CN105983436A - Alkylation reaction catalyst, preparation method and application thereof - Google Patents
Alkylation reaction catalyst, preparation method and application thereof Download PDFInfo
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Abstract
An alkylation reaction catalyst is characterized in that a catalytic active component contains a MWW-structure molecular sieve, which is not less than 30 [mu]mol/g in adsorption quantity on 2,4,6-trimethylpyridine after adsorption at 20 DEG C and desorption at 200 DEG C. When being used in an ethylene and benzene liquid-phase alkylation reaction, the catalyst, compared with a conventional MWW-structure molecular sieve synthesized in a hydrothermal manner, has higher ethylene conversion rate and higher ethylbenzene selectivity.
Description
Technical field
The present invention is about a kind of catalyst for alkylation reaction, preparation method and application, exactly, is
About a kind of catalyst for alkylation reaction containing MWW structure molecular screen, preparation method and in Ethenylbenzene liquid phase
Application in alkylated reaction.
Background technology
Ethylbenzene, as important industrial chemicals, is mainly used in dehydrogenation and produces styrene, and then produce polystyrene
Row resin such as polystyrene (PS), acrylonitrile-butadiene-styrene (ABS) (ABS), styrene-acrylonitrile (SAN)
And butadiene-styrene rubber (SBR) etc..It addition, a small amount of ethylbenzene is also used for solvent, diluent and generates two
Ethylo benzene etc..In recent years, cinnamic development is the rapidest, and cinnamic thriving demand is driven by market
The sustainable growth of ethylbenzene yield；From 1998 to 2015 years, the whole world ethylbenzene demand by with 3.7% speed
Degree increases.Industrial, ethylbenzene is mainly synthesized by ethylene and benzene alkylation reaction, only has the ethylbenzene of about 2%
It is to pass through C8The separation method of fraction produces.
At present, the production technology of ethylbenzene mainly has: AlCl3Method, Alkar vapor phase method, catalytic distillation technology divide
Son sieve vapor phase method and molecular sieve liquid phase method etc..AlCl3Method and Alkar vapor phase method set due to environmental pollution, corrosion
The shortcomings such as standby, energy consumption is big, are phased out.From the eighties in 20th century, the production of ethylbenzene start from
Traditional AlCl3Catalyst Friedel-Crafts benzene-alkylation technique is to molecular sieve catalytic process changeover.Molecule
Sieve catalysis ethylbenzene synthesis technique is divided into again vapor phase method and liquid phase method two kinds.The major defect of molecular sieve vapor phase method is
Xylene content is high, affects the quality of product.Molecular sieve liquid phase method reaction temperature is low, the life of side reaction product
One-tenth amount reduces, and particularly greatly reduces the growing amount of dimethylbenzene, can improve the quality of ethylbenzene product.Mesh
Before, realize in industrialized molecular sieve liquid phase method synthesizing ethyl benzene technique, used Y, Beta and MCM-22
Molecular sieve is catalyst activity constituent element.
Mobli company Cheng etc. (Studies in Surface Science and Catalysis, 1999,
121:53-60.) by reaction temperature 220 DEG C, reaction pressure 3.44MPa, benzene and ethylene molar ratio 4:1
Under Experimental comparison find, Beta molecular sieve activity is the highest, MCM-22 molecular sieve ethylbenzene, ethylization selectivity
Preferably, owing to there is supercage in Y type molecular sieve, selectivity is worst, inactivation is very fast in its pore passage structure.
The MWW structure molecular screens such as MCM-22, MCM-49, MCM-56 are all extraordinary alkene and benzene alkylation
The catalyst of reaction, such catalyst has reaction temperature gentleness, benzene alkene than features such as low, environmental friendliness.
US 5600048 (1997) have studied the liquid-phase alkylation performance of MWW structure molecular screen, and result shows identical
Under conditions of conversion of ethylene, MWW structural molecule sieve catalyst has a more preferable ethylbenzene selectivity, but its
Treating capacity is less than Beta molecular sieve catalyst.
MWW structure molecular screen includes MCM-22, MCM-49, MCM-36, MCM-56, ITQ-1 and ITQ-2
Equimolecular sieves.Nineteen ninety, Mobil company goes out MCM-22 with hexamethylene imine for template Hydrothermal Synthesis first
Molecular sieve (US, 4954325,1990), and parsed its structure first in 1994, and named with this
MWW structure molecular screen, the lamellar zeolite therefore with MWW topological structure is also called MCM-22 family molecular sieves.
MWW structure molecular screen has the independent duct that two sets are non-cross: layer internal orifice dimension is 0.40 × 0.59nm's
Oval 10MR two dimension sine duct；Interlayer is the 12MR supercage of 0.71 × 0.71 × 1.82nm, and with
The 10MR opening of 0.40 × 0.54nm communicates with the external world；Some 12MR holes additionally also it are distributed on its surface,
Being the half of supercage, the degree of depth is about 0.91nm (Science, 1994,264:1910).MWW structural molecule
Sieve because pore passage structure and the physico-chemical property of its uniqueness (are urged in alkylation (US 5600048,1997), aromatisation
Chemistry report, 2002,23:24), catalytic cracking (J.Catal., 1997,167:438) and isomerization
The reaction such as (J.Catal., 1996,158:561) has broad application prospects.
