality % | 98.0 | 98.2 |
| H 2+C 1+C 2Productive rate, quality % | 70.7 | 76.1 |
| C 3+C 4Productive rate, quality % | 12.6 | 6.8 |
| C 5 +Gasoline yield, quality % | 16.7 | 17.1 |
| Aromatic hydrocarbons, quality % | 7.0 | 7.3 |
| C 5 +Middle aromaticity content, quality % | 41.9 | 42.7 |
| C 5 +Middle olefin(e) centent, quality % | 4.0 | 3.5 |
| C 5 +Middle benzene content, quality % | 1.3 | 1.5 |
Example 7～9
In three 10 milliliters of identical reactors, each loads 7 gram catalyst A.Take raw material 1 as charging, be 1.0h in the feed volume air speed
-1, pressure is under the condition of 0.3MPa, investigates temperature of reaction to result's impact, temperature of reaction and the reaction result of each example see Table 4.
Table 4
| |
7 | 8 | 9 |
| Temperature of reaction, ℃ | 250 | 280 | 320 |
| Conversion of ethylene, quality % | 95.2 | 98.0 | 98.5 |
| H 2+C 1+C 2Productive rate, quality % | 68.2 | 70.7 | 75.2 |
| C 3+C 4Productive rate, quality % | 18.3 | 12.6 | 7.6 |
| C 5 +Gasoline yield, quality % | 13.5 | 16.7 | 17.2 |
| Aromatic hydrocarbons, quality % | 2.3 | 7.0 | 9.2 |
| C 5 +Middle aromaticity content, quality % | 17.0 | 41.9 | 53.5 |
| C 5 +Middle olefin(e) centent, quality % | 4.9 | 4.0 | 2.9 |
| C 5 +Middle benzene content, quality % | 0.8 | 1.3 | 1.9 |
As can be known from Table 4, with the rising of temperature of reaction, conversion of ethylene increases, and gasoline yield and Aromatic Hydrocarbon in Gasoline content increase, but dry gas yied also increases to some extent.Thus explanation, in dry gas yield acceptable situation, it is favourable for increasing gasoline yield suitably to improve temperature of reaction, but temperature is higher than after 280 ℃, and yield of gasoline increases less, and that the dry gas yield increases is more.
Example 10～12
In three 10 milliliters of identical reactors, each loads 7 gram catalyst A.Take raw material 1 as charging, be 1.0h in the feed volume air speed
-1, temperature of reaction is under 280 ℃ the condition, investigates reaction pressure to result's impact, pressure and reaction result that each example is used see Table 5.
Table 5
| |
10 | 11 | 12 |
| Reaction pressure, MPa | 0.1 | 0.3 | 1.0 |
| Conversion of ethylene, quality % | 97.8 | 98.0 | 98.0 |
| H 2+C 1+C 2Productive rate, quality % | 70.8 | 70.7 | 69.2 |
| C 3+C 4Productive rate, quality % | 12.7 | 12.6 | 13.8 |
| C 5 +Gasoline yield, quality % | 16.5 | 16.7 | 17.0 |
| Aromatic hydrocarbons, quality % | 7.2 | 7.0 | 6.9 |
| C 5 +Middle aromaticity content, quality % | 43.6 | 41.9 | 40.6 |
| C 5 +Middle olefin(e) centent, quality % | 3.8 | 4.0 | 4.1 |
| C 5 +Middle benzene content, quality % | 1.6 | 1.3 | 1.2 |
As known from Table 5, with the raising of reaction pressure, conversion of ethylene, C
5 +Gasoline yield and Aromatic Hydrocarbon in Gasoline content have increased slightly, but change little, mainly be because, the reaction of ethylene production gasoline is accompanied by the output of macromole gasoline and small molecules dry gas, molecule number changes little.Therefore, reaction pressure is less on the reaction impact.
Example 13～15
In three 10 milliliters of identical reactors, each loads 7 gram catalyst A.Take raw material 1 as charging, under the condition of 400 ℃ of temperature of reaction, pressure 0.3MPa, investigate the charging air speed to result's impact, the used air speed of each example and reaction result see Table 6.
Table 6
| Instance number | 13 | 14 | 15 |
| Volume space velocity, h -1 | 0.5 | 1.0 | 2.0 |
| Conversion of ethylene, quality % | 99.1 | 98.0 | 96.5 |
| H 2+C 1+C 2Productive rate, quality % | 72.2 | 70.7 | 67.9 |
| C 3+C 4Productive rate, quality % | 11 | 12.6 | 15.9 |
| C 5 +Gasoline yield, quality % | 16.8 | 16.7 | 16.2 |
| Aromatic hydrocarbons, quality % | 7.5 | 7.0 | 6.3 |
| C 5 +Middle aromaticity content, quality % | 44.6 | 41.9 | 38.9 |
| C 5 +Middle olefin(e) centent, quality % | 3.6 | 4.0 | 4.2 |
| C 5 +Middle benzene content, quality % | 1.6 | 1.3 | 1.0 |
As can be known from Table 6, with the raising of charging air speed, conversion of ethylene and dry gas yied all decrease, C
5 +Gasoline yield and Aromatic Hydrocarbon in Gasoline content.It can be said that brightly, suitably reduce the charging air speed to reacting favourable.
