CN104710263B - A kind of method of dilute ethene liquid phase legal system ethylbenzene - Google Patents
A kind of method of dilute ethene liquid phase legal system ethylbenzene Download PDFInfo
- Publication number
- CN104710263B CN104710263B CN201310688208.2A CN201310688208A CN104710263B CN 104710263 B CN104710263 B CN 104710263B CN 201310688208 A CN201310688208 A CN 201310688208A CN 104710263 B CN104710263 B CN 104710263B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- beta
- sio
- ethene
- benzene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A kind of method of dilute ethene liquid phase legal system ethylbenzene, is dilute ethene is contacted with benzene in the presence of the catalyst containing beta-molecular sieve, it is characterised in that in described beta-molecular sieve, uses TEM EDX methods to characterize and obtains the Distribution Value of aluminium for D, D is expressed as SCWith SERatio and D >=2, wherein, SCFor the average value of the aluminium content of zeolite crystal center, SEFor zeolite crystal from edge to a quarter at center at aluminium content average value.This method has preferable conversion of ethylene and ethylbenzene selectivity.
Description
Technical field
The present invention relates to a kind of method of dilute ethylbenzene manufactured from ethylene, more specifically a kind of dilute ethene liquid phase legal system ethylbenzene
Method.
Background technology
Ethylbenzene is important Organic Chemicals, mainly for the production of styrene monomer, so synthesize various engineering plastics,
Synthetic resin, synthetic rubber Polymer material.
With the fast development of China's economy, the demand of ethylbenzene is very vigorous, and external dependence degree reaches more than 50%.It is another
Aspect, domestic catalytic cracking technology working ability is more than 120Mt/a, by-product dry gas about 5Mt/a；These ethylene contents are averagely about
20wt% oil refinery dry gas is not fully used, and is partially merely as fuel and is used, and causes the ethene wasting of resources.
Rationally to utilize various forms and various concentrations, especially low-concentration ethane resource, just opened from the seventies both at home and abroad
The research work that dilute ethene produces ethylbenzene with benzene alkylation is opened up.Dilute ethylbenzene manufactured from ethylene technique is according to reaction raw materials benzene in alkylation
Phase present in reactor is divided into vapor phase method and the major class of liquid phase method two.
Vapor phase method is a kind of relatively early technology succeeded in developing with commercial Application, category gas-particle two-phase reaction.Mainly have at present
Mobil/Badger techniques, the gas-phase process of ABB Lummus Global Inc., the vapor phase method work of the Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences
The SGEB preparing ethylbenzene from dry gas technologies of skill and sinopec, and domestic be completed covers industrialized units more.Because reaction temperature is higher
（300 DEG C~500 DEG C）, the requirement to equipment and operating process is higher, and energy consumption is larger, and byproduct of reaction is more, and ethylbenzene selectivity is not
Height, used catalyst is easier to inactivation；In addition, there is 800 μ g/g or so impurity dimethylbenzene in reaction product ethylbenzene（Industrially
Xylene content in ethylbenzene is asked to be less than 100 μ g/g）, the quality so to subsequent product polystyrene has larger adverse effect.
Liquid phase method makes benzene feedstock be in liquid phase, pure ethylene technique by elevated pressures, and ethene is present in liquid phase form
In reactor, belong to liquid-solid two phase reaction type, both at home and abroad existing highly developed technology.And for dilute ethylene process, it is dilute
Inert gas in ethene still exists in gaseous form, belongs to gas-liquid-solid reaction, and this is dilute ethylene process and pure ethylene
The essential difference of technique.Due to the difference of mechanism of catalytic reaction, both technologies are relatively independent deposit in alkylated reaction part
, without propagation.One patent business may possess both technologies simultaneously, but its both technologies are also independently to deposit
Do not passing on and substitutional relation.
The external dilute ethylbenzene manufactured from ethylene technique of liquid phase method mainly has the Alkar techniques of Uop Inc. of the U.S.（Catalyst is Al2O3-
BF3）, CDTech companies catalytic rectification process（Catalyst chief active constituent element is Y type molecular sieve）、Monsanto/Lummus
The AlCl of company's improvement3Method, the fixed-bed process of Fina companies（Catalyst activity constituent element is the beta-molecular sieve that Ce is modified）, and it is dilute
Other components in ethene are only limitted to methane and ethane, are not suitable for the oil refinery dry gas containing fixed gases such as a large amount of nitrogen, hydrogen.
Mainly there is the catalytic rectification process that the Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences and Beijing Institute of Clothing Tech develop respectively the country.
" oil and gas chemical industry, 2001,30 (2), 53-54, the catalysis using β zeolites as acid ingredient is have studied in 57 "
Ethylbenzene process is produced in the alkylation of ethene and benzene in catalytic cracked dry gas under cryogenic for agent.
