CN106244224A - Dry gas produces the method for gasoline mediation component - Google Patents
Dry gas produces the method for gasoline mediation component Download PDFInfo
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Abstract
The present invention relates to a kind of method that dry gas produces gasoline mediation component, the step contacted on a catalyst including dry gas with benzene；Described catalyst is silica alumina ratio SiO2/Al2O3Be 30～900, crystal grain diameter be the adhesiveless ZSM-5 molecular sieve of 10～800 nanometers；Described catalyst is through steam treatment.The method can be used for oil refinery dry gas and reacts production clean gasoline with high octane mediation component with benzene.
Description
Technical field
The present invention relates to a kind of method that dry gas produces gasoline mediation component.
Background technology
Petroleum refining industry of current China faces the shortage of domestic crude resources, and crude resources external dependence degree increases
Add, the ever-increasing severe situation of import sulfur-bearing, sour crude, heavy inferior crude oil processing quantity.
The shortage of crude resources has become the bottleneck of restriction China economy and society sustainable development.Meanwhile,
Along with people's growing interest to environmental issue, countries in the world are to product oil (gasoline and diesel oil) matter
Amount specification requirement is more and more higher, particularly improves constantly the restriction index of sulfur and olefin(e) centent.Vapour
Sulfur in oil and alkene are essentially from catalytically cracked gasoline, the gasoline main component of China more than 70%
Being catalytically cracked gasoline, sulfur and olefin(e) centent are higher, and arene content is relatively low, need to be hydrogenated with further
Desulfurization is to reduce the sulfur in gasoline and olefinic component, but this process can cause the loss of octane number.
Therefore, proceeding from our national conditions, reduce sulfur and the olefin(e) centent of catalytically cracked gasoline the most as far as possible,
Improve its composition；On the other hand, reduce the use ratio of catalytic cracking in motor petrol, improve it
Composition structure, increases high octane gasoline component, including increasing Reformed Gasoline, alkylate oil, different
The high-quality antiknock components such as structure carburetion and oxygen-containing ether compound, will be the development of oil refining enterprise of China
Striving direction.Wherein, alkylate oil is a kind of high uprising index, super-low sulfur, low alkene and virtue
The premium component of hydrocarbon content, increases its ratio in the oil as far as possible, is conducive to improving vapour
The uprising performance of oil, to overcome the too high drawback brought of catalytically cracked gasoline ratio and deficiency.
Oil refinery dry gas, essentially from the secondary processing process of crude oil, such as catalytic cracking, thermal cracking, prolongs
Late coking, it is hydrocracked.Catalyzed cracking processing amount is relatively big, accounts for the 35% of crude oil time processing amount
Left and right.Containing hydrogen, ethylene, ethane, nitrogen and a small amount of propylene, butylene in catalytic cracked dry gas
Etc. component, wherein ethylene contents is about 12-20 volume %.At present, the valuable ethylene money of oil refinery dry gas
The Application way in source is less, and the dry gas that wherein industry is more ripe utilizes one of technology to be to pass through dry gas
In ethylene directly and benzene reaction produces ethylbenzene, and then dehydrogenation production styrene.But this technology exists
Investment is big, flow process is complicated, energy consumption is high, poor catalyst stability, the shortcomings such as the regeneration period is short.
Document CN101857808A discloses a kind of method of preparing gasoline from liquefied gas through aromatization.First
By material liquid activating QI through pretreatment, it is heated to about 300 DEG C and enters from the top of fixed bed reactors
Enter, the available research octane number (RON) gasoline more than 93, but without reference to the regeneration period of catalyst
And service life.
Document CN102851063A discloses a kind of dry gas and liquefied gas through aromatization produces high-octane rating
The method of clean gasoline.The material liquid activating QI of olefin-containing enters the top of fixed bed reactors after heat exchange
Portion, overlaps under the effect of liquefied gas through aromatization catalyst, is cyclized and aromatization generation
Aromatic naphtha；The cold dry gas of raw material enters from equipped with between the reactor filler bed of dry gas aromatized catalyst
Enter, overlap, be cyclized and aromatization generate aromatic naphtha, separated after obtain petrol and diesel oil produce
Product, but the most do not mention regeneration period and the service life of catalyst.