US 4954325 (1990) and US5326575 (1993) reported first MCM-22, MCM-49 molecular sieve
And synthetic method, its technical characteristic is with hexamethylene imine as template, and crystallization temperature is 80～225
DEG C, crystallization time is 1～60 day.But this MWW structure molecular screen synthetic water silicon ratio is high, and crystallization time is long,
And assemble serious, bad dispersibility.Document J.Phys.Chem.1996,100:3788 describes compound body
Under system, low silica-alumina ratio is beneficial to MCM-49 molecular sieve and generates, and it is raw that high silica alumina ratio is then beneficial to MCM-22 molecular sieve
Become；It addition, under the conditions of dynamic crystallization, HMI/Na+Mol ratio is less than 2.0, it is intended to generate MCM-49 molecule
Sieve, tends to MCM-22 molecular sieve more than 2.0.CN 1500723A (2004) reports a kind of MCM-22
The synthetic method of family molecular sieves, its technical characteristic is with hexamethylene imine as template and controls reaction mixing
Alkaloids degree and digestion time, thus shorten the generated time of MWW structure molecular screen.CN 101489677A(2007)
By the template range expansion of synthesis MWW structure molecular screen it is: Aminocyclopentane, cyclohexylamine, cycloheptylamine, six Asias
Methylene imine, heptamethylene imines, homopiperazine and their conjugate.CN 102452665A (2012) reports
With non-equivalence tetraalkylammonium cation as template, add alkali metal chloride and the mixture of hydroxide,
Crystal seeds etc. successfully synthesize MWW structure molecular screen.CN 101618336A (2010) synthesis one has multi-stage porous
Road structure, metal supported MCM-22 molecular sieve hollow sphere bifunctional catalyst preparation method, is to utilize
White carbon black spherolite and hexamethylene imine are template, take a step hydrothermal crystallization method to prepare and have hollow knot
The molecular sieve hollow sphere catalyst of structure and multi-stage artery structure.
CN103771435A discloses the synthetic method of a kind of MCM-22 molecular sieve, it is characterised in that the method
Including, the raw material including silicon source, aluminum source, alkali source, template and deionized water is mixed to get mixing
Thing A, processes described mixture A under the conditions of hydrothermal crystallizing and obtains directed agents, by described directed agents with
Silicon source, aluminum source, alkali source, aniline and deionized water mixing, obtain mixture B, existed by described mixture B
Crystallization reclaim product under hydrothermal condition, wherein, described template is hexamethylene imine or is six sub-
Methylene imine is at least the hexamethylene imine of 0.05:1 and the mixture of aniline with the mol ratio of aniline,
In described mixture B, from the silicon source in described directed agents and the total silicon source in described mixture B
With SiO2The part by weight of meter is 0.05～1:1.
Summary of the invention
Inventor has been surprisingly found that on the basis of lot of experiments, and LTA structure molecular sieve can not suffer from amorphous rank
Section turns crystalline substance and becomes MWW structure molecular screen, and the MWW structure molecular screen obtained to have accessibility high and further
The feature of surface Silicon-rich.Catalyst with it as active component, with the MWW structural molecule of conventional hydrothermal synthesis
Sieve catalyst is compared has more preferable conversion of ethylene and ethylbenzene in ethylene and benzene liquid-phase alkylation synthesizing ethyl benzene
Selectivity, reduces the selectivity of diethylbenzene and triethylbenzene (TEB) simultaneously.Based on this, form the present invention.
An object of the present invention is to provide a kind of catalyst for alkylation reaction containing MWW structure molecular screen, mesh
Two be to provide its preparation method, the three of purpose are to provide it in the side such as ethylene and benzene liquid phase alkylation reaction
The application in face.
In order to realize one of purpose, the catalyst for alkylation reaction that the present invention provides, it is characterised in that catalysis is lived
Property constituent element contain a kind of MWW structure molecular screen, described MWW structure molecular screen, its 20 DEG C absorption, 200
The adsorbance of 2,4,6-trimethylpyridine after DEG C desorption is >=30 μm ol/g.
In the present invention, with 2，4，6-trimethylpyridine as probe molecule, measure 20 DEG C of absorption and in 200 DEG C
The amount that the trimethylpyridine of removing physical absorption adsorbs the most over a molecular sieve characterizes the catalysis limiting the present invention
MWW structure molecular screen in agent.2，4，6-trimethylpyridine adsorbance is the most, and show molecular sieve can be close
Property is the best.The MWW structure molecular screen of conventional hydrothermal synthesis, its adsorbance is respectively less than 30 μm ol/g, such as,
The 2,4,6-trimethyl of the MWW structure molecular screen sample (comparative example 1 and comparative example 2) of conventional hydrothermal synthesis
The adsorbance of pyridine is 24 μm ol/g, 26 μm ol/g.Therefore, the molecular sieve that the present invention provides, have more
Good accessibility.Preferably, the suction after 2，4，6-trimethylpyridine adsorbs through 20 DEG C and is desorbed in 200 DEG C
Attached amount is 30～50 μm ol/g, and preferred adsorbance is 32～42 μm ol/g.2,4,6-trimethylpyridine
Adsorbance characterisitic parameter be sieve sample is pressed into 10 to 20mg from blade, be placed in situ in pond,
2，4，6-trimethylpyridine is adsorbed in 20 DEG C, and in the 2，4，6-trimethylpyridine of 200 DEG C of removing physical absorptions,
Recorded by Fourier transform infrared spectroscopy.
In the catalyst of the present invention, described MWW structure molecular screen has the feature of surface Silicon-rich, at molecule
The silica alumina ratio value of sieve crystal morphology edge is generally higher than pattern center silica alumina ratio.With STEM-EDS
Characterizing, along pattern center to the direction of feature edges, silicon oxide is gradually increased with the molar ratio of aluminium oxide.
(see accompanying drawing 3), pattern limit is illustrated as a example by the STEM-EDS spectrogram of the sample A-2-3 of embodiment 2
Being O1 at edge air line distance 50nm, pattern center is O3, then chooses O2 (O2 is between O1 and O3).
From figure 3, it can be seen that its silica alumina ratio data are distributed, O1, O2 and O3 are respectively 45.4,36.3 and 22.0,
Illustrate that this molecular sieve is rich surface silicon type.The molecular sieve of the present invention connects with pattern center with the feature edges of crystal
Line, is molecule at the silicon oxide of distance feature edges air line distance 50nm position and the molar ratio of aluminium oxide
At least 1.2 times of the molar ratio of silicon oxide and the aluminium oxide of the pattern center position of sieve crystal, the most extremely
Few 1.5 times, at least 2 times be more highly preferred to.It is more highly preferred to, the MWW structure molecular screen that the present invention provides,
With feature edges and the pattern line of centres of crystal, the silicon oxide at distance feature edges air line distance 50nm
It is 30～90 with the molar ratio of aluminium oxide.Appearance center described for molecular sieve crystal is in geometry
The heart.