CN1207960A reports a kind of use benzene and oil refinery dry gas is alkylated the method and its used catalyst of ethylbenzene processed.Institute
There is special total acid content, B acid amount and the sour ratios of B acid/L with the modified zeolite in catalyst as active component.In this method
In, the mixture that benzene feeds the ethene and other compositions that remain in liquid, dry gas remains gaseous state, and both are incorporated into anti-cocurrent
Answer in device and produced on fixed bed catalyst after haptoreaction, obtained product mixtures export reactor through isolated target
Thing ethylbenzene.The external reflux ratio of this method benzene is larger, causes the separation heavy load of benzene and product ethylbenzene；Benzene feed alkene than too high,
Limit the production capacity of catalyst.
The content of the invention
It is an object of the invention to have higher catalyst stability, second there is provided a kind of on the basis of existing technology
The method of alkene conversion ratio and dilute ethene liquid phase legal system ethylbenzene of ethylbenzene selectivity.
The method for dilute ethene liquid phase legal system ethylbenzene that the present invention is provided, is in alkylation reaction condition and containing beta-molecular sieve
Dilute ethene is set to be contacted with benzene in the presence of catalyst, it is characterised in that in described beta-molecular sieve, using TEM-EDX method tables
The Distribution Value for obtaining aluminium is D, and D represents SCWith SERatio and D >=2, wherein, SCFor the aluminium content of zeolite crystal center
Average value, SEFor zeolite crystal from edge to a quarter at center at aluminium content average value.
The beta-molecular sieve of the method that the present invention is provided, the few aluminium of body phase outer layer or the surface Silicon-rich without aluminium is catalyst activity group
Member, reduces the acidity of molecular sieve outer surface, makes reaction is main to be carried out in molecular sieve pore passage, improves the shape-selective spy of catalyst
Property.Compared with using conventional beta-molecular sieve for the method for dilute ethene liquid phase legal system ethylbenzene of the catalyst of active component, ethene
Conversion ratio can increase at least 1.3 percentage points, and ethylbenzene selectivity improves at least 1.9 percentage points, and catalyst stability is also obvious
Improve.
Embodiment
The method for dilute ethene liquid phase legal system ethylbenzene that the present invention is provided, is in alkylation reaction condition and containing beta-molecular sieve
Dilute ethene is set to be contacted with benzene in the presence of catalyst, it is characterised in that in described beta-molecular sieve, using TEM-EDX method tables
The Distribution Value for obtaining aluminium is D, and D represents SCWith SERatio and D >=2, wherein, SCFor the aluminium content of zeolite crystal center
Average value, SEFor zeolite crystal from edge to a quarter at center at aluminium content average value.
In the method for the present invention, described catalyst is main active component, its SiO containing beta-molecular sieve2/Al2O3Mole
Than being preferably 20~100.Described beta-molecular sieve is surface Silicon-rich beta-molecular sieve, and described surface Silicon-rich refers in framework of molecular sieve
Aluminium element be not uniformly distributed, most aluminium concentrate on molecular sieve body phase center（Stratum nucleare）, molecular sieve body phase outer layer（Shell）It is few
Aluminium or without aluminium.Distribution Value D >=2 of obtained aluminium are characterized using TEM-EDX methods, further D values are preferably 2~10.
Described surface Silicon-rich beta-molecular sieve, be the H- beta-molecular sieves after by roasting through acid solution dealuminzation, then with tetraethyl
The step of mixture that ammonium hydroxide and tetraethyl orthosilicate contact are obtained carries out secondary hydrothermal crystallizing and recovery product obtains, wherein
A mole composition for described mixture is SiO2/Al2O3=30~200, TEAOH/SiO2=0.12~0.18, H2O/SiO2=3~6,
Tetraethyl orthosilicate is with SiO2Meter accounts for SiO in described mixture210~20 moles of % of total amount.
Described H- beta-molecular sieves, its preparation process is generally included, and beta-molecular sieve is carried out into ammonium exchange makes NaO therein2Contain
Amount is less than 0.05 heavy %, wherein it is usually to be handed over beta-molecular sieve with ammonium salt aqueous solution at 80 DEG C~90 DEG C that described ammonium, which is exchanged,
Change（Ammonium salt is 1.0~2.0 with molecular sieve ratio）, then washed, filtered, 2~8 are dried at 100 DEG C~120 DEG C small
When.The preferred NH of described ammonium salt4Cl、(NH4)2SO4Or NH4NO3。
One embodiment of described acid solution dealuminzation is that a certain amount of conventional beta-molecular sieve is put into three-necked flask
In, the HNO3 aqueous solution of 10~30 times of addition（If molar concentration is 0.05M）, 80~90 are warming up in the case of being stirred at reflux
DEG C, product is stood 10 minutes, is then filtered, washs 3 times, 80 by heating stirring backflow simultaneously pickling 4 hours, stopping stirring
DEG C dry 10h.