Document CN103623862A discloses the aromatisation of a kind of oil refinery dry gas production gasoline components and urges
Agent and preparation method thereof, this catalyst is by the borosilicate ZSM-5 molecular sieve of 10-90% and 10-90%
Aluminium oxide composition, wherein, containing VA race element oxide 0.5-15%；Rare earth oxide
0.1-3.0%.This catalyst was air speed 1.0 hours-1Reaction condition under, conversion of ethylene is 95%,
Regeneration period is only 2 months, obtains the octane number gasoline concoction component more than 95.
Document CN103289730A discloses a kind of alkene lower carbon number hydrocarbons and produces higher octane with benzene alkylation
The method of value gasoline, is divided into olefin-containing lower carbon number hydrocarbons multichannel and enters each layer of multi-stage fixed-bed reactor,
The benzene entered with reactor head occurs alkylated reaction to generate Gaoxin after mixing under catalyst action
Alkane value gasoline component, but used catalyst still continues to use former preparing ethylbenzene from dry gas alkylation catalyst, and do not have
Relate to regeneration period and the service life of catalyst.
Summary of the invention
A kind of method that present invention aim at providing dry gas to produce gasoline mediation component.The method has
There are total alkene conversion height, good stability, regeneration period and length in service life and gasoline mediation group
The feature that part octane number is high.
For achieving the above object, the technical solution used in the present invention is as follows: a kind of dry gas produces
The method of gasoline mediation component, the step contacted on a catalyst with benzene including dry gas；Described catalysis
Agent is silica alumina ratio SiO2/Al2O3Be 30～900, crystal grain diameter be 10～800 nanometers without viscous
Knot agent ZSM-5 molecular sieve；Described catalyst is through steam treatment.
In technique scheme, it is preferable that the crystal grain diameter of described adhesiveless ZSM-5 molecular sieve
It is 50～700 nanometers.It is highly preferred that the crystal grain diameter of described adhesiveless ZSM-5 molecular sieve is
100～600 nanometers.
In technique scheme, it is preferable that described adhesiveless ZSM-5 molecular sieve silica alumina ratio
SiO2/Al2O3It is 50～600.
In technique scheme, it is preferable that steam treatment condition for normal pressure, temperature be 400～
Under the conditions of 800 DEG C, process 1～20 hour.
In technique scheme, it is preferable that described dry gas is catalytic cracking, catalytic pyrolysis or coking
Dry gas；Described dry gas is more than 5.0 volume %, H without free water, ethylene contents2S content is less than
300ppm、C3 =And C4 =Content is less than 3.5 volume %, is not required to refine in advance and directly can react with benzene.
In technique scheme, it is preferable that dry gas with the reaction condition of benzene is: reaction temperature
280～460 DEG C, reaction pressure is 0.5～4.5MPa, total olefin weight space velocity 0.2～5.0 hours-1, total benzene
/ olefin molar ratio 2～10.
Catalyst in the present invention is prepared in accordance with the following methods:
1) silica alumina ratio SiO2/Al2O3 be 30～900, crystal grain diameter be 10～800 nanometers
Adhesiveless ZSM-5 molecular sieve exchanges through hydrochloric acid, wash, dry and roasting obtains binder free
HZSM-5 molecular sieve.Wherein, acid is handed over, washs, is dried and the condition of roasting is ripe for this area
Know.
2) steam treatment above-mentioned binder free HZSM-5 molecular sieve, obtains finished catalyst.Water
Steam treated temperature 400～800 DEG C, the process time is 1～20 hour, to improve the water of catalyst
Heat stability.
Difficult recovery is there is, the weakness such as big, molding is lost in molecular sieve powder in actual application
Cheng Zhongxu adds inert binder, and binding agent typically uses silicon oxide and aluminium oxide.The addition of binding agent
Make catalyst specific surface reduce, and have the effect of plug-hole, affect the diffusion of catalyst, cause
The decline of catalyst catalytic performance.Adhesive-free Molecular Sieve refers to glue without inertia in sieve particle
Tying agent or comprise only a small amount of binding agent, having higher molecular sieve content, the most available have
Effect surface area is big, has more preferable catalytic perfomance.