The catalyst for alkylation reaction of the present invention, containing the MWW structure molecular screen of 30～70 weight %, with oxygen
The inorganic oxide carrier of compound meter 1～40 weight %；Preferably, the MWW molecule containing 50～70 weight %
Sieve and the inorganic oxide carrier of 10～30 weight %；It is furthermore preferred that the molecular sieve containing 60～70 weight %
And 20～30 inorganic oxide carriers of weight %.
In order to realize the two of purpose, present invention also offers the preparation method of a kind of catalyst, it is characterised in that
Including MWW structure molecular screen is mixed with inorganic oxide carrier, molding, it is dried and roasting is catalyzed
The process of agent, wherein, the process of described synthesis MWW structure molecular screen is by LTA structure molecular sieve and silicon
Source, alkali source, template, the mixture colloid crystallization under hydrothermal conditions of deionized water formation also reclaim product,
Described template is the template that can be used in synthesizing MWW structure molecular screen.
In described preparation method, MWW structure molecular screen is prepared through following process: LTA structure divided
The mixture colloid crystallization under hydrothermal conditions that son sieve and silicon source, alkali source, template, deionized water are formed is also
Reclaiming the MWW structure molecular screen obtained, described template is to can be used in synthesizing MWW structure molecular screen
Template.
In the preparation process of above-mentioned MWW structure molecular screen, the Si-Al molecular sieve with LTA structure act as aluminum
Source and the role in part silicon source.Described LTA structure molecular sieve is mainly A type molecular sieve, can be selected from not
With cation type molecular sieve, such as NaA, KA, CaA, NH4A, HA or ReA.For described LTA
The crystallite dimension of structure molecular screen has no particular limits, can be selected from the molecular sieve of various grain sizes, example
Molecular sieve such as little crystal grain.
In the preparation process of above-mentioned MWW structure molecular screen, described silicon source selected from Ludox, solid silicone,
At least one in white carbon and waterglass；Described alkali source is selected from Lithium hydrate, sodium hydroxide, hydroxide
At least one in potassium, rubidium hydroxide and Cesium hydrate.；Described can be used in synthesis MWW structure molecular screen
Template selected from pentamethylene imines, hexamethylene imine, heptamethylene imines, 1,4-phenodiazine cycloheptane,
Cycloheptyl alkanamine, hexamethylene alkanamine, Aminocyclopentane, aniline, piperidines and piperazine, N, N, N-trimethyl adamantyl hydrogen
Amine-oxides, Me3N+(CH2)5N+Me3(Me2CH)2HN+(CH2)5NH+(Me2CH)2In (Me represents methyl) extremely
Few one, it is preferred that described template at least includes hexamethylene imine, can be individually sub-with six
Methylene imine is template, and template can also be the mixture of hexamethylene imine and aniline.Work as template
During for the mixture of hexamethylene imine and aniline, the mol ratio of hexamethylene imine and aniline is at least
0.05:1.In a preferred embodiment in accordance with this invention, silicon source is solid silicone；Template is six Asias
Methylene imine.
In the preparation process of above-mentioned MWW structure molecular screen, described mixture colloid, mol ratio is
SiO2/Al2O3=15～200, OH-/SiO2=0.001～1, H2O/SiO2=5～100, R/SiO2=0.01～5；
Preferably, described mixture colloid, mol ratio is SiO2/Al2O3=16～80, OH-/SiO2=0.01～
0.5、H2O/SiO2=5～50, R/SiO2=0.05～0.5；It is furthermore preferred that described mixture colloid, rub
Your proportioning is SiO2/Al2O3=20～40, OH-/SiO2=0.05～0.30, H2O/SiO2=10～30,
R/SiO2=0.05～0.35.
In the preparation process of above-mentioned MWW structure molecular screen, crystallization under described hydrothermal condition, its temperature is permissible
It is 100～180 DEG C, is preferably 130～150 DEG C.Under different raw materials and proportioning, crystallization time also has difference,
The crystallization time being usually as low as 5 hours just may occur in which MWW crystal structure, but generally crystallization time is less than
60h, obtain is LTA structure and composite molecular screen that MWW structure coexists.In the method for the present invention, crystallization
Time can be adjusted according to the situation of the proportioning of mixture colloid and raw material, to guarantee to form MWW structure
Molecular sieve, for example, it may be 60～240h, preferably 70～100h.
In the preparation process of above-mentioned MWW structure molecular screen, the described process reclaiming product is art technology
Personnel are familiar with, it is common that cool down after crystallization terminates, taken out by anti-product, filter, and are dried, are divided
Son sieves former powder；Roasting is with the process of removed template method.
The preparation process of above-mentioned MWW structure molecular screen, uses LTA structure molecular sieve with " topological structure reconstruct "
Mode synthesizes MWW structure molecular screen.On the basis of there is LTA structure molecular sieve, be aided with supplementary silicon source,
Under the raw material effect such as template and alkali, directly turn crystalline substance and become there is MWW structure molecular screen.First in LTA structure
The MWW structure molecular screen with monolayer lamellar is formed, along with turn prolongation of brilliant time, lamellar MWW on crystal grain
Structure gradually increases, and LTA structure is gradually consumed.The macro manifestations of preparation process is MWW structure molecular screen
It is the MWW (shell) and LTA (core) two kinds generating from outside to inside on LTA structure crystal grain and there is nucleocapsid structure
The intermedium that structure coexists, turns brilliant one-tenth MWW structure the most completely.Through the MWW structure that this turn of brilliant process obtains
Molecular sieve, its crystallite dimension is close with the crystallite dimension of former LTA structure molecular sieve.Never with crystallization time point
The XRD spectra of the intermediate product obtained is observed, and changes over and presents LTA structure characteristic diffraction peak and gradually drop
Feature low, that MWW structure diffraction peak gradually strengthens simultaneously.