One embodiment of described secondary hydrothermal crystallizing is that the sample after above-mentioned dealuminzation is added into tetraethyl hydrogen
Amine-oxides（TEAOH）- tetraethyl orthosilicate（TEOS）System in, stir 2 hours, be well mixed, then mixed system is put into
In closed crystallizing kettle, 120 DEG C of crystallization 36h.
The step of described recovery product for the product that obtains above-mentioned secondary hydrothermal crystallizing through filtering, washing, dry and
Roasting, is well known to the skilled person, no longer numerous herein to state.
In the method for the present invention, described catalyst can also contain inorganic oxide matrix, described inorganic oxide
Matrix is high-temperature inorganic oxide commonly used in the art, such as silica or aluminum oxide.Described matrix alumina is selected from without fixed
It is one or more of in type aluminum oxide, various low temperature transition aluminas, various high temperature transition aluminas or Alpha-alumina
Mixture, wherein it is preferred that gama-alumina.The weight ratio of described beta-molecular sieve and described inorganic oxide matrix is 95:5 to
60:40th, preferred weight ratio is 90:10 to 70:30.
In the method for the present invention, the catalyst of described inorganic oxide matrix, its preparation process be with catalyst proportion,
By beta-molecular sieve, described inorganic oxide matrix and the deionized water mixed-forming of above-mentioned described surface Silicon-rich, then pass through
What the steps such as dry, roasting were obtained, it is well known to those skilled in the art.
Shaping of catalyst can be carried out according to a conventional method, and microballoon, spherical, bar shaped, cloverleaf pattern, piece shape, Raschig ring is such as made
Shape or honeycombed etc..Appropriate extrusion aid and/or peptizing agent can be added during extrusion molding, the extrusion aid can be sesbania powder, peptization
Agent can be inorganic acid, such as nitric acid or hydrochloric acid.
In the method for the present invention, raw material is dilute ethene and benzene, and described dilute ethylene raw is to contain low-concentration ethane（10
~60%）Refinery catalytic cracking or catalytic pyrolysis dry gas form raw material, it is or mixed with above-mentioned dry gas and pure ethylene
Gas is raw material.Catalytic cracking (FCC) and catalytic pyrolysis are important petroleum refining process, the useless tail that these process are produced
Gas (FCC dry gas and catalytic pyrolysis dry gas etc.), is referred to as catalysis drying gas.Catalysis drying gas is in addition to containing ethene, also a small amount of C3H6,
H2, CH4, C2H6, C3H8, CO, CO2, H2O,H2The components such as S.The dry gas has to pass through before entering reactor to be refined to deviate from acidity
Gas, alkali nitrogen and water, wherein sour gas include hydrogen sulfide and cos etc., and alkali nitrogen includes ammonia and other alkaline nitrogenous chemical combination
Thing.
The present invention method in, be alkylated reaction reactor can be, but not limited to be fixed bubbling bed reactor,
Fixed trickle bed reactor or paste state bed reactor.During using fixed bubbling bed reactor, dilute ethene and benzene are all under reactor
Endfeed, reaction product is drawn from top.During using fixed trickle bed reactor, dilute ethene is fed from reactor bottom, benzene from
In the middle part of reactor or top charging, reaction product is drawn from reactor bottom.Alkylation reactor preferably fixes bubbling bed reaction
Device.
In the method for the present invention, described alkylation reaction condition can be 140~220 DEG C of temperature, preferably 140~200
DEG C, more preferably 150~180 DEG C, 1.6~3.6MPa of pressure, preferably 1.6~3.0MPa, more preferably 1.6~2.5MPa, in charging
The mol ratio of benzene and ethene is that 2~6, preferably benzene alkene ratio is that 2~5, more preferably benzene alkene ratio is 2~4, and weight ethylene air speed is 0.1
~0.5h-1, preferably 0.1~0.3h-1, more preferably 0.2~0.3h-1。
Below by embodiment, the invention will be further described, but content not thereby limiting the invention.
In embodiment and comparative example, X-ray diffraction spectrum uses the A type X-ray diffractometers of Rigaku D/MAX- III, Cu-K
α targets；The content of aluminium element and distribution are by scanning transmission electron microscope-energy-dispersive X-ray fluorescence (EDXRF) spectroscopic assay in molecular sieve.
Distribution Value D is determined using following methods：In the TECNAIG of FEI Co.2F20（200kv）Type transmission electron microscope
Upper to determine, using suspension method sample preparation, 0.01 gram of sieve sample puts 2ml vials.Scattered, the shaken well with absolute ethyl alcohol, is used
Dropper takes a drop, drops on diameter 3mm specimen screens, it is to be dried after, be placed in injector, be inserted into Electronic Speculum and observed.Often
Individual sieve sample system analyzes 10, sample, and each analysis sample in the range of field of microscope, randomly selects 10 points in analysis
Son sieve crystal grain, then uniformly chooses 8 points on the body diagonal of each crystal grain, using TEM-EDX method, analyzes each point
Aluminium content.D represents SCWith SERatio, wherein, SCFor the average value of the aluminium content of zeolite crystal center, SEFor molecule
Sieve crystal grain from edge to a quarter at center at aluminium content average value.