During ethylene, propylene and butylene in oil refinery dry gas and benzene vapor phase alkylation, due to
Reaction is carried out under the high temperature conditions, and therefore catalyst is easy to inactivate because of coking, activity stability
Poor, the regeneration period is short.First, the present invention uses nano level MFI structure molecular sieve, due to hole
Journey is relatively short, and reactant and product shortened in the time of pore diffusion, generation oligomerisation in hole,
The side reactions such as cyclisation generate the probability of polycyclic aromatic hydrocarbon and reduce, thus effectively inhibit catalyst coking
Occur, improve the activity stability of catalyst.Secondly, the present invention uses Adhesive-free Molecular Sieve
For catalyst, increase considerably the effective active component of catalyst, thus improve turning of reaction
Rate, selectivity and stability.Meanwhile, the present invention uses high-temperature vapor to process, and carries further
The high hydrothermal stability of catalyst, improves catalyst water repelling property at reaction conditions.Always
It, the present invention uses nanometer Adhesive-free Molecular Sieve and uses high-temperature vapor to process the side combined
Method, with the catalytic cracked dry gas containing 10% (volume) ethylene, 2.5% (body) propylene be raw material and
When benzene is alkylated reaction, in reaction pressure 0.9MPa, total olefin weight space velocity 0.6 hour-1,
Under conditions of total benzene olefin mol ratio is 6, total alkene conversion is up to 99.9%, and catalyst regeneration is all
Phase has reached more than 1 year, in more than 3 years life-span, achieves preferable technique effect.
Further instruction is given to the present invention below by embodiment.
Detailed description of the invention
[embodiment 1]
20 grams of silica alumina ratio SiO2/Al2O3=80, crystallite dimension 150 nanometer, a diameter of Φ 1.8
The adhesiveless ZSM-5 molecular sieve catalyst of millimeter, with the hydrochloric acid 0.5 liter 85 DEG C of 0.1 mol/L
Exchange three times, be washed with deionized to without chlorine root, 110 DEG C of drying, less 580 DEG C of roastings 4
Shi Houbei uses.
Above-mentioned catalyzer with water steam is processed 3 hours normal pressure 580 DEG C, obtains finished catalyst.
Flowing continuously on pressurization static bed reaction unit, evaluating catalyst activity stabilized of preparation
Property, i.e. the regeneration period of catalyst.Reaction condition: reaction temperature 400 DEG C, reaction pressure 1.0MPa,
Benzene olefin=1.0 (moles/mole), total olefin weight space velocity (WHSV)=4.0 hour-1, reaction
Time is 100 hours.The octane number (RON) of obtained gasoline mediation component is 113, specifically
Reaction result be shown in Table 1.
[embodiment 2]
By 20 grams of silica alumina ratio SiO2/Al2O3=80, crystallite dimension is 500 nanometers, a diameter of Φ
The adhesiveless ZSM-5 molecular sieve catalyst of 1.8 millimeters, with the hydrochloric acid 0.5 liter 85 of 0.1 mol/L
DEG C exchange three times, is washed with deionized to without chlorine root, 110 DEG C of drying, then 580 DEG C of roastings 4
After hour standby.
Above-mentioned catalyzer with water steam is obtained finished catalyst after normal pressure 520 DEG C processes 5 hours.
Flowing continuously on pressurization static bed reaction unit, evaluating catalyst activity stabilized of preparation
Property, i.e. the regeneration period of catalyst.Reaction condition: reaction temperature 400 DEG C, reaction pressure 1.0MPa,
Benzene olefin=1.0 (moles/mole), total olefin weight space velocity (WHSV)=4.0 hour-1, reaction
Time is 100 hours.The octane number (RON) of obtained gasoline mediation component is 109, specifically
Reaction result be shown in Table 1.
[embodiment 3]
By 20 grams of silica alumina ratio SiO2/Al2O3=400, crystallite dimension is 50 nanometers, a diameter of Φ
The adhesiveless ZSM-5 molecular sieve catalyst of 1.8 millimeters, with the hydrochloric acid 0.5 liter 85 of 0.1 mol/L
DEG C exchange three times, is washed with deionized to without chlorine root, 110 DEG C of drying, then 580 DEG C of roastings 4
After hour standby.
Above-mentioned catalyzer with water steam is obtained finished catalyst after normal pressure 480 DEG C processes 8 hours.