The sample that the preparation process of above-mentioned MWW structure molecular screen obtains, for having three dimensional structure time the most fired
MCM-49 molecular sieve rather than there is the MCM-22P molecular sieve of interlayer structure, this also illustrates this turn of brilliant mistake
Journey is directly to occur, and turn brilliant concept experiencing amorphous state is entirely different with needing, i.e. the system of the present invention
Preparation Method is under additional silicon source and template etc. act on, the LTA structure with three dimensional structure directly change into
There is the MCM-49 molecular sieve of three-dimensional MWW structure.
The preparation method of the catalyst that the present invention provides also includes that MWW structure molecular screen first carries out ammonium and hands over reduction alkali
Tenor in terms of alkali metal oxide less than the process of 0.05 weight %.Wherein, described inorganic oxide
Thing carrier accounts for 1～40%, preferably 20～30% of catalyst weight in terms of oxide.
Described inorganic oxide carrier, its precursor is selected from SB powder, dry glue powder, Alumina gel and the thin water of plan
One or more in aluminum stone.Described inorganic oxide carrier is dry glue powder.
The preparation method of the catalyst that the present invention provides, including MWW structure molecular screen and inorganic oxide carrier
Mixing, molding, the process that dry, roasting obtains catalyst.As it is known to those skilled in the art that for side
Just kneading and compacting, also includes that adding extrusion aid and water etc. is conventionally used for preparing the material of catalyst.Described helps
Squeeze one or several in sesbania powder, starch, nitric acid and citric acid of agent, the most preferably nitric acid.
As a example by nitric acid, its addition is 0.5～5 weight %, preferably 1～3 weight %.
Described inorganic oxide carrier is from silicon oxide, aluminium oxide, magnesium oxide, titanium oxide or zirconium oxide.
Preferably, described inorganic oxide carrier carrys out self-alumina, is selected from SB powder, dry glue powder, Alumina gel
Or boehmite, wherein, more preferably dry glue powder.
In order to realize the three of purpose, present invention also offers a kind of ethylene and benzene liquid phase alkylation reaction, it is special
Levying and be that ethylene and benzene are 180～280 DEG C in a kind of catalyst existence and reaction temperature, reaction pressure is
2.0～4.0MPa, benzene weight space velocity 1～5h-1, benzene and ethylene molar ratio are to carry out under conditions of 2～12
Alkylated reaction, wherein said catalyst is the catalyst of the invention described above；The process conditions being more highly preferred to
For: reaction temperature is 200～260 DEG C, and reaction pressure is 3.0～3.5MPa, benzene weight space velocity 3～5h-1,
Benzene and ethylene molar ratio are 2～12.
The catalyst that the present invention provides, compared with the catalyst of conventional hydrothermal synthesis, has in synthesizing ethyl benzene
Preferably conversion of ethylene and ethylbenzene selectivity.While maintaining high ethylbenzene selectivity, it is remarkably improved
Conversion of ethylene.Compared with current industrial wide variety of BEA molecular sieve catalyst, there is more preferable second
Benzene selective, more can meet the operating condition of low benzene alkene ratio, have good application prospect.
The catalyst that the present invention provides, can be additionally used in Alkylation benzene with propylene simultaneously and reacts, other aromatisation,
The reaction such as cracking, isomerization can also use this catalyst.
Ethylene and benzene compared to the MWW structure molecular screen synthesized with the conventional hydrothermal catalyst as active component
Liquid phase alkylation reaction method, the conversion of ethylene showed of the present invention and ethylbenzene selectivity are along with urging
The reduction of agent active component MWW structure molecular screen crystal grain and raise simultaneously, broken ethylene and benzene alkylation
Traditional rule " conversion ratio raises, and selectivity declines " of reaction, jumps out " lifting up of activity and selectivity contradiction
Plate ".Conversion of ethylene as shown in Figure 4 and Figure 5 and ethylbenzene selectivity variation with temperature, with reaction temperature
Illustrate as a example by 220 DEG C: when 220 DEG C, LTA structure " topology reconstruction " method synthesis MWW structure molecular screen urge
Agent sample CAT-1, CAT-2, CAT-3, its conversion of ethylene is respectively 98.9%, 99.9%, 100
%, ethylbenzene selectivity is respectively 95.9%, 96.3%, 96.5%；Can be seen that silica alumina ratio reduces, its second
Alkene conversion ratio raises, and ethylbenzene selectivity raises simultaneously；The change of other temperature spots is consistent with this temperature spot rule,
This explanation synthesizes MWW structure molecular screen for LTA structure " topology reconstruction " method, at ethylene and benzene liquid phase alkane
Glycosylation reaction can improve conversion of ethylene and ethylbenzene selectivity simultaneously.
Accompanying drawing explanation
Fig. 1 is the XRD spectra that the sample A-2 sample that embodiment 2 obtains turns brilliant process.
Fig. 2 is the SEM spectrogram that the sample A-2 sample that embodiment 2 obtains turns brilliant process.
Fig. 3 is the STEM-EDS spectrogram of the sample A-2-3 that embodiment 2 obtains.
Fig. 4 is conversion of ethylene (%) comparison diagram of different catalysts ethylene and benzene liquid phase alkylation reaction.
Fig. 5 is ethylbenzene selectivity (%) comparison diagram of different catalysts ethylene and benzene liquid phase alkylation reaction.
Detailed description of the invention
Below by embodiment, the invention will be further described, but model not thereby limiting the invention
Enclose.
In embodiment and comparative example, X-ray diffraction (XRD) the crystalline phase figure of sample is at Siemens D5005
It is measured on type x-ray diffractometer.It is between 22.5 °～25.0 ° with sample and authentic specimen at 2 θ
The ratio of diffracted intensity (peak height) sum at diffractive features peak represents the sample crystallization relative to authentic specimen
Degree, i.e. relative crystallinity.Sample on the basis of comparative example 1 sample, its degree of crystallinity is calculated as 100%.
In embodiment and comparative example, the adsorbance characterisitic parameter of 2，4，6-trimethylpyridine is by molecular sieve sample
Product be pressed into 10 to 20mg from blade, be placed in situ in pond, adsorb 2，4，6-trimethylpyridine in 20 DEG C,
And in the 2，4，6-trimethylpyridine of 200 DEG C of removing physical absorptions, Fourier transform infrared spectroscopy record.