Dilute ethylene concentration is 15% in embodiment, and ethylene source is to be formulated using pure ethylene with nitrogen.
Embodiment carries out the process of dilute ethene liquid phase legal system ethylbenzene using bubbling bed reactor.Reactor is stainless steel tubular type
Isothermal reaction pipe, internal diameter 22mm, catalyst loading amount 60mL, benzene and dilute ethene are introduced by reaction bottom of the tube.Material is carried out to device
Account, liquid receives more than 96%.
Conversion of ethylene and ethylbenzene selectivity are calculated by following equation：
Conversion of ethylene XE=（Second in ethylene molar number-gas discharge during the molal quantity of ethene-liquid discharges in charging
Alkene molal quantity）Molal quantity × 100% of ethene in/charging
Ethylbenzene selectivity SEBThe molar fraction of=ethylbenzene/（The molar fraction of 1- benzene）×100%
Embodiment 1
Prepare conventional beta-molecular sieve：By sodium aluminate solution（Sodium oxide molybdena 145.8g/L, aluminum oxide 102.8g/L）, tetraethyl
Ammonium hydroxide（TEAOH, 2.417N, Guangzhou great You Fine Chemical Co., Ltd）Add in deionized water, dissolve by heating, stirring is equal
It is even, working solution is made, by silochrom（150-250 μm, 500m2/ g, 0.9mL/g, Haiyang Chemical Plant, Qingdao）With above-mentioned work
Make solution mixing, Silica Surface is soaked by working solution, obtain reactant mixture, the mol ratio of wherein each component is
SiO2/Al2O3=20, Na2O/SiO2=0.075, TEAOH/SiO2=0.09, H2O/SiO2=6.5.By the reactant mixture in high pressure
120 DEG C of crystallization 24 hours in reactor, then in 140 DEG C of crystallization 48 hours, be cooled to after room temperature and isolate solid product, wash,
110 DEG C are drying to obtain SiO2/Al2O3The former powder of=20 beta-molecular sieve.
Prepare the beta-molecular sieve of surface Silicon-rich：The former powder of 8 grams of above-mentioned beta-molecular sieves is weighed, is put into three-necked flask, adds 240mL
HNO3The aqueous solution, its molar concentration is 0.05M, and 80 DEG C are warming up in the case of being stirred at reflux, under the conditions of 80 DEG C, heating stirring
Flow back and pickling 4 hours.Stop stirring, product is stood 10 minutes, is then filtered, washed 3 times, 80 DEG C of dry 10h.Will
Gained sample adds tetraethyl ammonium hydroxide（TEAOH）- tetraethyl orthosilicate（TEOS）System in, system composition be SiO2/
Al2O3=32, TEAOH/SiO2=0.15, the SiO in tetraethyl orthosilicate2Account for SiO28.5 moles of %, H of total amount2O/SiO2=4.2, stir
Mix 2 hours, be well mixed, then mixed system is put into closed crystallizing kettle and carries out secondary crystallization, 120 DEG C of crystallization 36h.Will
Product obtains the beta-molecular sieve of surface Silicon-rich through filtering, washing, dry and roasting, and D values are 2.
Prepare catalyst：By the beta-molecular sieve of surface Silicon-rich and SB powder（Chang Ling catalyst plant, the mass % of alumina content 80）
Mixing, adds a small amount of nitric acid mixing extrusion, is dried at 110 DEG C 6 hours, 550 DEG C are calcined 3 hours, catalyst A are obtained, wherein dividing
Son sieve content is 80 mass %, and matrix content is 20 mass %.
Alkylation reaction condition is pressure 3MPa, 210 DEG C of temperature, benzene alkene than 6, weight ethylene air speed 0.2h-1.Alkylation is anti-
Should result be listed in table 1.
Comparative example 1
This comparative example illustrates the catalytic process and result for the catalyst that conventional beta-molecular sieve is active component.
Same as Example 1, difference is that described beta-molecular sieve is conventional beta-molecular sieve（SiO2/Al2O3=20）, urged
Agent DB-A, wherein molecular sieve content are 80 mass %, and matrix content is 20 mass %.
Alkylation reaction condition be the same as Example 1, alkylated reaction result is listed in table 1.
Embodiment 2
By sodium aluminate solution（Sodium oxide molybdena 145.8g/L, aluminum oxide 102.8g/L）, tetraethyl ammonium hydroxide（TEAOH,
2.417N, Guangzhou great You Fine Chemical Co., Ltd）Add in deionized water, dissolve by heating, stir, work is made molten
Liquid, by silochrom（150-250 μm, 500m2/ g, 0.9mL/g, Haiyang Chemical Plant, Qingdao）Mix, make with above-mentioned working solution
Silica Surface is soaked by working solution, obtains reactant mixture, the wherein mol ratio of each component is SiO2/Al2O3=60,
Na2O/SiO2=0.075, TEAOH/SiO2=0.09, H2O/SiO2=6.5.By the reactant mixture 120 DEG C in autoclave
Crystallization 24 hours, then in 140 DEG C of crystallization 48 hours, be cooled to after room temperature and isolate solid product, wash, 110 DEG C are drying to obtain
SiO2/Al2O3The former powder of=60 beta-molecular sieve.