Flowing continuously on pressurization static bed reaction unit, evaluating catalyst activity stabilized of preparation
Property, i.e. the regeneration period of catalyst.Reaction condition: reaction temperature 400 DEG C, reaction pressure 1.0MPa,
Benzene olefin=1.0 (moles/mole), total olefin weight space velocity (WHSV)=4.0 hour-1, reaction
Time is 100 hours.The octane number (RON) of obtained gasoline mediation component is 108, specifically
Reaction result be shown in Table 1.
[embodiment 4]
By 20 grams of silica alumina ratio SiO2/Al2O3=600, crystallite dimension is 150 nanometers, a diameter of
The adhesiveless ZSM-5 molecular sieve catalyst of Φ 1.8 millimeters, with the hydrochloric acid 0.5 liter of 0.1 mol/L
85 DEG C exchange three times, are washed with deionized to without chlorine root, 110 DEG C of drying, then 580 DEG C of roastings
After 4 hours standby.
Above-mentioned catalyzer with water steam is obtained finished catalyst after normal pressure 600 DEG C processes 2 hours.
Flowing continuously on pressurization static bed reaction unit, evaluating catalyst activity stabilized of preparation
Property, i.e. the regeneration period of catalyst.Reaction condition: reaction temperature 400 DEG C, reaction pressure 1.0MPa,
Benzene olefin=1.0 (moles/mole), total olefin weight space velocity (WHSV)=4.0 hour-1, reaction
Time is 100 hours.The octane number (RON) of obtained gasoline mediation component is 111, specifically
Reaction result be shown in Table 1.
[embodiment 5]
By 20 grams of silica alumina ratio SiO2/Al2O3=350, crystallite dimension is 300 nanometers, a diameter of
The adhesiveless ZSM-5 molecular sieve catalyst of Φ 1.8 millimeters, with the hydrochloric acid 0.5 liter of 0.1 mol/L
85 DEG C exchange three times, are washed with deionized to without chlorine root, 110 DEG C of drying, then 580 DEG C of roastings
After 4 hours standby.
Above-mentioned catalyzer with water steam is obtained finished catalyst after normal pressure 500 DEG C processes 7 hours.
Flowing continuously on pressurization static bed reaction unit, evaluating catalyst activity stabilized of preparation
Property, i.e. the regeneration period of catalyst.Reaction condition: reaction temperature 400 DEG C, reaction pressure 1.0MPa,
Benzene olefin=1.0 (moles/mole), total olefin weight space velocity (WHSV)=4.0 hour-1, reaction
Time is 100 hours.The octane number (RON) of obtained gasoline mediation component is 112, specifically
Reaction result be shown in Table 1.
[embodiment 6]
By 20 grams of silica alumina ratio SiO2/Al2O3=450, crystallite dimension is 200 nanometers, a diameter of
The adhesiveless ZSM-5 molecular sieve catalyst of Φ 1.8 millimeters, with the hydrochloric acid 0.5 liter of 0.1 mol/L
85 DEG C exchange three times, are washed with deionized to without chlorine root, 110 DEG C of drying, then 580 DEG C of roastings
After 4 hours standby.
Above-mentioned catalyzer with water steam is obtained finished catalyst after normal pressure 580 DEG C processes 3 hours.
Flowing continuously on pressurization static bed reaction unit, evaluating catalyst activity stabilized of preparation
Property, i.e. the regeneration period of catalyst.Reaction condition: reaction temperature 400 DEG C, reaction pressure 1.0MPa,
Benzene olefin=1.0 (moles/mole), total olefin weight space velocity (WHSV)=4.0 hour-1, reaction
Time is 100 hours.The octane number (RON) of obtained gasoline mediation component is 113, specifically
Reaction result be shown in Table 1.
[embodiment 7]
By 20 grams of silica alumina ratio SiO2/Al2O3=300, crystallite dimension is 200 nanometers, a diameter of
The adhesiveless ZSM-5 molecular sieve catalyst of Φ 1.8 millimeters, with the hydrochloric acid 0.5 liter of 0.1 mol/L
85 DEG C exchange three times, are washed with deionized to without chlorine root, 110 DEG C of drying, then 580 DEG C of roastings
After 4 hours standby.
Above-mentioned catalyzer with water steam is obtained finished catalyst after normal pressure 650 DEG C processes 2 hours.
Flowing continuously on pressurization static bed reaction unit, evaluating catalyst activity stabilized of preparation
Property, i.e. the regeneration period of catalyst.Reaction condition: reaction temperature 400 DEG C, reaction pressure 1.0MPa,
Benzene olefin=1.0 (moles/mole), total olefin weight space velocity (WHSV)=4.0 hour-1, reaction
Time is 100 hours.The octane number (RON) of obtained gasoline mediation component is 114, specifically
Reaction result be shown in Table 1.
[embodiment 8]
By 20 grams of silica alumina ratio SiO2/Al2O3=100, crystallite dimension is 200 nanometers, a diameter of
The adhesiveless ZSM-5 molecular sieve catalyst of Φ 1.8 millimeters, with the hydrochloric acid 0.5 liter of 0.1 mol/L
85 DEG C exchange three times, are washed with deionized to without chlorine root, 110 DEG C of drying, then 580 DEG C of roastings
After 4 hours standby.
Above-mentioned catalyzer with water steam is obtained finished catalyst after normal pressure 550 DEG C processes 3 hours.
Flowing continuously on pressurization static bed reaction unit, evaluating catalyst activity stabilized of preparation
Property, i.e. the regeneration period of catalyst.Reaction condition: reaction temperature 400 DEG C, reaction pressure 1.0MPa,
Benzene olefin=1.0 (moles/mole), total olefin weight space velocity (WHSV)=4.0 hour-1, reaction
Time is 100 hours.The octane number (RON) of obtained gasoline mediation component is 108, specifically
Reaction result be shown in Table 1.
[embodiment 9]
By 20 grams of silica alumina ratio SiO2/Al2O3=100, crystallite dimension is 200 nanometers, a diameter of
The adhesiveless ZSM-5 molecular sieve catalyst of Φ 1.8 millimeters, with the hydrochloric acid 0.5 liter of 0.1 mol/L
85 DEG C exchange three times, are washed with deionized to without chlorine root, 110 DEG C of drying, then 580 DEG C of roastings
After 4 hours standby.
Above-mentioned catalyzer with water steam is obtained finished catalyst after normal pressure 650 DEG C processes 2 hours.
Flowing continuously on pressurization static bed reaction unit, evaluating catalyst activity stabilized of preparation
Property, i.e. the regeneration period of catalyst.Reaction condition: reaction temperature 400 DEG C, reaction pressure 1.0MPa,
Benzene olefin=1.0 (moles/mole), total olefin weight space velocity (WHSV)=4.0 hour-1, reaction
Time is 100 hours.The octane number (RON) of obtained gasoline mediation component is 112, specifically
Reaction result be shown in Table 1.
[embodiment 10]
By 20 grams of silica alumina ratio SiO2/Al2O3=100, crystallite dimension is 200 nanometers, a diameter of
The adhesiveless ZSM-5 molecular sieve catalyst of Φ 1.8 millimeters, with the hydrochloric acid 0.5 liter of 0.1 mol/L
85 DEG C exchange three times, are washed with deionized to without chlorine root, 110 DEG C of drying, then 580 DEG C of roastings
After 4 hours standby.
Above-mentioned catalyzer with water steam is obtained finished catalyst after normal pressure 550 DEG C processes 3 hours.
Flowing continuously on pressurization static bed reaction unit, evaluating catalyst activity stabilized of preparation
Property, i.e. the regeneration period of catalyst.Reaction condition: reaction temperature 400 DEG C, reaction pressure 1.0MPa,
Benzene olefin=1.0 (moles/mole), total olefin weight space velocity (WHSV)=4.0 hour-1, reaction
Time is 100 hours.The octane number (RON) of obtained gasoline mediation component is 109, specifically
Reaction result be shown in Table 1.
[comparative example 1]
Identical with [embodiment 1], simply catalyst is without steam treatment.Reacted evaluation, institute
The octane number (RON) of the gasoline mediation component obtained is 113, and concrete reaction result is shown in Table 1.
[comparative example 2]
Identical with [embodiment 1], simply ZSM-5 molecular sieve crystallite dimension is 5 nanometers.Through anti-
Should evaluate, the octane number (RON) of obtained gasoline mediation component is 105, concrete reaction knot
Fruit is shown in Table 1.
[comparative example 3]
Identical with [embodiment 1], simply ZSM-5 molecular sieve crystallite dimension is 850 nanometers.Warp
Reaction evaluating, the octane number (RON) of obtained gasoline mediation component is 103, concrete reaction
The results are shown in Table 1.