In embodiment and comparative example, transmission electron microscope (TEM) is analyzed and is used Tecnai F20 G2 S-TWIN
Test, applies angle of elevation annular dark field adnexa (HAADF) configured together and the X-ray energy spectrometer of integration
EDAX carries out micro-raman spectra and elementary analysis.The regional choice that microregion element is analyzed, as a example by accompanying drawing 3, by
Outer and interior position is followed successively by O1 (at crystal edge air line distance 50nm), O2 and O3 (pattern center),
The regional choice of remaining sample microregion element analysis is substantially the same.
Comparative example 1
The explanation of this comparative example uses industrial wide variety of with Beta molecular sieve urging for catalysis active component
The preparation of agent and ethylene and benzene liquid phase alkylation reaction method.
Beta molecular sieve (SiO2/Al2O3=25) ammonium exchange: under 90 DEG C of water bath condition, ammonium exchange 2h,
Take out, filter, dry for standby.Wherein ammonium ion precursor is ammonium nitrate, exchange liquid proportioning: 1g molecule
Sieve: 1g ammonium nitrate: 20g deionized water.
Beta molecular sieve (butt 80%) after being handed over by ammonium mixes with carrier dry gel powder (butt 70%)
Uniformly, then being slowly added to after nitric acid and appropriate amount of deionized water are mixed into homogeneous liquid, the mixing of addition limit, limit is all
Even.The mass ratio of gained mixture is: 70% molecular sieve butt: the dry glue powder butt of 30%: 100% deionization
Water (catalyst butt=molecular sieve butt+carrier butt, be defined as 100%).Then by mixture in extrusion
Further mix homogeneously on machine, and then it is squeezed into bar, drying, roasting obtain comparative catalyst, numbering
DB-CAT-1。
Alkylation properties is evaluated: Solid Bed micro-reactor, and it is 16～20 mesh granules that catalyst grinds,
Loadings is 8mL.Process conditions are: reaction temperature is 200～260 DEG C；Reaction pressure is 3.5MPa,
Benzene weight space velocity 3h-1, benzene and ethylene molar ratio are 12.
For guaranteeing data reliability and repeatability, take 7 temperature spots: 200 DEG C, 210 DEG C, 220 DEG C, 230
DEG C, 240 DEG C, 250 DEG C and 260 DEG C, each temperature spot adopts three instantaneous samples, and its product of chromatography forms,
Then calculate conversion of ethylene and ethylbenzene selectivity, take its meansigma methods.
Alkylation result is shown in Fig. 4 and Fig. 5, and wherein, when reaction temperature 220 DEG C, conversion of ethylene is 100%,
Ethylbenzene selectivity is 92.8%.
Comparative example 2
MCM-49 molecular sieve is prepared: by sodium metaaluminate (traditional Chinese medicines collection according to the method for US 5236575
Group, analytical pure) it is dissolved in deionized water with sodium hydroxide (Beijing Reagent Company, analytical pure), stirring is extremely
It is completely dissolved, solid silicone (Haiyang Chemical Plant, Qingdao, butt 97%) is added above-mentioned solution, adds
Hexamethylene imine, after stirring, gained mixture colloid mol ratio is: 0.18NaOH:SiO2:
0.033Al2O3: 0.30HMI:15H2O.Then gained mixture colloid is transferred in airtight crystallizing kettle,
Dynamic crystallization 72h at 145 DEG C, takes out product after cooling, through filtering, washing, be dried and roasting.
Obtaining comparative sample, test the XRD diffraction pattern of this comparative sample, this comparative sample is that MCM-49 divides
Son sieve, is set to 100% with the degree of crystallinity of this comparative sample, the relative crystallinity number of embodiment sample hereafter
According to this on the basis of this.
By sem test, the grain size of this comparative sample is about 5.0 μm.
This comparative sample uses 2，4，6-trimethylpyridine to be the absorption of probe molecule infrared analysis instrument, 20 DEG C of suctions
Attached and in the trimethylpyridine of 200 DEG C of removing physical absorptions, measuring its final adsorbance the most over a molecular sieve is
24μmol/g。
The silica alumina ratio of STEM-EDS this comparative sample of analysis and characterization, edge to center (O1, O2 and
O3) SiO2/Al2O3It is followed successively by 30.2,29.9,30.1.The wherein feature edges of crystal and pattern center
Line, the silicon oxide at distance feature edges air line distance 50nm with the molar ratio (30.1) of aluminium oxide is
The 1.00 of the molar ratio (30.2) of the silicon oxide of the pattern center position of molecular sieve crystal and aluminium oxide
Times.
Ammonium exchange, catalyst are prepared with comparative example 1, comparative catalyst's numbering DB-CAT-2.
Alkylation properties is evaluated with comparative example 1.
Alkylation result is shown in Fig. 4 and Fig. 5, wherein, is 220 DEG C in temperature, and the ethylene of this catalyst converts
Rate is 87.4%, and ethylbenzene selectivity is 96.2%.
Embodiment 1
Preparing molecular sieve: be dissolved in deionized water by sodium hydroxide, stirring is to being completely dissolved, by solid silicon
Glue and production piece NaA (SiO2/Al2O3=2.0), during molecular sieve adds above-mentioned solution, after stirring, add
Enter hexamethylene imine, continue to stir.Gained mixture colloid mol ratio is: 0.18NaOH:SiO2:
0.033Al2O3: 0.30HMI:15H2O.Then, gained mixture is transferred in airtight crystallizing kettle, 145 DEG C,
Dynamic crystallization 72h, takes out product after cooling, through filtering, washing, be dried and roasting.
Obtain sample, numbering AM-1.The XRD diffraction pattern of test sample AM-1, it is MCM-49 molecule
Sieve, relative crystallinity is 93%.
By sem test, its grain size is about 2.0 μm.
Using 2，4，6-trimethylpyridine is the absorption of probe molecule infrared analysis instrument, and 20 DEG C adsorb and in 200
The trimethylpyridine of DEG C removing physical absorption, measuring its final adsorbance the most over a molecular sieve is 32 μm ol/g.