The former powder of 8 grams of above-mentioned beta-molecular sieves is weighed, is put into three-necked flask, adds 240mL HNO3The aqueous solution, its molar concentration
For 0.05M, 80 DEG C are warming up in the case of being stirred at reflux, under the conditions of 80 DEG C, heating stirring backflow and pickling 4 hours.Stop
Stirring, stands 10 minutes by product, is then filtered, washed 3 times, 80 DEG C of dry 10h.Gained sample is added into tetraethyl hydrogen
Amine-oxides（TEAOH）- tetraethyl orthosilicate（TEOS）System in, system composition be SiO2/Al2O3=100, TEAOH/SiO2=
0.18, the SiO in tetraethyl orthosilicate2Account for SiO28.5 moles of %, H of total amount2O/SiO2=5, stir 2 hours, be well mixed, then
Mixed system is put into closed crystallizing kettle and carries out secondary crystallization, 120 DEG C of crystallization 36h.By product through filtering, washing, dry
And roasting, the beta-molecular sieve of surface Silicon-rich is obtained, D values are 3.
By the beta-molecular sieve and Ludox of surface Silicon-rich（Chang Ling catalyst plant, the mass % of silica content 30）Mixing, spin
Shaping, wet bulb is dried 4 hours in 120 DEG C, 550 DEG C are calcined 3 hours, obtains catalyst B, wherein molecular sieve content is 95 matter
% is measured, matrix content is 5 mass %.
Alkylation reaction condition be the same as Example 1, alkylated reaction result is listed in table 1.
Comparative example 2
This comparative example illustrates the catalytic process and result for the catalyst that conventional beta-molecular sieve is active component.
Same as Example 2, difference is that described beta-molecular sieve is conventional beta-molecular sieve（SiO2/Al2O3=60）, urged
Agent DB-B.
Alkylation reaction condition be the same as Example 1, alkylated reaction result is listed in table 1.
Embodiment 3
By sodium aluminate solution（Sodium oxide molybdena 145.8g/L, aluminum oxide 102.8g/L）, tetraethyl ammonium hydroxide（TEAOH,
2.417N, Guangzhou great You Fine Chemical Co., Ltd）Add in deionized water, dissolve by heating, stir, work is made molten
Liquid, by silochrom（150-250 μm, 500m2/ g, 0.9mL/g, Haiyang Chemical Plant, Qingdao）Mix, make with above-mentioned working solution
Silica Surface is soaked by working solution, obtains reactant mixture, the wherein mol ratio of each component is SiO2/Al2O3=40,
Na2O/SiO2=0.075, TEAOH/SiO2=0.09, H2O/SiO2=6.5.By the reactant mixture 120 DEG C in autoclave
Crystallization 24 hours, then in 140 DEG C of crystallization 48 hours, be cooled to after room temperature and isolate solid product, wash, 110 DEG C are drying to obtain
SiO2/Al2O3The former powder of=40 beta-molecular sieve.
8 grams of Beta molecular sieves are weighed, are put into three-necked flask, 240mL HNO are added3The aqueous solution, its molar concentration is
0.05M, is warming up to 80 DEG C in the case of being stirred at reflux, under the conditions of 80 DEG C, heating stirring backflow and pickling 4 hours.Stopping is stirred
Mix, product is stood 10 minutes, is then filtered, washed 3 times, 80 DEG C of dry 10h.Gained sample is added into tetraethyl hydrogen-oxygen
Change ammonium（TEAOH）- tetraethyl orthosilicate（TEOS）System in, system composition be SiO2/Al2O3=80, TEAOH/SiO2=0.15,
SiO in tetraethyl orthosilicate2Account for SiO29 moles of %, H of total amount2O/SiO2=6, stir 2 hours, be well mixed, then will mixing
System, which is put into closed crystallizing kettle, carries out secondary crystallization, 120 DEG C of crystallization 36h.By product through filtering, washing, dry and roasting,
The molecular sieve of surface Silicon-rich is obtained, D values are 4.
By the beta-molecular sieve and Ludox of surface Silicon-rich（Chang Ling catalyst plant, silica content 30%）Mix in proportion,
φ 1.2mm cylinder orifice plate extruded mouldings are used on banded extruder, wet bar is dried 4 hours in 110 DEG C, and dry bar is broken into 20~40 mesh,
It is calcined 4 hours at 550 DEG C afterwards, obtains catalyst C, wherein molecular sieve content is 70 mass %, and matrix silica content is 30 matter
Measure %.
Alkylation reaction condition be the same as Example 1, alkylated reaction result is listed in table 1.