Example 16～19
In three 10 milliliters of identical reactors, load respectively 7 gram catalyst A～D.Take raw material 1 as charging, at 280 ℃, 0.3MPa, feed volume air speed 1.0h
-1Condition under, investigate the reactivity worth of catalyzer, each example catalyst system therefor and reaction result see Table 7.
Table 7
| Instance number | 16 | 17 | 18 | 19 |
| The catalyzer numbering | A | B | C | D |
| Conversion of ethylene, quality % | 98.0 | 98.9 | 98.6 | 98.0 |
| H 2+C 1+C 2Productive rate, quality % | 70.7 | 68.6 | 69.2 | 68.6 |
| C 3+C 4Productive rate, quality % | 12.6 | 13.9 | 13.6 | 13.8 |
| C 5 +Gasoline yield, quality % | 16.7 | 17.5 | 17.2 | 17.6 |
| Aromatic hydrocarbons, quality % | 7.0 | 7.9 | 7.7 | 8.1 |
| C 5 +Middle aromaticity content, quality % | 41.9 | 45.4 | 45.0 | 46.1 |
| C 5 +Middle olefin(e) centent, quality % | 4.0 | 3.8 | 3.8 | 3.7 |
| C 5 +Middle benzene content, quality % | 1.3 | 1.5 | 1.4 | 1.7 |
As known from Table 7, the conversion of ethylene of reaction time catalizer B, C, D, gasoline yield and Aromatic Hydrocarbon in Gasoline content are all slightly high than catalyst A.
Claims (11)
1. method of utilizing oil refinery dry gas to produce gasoline, comprise and make oil refinery dry gas under conditions of non-hydrogen, under 0.1～3.0MPa, 200～400 ℃ condition, contact with catalyzer and react, described catalyzer comprises the VA family element oxide of 1.0～13.0 quality %, the rare earth oxide of 0.1～5.0 quality % and the complex carrier of 86～98.9 quality %, and described complex carrier comprises the ZSM-35 zeolite of 15～85 quality % and the binding agent of 15～85 quality %.
2. in accordance with the method for claim 1, it is characterized in that described catalyzer comprises the VA family element oxide of 1.0～7.0 quality %, the rare earth oxide of 0.1～2.0 quality % and the complex carrier of 91～98.9 quality %.
3. according to claim 1 or 2 described methods, it is characterized in that described complex carrier comprises the ZSM-5 zeolite of 15～75 quality %, the ZSM-35 of 15～75 quality % and the binding agent of 10～70 quality %.
4. in accordance with the method for claim 3, it is characterized in that described complex carrier comprises the ZSM-5 zeolite of 20～50 quality %, the ZSM-35 of 20～50 quality % and the binding agent of 20～50 quality %.
5. the silica/alumina molar ratio that in accordance with the method for claim 1, it is characterized in that described ZSM-35 zeolite is 8～100.
6. in accordance with the method for claim 3, the silica/alumina molar ratio that it is characterized in that described ZSM-35 zeolite is 8～100, and the silica/alumina molar ratio of ZSM-5 zeolite is 30～200.
7. in accordance with the method for claim 1, it is characterized in that described binding agent is aluminum oxide, VA family element is phosphorus or antimony, and rare earth oxide is mixed rare-earth oxide.
8. according to claim 1 or 3 described methods, the α value that it is characterized in that complex carrier is 10～100.
9. in accordance with the method for claim 1, it is characterized in that temperature of reaction is that 200～300 ℃, pressure are 0.1～2.0MPa.
10. in accordance with the method for claim 1, the volume space velocity of dry gas is 0.1～8.0h when it is characterized in that reacting
-1
11. in accordance with the method for claim 1, it is characterized in that ethylene content is 5～50 quality % in the described dry gas.
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| CN1485414A (en) * | 2002-09-26 | 2004-03-31 | 中国科学院大连化学物理研究所 | Method for non-hydroaromatizating and desulfurizing catalytically cracked gasoline |
| CN101172250A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Light hydrocarbon aromatization catalyst and its preparing process |
| CN101429452A (en) * | 2007-11-08 | 2009-05-13 | 中国石油天然气股份有限公司 | Method for producing high-octane gasoline |
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