The silica alumina ratio of STEM-EDS this sample of analysis and characterization, edge to center (O1, O2 and O3)
SiO2/Al2O3Order is 50.9,42.3,28.7.The wherein feature edges of crystal and the pattern line of centres,
Silicon oxide at distance feature edges air line distance 50nm is molecular sieve with the molar ratio (50.9) of aluminium oxide
1.77 times of the molar ratio (28.7) of the silicon oxide of the pattern center position of crystal and aluminium oxide.
Ammonium exchange, catalyst are prepared with comparative example 1, comparative catalyst's numbering CAT-1.
Alkylation properties is evaluated with comparative example 1.
Alkylation result is shown in Fig. 4 and Fig. 5.Wherein, being 220 DEG C in temperature, the ethylene of this catalyst converts
Rate is 98.9%, and ethylbenzene selectivity is 95.9%.
Comparative example 3
The process of MCM-49 molecular sieve is prepared: with comparative example 2, district according to the method for US 5236575
It is not that mixture colloid mol ratio is changed into: 0.18NaOH:SiO2: 0.04Al2O3: 0.30HMI:15H2O。
Obtaining comparative sample, test the XRD diffraction pattern of this comparative sample, this comparative sample is that MCM-49 divides
Son sieve, the relative crystallinity of this sample is 105%.
By sem test, its grain size is about 5.0 μm.
Comparative sample uses 2，4，6-trimethylpyridine to be the absorption of probe molecule infrared analysis instrument, 20 DEG C of absorption
And in the trimethylpyridine of 200 DEG C of removing physical absorptions, measuring its final adsorbance over a molecular sieve is 26
μmol/g。
The silica alumina ratio of STEM-EDS this comparative sample of analysis and characterization, edge to center (O1, O2 and
O3) SiO2/Al2O3Order is 23.2,23.5,23.6.The wherein feature edges of crystal and pattern center
Line, the silicon oxide at distance feature edges air line distance 50nm with the molar ratio (23.2) of aluminium oxide is
The 0.98 of the molar ratio (23.6) of the silicon oxide of the pattern center position of molecular sieve crystal and aluminium oxide.
Ammonium exchange, catalyst are prepared with comparative example 1, comparative catalyst's numbering DB-CAT-3.
Alkylation properties is evaluated with comparative example 1.
Alkylation result is shown in Fig. 4 and Fig. 5.Wherein, being 220 DEG C in temperature, the ethylene of this catalyst converts
Rate is 91.2%, and ethylbenzene selectivity is 96.0%.
Embodiment 2
Preparing molecular sieve: same as in Example 1, difference is that mixture colloid mol ratio is changed into:
0.18NaOH:SiO2: 0.04Al2O3: 0.30HMI:15H2O。
Take the numbering of different crystallization time (36h, 54h, 96h) be respectively AM-2-1, AM-2-2 and
The sample of AM-2-3 is analyzed.
The XRD diffraction pattern of test AM-2-1, AM-2-2 and AM-2-3, shows sample AM-2-1 and AM-2-2
The composite molecular screen coexisted for LTA structure and MWW structure, and AM-2-3 (Fig. 1) is MCM-49 molecular sieve,
Relative crystallinity is 103%.
The SEM spectrogram turning brilliant process is shown in that Fig. 2, sample AM-2-3 pass through sem test, and its crystal grain is big
Little about 2.0 μm.
Sample AM-2-3 uses 2，4，6-trimethylpyridine to be the absorption of probe molecule infrared analysis instrument, 20 DEG C of suctions
Attached and in the trimethylpyridine of 200 DEG C of removing physical absorptions, measuring its final adsorbance the most over a molecular sieve is
35μmol/g.The silica alumina ratio of STEM-EDS (Fig. 3) this sample of analysis and characterization, edge to center (O1,
O2 and O3) SiO2/Al2O3Order is 45.4,36.3,22.0.The wherein feature edges of crystal and pattern
The line of centres, the silicon oxide at distance feature edges air line distance 50nm and the molar ratio (45.4) of aluminium oxide
Be silicon oxide and the aluminium oxide of the pattern center position of molecular sieve crystal molar ratio (22.0) 2.06
Times.
Ammonium exchange, catalyst are prepared with comparative example 1, comparative catalyst's numbering CAT-2.
Alkylation properties is evaluated with comparative example 1.
Alkylation result is shown in Fig. 4 and Fig. 5.Wherein, being 220 DEG C in temperature, the ethylene of this catalyst converts
Rate is 99.9%, and ethylbenzene selectivity is 96.3%.
Comparative example 4
The process of MCM-49 molecular sieve is prepared: with comparative example 2, difference according to the method for US 52365755
It is that mixture colloid mol ratio is changed into: 0.18NaOH:SiO2: 0.05Al2O3: 0.30HMI:15H2O。
Obtaining comparative sample, test the XRD diffraction pattern of this comparative sample, this comparative sample is that MCM-49 divides
Son sieve, the relative crystallinity of this sample is 109%.
By sem test, its grain size is about 5.0 μm.
Comparative sample uses 2，4，6-trimethylpyridine to be the absorption of probe molecule infrared analysis instrument, 20 DEG C of absorption
And in the trimethylpyridine of 200 DEG C of removing physical absorptions, measuring its final adsorbance over a molecular sieve is 27
μmol/g。
The silica alumina ratio of STEM-EDS this comparative sample of analysis and characterization, edge to center (O1, O2 and
O3) SiO2/Al2O3It is 19.2,18.9,19.3.The wherein feature edges of crystal and the pattern line of centres,
Silicon oxide at distance feature edges air line distance 50nm is molecular sieve with the molar ratio (19.2) of aluminium oxide
1.00 times of the molar ratio (19.3) of the silicon oxide of the pattern center position of crystal and aluminium oxide.
Ammonium exchange, catalyst are prepared with comparative example 1, comparative catalyst's numbering DB-CAT-4.
Alkylation properties is evaluated with comparative example 1.
Alkylation result is shown in Fig. 4 and Fig. 5.Wherein, being 220 DEG C in temperature, the ethylene of this catalyst converts
Rate is 93.9%, and ethylbenzene selectivity is 94.9%.