Comparative example 3
This comparative example illustrates the catalytic process and result for the catalyst that conventional beta-molecular sieve is active component.
Same as Example 3, difference is that described beta-molecular sieve is conventional beta-molecular sieve（SiO2/Al2O3=40）, urged
Agent DB-C.
Alkylation reaction condition be the same as Example 1, alkylated reaction result is listed in table 1.
Embodiment 4
By sodium aluminate solution（Sodium oxide molybdena 145.8g/L, aluminum oxide 102.8g/L）, tetraethyl ammonium hydroxide（TEAOH,
2.417N, Guangzhou great You Fine Chemical Co., Ltd）Add in deionized water, dissolve by heating, stir, work is made molten
Liquid, by silochrom（150-250 μm, 500m2/ g, 0.9mL/g, Haiyang Chemical Plant, Qingdao）Mix, make with above-mentioned working solution
Silica Surface is soaked by working solution, obtains reactant mixture, the wherein mol ratio of each component is SiO2/Al2O3=100,
Na2O/SiO2=0.075, TEAOH/SiO2=0.09, H2O/SiO2=6.5.By the reactant mixture 120 DEG C in autoclave
Crystallization 24 hours, then in 140 DEG C of crystallization 48 hours, be cooled to after room temperature and isolate solid product, wash, 110 DEG C are drying to obtain
Silica alumina ratio is SiO2/Al2O3The former powder of=100 beta-molecular sieve.
The former powder of 8 grams of beta-molecular sieves is weighed, is put into three-necked flask, adds 240mL HNO3The aqueous solution, its molar concentration is
0.05M, is warming up to 80 DEG C in the case of being stirred at reflux, under the conditions of 80 DEG C, heating stirring backflow and pickling 4 hours.Stopping is stirred
Mix, product is stood 10 minutes, is then filtered, washed 3 times, 80 DEG C of dry 10h.Gained sample is added into tetraethyl hydrogen-oxygen
Change ammonium（TEAOH）- tetraethyl orthosilicate（TEOS）System in, system composition be SiO2/Al2O3=200, TEAOH/SiO2=0.15,
SiO in tetraethyl orthosilicate2Account for SiO210 moles of %, H of total amount2O/SiO2=3, stir 2 hours, be well mixed, then will mixing
System, which is put into closed crystallizing kettle, carries out secondary crystallization, 120 DEG C of crystallization 36h.By product through filtering, washing, dry and roasting,
The molecular sieve of surface Silicon-rich is obtained, D values are 2
By the beta-molecular sieve of surface Silicon-rich and SB powder（Chang Ling catalyst plant, alumina content 80%）Feed intake, add in proportion
A small amount of nitric acid mixing extrusion, gained catalyst is dried 4 hours in 110 DEG C, and 550 DEG C are calcined 4 hours, catalyst D are obtained, wherein dividing
Son sieve content is 60 mass %, and matrix content is 40 mass %.
Alkylation reaction condition be the same as Example 1, alkylated reaction result is listed in table 1.
Comparative example 4
This comparative example illustrates the catalytic process and result for the catalyst that conventional beta-molecular sieve is active component.
Same as Example 4, difference is that described beta-molecular sieve is conventional beta-molecular sieve（Si/Al2=100）, it is catalyzed
Agent DB-D.
Alkylation reaction condition be the same as Example 1, alkylated reaction result is listed in table 1.
Embodiment 5
Conventional beta-molecular sieve（SiO2/Al2O3=20）Preparation process be the same as Example 1.
Prepare surface Silicon-rich beta-molecular sieve process be：8 grams of beta-molecular sieves are weighed, are put into three-necked flask, 240mL is added
HNO3The aqueous solution, its molar concentration is 0.05M, and 80 DEG C are warming up in the case of being stirred at reflux, under the conditions of 80 DEG C, heating stirring
Flow back and pickling 4 hours.Stop stirring, product is stood 10 minutes, is then filtered, washed 3 times, 80 DEG C of dry 10h.Will
Gained sample adds tetraethyl ammonium hydroxide（TEAOH）- tetraethyl orthosilicate（TEOS）System in, system composition be SiO2/
Al2O3=100, TEAOH/SiO2=0.15, the SiO in tetraethyl orthosilicate2Account for SiO29 moles of %, H of total amount2O/SiO2=4.2, stir
Mix 2 hours, be well mixed, then mixed system is put into closed crystallizing kettle and carries out secondary crystallization, 120 DEG C of crystallization 36h.Will
Product obtains the molecular sieve of surface Silicon-rich through filtering, washing, dry and roasting, and D values are 5.
By the beta-molecular sieve of surface Silicon-rich and SB powder（Chang Ling catalyst plant, alumina content 80%）Feed intake, add in proportion
A small amount of nitric acid mixing extrusion, is dried 6 hours, 550 DEG C are calcined 3 hours, obtain catalyst E, wherein molecular sieve content is at 110 DEG C
80 mass %, matrix content is 20 mass %.