[comparative example 4]
By 20 grams of silica alumina ratio SiO2/Al2O3=80, crystal grain diameter is the ZSM-5 of 200 nanometers
Molecular sieve and alumina binder press 70:30 mixing, and add sesbania powder and 10 weight % of 2%
After dilute nitric acid solution kneading, extruded moulding is Φ 1.8 millimeters.After drying 10 hours at 110 DEG C, then
550 DEG C of roastings 4 hours；Above-mentioned catalyzer with water steam is obtained after normal pressure 580 DEG C processes 3 hours
To finished catalyst.
Flowing continuously on pressurization static bed reaction unit, evaluating catalyst activity stabilized of preparation
Property, i.e. the regeneration period of catalyst.Reaction condition: reaction temperature 400 DEG C, reaction pressure 1.0MPa,
Benzene olefin=1.0 (moles/mole), total olefin weight space velocity (WHSV)=4.0 hour-1, reaction
Time is 100 hours.The octane number (RON) of obtained gasoline mediation component is 104, specifically
Reaction result be shown in Table 1.
Table 1
Visible, the catalyst in the present invention has minimum deactivation rate, shows optimum activity steady
Qualitative, the octane number of obtained gasoline mediation component is also above comparative example.On commercial plant
Running, catalyst regeneration cycle has reached more than 1 year, and the life-span reaches more than 3 years.
Claims (7)
1. the method that dry gas produces gasoline mediation component, connects with benzene on a catalyst including dry gas
The step touched；Described catalyst is silica alumina ratio SiO2/Al2O3Be 30～900, crystal grain diameter be
The adhesiveless ZSM-5 molecular sieve of 10～800 nanometers；Described catalyst is through steam treatment.
The method that the most according to claim 1, dry gas produces gasoline mediation component, it is characterised in that
The crystal grain diameter of described adhesiveless ZSM-5 molecular sieve is 50～700 nanometers.
The method that the most according to claim 2, dry gas produces gasoline mediation component, it is characterised in that
The crystal grain diameter of described adhesiveless ZSM-5 molecular sieve is 100～600 nanometers.
The method that the most according to claim 1, dry gas produces gasoline mediation component, it is characterised in that
Described adhesiveless ZSM-5 molecular sieve molecular sieve silica alumina ratio SiO2/Al2O3It is 50～600.
The method that the most according to claim 1, dry gas produces gasoline mediation component, it is characterised in that
Steam treatment condition, under the conditions of normal pressure, temperature are 400～800 DEG C, processes 1～20 hour.
The method that the most according to claim 1, dry gas produces gasoline mediation component, it is characterised in that
Described dry gas is catalytic cracking, catalytic pyrolysis or coking dry gas；Described dry gas does not contains free water, second
Alkene content is more than 5.0 volume %, H2S content is less than 300ppm, C3 =And C4 =Content is less than 3.5 bodies
Long-pending %, is not required to refine in advance and directly can react with benzene.
The method that the most according to claim 1, dry gas produces gasoline mediation component, it is characterised in that
Dry gas with the reaction condition of benzene is: reaction temperature 280～460 DEG C, and reaction pressure is 0.5～4.5MPa,
Total olefin weight space velocity 0.2～5.0 hours-1, total benzene olefin mol ratio 2～10.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4150062A (en) * | 1976-12-20 | 1979-04-17 | Mobil Oil Corporation | Light olefin processing |
| CN102875316A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Method for preparing ethylbenzene by alkylation of dry gas and benzene |
| CN102872900A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Catalyst for dry gas and benzene alkylation to prepare ethylbenzene |
-
2015
- 2015-06-12 CN CN201510324494.3A patent/CN106244224A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4150062A (en) * | 1976-12-20 | 1979-04-17 | Mobil Oil Corporation | Light olefin processing |
| CN102875316A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Method for preparing ethylbenzene by alkylation of dry gas and benzene |
| CN102872900A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Catalyst for dry gas and benzene alkylation to prepare ethylbenzene |
Non-Patent Citations (1)
| Title |
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| 王清遐等: ""催化裂化干气中乙烯制乙苯的催化剂研究"", 《催化学报》 * |
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Application publication date: 20161221 |