Embodiment 3
This example demonstrates that synthetic method and molecular sieve that the present invention provides.
Same as in Example 1, difference is that mixture colloid mol ratio is changed into: 0.18NaOH:SiO2:
0.05Al2O3: 0.30HMI:15H2O。
Obtain sample, numbered AM-3.The XRD diffraction pattern of test sample AM-3, sample AM-3 is MCM-49
Molecular sieve, relative crystallinity is 101%.
By sem test, its grain size is about 2.0 μm.
Sample AM-3 uses 2，4，6-trimethylpyridine to be the absorption of probe molecule infrared analysis instrument, 20 DEG C of absorption
And in the trimethylpyridine of 200 DEG C of removing physical absorptions, measuring its final adsorbance over a molecular sieve is 38
μmol/g。
STEM-EDS analyzes its silica alumina ratio edge SiO to center (O1, O2 and O3)2/Al2O3
Order is 39.2,30.5,18.4.The wherein feature edges of crystal and the pattern line of centres, distance pattern limit
The molar ratio (39.2) of the silicon oxide at edge air line distance 50nm and aluminium oxide is the pattern of molecular sieve crystal
2.13 times of the molar ratio (18.4) of the silicon oxide of center position and aluminium oxide.
Ammonium exchange, catalyst are prepared with comparative example 1, comparative catalyst's numbering CAT-3.
Alkylation properties is evaluated with comparative example 1.
Alkylation result is shown in Fig. 4 and Fig. 5.Wherein, being 220 DEG C in temperature, the ethylene of this molecular sieve converts
Rate is 100%, and ethylbenzene selectivity is 96.6%.
Fig. 4 and Fig. 5 provides the ethylene that catalyst is showed in ethylene with benzene liquid phase alkylation reaction
Conversion ratio and ethylbenzene selectivity.It can be seen that the contrast catalysis that industrial agent is with beta molecular sieve as active component
Agent (DB-CAT-1), conversion of ethylene 100%, ethylbenzene selectivity best for 93.2%, hence it is evident that be less than
MWW structure molecular screen；DB-CAT-2, DB-CAT-3 and DB-CAT-4 that conventional hydrothermal synthetic method synthesizes
Catalyst, its crystal grain about 5 μm, conversion of ethylene is low, so the reference significance of its ethylbenzene selectivity is little.
It addition, along with the reduction of silica alumina ratio, the conversion of ethylene of its comparative example MWW structural molecule sieve catalyst increases,
Ethylbenzene selectivity declines simultaneously.The MWW structure molecular screen being turned brilliant preparation by LTA structure molecular sieve of the present invention
The conversion of ethylene of CAT-1, CAT-2, CAT-3 catalyst and the result of ethylbenzene selectivity are it can be seen that LTA
The conversion of ethylene of structure " topology reconstruction " method synthesis MWW structural molecule sieve catalyst increases, its second simultaneously
Benzene selective also increases, this rule breach traditional " seesaw " rule i.e. improve ethylene selectivity must
So bring the reduction of conversion of ethylbenzene.
Embodiment 4
This example demonstrates that catalyst, preparation method and alkylated reaction that the present invention provides.
With embodiment 2, difference is in catalyst, and molecular sieve butt is 85%.
Prepared by catalyst: the A2 molecular sieve (butt 80%) after being handed over by ammonium and carrier dry gel powder (butt
70%) mix homogeneously, then be slowly added to after nitric acid and appropriate amount of deionized water are mixed into homogeneous liquid, Bian Jia
Enter limit mix homogeneously.The mass ratio of gained mixture is: 85% molecular sieve butt: the dry glue powder butt of 15%:
100% deionized water (catalyst butt=molecular sieve butt+carrier butt, be defined as 100%).Then will be mixed
Compound is further mix homogeneously on banded extruder, and then is squeezed into bar, and drying, roasting obtain comparative catalyst,
Numbering CAT-4.
In alkylation result, when reaction temperature 220 DEG C, conversion of ethylene is 100%, and ethylbenzene selectivity is
96.4%.
Embodiment 5
This example demonstrates that catalyst, preparation method and alkylated reaction that the present invention provides.
With embodiment 2, difference is alkylation reaction condition.
Alkylation performance appreciation condition: alkylation performance appreciation condition: 8mL catalyst, pressure 3.5MPa,
Benzene and ethylene molar ratio 2, temperature 200～260 DEG C.
In alkylation result, when reaction temperature 220 DEG C, conversion of ethylene is 100%, ethylbenzene selectivity
It is 96.7%.
Claims (31)
1. a catalyst for alkylation reaction, it is characterised in that catalysis active component contains a kind of MWW structure
Molecular sieve, described MWW structure molecular screen, 2,4,6-trimethyls after its 20 DEG C absorption, 200 DEG C of desorptions
The adsorbance of pyridine is >=30 μm ol/g.
2. according to the catalyst of claim 1, wherein, described MWW structure molecular screen, its 20 DEG C suctions
The adsorbance of 2,4,6-trimethylpyridine after attached, 200 DEG C of desorptions is 30～50 μm ol/g.
3. according to the catalyst of claim 1, wherein, described MWW structure molecular screen, its 20 DEG C suctions
The adsorbance of 2,4,6-trimethylpyridine after attached, 200 DEG C of desorptions is 32～42 μm ol/g.
4. according to the catalyst of claim 1, wherein, described MWW structure molecular screen, its crystal with
STEM-EDS characterizes, along pattern center to the direction of feature edges, the molar ratio of silicon oxide and aluminium oxide by
Cumulative height.
5. according to the catalyst of one of claim 1-4, wherein, described MWW structure molecular screen is with crystalline substance
The feature edges of body and the pattern line of centres, at the silicon oxide of distance feature edges air line distance 50nm position
With the silicon oxide of the pattern center position that the molar ratio of aluminium oxide is molecular sieve crystal and aluminium oxide mole
At least 1.2 times of ratio.
6. according to the catalyst of claim 5, wherein, described MWW structure molecular screen is with the shape of crystal
Looks edge and the pattern line of centres, in silicon oxide and the oxidation of distance feature edges air line distance 50nm position
The molar ratio of aluminum is the silicon oxide molar ratio with aluminium oxide of the pattern center position of molecular sieve crystal
At least 1.5 times.
7. according to the catalyst of claim 6, wherein, described MWW structure molecular screen is with the shape of crystal
Looks edge and the pattern line of centres, in silicon oxide and the oxidation of distance feature edges air line distance 50nm position
The molar ratio of aluminum is the silicon oxide molar ratio with aluminium oxide of the pattern center position of molecular sieve crystal
At least 2 times.
8. according to the catalyst of one of claim 1-4, wherein, described MWW structure molecular screen, with
The feature edges of crystal and the pattern line of centres, oxidation in distance feature edges air line distance 50nm position
Silicon is 30～90 with the molar ratio of aluminium oxide.
9. according to the catalyst of claim 1, wherein, the MWW structural molecule containing 30～70 weight %
Sieve, the inorganic oxide carrier in terms of oxide of 1～40 weight %.
10. according to the catalyst of claim 9, wherein, described inorganic oxide carrier accounts for catalyst
20～30 weight %.
11. according to the catalyst of claim 9 or 10, and wherein, described inorganic oxide is selected from oxygen
One in SiClx, aluminium oxide, magnesium oxide, zirconium oxide and titanium oxide.
The preparation method of 12. 1 kinds of catalyst for alkylation reaction, it is characterised in that include that synthesizing MWW structure divides
Son sieve and molecular sieve and inorganic oxide carrier are blended, molding, be dried, roasting obtains the mistake of catalyst
Journey, wherein, described synthesis MWW structure molecular screen, its process be by LTA structure molecular sieve and silicon source,
Alkali source, template, deionized water formed mixture colloid crystallization under hydrothermal conditions and reclaim product, institute
The template stated is the template that can be used in synthesizing MWW structure molecular screen.
13. according to the preparation method of claim 12, and wherein, described LTA structure molecular sieve is A type
Molecular sieve.
14. according to the preparation method of claim 13, wherein, described A type molecular sieve selected from NaA,
KA or CaA.
15. according to the preparation method of claim 12, and wherein, described silicon source is selected from Ludox, solid
At least one in silica gel, white carbon and waterglass, described alkali source selected from Lithium hydrate, sodium hydroxide,
At least one in potassium hydroxide, rubidium hydroxide and Cesium hydrate..
16. according to the preparation method of claim 12, and wherein, described can be used in synthesizes MWW structure
The template of molecular sieve is selected from pentamethylene imines, hexamethylene imine, heptamethylene imines, 1,4-phenodiazine
Cycloheptane, cycloheptyl alkanamine, hexamethylene alkanamine, Aminocyclopentane, aniline, piperidines, piperazine, N, N, N-front three fund
Just alkyl ammonium hydroxide, Me3N+(CH2)5N+Me3(Me2CH)2HN+(CH2)5NH+(Me2CH)2In at least one,
Me represents methyl.
17. according to the preparation method of claim 12, and wherein, described template at least includes six methylenes
Base imines.
18. according to the preparation method of claim 17, and wherein, template is that mol ratio is at least 0.05:
1 hexamethylene imine and the mixture of aniline.
19. according to the preparation method of claim 12, wherein, described mixture colloid, mol ratio
For SiO2/Al2O3=15～200, OH-/SiO2=0.001～1, H2O/SiO2=5～100, R/SiO2=0.01～5,
R represents template.
20. according to the preparation method of claim 19, wherein, described mixture colloid, mol ratio
For SiO2/Al2O3=15～80, OH-/SiO2=0.01～0.5, H2O/SiO2=5～50, R/SiO2=0.05～0.5.
21. according to the preparation method of claim 20, wherein, described mixture colloid, mol ratio
For SiO2/Al2O3=20～40, OH-/SiO2=0.05～0.30, H2O/SiO2=10～30, R/SiO2=0.05～
0.35。
22. according to the preparation method of claim 12, and wherein, described MWW structure molecular screen is by LTA
Structure molecular screen directly turns crystalline substance and obtains.
23. according to the preparation method of claim 22, wherein, the described brilliant process that directly turns is at LTA
The MWW structure molecular screen with lamellar basic structure is gradually formed from outside to inside on the parent of structure molecular screen
Process.
24. according to the preparation method of claim 12, the grain size of described MWW structure molecular screen with
Described LTA structure molecular sieve grain size is close.
25. according to the preparation method of claim 12, wherein, described synthesis MWW structure molecular screen
During, LTA structure characteristic diffraction peak is gradually lowered, and MWW structure diffraction peak gradually strengthens simultaneously.
26. according to the preparation method of claim 12, wherein, also includes MWW structure molecular screen advanced
Row ammonium hands over the process reducing alkali metal content, Na in terms of alkali metal oxide2O is less than 0.05 weight %.
27. select according to the preparation method of claim 12, described inorganic oxide carrier, its precursor
One or more in SB powder, dry glue powder, Alumina gel and boehmite.
28. 1 kinds of ethylene and benzene liquid phase alkylation reaction method, it is characterised in that in claim 1-11
One of catalyst in the presence of make ethylene contact with benzene to carry out liquid phase alkylation reaction.
29. according to the ethylene of claim 28 and benzene liquid phase alkylation reaction, it is characterised in that reaction temperature
Being 180～280 DEG C, reaction pressure is 2.0～4.0MPa, benzene weight space velocity 1～5h-1, benzene rubs with ethylene
Your ratio is 2～12.
30. according to the ethylene of claim 29 and benzene liquid phase alkylation reaction, wherein, described reaction temperature
Degree is 200～260 DEG C, and reaction pressure is 3.0～3.5MPa, benzene weight space velocity 3～5h- 1。
The catalyst of one of 31. claim 1-11 is at aromatisation, cracking, isomerization and benzene and propylene
Application in alkylated reaction.
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| CN112705252A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Liquid-phase alkylation catalyst, preparation method and application thereof, and method for carrying out liquid-phase alkylation reaction on benzene and ethylene |
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