Alkylation reaction condition be the same as Example 1, alkylated reaction result is listed in table 1.
Embodiment 6
Molecular sieve（SiO2/Al2O3=20）Preparation process be the same as Example 1.Prepare surface Silicon-rich beta-molecular sieve process be：
8 grams of above-mentioned Beta molecular sieves are weighed, are put into three-necked flask, 240mL HNO are added3The aqueous solution, its molar concentration is 0.05M,
80 DEG C are warming up in the case of being stirred at reflux, under the conditions of 80 DEG C, heating stirring backflow and pickling 4 hours.Stop stirring, will produce
Product stand 10 minutes, are then filtered, washed 3 times, 80 DEG C of dry 10h.Gained sample is added into tetraethyl ammonium hydroxide
（TEAOH）- tetraethyl orthosilicate（TEOS）System in, system composition be SiO2/Al2O3=300, TEAOH/SiO2=0.18, positive silicon
SiO in acetoacetic ester2Account for SiO215%, H of integral molar quantity2O/SiO2=6, stir 2 hours, be well mixed, then by mixed system
It is put into closed crystallizing kettle and carries out secondary crystallization, 120 DEG C of crystallization 36h.By product through filtering, washing, dry and roasting, obtain
The molecular sieve of surface Silicon-rich, D values are 10.
By the beta-molecular sieve of surface Silicon-rich and SB powder（Chang Ling catalyst plant, alumina content 80%）Feed intake, add in proportion
A small amount of nitric acid mixing extrusion, is dried 6 hours, 550 DEG C are calcined 3 hours, obtain catalyst F, wherein molecular sieve content is at 110 DEG C
80 mass %, matrix content is 20 mass %.
Alkylation reaction condition be the same as Example 1, alkylated reaction result is listed in table 1.
Embodiment 7
The present embodiment uses catalyst F, changes alkylation reaction condition be pressure 2.5MPa, 180 DEG C of temperature, benzene alkene than 3,
Weight ethylene air speed 0.4h-1。
Alkylated reaction result is listed in table 1.
Embodiment 8
The present embodiment use catalyst F, changes alkylation reaction condition be pressure 2.0MPa, 140 DEG C of temperature, benzene alkene compares 4,
Weight ethylene air speed 0.1h-1。
Alkylated reaction result is listed in table 1.
Table 1
As it can be seen from table 1 the dilute second of the invention carried out using the beta-molecular sieve of surface Silicon-rich as the catalyst of active component
During alkene liquid phase legal system ethylbenzene, conversion of ethylene and ethylbenzene selectivity are more preferable, and stability is preferable.
Claims (6)
1. a kind of method of dilute ethene liquid phase legal system ethylbenzene, be in fixed bubbling bed reactor or fixed trickle bed reactor,
Dilute ethene is set to be contacted with benzene in the presence of alkylation reaction condition and catalyst containing beta-molecular sieve, it is characterised in that described
In beta-molecular sieve, use TEM-EDX methods to characterize and obtain the Distribution Value of aluminium for D, D represents SCWith SERatio and D=2~10, its
In, SCFor the average value of the aluminium content of zeolite crystal center, SEFor zeolite crystal from edge to a quarter at center at
Aluminium content average value, and the H- beta-molecular sieves of described beta-molecular sieve after by roasting are through acid solution dealuminzation, then with tetraethyl
The step of mixture that ammonium hydroxide and tetraethyl orthosilicate contact are obtained carries out secondary hydrothermal crystallizing and recovery product obtains, described
Mixture mole composition be SiO2/Al2O3=30~200, TEAOH/SiO2=0.12~0.18, H2O/SiO2=3~6,
Tetraethyl orthosilicate is with SiO2It is calculated as the SiO of described mixture210~20 moles of % of total amount；Described alkylation reaction condition
Mol ratio 2~5, weight ethylene air speed for benzene and ethene in 140~200 DEG C of temperature, 1.6~3.0MPa of pressure, charging are 0.1
~0.3h-1；Described dilute ethene be using the refinery catalytic cracking or catalytic pyrolysis dry gas containing 10~60% ethene as raw material, or
Person is using above-mentioned dry gas and the mixed gas of pure ethylene as raw material.
2. according to the method for claim 1 wherein, described beta-molecular sieve, the mol ratio of silica and aluminum oxide is 20~100.
3. according to the method for claim 1 wherein, the described catalyst containing beta-molecular sieve also contains inorganic oxide matrix,
The weight ratio of described beta-molecular sieve and described inorganic oxide matrix is 95:5 to 60:40.
4. according to the method for claim 1 wherein, described alkylation reaction condition is 150~180 DEG C of temperature, pressure 1.6~
The mol ratio of benzene and ethene is that 2~4, weight ethylene air speed is 0.2~0.3h in 2.5MPa, charging-1。
5. according to the method for claim 1, it is characterised in that when this method is carried out in fixed bubbling bed reactor, described is dilute
Ethene and the benzene endfeed under reactor, reaction product are drawn from top.
