CN102952567B - 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 utilizing oil refinery dry gas to produce gasoline, specifically, is that a kind of ZSM series zeolite that utilizes is for catalyzer is by the method for ethylene synthase gasoline component.
Background technology
Oil refinery dry gas is mainly derived from the secondary processing process of crude oil, as catalytic cracking, thermally splitting, delayed coking, hydrocracking etc.Wherein, catalytic cracked dry gas output is maximum, and productive rate is the highest.Containing components such as hydrogen, ethene, ethane, propylene in catalytic cracked dry gas, ethylene content about 12 ~ 20 volume %, owing to effectively not utilizing means, this part ethene is arranged to be burnt into gas pipe network as fuel.According to statistics, national catalyzed cracking processing ability about 1,200 ten thousand tons/year in 2009, nearly 1,200,000 tons of total ethene potential content, ethene stock number is very considerable.If this part ethylene separation of oil refinery dry gas can be purified and effectively utilize, huge economic benefit will be brought.
At present, less to the Application way of ethene resource in oil refinery dry gas, it is concentrate the ethene in dry gas that feasible application mode mainly contains two kinds: one, and be then separated and obtain polymer grade ethylene, main method has separation by deep refrigeration, adsorption method of separation and membrane separation process etc.; Two is directly use dry gas as raw material, utilizes ethene wherein directly to react with benzene and produces ethylbenzene, and external main production has the ZSM-5 vapor phase process production ethylbenzene process of the ALKAR technique of American UOP company, Monsanto-Lummus technique and Mobil company.Front a kind of method separation investment is relatively large, energy consumption is high, causes ethylene recovery cost high, and a kind of rear method needs relatively large benzene as raw material, and application seldom.
Along with the continuous increase of minimizing and the gasoline demand amount day by day of petroleum resources, utilize low-carbon alkene to produce gasoline fraction and become one of target pursued in recent years, mainly make low-carbon alkene that the series of complex reactions such as superimposed, hydrogen transference, aromizing, alkylation and isomerization occur on a catalyst, 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 oil refinery dry gas little, 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 the technology that rare ethene is converted into iso-butylene and gasoline on ZSM-5 zeolite, catalyzer is by ZSM-5 zeolite and binding agent Al
2o
3composition.
CN1011966B discloses and a kind ofly produces the catalyst composition of aromatic hydrocarbons by aliphatic hydrocarbon, is made up of phosphorous aluminum oxide, Ga and ZSM-5 zeolite, adopts this catalyzer effectively can reduce carbon deposit on catalyzer, the life-span of extending catalyst.
CN98101358.9 discloses a kind of aromatizing catalyst for light hydrocarbon and preparation method thereof, containing Zn, mishmetal and HZSM-5 component in catalyzer.This catalyzer is used for mixed C
4aromatization, the catalyzer one way reaction life-span is 300 hours, and aromatic hydrocarbons average yield is 47.9m%.
CN1651141A discloses a kind of aromatized catalyst and its preparation method and application, this catalyzer by the molecular sieve of 50 ~ 90%, the carrier of 0 ~ 32% and 4 ~ 20% binding agent form, 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 overall catalyst weight.
CN200610114158.7 discloses a kind of aromatizing catalyst for light hydrocarbon and preparation method thereof, this catalyzer comprises the complex carrier and ZnO, rare earth oxide and VA race element that are made up of the ZSM series zeolite of 20 ~ 70 quality % or the binding agent of MCM series zeolite and 30 ~ 80 quality %, and this catalyzer has higher aromatics yield and longer work-ing life.
Summary of the invention
The object of this invention is to provide a kind of oil refinery dry gas that utilizes and produce the method for gasoline, this method effectively can utilize the ethene in dry gas, makes it be converted into alkene and the lower high octane gasoline component of benzene content and high-quality liquefied gas.
The method utilizing oil refinery dry gas to produce gasoline provided by the invention, comprise and make oil refinery dry gas under conditions of non-hydrogen, react with catalyst exposure under 0.1 ~ 3.0MPa, the condition of 200 ~ 400 DEG C, described catalyzer comprises the VA race 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, catalyzer made by supported V A race element and rare earth oxide again, use this catalyzer under appropriate conditions, ethylene production olefin(e) centent in oil refinery dry gas can being utilized lower than 5 quality %, benzene content lower than the stop bracket gasoline blend component of 2.0 quality %, research octane number (RON) RON >=90, can significantly reduce its olefin(e) centent for being in harmonious proportion catalytically cracked gasoline.
Accompanying drawing explanation
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 the ethene in oil refinery dry gas under the effect of used catalyst of the present invention, there is the series reaction such as superimposed, hydrogen transference, aromizing, alkylation and isomerization under certain condition, generate high octane gasoline component and high-quality liquefied gas.The catalyzer that the present invention uses has good stability and regenerability, is 0.5h in feed volume air speed
-1reaction conditions under, single-pass reaction period can reach more than 1 month, can provide the approach of an effectively processing residue dry gas resource for refinery.
Can ZSM-35 zeolite be contained in the complex carrier of the catalyzer that the present invention is used, also can contain ZSM-35 zeolite and ZSM-5 zeolite.
Catalyzer of the present invention preferably includes the VA race 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 ZSM-35 zeolite in 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 complex carrier, described complex carrier comprises the binding agent of the ZSM-5 zeolite of 15 ~ 75 quality %, the ZSM-35 of 15 ~ 75 quality % and 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 %.
Binding agent preferential oxidation aluminium described in catalyzer of the present invention, more preferably gama-alumina.The preferred phosphorus of VA race element or antimony, the preferred mixed rare-earth oxide of rare earth oxide.Containing (with oxide basis) lanthanum 20 ~ 40 quality %, cerium 40 ~ 60 quality %, praseodymium 10 ~ 18 quality %, neodymium 2 ~ 10 quality % in mishmetal.
The silica/alumina molar ratio of described ZSM-35 zeolite is 8 ~ 100, preferably 10 ~ 50, and the silica/alumina molar ratio of ZSM-5 zeolite is 30 ~ 200, preferably 40 ~ 80.
Temperature of reaction described in the inventive method preferably 200 ~ 300 DEG C, pressure preferably 0.1 ~ 2.0MPa.During reaction, the volume space velocity of dry gas is 0.1 ~ 8.0h
-1, preferred 0.2 ~ 2.0h
-1.
The α value of described catalyzer complex carrier is 10 ~ 100, preferably 15 ~ 60.The measuring method of α value writes " Petrochemical Engineering Analysis method (RIPP experimental technique) " with reference to Yang Cuiding etc., and Science Press publishes, P255 " constant temperature method measures 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 are mixed with hydrated aluminum oxide, extruded moulding, dry, roasting obtains complex carrier,
(2) by complex carrier steam-treated,
(3) by the impregnation fluid of the complex carrier after hydrothermal treatment consists containing VA group element compound and rare earth compound, then dry, roasting.
In aforesaid method, (1) step is the preparation of complex carrier, the preferred pseudo-boehmite of described hydrated aluminum oxide.Peptizing agent is preferably added by powder kneading, the preferred nitric acid of peptizing agent or acetic acid time shaping.
(2) step is for carry out steam-treated to complex carrier, to regulate the α value of complex carrier.The temperature of steam-treated is 450 ~ 700 DEG C, preferably 500 ~ 600 DEG C, preferably 0.5 ~ 8.0 hour treatment time, more preferably 2 ~ 6 hours.The standard of adjustment is the acid cracked activity α value making complex carrier after steam-treated is 10 ~ 100, be preferably 15 ~ 60.
(3) step is in complex carrier, introduce VA race element and rare earth, the described preferred phosphorus of VA group element compound or antimony, the soluble compound preferably phosphoric acid of phosphorus, and the water-soluble cpds of antimony is its nitrate or acetate.The preferred mixed rare earth compound of described rare earth compound, mishmetal can introduce complex carrier with muriate or nitrate salts by the method for dipping or ion-exchange, or adds when shaping of catalyst in the form of the oxide.Dipping temperature is 20 ~ 100 DEG C, preferably 25 ~ 85 DEG C.
In aforesaid method, the drying temperature of complex carrier and dipping rear catalyst is 80 ~ 140 DEG C, preferably 90 ~ 120 DEG C, and time of drying is 5 ~ 30 hours, preferably 8 ~ 24 hours, and maturing temperature is 500 ~ 650 DEG C, preferably 550 ~ 600 DEG C, roasting time is 1 ~ 10 hour, preferably 3 ~ 5 hours.(2) the high-temperature water vapor process of step also can be carried out before or after shaping of catalyst.
The inventive method oil refinery dry gas be applicable to containing ethene produces the reaction of 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 in dry gas, ethylene content is 5 ~ 50 quality %, preferably 10 ~ 30 quality %.Reaction raw materials oil refinery dry gas is refining without the need to giving, and 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 may be used for the catalytically cracked gasoline of mediation high olefin content, to reduce the olefin(e) centent of catalytically cracked gasoline.
After catalyst deactivation of the present invention, can Reusability by regeneration.Catalyst regeneration adopts oxygen containing rare gas element to carry out, and wherein oxygen level is 0.5 ~ 5.0 volume %, rare gas element preferred nitrogen.Suitable regeneration temperature is 400 ~ 500 DEG C, and pressure is 0.1 ~ 3.0MPa, and gas/agent volume ratio is 250 ~ 1000.
Below in conjunction with accompanying drawing, the present invention is described.In Fig. 1, raw material oil refinery dry gas is exported by volume pump 1, through interchanger 4, with reactor 3 reaction product heat exchange out, enter process furnace 2, be heated to temperature of reaction, enter reactor 3 and catalyst exposure from top to bottom, react under the effect of catalyzer, generate stop bracket gasoline, by-product part liquefied gas and unreacted dry gas simultaneously, reacted product after interchanger 4 with raw material heat exchange through overcooling, enter flash tank 5 and be separated into gas-liquid two-phase, tank deck rich gas enters absorption and desorption tower 6 after compressor compresses, fuel gas discharges system by overhead line 9, enter in the middle part of stabilizer tower 7 after isolated liquid mixing bottom materials at bottom of tower and flash tank 5, in stabilizer tower 7, liquefied gas is separated with high octane gasoline component, liquefied gas is discharged by overhead line 10, the part of gasoline component pumped back absorption and desorption tower 6 extracted out at the bottom of stabilizer tower 7 tower, as absorption agent, rest part by pipeline 8 carrying device as gasoline product.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
Prepare used catalyst of the present invention.
(1) carrier is prepared
Get the HZSM-35 zeolite powder (production of molecular sieve of founding the factory factory) that 130 grams of silica/alumina molar ratio are 15, (German Sasol company produces 70 grams of pseudo-boehmite powder, alumina content 75 quality %), add the aqueous nitric acid peptization that 100g concentration is 1.0 quality %, mediate extrusion, 110 DEG C of dryings 8 hours, pelletizing, 550 DEG C of roastings 4 hours complex carrier.
(2) steam-treated
Complex carrier step (1) prepared loads in tubular reactor, and in airflow, be warming up to 550 DEG C under 0.1MPa, pass into steam-treated 4 hours, its α value is 35.
(3) Kaolinite Preparation of Catalyst
Get the complex carrier after steam-treated prepared by 100 grams of (2) steps, 1 hour is flooded with the phosphoric acid solution that 50ml concentration is 100mg/ml, be the chlorination mishmetal aqueous solution (Inner Mongol Baotou rare earth industrial production of 10mg/ml again by 100ml concentration, wherein containing 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) flood 2 hours at 80 DEG C, collect solids in 120 DEG C of dryings 8 hours, 550 DEG C of roastings 4 hours, the composition of obtained catalyst A is in table 1.
Example 2
Preparation the present invention double zeolite catalyst used.
(1) carrier is prepared
Get the HZSM-5 zeolite powder that 65 grams of silica/alumina molar ratio are 56,65 grams of silica/alumina molar ratio are the HZSM-35 zeolite powder of 15,70 grams of pseudo-boehmite powder, add the aqueous nitric acid peptization that 100g concentration is 1.0 quality %, mediate extrusion, 110 DEG C of dryings 8 hours, pelletizing, 550 DEG C of roastings 4 hours complex carrier.
(2) steam-treated
The complex carrier (1) step prepared loads in tubular reactor, is warming up to 550 DEG C under 0.1MPa in airflow, and pass into steam-treated and obtain complex carrier in 4 hours, its α value is 31.
(3) Kaolinite Preparation of Catalyst
Get the complex carrier of (2) step after steam-treated 100 grams, 1 hour is flooded with the phosphoric acid solution that 50ml concentration is 100mg/ml, by 100ml concentration be again 10mg/ml the chlorination mishmetal aqueous solution in 80 DEG C dipping 2 hours, collect solids in 120 DEG C of dryings 8 hours, 550 DEG C of roastings 4 hours, the composition of obtained catalyst B is in table 1.
Example 3
By the method Kaolinite Preparation of Catalyst of example 2, HZSM-35 zeolite powder and the 70 grams of pseudo-boehmite powder mixings that 92.8 grams of silica/alumina molar ratio are the HZSM-5 zeolite powder of 56,37.2 grams of silica/alumina molar ratio are 15 are got unlike (1) step, add the aqueous nitric acid peptization that 100g concentration is 1.0 quality %, obtain complex carrier through extrusion, drying, roasting, after steam-treated, its α value is 29.Then the carrier after steam-treated is introduced phosphorus and mishmetal by the method for (3) step, the composition of obtained catalyzer C is in table 1.
Example 4
By the method Kaolinite Preparation of Catalyst of example 2, the HZSM-5 zeolite powder that 65 grams of silica/alumina molar ratio are 56 is got unlike (1) step, 65 grams of silica/alumina molar ratio are HZSM-35 zeolite powder and 70 grams of pseudo-boehmite powder of 15, add the aqueous nitric acid peptization that 100g concentration is 1.0 quality %, obtain complex carrier through extrusion, drying, roasting, after steam-treated, its α value is 31.Then the carrier after steam-treated is introduced modified component by the method for (3) step, unlike the nitric acid antimony solution impregnating carrier 1 hour by 50ml concentration being 40mg/ml, be the chlorination mishmetal aqueous impregnation 2 hours of 10mg/ml again by 100ml concentration, the composition of obtained catalyzer D is in table 1.
Table 1
Example 5 ~ 6
In 10 milliliters of continuous flow reactor of fixed bed, load 10 milliliters of (7 grams) catalyst A, carry out ethylene conversion reaction evaluating in oil refinery dry gas.Use two kinds to form different raw materials, its composition is in table 2.Raw materials used through volume pump send into reactor react, control reaction conditions be: feed volume air speed 1.0h
-1, temperature of reaction is 280 DEG C, pressure is 0.3MPa.Reaction product enters watercooler, is separated into gas-liquid two-phase, measures respectively and carries out compositional analysis, and the dry gas reaction result of different composition is in table 3.
As seen from the results in Table 3, the raw material of two kinds of differing ethylene contents all can produce gasoline, and conversion of ethylene is all at more than 95 quality %, and stable gasoline productive rate reaches more than 15 quality %.
Table 2
| Component, quality % | Dry gas raw material 1 | Dry gas raw material 2 |
| 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 | Raw material 2 |
| 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 identical 10 milliliters of reactors, each filling 7 grams of catalyst A.With raw material 1 be charging, in feed volume air speed for 1.0h
-1, pressure is under the condition of 0.3MPa, investigate temperature of reaction to the impact of result, the temperature of reaction of each example and reaction result are in table 4.
Table 4
| Instance number | 7 | 8 | 9 |
| Temperature of reaction, DEG C | 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.Illustrate thus, in dry gas yield acceptable situation, suitably improve temperature of reaction favourable for increase gasoline yield, but temperature is higher than after 280 DEG C, yield of gasoline increases less, and dry gas yield increases more.
Example 10 ~ 12
In three identical 10 milliliters of reactors, each filling 7 grams of catalyst A.With raw material 1 be charging, in feed volume air speed for 1.0h
-1, temperature of reaction is under the condition of 280 DEG C, investigate reaction pressure to the impact of result, the pressure that each example is used and reaction result are in table 5.
Table 5
| Instance number | 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 is little, mainly because the reaction of ethylene production gasoline is along with the output of macromole gasoline and small molecules dry gas, and molecule number change is little.Therefore, reaction pressure is less on reaction impact.
Example 13 ~ 15
In three identical 10 milliliters of reactors, each filling 7 grams of catalyst A.With raw material 1 be charging, under the condition of temperature of reaction 400 DEG C, pressure 0.3MPa, investigate Feed space velocities on the impact of result, each example air speed used and reaction result are in 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 Feed space velocities, conversion of ethylene and dry gas yied all decrease, C
5 +gasoline yield and Aromatic Hydrocarbon in Gasoline content reduce.It can be said that bright, suitably reduce Feed space velocities favourable to reaction.
Example 16 ~ 19
In three identical 10 milliliters of reactors, load 7 grams of catalyst A ~ D respectively.With raw material 1 be charging, at 280 DEG C, 0.3MPa, feed volume air speed 1.0h
-1condition under, investigate the reactivity worth of catalyzer, each example used catalyst and reaction result are in table 7.
Table 7
| Instance number | 16 | 17 | 18 | 19 |
| Catalyzer is numbered | 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, all comparatively catalyst A is slightly high for the conversion of ethylene of reaction time catalizer B, C, D, gasoline yield and Aromatic Hydrocarbon in Gasoline content.
Claims (8)
1. the method utilizing oil refinery dry gas to produce gasoline, comprise and make oil refinery dry gas under conditions of non-hydrogen, at 0.1 ~ 3.0MPa, react with catalyst exposure under the condition of 200 ~ 400 DEG C, described catalyzer comprises the VA race 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 %, 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 %, the silica/alumina molar ratio of described ZSM-35 zeolite is 8 ~ 100, the silica/alumina molar ratio of described ZSM-5 zeolite is 40 ~ 80.
2. in accordance with the method for claim 1, it is characterized in that described catalyzer comprises the VA race 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. in accordance with the method for claim 1, it is characterized in that described complex carrier comprises the binding agent of the ZSM-5 zeolite of 20 ~ 50 quality %, the ZSM-35 of 20 ~ 50 quality % and 20 ~ 50 quality %.
4. in accordance with the method for claim 1, it is characterized in that described binding agent is aluminum oxide, VA race element is phosphorus or antimony, and rare earth oxide is mixed rare-earth oxide.
5. in accordance with the method for claim 1, it is characterized in that the α value of complex carrier is 10 ~ 100.
6. in accordance with the method for claim 1, it is characterized in that temperature of reaction is 200 ~ 300 DEG C, pressure is 0.1 ~ 2.0MPa.
7. when in accordance with the method for claim 1, it is characterized in that reacting, the volume space velocity of dry gas is 0.1 ~ 8.0h
-1.
8. in accordance with the method for claim 1, it is characterized in that in described dry gas, ethylene content is 5 ~ 50 quality %.
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|---|---|---|---|---|
| US4795844A (en) * | 1987-07-20 | 1989-01-03 | Uop Inc. | Process for conversion of light olefins to LPG and aromatics |
| 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 |
-
2011
- 2011-08-26 CN CN201110246922.7A patent/CN102952567B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4795844A (en) * | 1987-07-20 | 1989-01-03 | Uop Inc. | Process for conversion of light olefins to LPG and aromatics |
| 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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