6. according to the method for claim 1, it is characterised in that when this method is carried out in fixed trickle bed reactor, described is dilute
Ethene is fed from reactor bottom, and described benzene is from reactor middle part or top charging, and reaction product is drawn from reactor bottom.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310688208.2A CN104710263B (en) | 2013-12-16 | 2013-12-16 | A kind of method of dilute ethene liquid phase legal system ethylbenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310688208.2A CN104710263B (en) | 2013-12-16 | 2013-12-16 | A kind of method of dilute ethene liquid phase legal system ethylbenzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104710263A CN104710263A (en) | 2015-06-17 |
| CN104710263B true CN104710263B (en) | 2017-07-25 |
Family
ID=53410060
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310688208.2A Active CN104710263B (en) | 2013-12-16 | 2013-12-16 | A kind of method of dilute ethene liquid phase legal system ethylbenzene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104710263B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109592697B (en) * | 2017-09-30 | 2022-07-12 | 中国石油化工股份有限公司 | IM-5 molecular sieve and synthetic method thereof |
| CN109721449A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of dilute ethylene reacts the method for producing ethylbenzene with benzene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050463A (en) * | 2009-10-28 | 2011-05-11 | 中国石油化工股份有限公司 | Mesoporous Beta molecular sieve and silicification preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1020041C (en) * | 1990-12-18 | 1993-03-10 | 中国石油化工总公司 | Process for making ethyl benzene by reacting dilute ethylene with benzene |
| US5227558A (en) * | 1992-02-10 | 1993-07-13 | Fina Technology, Inc. | Aromatic alkylation process employing steam modified zeolite beta catalyst |
| CN102441414B (en) * | 2010-10-13 | 2013-08-28 | 中国石油化工股份有限公司 | Catalyst used in alkylation reaction, preparation method and application of catalyst |
-
2013
- 2013-12-16 CN CN201310688208.2A patent/CN104710263B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050463A (en) * | 2009-10-28 | 2011-05-11 | 中国石油化工股份有限公司 | Mesoporous Beta molecular sieve and silicification preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 催化裂化干气中乙烯与苯液相烷基化反应的研究;白杰等;《石油与天然气化工》;20011231;第30卷(第2期);第53-54页下转第57页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104710263A (en) | 2015-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102066257B (en) | Selective catalyst for aromatics conversion | |
| US20100145127A1 (en) | Catalytic composition for producing olefins by catalytic cracking | |
| CN106807442A (en) | A kind of shape-selective catalyst with toluene methylation efficiency high and its preparation method and application | |
| CN102066529A (en) | Novel transalkylation process | |
| CN104549452B (en) | Toluene and methanol alkylation catalyst and preparation method and application thereof | |
| CN105712379B (en) | A kind of synthetic method of multi-stage porous ZSM-5 molecular sieve | |
| CN104056653B (en) | A kind of catalyst for producing propylene with methanol | |
| CN114471672B (en) | Catalyst for alkylation of benzene and ethylene and preparation method and application thereof | |
| CN104437601B (en) | A kind of ZSM-5 Type Zeolites agent and its application for preparing propylene from methanol | |
| CN104710263B (en) | A kind of method of dilute ethene liquid phase legal system ethylbenzene | |
| CN107285330A (en) | A kind of preparation method of NU-88 molecular sieves | |
| CN102039150B (en) | Preparation method of binderless Y zeolite catalyst | |
| CN105983434B (en) | A kind of preparation method and application of the ZSM-11 molecular sieve catalyst of binder free | |
| CN102039165A (en) | Binder-free zeolite socony mobil (ZSM)-5/mordenite symbiotic molecular sieve catalyst and preparation method thereof | |
| CN102039157B (en) | Non-binder MCM-22 molecular sieve catalyst and preparation method thereof | |
| CN105582933B (en) | Catalyst for double-bond isomerization | |
| CN102039152B (en) | Preparation method of binder-free mordenite catalyst | |
| CN104549468B (en) | Hydrocracking catalyst and preparation method | |
| CN102039162B (en) | Binderless ZSM-5/beta zeolite symbiotic molecular sieve catalyst and preparation method thereof | |
| CN101992121B (en) | Binderless ZSM-5/Magadiite symbiotic material catalyst and preparation method thereof | |
| CN101992123A (en) | Adhesive-free mordenite/MCM-22 intergrowth molecular sieve catalyst and preparation method thereof | |
| CN102039156B (en) | Preparation method of binder-free beta zeolite catalyst | |
| CN102039172B (en) | Binderless beta zeolite/MCM-22 symbiotic molecular sieve catalyst and preparation method thereof | |
| CN104710264B (en) | A kind of method of the dilute ethylbenzene manufactured from ethylene of liquid phase method | |
| CN102039163B (en) | Method for preparing adhesive-free mordenite/MCM-22 symbiotic molecular sieve catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |