CN109384637A

CN109384637A - The method of benzene and preparing ethylbenzene by liquid phase alkylation of ethylene

Info

Publication number: CN109384637A
Application number: CN201710661832.1A
Authority: CN
Inventors: 陈俊文; 孙明毅; 王永睿; 余少兵; 慕旭宏; 舒兴田
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2017-08-04
Filing date: 2017-08-04
Publication date: 2019-02-26
Anticipated expiration: 2037-08-04
Also published as: CN109384637B

Abstract

The present invention relates to the method for benzene and preparing ethylbenzene by liquid phase alkylation of ethylene, the process employs the catalyst containing a kind of novel structure molecular sieve, with higher reactivity and more preferably ethylbenzene selectivity.Recruit's sifter device therein has schematic chemical composition representated by formula " first the second oxide of oxide " or formula " first oxide the second oxide organic formwork agent water ", wherein the molar ratio of first oxide and second oxide is from 5 to ∞；The molar ratio of water and first oxide is from 5 to 50；The molar ratio of organic formwork agent and first oxide is from 0.02 to 0.5, and the molecular sieve has unique X-ray diffraction pattern.

Description

The method of benzene and preparing ethylbenzene by liquid phase alkylation of ethylene

Technical field

The present invention relates to the methods of benzene and preparing ethylbenzene by liquid phase alkylation of ethylene, and in particular to is urged using a kind of novel molecular sieve Change the method for benzene and preparing ethylbenzene by liquid phase alkylation of ethylene.

Background technique

Ethylbenzene is important Organic Chemicals, mainly for the production of styrene monomer, and then synthesize various engineering plastics, The high molecular materials such as synthetic resin, synthetic rubber.Industrial ethylbenzene is mainly using benzene and ethylene as raw material, under the action of catalyst, It is made through alkylated reaction.The progress of ethylbenzene synthetic technology has very important significance, and key therein is exactly to develop height The alkylation catalyst of reactivity and ethylbenzene selectivity.

Ethylbenzene alkylation process mainly has alchlor liquid catalytic, molecular sieve gas-phase catalysis and molecular sieve liquid phase to urge Change method.Wherein, before alchlor liquid catalytic starts from the seventies, due to very strong corrosivity, plant maintenance and product are given Separation brings big inconvenience, now substantially without using again.Therefore, the solid acid catalyst of development environment close friend seems especially Urgently.

1976, Mobil and Badger company developed ZSM-5 molecular sieve catalyst cooperatively and has synthesized second for vapor phase method Benzene, and industrialization was realized in 1980.Mobil/Badger technique is the representative of vapor phase method, and feature is that ethylbenzene yield reaches 99.5%；And it is corrosion-free, pollution-free, low energy consumption；Ethylene air speed is high, reaches 0.4h^-1~6h^-1；Catalyst entire life be 2 years with On, and plant investment ratio AlCl₃Method is low.The disadvantage is that reaction temperature height (generally 350 DEG C~450 DEG C), to equipment and operated Journey it is more demanding, energy consumption is larger, and byproduct of reaction is more, and ethylbenzene selectivity is not high, the easy coking and deactivation of used catalyst；In addition, There is the impurity dimethylbenzene of 800 μ g/g or so (xylene content in ethylbenzene industrially to be required to be less than 100 μ g/ in reaction product ethylbenzene G), there is biggish adverse effect to the quality of subsequent product polystyrene in this way.

Liquid phase method makes benzene feedstock be in liquid phase by elevated pressures, and in benzene alkylation with ethylene technique, ethylene is with liquid phase Form is present in reactor, belongs to liquid-solid two phase reaction type, has highly developed technology both at home and abroad.External liquid phase method Ethylbenzene manufactured from ethylene technique mainly has the EB One technique of Lummus/UOP, the EB Max technique of Mobil/Badger and domestic stone The oily graduate circulating fixed bed reactor new process of chemical engineering science.150 DEG C~300 DEG C of reaction temperature, reaction pressure 3.5MPa ~4MPa, benzene alkene are than 2~15, weight ethylene air speed 0.1h^-1~4.4h^-1.Reaction temperature is easily controllable, catalyst stability is good, Service life is long, and the regeneration period, entire life was up to 10 years or more up to 5 years.Because reaction temperature is low, equipment can be all using carbon steel, capital cost With relatively low.The selectivity for generating ethylbenzene is high, and the content of dimethylbenzene can be reduced to 10ppm~50ppm in product ethylbenzene, completely The industrial requirements of production food polystyrene can be met.

It is mainly at present Y molecular sieve, beta-molecular sieve and MCM-22 molecule to the active component of liquid phase legal system ethylbenzene catalyst Sieve.Wherein beta-molecular sieve catalytic activity highest, ethylbenzene selectivity reach as high as 93% or so；The selectivity of MCM-22 molecular sieve It is relatively more preferable；And the selectivity of Y type molecular sieve is then relatively worse.

Summary of the invention

The present inventor passes through diligent research on the basis of existing technology, it was found that a kind of novel molecular sieve is gone forward side by side One step has found that the molecular sieve is alkylated the good behaviour in reaction in catalysis benzene and ethylene, has thus completed the present invention.

Specifically, the present invention relates to the contents of following aspect:

1. a kind of method of benzene and preparing ethylbenzene by liquid phase alkylation of ethylene, including depositing in alkylation reaction condition and catalyst Under, make ethylene and benzene haptoreaction, which is characterized in that contain a kind of molecular sieve in the catalyst, which has formula Representated by " first the second oxide of oxide " or formula " first oxide the second oxide organic formwork agent water " Schematic chemical composition, wherein the molar ratio of first oxide and second oxide be from 5 to ∞ (preferably from 30 to 150, more preferably from 40 to 120)；First oxide be selected from silica, germanium dioxide, stannic oxide, titanium dioxide and At least one of zirconium dioxide (the preferably combination of silica or silica and germanium dioxide), second oxide Selected from least one of aluminium oxide, boron oxide, iron oxide, gallium oxide, rare earth oxide, indium oxide and vanadium oxide (preferably oxygen Change aluminium)；The molar ratio of water and first oxide is from 5 to 50 (preferably from 5 to 15)；The organic formwork agent and described the The molar ratio of monoxide is from 0.02 to 0.5 (preferably from 0.05 to 0.5, from 0.15 to 0.5 or from 0.3 to 0.5), and With X-ray diffraction pattern substantially as shown in the table,

2. according to the method for any one of aforementioned alkylation ethylbenzene processed, wherein the X-ray diffraction pattern further includes basic Upper X-ray diffraction peak as shown in the table,

3. according to the method for any one of aforementioned alkylation ethylbenzene processed, wherein the X-ray diffraction pattern further includes basic Upper X-ray diffraction peak as shown in the table,

4. the ethylene raw used is pure ethylene, containing ethylene according to the method for any one of aforementioned alkylation ethylbenzene processed Refinery catalytic cracking dry gas (optimal ethylene volume fraction is 10%~60%) and the plant catalytic containing ethylene crack dry gas (preferably One or more of volume of ethylene score is 10%~60%).

5. the catalyst is by binder (aluminium oxide and/or oxygen according to the method for any one of aforementioned alkylation ethylbenzene processed SiClx) and molecular sieve composition ((preferably in terms of the quality of catalyst, the mass fraction of the molecular sieve is 10%~ 95%)).

6. the catalyst is made by following methods: will be described according to the method for any one of aforementioned alkylation ethylbenzene processed Molecular screen primary powder and silicon-containing compound and/or aluminum contained compound, nitric acid and deionized water kneading and compacting, it is dry after in air in 450 DEG C~550 DEG C burning-off templates, then swap in 80 DEG C~90 DEG C of ammonium salt aqueous solution, finally 500 DEG C~ 600 DEG C roasting deamination 1 hour~5 hours to get catalyst；Wherein, the silicon-containing compound is selected from silica solution, positive silicic acid first One of ester and ethyl orthosilicate are a variety of, and the aluminum contained compound is selected from boehmite, SB powder, Aluminum sol and isopropyl One of aluminium alcoholates is a variety of；The ammonium salt is selected from one of ammonium nitrate, ammonium chloride and ammonium sulfate or a variety of.

7. according to the method for claim 6, which is characterized in that use the mixing of silicon-containing compound and aluminum contained compound Object, molar ratio of the two in terms of silica and aluminium oxide are 1:1 to 1:2.

8. according to the method for claim 1, which is characterized in that this method is in fixed bubbling bed reactor (preferably second Alkene and benzene are fed from reactor lower part, and reaction product is drawn from reactor top), fixed trickle bed reactor or slurry bed system it is anti- It answers in device and carries out；And/or

The alkylation reaction condition are as follows: 150 DEG C~280 DEG C of reaction temperature, reaction pressure 1MPa~4MPa, benzene and second The molar ratio of alkene is 1:1~15:1, and the weight (hourly) space velocity (WHSV) in terms of ethylene is 0.1h^-1~0.8h^-1(preferred alkylation conditions are as follows: anti- Answer 160 DEG C~250 DEG C of temperature, reaction pressure 1.2MPa~3.6MPa, the molar ratio of benzene and ethylene is 3:1~12:1, with ethylene The weight (hourly) space velocity (WHSV) of meter is 0.1h^-1~0.5h^-1)。

9. a kind of method of benzene and preparing ethylbenzene by liquid phase alkylation of ethylene, including depositing in alkylation reaction condition and catalyst Under, make ethylene and benzene haptoreaction, which is characterized in that the catalyst contains a kind of molecular sieve, and the molecular sieve is by with lower section Method is made: make the first oxide source, the second oxide source, optional alkali source, organic formwork agent and water contact under crystallization condition, To obtain the molecular sieve；Wherein, optionally, include the steps that the molecular sieve for roasting the acquisition；The organic formwork agent Comprising compound representated by lower formula (I),

Wherein, group R₁And R₂It is same or different to each other, is each independently selected from C_3-12Linear chain or branched chain alkylidene and C_3-12 Linear chain or branched chain oxaalkylene, is preferably each independently selected from C_3-12Straight-chain alkyl-sub and C_3-12Straight chain oxaalkylene, or One is selected from C preferably wherein_3-12Linear chain or branched chain alkylidene, another is selected from C_3-12Linear chain or branched chain alkylidene and C_3-12Straight chain Or branch oxaalkylene, more preferably one of them is selected from C_3-12Straight-chain alkyl-sub, another is selected from C_3-12Straight-chain alkyl-sub and C_3-12Straight chain oxaalkylene, particularly preferably one of them is selected from C_3-12Straight-chain alkyl-sub, another is selected from C_4-6Straight-chain alkyl-sub And C_4-6Straight chain oxaalkylene (preferably C_4-6One oxaalkylene of straight chain, more preferably-(CH₂)_m-O-(CH₂)_m, wherein each numerical value M is same or different to each other, and is independently represented each other 2 or 3)；Multiple group R are same or different to each other, and are each independently selected from C_1-4 Linear or branched alkyl group is preferably each independently selected from methyl and ethyl, is more preferably methyl；X is OH.

10. according to the method for any one of aforementioned alkylation ethylbenzene processed, wherein first oxide source is selected from titanium dioxide At least one of silicon source, titanium dioxide ge source, titanium dioxide tin source, titania source and zirconium dioxide source, preferably silica source Or the combination of silica source and titanium dioxide ge source, second oxide source are selected from alumina source, oxidation boron source, iron oxide At least one of source, gallium oxide source, rare earth oxide source, indium oxide source and vanadium oxide source, preferably alumina source.

11. according to the method for any one of aforementioned alkylation ethylbenzene processed, wherein the crystallization condition includes: that crystallization temperature is From 80 DEG C to 120 DEG C, preferably from 120 DEG C to 170 DEG C or from 120 DEG C to 200 DEG C, crystallization time is at least 1 day, preferably at least 2 days, preferably from 3 days to 8 day, from 5 days to 8 day or from 4 days to 6 day, and the roasting condition include: maturing temperature be from 300 DEG C to 750 DEG C, preferably from 400 DEG C to 600 DEG C, calcining time is from 1 hour to 10 hour, preferably from 3 hours to 6 hour.

12. according to the method for any one of aforementioned alkylation ethylbenzene processed, wherein first oxide source is (with described first Oxide be meter) with second oxide source (by second oxide be in terms of) molar ratio be from 5 to ∞, preferably from 25 To 95, more preferably from 30 to 70；The molar ratio of water and first oxide source (in terms of being by first oxide) be from 5 to 50, preferably from 5 to 15；The molar ratio of the organic formwork agent and first oxide source (by first oxide in terms of) It is from 0.02 to 0.5, preferably from 0.05 to 0.5, from 0.15 to 0.5 or from 0.3 to 0.5；The alkali source is (with OH^-For meter) with The molar ratio of first oxide source (in terms of being by first oxide) for from 0 to 1, preferably from 0.04 to 1, from 0.1 to 1, from 0.2 to 1, from 0.3 to 0.7 or from 0.45 to 0.7.

13. according to the method for any one of aforementioned alkylation ethylbenzene processed, used in ethylene raw be pure ethylene, contain second The refinery catalytic cracking dry gas (optimal ethylene volume fraction is 10%~60%) of alkene and the plant catalytic containing ethylene crack dry gas One or more of (optimal ethylene volume fraction is 10%~60%).

14. according to the method for any one of aforementioned alkylation ethylbenzene processed, wherein the catalyst is by binder (aluminium oxide And/or silica) and molecular sieve composition ((preferably in terms of the quality of catalyst, the mass fraction of the molecular sieve is 10% ~95%)).

15. according to the method for any one of aforementioned alkylation ethylbenzene processed, wherein the catalyst is made by following methods: will The molecular screen primary powder and silicon-containing compound and/or aluminum contained compound, nitric acid and deionized water kneading and compacting, in air after drying In in 450 DEG C~550 DEG C burning-off templates, then swapped in 80 DEG C~90 DEG C of ammonium salt aqueous solution, finally at 500 DEG C ~600 DEG C roasting deamination 1 hour~5 hours to get catalyst；Wherein, the silicon-containing compound is selected from silica solution, positive silicic acid One of methyl esters and ethyl orthosilicate are a variety of, and the aluminum contained compound is selected from boehmite, SB powder, Aluminum sol and different One of aluminium propoxide is a variety of；The ammonium salt is selected from one of ammonium nitrate, ammonium chloride and ammonium sulfate or a variety of.

16. according to the method for any one of aforementioned alkylation ethylbenzene processed, wherein using silicon-containing compound and aluminum contained compound Mixture, molar ratio of the two in terms of silica and aluminium oxide is 1:1 to 1:2.

17. wherein the method for the alkylation ethylbenzene is in fixation according to the method for any one of aforementioned alkylation ethylbenzene processed Bubbling bed reactor (optimal ethylene and benzene are fed from reactor lower part, and reaction product is drawn from reactor top), fixed drop It is carried out in fluidized bed reactor or paste state bed reactor；And/or

Present invention employs a kind of recruit sieves, have the following characteristics that the skeleton pore structure of (1) super big hole, this point It at least can hold data from its higher hole to be reflected；(2) good heat/hydrothermal stability, and there is bigger Kong Rong； As a result, molecular sieve of the invention can adsorb more/bigger molecules, to show excellent absorption/catalytic performance； (3) there is unique X-ray diffraction spectrogram (XRD), while there is unique Si/Al₂Than this is that the prior art did not manufactured Molecular sieve；(4) there is stronger acidity, the quantity in the especially acid site L is more.This is point that the prior art had not manufactured Son sieve；As a result, molecular sieve of the invention especially has more excellent performance in acid catalyzed reaction；(5) this point The manufacturing method of son sieve, has used a kind of organic formwork agent of specified chemical structure, thus shows that process conditions are simple, product The characteristics of molecular sieve is readily synthesized.On the basis of aforementioned discovery, present inventors have further discovered that, the molecular sieve especially suitable for Catalysis benzene, which is alkylated with ethylene in liquid phase, to react to produce ethylbenzene, with higher reactivity and more preferably ethylbenzene choosing Selecting property.

Detailed description of the invention

Fig. 1 is the scanning electron microscope (SEM) photograph for the molecular sieve that embodiment 5 manufactures.

Fig. 2 is the XRD diagram for the molecular sieve that embodiment 5 manufactures.

Fig. 3 is the scanning electron microscope (SEM) photograph for the molecular sieve that embodiment 6 manufactures.

Fig. 4 is the XRD diagram for the molecular sieve that embodiment 6 manufactures.

Fig. 5 is the scanning electron microscope (SEM) photograph for the molecular sieve that embodiment 7 manufactures.

Fig. 6 is the XRD diagram for the molecular sieve that embodiment 7 manufactures.

Fig. 7 is the scanning electron microscope (SEM) photograph for the molecular sieve that embodiment 8 manufactures.

Fig. 8 is the XRD diagram for the molecular sieve that embodiment 8 manufactures.

Fig. 9 is the scanning electron microscope (SEM) photograph for the molecular sieve that embodiment 9 manufactures.

Specific embodiment

Detailed description of the preferred embodiments below, it should be noted however that protection of the invention Range is not limited to these specific embodiments, but is determined by claims.

All publications, patent application, patent and the other bibliography that this specification is mentioned all draw in this for reference. Unless otherwise defined, all technical and scientific terms used herein all has what those skilled in the art routinely understood to contain Justice.In case of conflict, it is subject to the definition of this specification.

When this specification with prefix " well known to those skilled in the art ", " prior art " or its export material similar to term Whens material, substance, method, step, device or component etc., object derived from the prefix is covered this field when the application proposes and is routinely made Those of with, but also include also being of little use at present, it will but become art-recognized for suitable for those of similar purpose.

In the context of the present specification, symbol "/" is generally understood as "and/or", for example states " more/bigger " " more and/or bigger " is meant that, unless the understanding does not meet the conventional understanding of those skilled in the art.

In the context of the present specification, so-called organic formwork agent, in the art otherwise referred to as structure directing agent or Organic directing agent.

In the context of the present specification, as C_1-4Linear or branched alkyl group, for example, can enumerate methyl, ethyl or Propyl etc..

In the context of the present invention, term " linear chain or branched chain oxaalkylene " refers to linear chain or branched chain alkylidene Carbon-chain structure is by the bivalent group that one or more (such as 1 to 3,1 to 2 or 1) miscellaneous group-O- is interrupted and is obtained. Preferably from structural stability angle, when there are multiple, not Direct Bonding between miscellaneous group described in any two.It is aobvious Right, so-called interruption refers to that the miscellaneous group is not at the linear chain or branched chain alkylidene or the linear chain or branched chain oxygen Any one end of miscellaneous alkylidene.For concrete example, C₄Straight-chain alkyl-sub (- CH₂-CH₂-CH₂-CH₂) by a miscellaneous base Group-O- can obtain-CH after interrupting₂-O-CH₂-CH₂-CH₂Or-CH₂-CH₂-O-CH₂-CH₂Wait C₄One oxa- alkylene of straight chain Base can obtain-CH after being interrupted by two miscellaneous group-O-₂-O-CH₂-O-CH₂-CH₂Or-CH₂-O-CH₂-CH₂-O-CH₂Etc. C₄Straight chain dioxy miscellaneous alkylidene can obtain-CH after being interrupted by three miscellaneous group-O-₂-O-CH₂-O-CH₂-O-CH₂Wait C₄Straight chain Trioxa alkylidene.Alternatively, for concrete example, C₄Branched alkylidene (- CH₂(CH₃)-CH₂-CH₂) by a miscellaneous group-O- - CH can be obtained after interruption₂(CH₃)-O-CH₂-CH₂-、-CH₂(CH₃)-CH₂-O-CH₂Or-CH₂(-O-CH₃)-CH₂-CH₂- Equal C₄One oxaalkylene of branch can obtain-CH after being interrupted by two miscellaneous group-O-₂(CH₃)-O-CH₂-O-CH₂-、-CH₂(- O-CH₃)-O-CH₂-CH₂Or-CH₂(-O-CH₃)-CH₂-O-CH₂Wait C₄Branch dioxy miscellaneous alkylidene, by three miscellaneous group-O- - CH can be obtained after interruption₂(-O-CH₃)-O-CH₂-O-CH₂Wait C₄Branch trioxa alkylidene.

In the context of the present specification, so-called total specific surface area, refers to the gross area possessed by unit mass molecular sieve, Including internal surface area and external surface area.Pore-free material only has external surface area, such as portland cement, some clay mineral powders Deng, and porous material has external surface area and internal surface area, such as asbestos fibre, diatomite and molecular sieve.

In the context of the present specification, so-called Kong Rong, also known as pore volume refer to hole possessed by unit mass molecular sieve Volume.Moreover, so-called micropore volume, refers to whole micropore possessed by unit mass molecular sieve (that is, channel diameter is less than 2nm's Hole) volume.

In the context of the present specification, in the XRD data of molecular sieve, w, m, s, vs represent diffraction peak intensity, and w is It is weak, m be it is medium, s be it is strong, vs for very by force, what this was well known to those skilled in the art.In general, w is less than 20；M is 20-40；S is 40-70；Vs is greater than 70.

In the case where not clearly indicating, all percentages, number, the ratio etc. being previously mentioned in this specification be all with On the basis of weight, unless not meeting the conventional understanding of those skilled in the art when using weight as benchmark.

In the context of the present specification, any two of the invention or many aspects can any combination, therefrom The technical solution of formation belongs to a part of this specification original disclosure, while also falling into protection scope of the present invention.

The present invention introduces the full content of Chinese patent application CN201710282848.1 in a manner of citation herein, as The full text of this application is directly recorded the same by this specification.The content of related previous molecular sieve and its manufacturing method, except below Except record, more detailed part can be found in Chinese patent application CN201710282848.1.

According to an aspect of the present invention, it is related to a kind of molecular sieve, wherein the molecular sieve has formula " the first oxide Schematic chemical composition representated by second oxide ".It is known that in molecular sieve sometimes (especially after freshly synthesized) Containing a certain amount of moisture, but it is considered herein that not it is necessary to the moisture amount carry out it is specific, because of the presence of the moisture Whether can't substantially influence the XRD spectra of the molecular sieve.In consideration of it, what the schematic chemical composition actually represented is this The anhydrous chemical composition of molecular sieve.It is also clear that the schematic chemical composition represent be the molecular sieve skeletonizing Learn composition.

According to an aspect of the present invention, after freshly synthesized, the molecular sieve is generally also possible to further contain in the composition Those of have organic formwork agent and water etc., for example be filled in its duct.Therefore, the molecular sieve is also possible to sometimes with formula Schematic chemical composition representated by " first oxide the second oxide organic formwork agent water ".Here, passing through roasting Point with schematic chemical composition representated by formula " first oxide the second oxide organic formwork agent water " Son sieve, to remove any organic formwork agent and water etc. present in its duct, so that it may obtain described with formula " the first oxidation The molecular sieve of schematic chemical composition representated by the second oxide of object ".In addition, the roasting can be according to this field routine Known any mode carries out, for example maturing temperature is generally from 300 DEG C to 750 DEG C, preferably from 400 DEG C to 600 DEG C, and roasts Time generally from 1 hour to 10 hour, preferably from 3 hours to 6 hour.In addition, the roasting it is general under an oxygen-containing atmosphere into Row, such as under air or oxygen atmosphere.

According to an aspect of the present invention, in schematic chemical composition above-mentioned, first oxide is usually four Valence oxide, for example can enumerate in silica, germanium dioxide, stannic oxide, titanium dioxide and zirconium dioxide extremely Few one kind, preferably silica (SiO₂) or silica and germanium dioxide combination.These first oxides can be independent Using one kind, or it is applied in combination with arbitrary ratio a variety of.When being applied in combination a variety of, between any two kind of first oxide Molar ratio be such as from 20:200 to 35:100.As the example being applied in combination, for example it can enumerate and be applied in combination two Silica and germanium dioxide, at this time the molar ratio between the silica and the germanium dioxide be such as from 20:200 to 35:100.

According to an aspect of the present invention, in schematic chemical composition above-mentioned, second oxide is usually three Valence oxide, for example can enumerate selected from aluminium oxide, boron oxide, iron oxide, gallium oxide, rare earth oxide, indium oxide and oxidation At least one of vanadium, preferably aluminium oxide (Al₂O₃).These second oxides can be used alone, or arbitrarily to compare Example is applied in combination a variety of.When being applied in combination a variety of, the molar ratio between any two kind of second oxide is such as from 30:200 To 60:150.

According to an aspect of the present invention, in schematic chemical composition above-mentioned, as the organic formwork agent, such as Any organic formwork agent used when manufacturing the molecular sieve can be enumerated, can especially enumerate present embodiment in manufacture point The organic formwork agent (detailed description that see below) used when son sieve.These organic formwork agents can be used alone, or Person is applied in combination a variety of with arbitrary ratio.Specifically, specifically can such as enumerate following formula as the organic formwork agent (I) compound representated by.

According to an aspect of the present invention, in formula (I), group R₁And R₂It is same or different to each other, is each independently selected from C_3-12Linear chain or branched chain alkylidene and C_3-12Linear chain or branched chain oxaalkylene, multiple group R are same or different to each other, respectively solely On the spot it is selected from C_1-4Linear or branched alkyl group, and X is OH.

According to an aspect of the present invention, in schematic chemical composition above-mentioned, first oxide and described the Molar ratio (such as the SiO of dioxide₂With Al₂O₃Molar ratio) generally from 5 to ∞, preferably from 25 to 95, more preferably from 30 To 70.Here, indicating to be not present second oxide or second oxide described when the molar ratio is ∞ Content in schematic chemical composition can be ignored.The present inventor has found that the prior art is not after conscientiously investigation Once the especially described molar ratio (such as SiO was produced₂With Al₂O₃Molar ratio) be from 25 to 95 (more particularly from 30 to 70) The molecular sieve.

According to an aspect of the present invention, in schematic chemical composition above-mentioned, water rubs with first oxide You are than generally from 5 to 50, preferably from 5 to 15.

According to an aspect of the present invention, in schematic chemical composition above-mentioned, the organic formwork agent and described the The molar ratio of monoxide is generally from 0.02 to 0.5, preferably from 0.05 to 0.5, from 0.15 to 0.5 or from 0.3 to 0.5.

According to an aspect of the present invention, starting material used in its manufacturing method is depended on, the molecular sieve is at it It (is generally filled in its duct) and is also possible to sometimes further containing metals such as alkali metal and/or alkaline earth metal cations in composition Cation is used as constituent.As the content of the metal cation at this time, such as the metal cation and described first The mass ratio of oxide is generally from 0 to 0.02, preferably from 0.0002 to 0.006, and but is not limited thereto.

According to an aspect of the present invention, the molecular sieve has X-ray diffraction pattern substantially as shown in the table.

According to an aspect of the present invention, in the X-ray diffraction pattern of the molecular sieve, base is preferably still further comprised X-ray diffraction peak as shown in the table in sheet.

According to an aspect of the present invention, when being observed using scanning electron microscope (SEM), the molecular sieve one As have columnar crystal morphology.Here, so-called crystal morphology, refers to the field of view in the scanning electron microscope In, individual molecule sieves (entirety) outer shape that crystal is presented.In addition, as the column, preferably prism-shaped, especially six Prism-shaped.Here, the prism refers to fin column, and generally referred to as right prism and regular polygon prism (such as positive six Prism).It is important to note that since the crystal of molecular sieve may be subjected to the interference of various factors during the growth process, Therefore its actual crystal morphology may compared with (real) right prism or (real) regular polygon prism on geometric meaning There are a degree of deviations, for example deviate 30%, 20% or 5%, cause to obtain oblique prism or irregular polygon (very To being curl polygon) prism, but the present invention is not intended to the specific, concrete departure degree.Moreover, any greater or lesser Deviate also all without departing from protection scope of the present invention.

According to an aspect of the present invention, when being observed using scanning electron microscope (SEM), the molecular sieve The effective diameter of (single crystal) is generally from 100nm to 1000nm, preferably from 300nm to 700nm.Here, so-called effectively straight Diameter refers on the cross section of the molecular sieve (single crystal), arbitrarily selects two along the profile (edge) of the cross section It is a, the linear distance between the two points is measured, using maximum linear distance as effective diameter.If the molecule The profile of the cross section of sieve is rendered as polygon such as hexagon, and the effective diameter is generally referred to as distance on the polygon Linear distance (diagonal distance) between two farthest vertex.Briefly, the effective diameter is approximately equivalent to institute State the external diameter of a circle of polygon representated by the profile of cross section.

According to an aspect of the present invention, when being observed using scanning electron microscope (SEM), the molecular sieve The height of (single crystal) is generally from 100nm to 1000nm, preferably from 150nm to 700nm.Here, so-called height, refers to Linear distance in the single crystal (column crystal) of the molecular sieve, between two end face centers of the column.Usual In the case of, what two end faces of the molecular sieve column were essentially parallel to each other, the linear distance is as described two at this time Vertical range between end face, but the present invention is not limited thereto.

According to an aspect of the present invention, when being observed using scanning electron microscope (SEM), the molecular sieve The ratio of height to diameter of (single crystal) is generally from 1/3 to 8, preferably from 1.5 to 5 or from 2 to 5.Here, so-called ratio of height to diameter, refers to It is the ratio of the height with the effective diameter.

According to an aspect of the present invention, total specific surface area of the molecular sieve is generally from 400m²/ g to 600m²/ g, it is excellent It selects from 450m²/ g to 580m²/g.Here, total specific surface area is calculated and is obtained by BET model by liquid nitrogen adsorption method 's.

According to an aspect of the present invention, the Kong Rong (micropore volume) of the molecular sieve is generally from 0.3ml/g to 0.5ml/ G, preferably from 0.30ml/g to 0.40ml/g.Molecular sieve of the invention has very high micropore volume, this shows that it belongs to super large Porous molecular sieve.Here, the Kong Rong is liquid nitrogen adsorption method, acquisition is calculated by Horvath-Kawazoe model.

According to an aspect of the present invention, the molecular sieve can be manufactured by following manufacturing method.Here, institute State manufacturing method include make under crystallization condition the first oxide source, the second oxide source, optional alkali source, organic formwork agent and Water contact, the step of to obtain molecular sieve (hereinafter referred to as contact procedure).

According to an aspect of the present invention, in the manufacturing method of the molecular sieve, the contact procedure can be according to this The conventionally known any mode in field carries out, for example can enumerate and make first oxide source, second oxide source, institute Optional alkali source, the organic formwork agent and water mixing are stated, and the mixture is made to carry out the side of crystallization under the crystallization condition Method.

According to an aspect of the present invention, in the contact procedure, the organic formwork agent includes at least lower formula (I) institute The compound of representative.Here, compound representated by the formula (I) can be used alone, or with arbitrary ratio group It closes using a variety of.

According to an aspect of the present invention, in the formula (I), group R₁And R₂It is same or different to each other, each independently Selected from C_3-12Linear chain or branched chain alkylidene and C_3-12Linear chain or branched chain oxaalkylene.

A kind of variant embodiment according to the present invention, in the formula (I), the group R₁And R₂It is mutually the same or not Together, one of them is selected from C_3-12Linear chain or branched chain alkylidene, another is selected from C_3-12Linear chain or branched chain alkylidene and C_3-12Straight chain or Branch oxaalkylene.

A kind of variant embodiment according to the present invention, in the formula (I), the group R₁And R₂It is mutually the same or not Together, one of them is selected from C_3-12Straight-chain alkyl-sub, another is selected from C_4-6Straight-chain alkyl-sub and C_4-6Straight chain oxaalkylene.

A kind of variant embodiment according to the present invention, in the formula (I), the group R₁And R₂It is mutually the same or not Together, it is each independently selected from C_3-12Linear chain or branched chain alkylidene.

A kind of variant embodiment according to the present invention, in the formula (I), the group R₁And R₂It is mutually the same or not Together, one of them is selected from C_3-12Straight-chain alkyl-sub, another is selected from C_4-6Straight-chain alkyl-sub.

A kind of variant embodiment according to the present invention, in the formula (I), the group R₁And R₂It is different from each other, wherein One is selected from C_3-12Linear chain or branched chain alkylidene, another is selected from C_3-12Linear chain or branched chain oxaalkylene.

According to an aspect of the present invention, as the C_3-12Linear chain or branched chain alkylidene, for example C can be enumerated_3-12Straight chain Alkylidene, specifically can such as enumerate sub- n-propyl, isopropylidene, sub- normal-butyl, isobutylidene, sub- tert-butyl, sub- n-pentyl, (or its is different for isoamylidene, sub- neopentyl, sub- n-hexyl, sub- isohesyl, sub- n-octyl, sub- iso-octyl, sub- new octyl, nonylene Structure body), decylene (or its isomers), alkylene undecyl (or its isomers) or sub-dodecyl (or its isomers), it is excellent Select sub- n-propyl, sub- normal-butyl, sub- n-pentyl, sub- n-hexyl, sub- n-heptyl, sub- n-octyl, sub- n-nonyl, sub- positive decyl, Asia N-undecane base or sub- dodecyl.In addition, as the C_3-12Straight-chain alkyl-sub more specifically can such as enumerate C_4-6 Straight-chain alkyl-sub can especially enumerate sub- normal-butyl, sub- n-pentyl or sub- n-hexyl.

According to an aspect of the present invention, as the C_3-12Linear chain or branched chain oxaalkylene, for example C can be enumerated_3-12 Straight chain oxaalkylene specifically can such as enumerate-(CH₂)₂-O-(CH₂)-、-(CH₂)₂-O-(CH₂)₂-、-(CH₂)-O- (CH₂)₃-、-(CH₂)₂-O-(CH₂)₃-、-(CH₂)-O- propylidene-,-(CH₂)-O-(CH₂)₄-、-(CH₂)-O-(CH₂)₂-O- (CH₂)-、-(CH₂)-O-(CH₂)₂-O-(CH₂)₂-、-(CH₂) Asia-O- tert-butyl-,-(CH₂)₂-O-(CH₂)₄-、、-(CH₂)₃-O- (CH₂)₃-、-(CH₂) Asia-O- neopentyl-,-(CH₂)₂-O-(CH₂)₆-、-(CH₂)₂-O-(CH₂)₇-、-(CH₂)-O-(CH₂)₈-、- (CH₂) Asia-O- iso-octyl-,-(CH₂)-O-(CH₂)₁₀-、-(CH₂)₂- O- decylene or its isomers-,-(CH₂)-O- (CH₂)₆-、-(CH₂)-O-(CH₂)₇-、-(CH₂)-O-(CH₂)₈-、-(CH₂)-O-(CH₂)₁₁-、-(CH₂)-O-(CH₂)₂-O- (CH₂)-、-(CH₂)₂-O-(CH₂)₂-O-(CH₂)₂-、-(CH₂)₂-O-(CH₂)₄-O-(CH₂)₂-、-(CH₂)₂-O-(CH₂)₆-O- (CH₂)₂Or-(CH₂)₂-O-(CH₂)₈-O-(CH₂)₂-.In addition, as the C_3-12Straight chain oxaalkylene, more specifically such as C can be enumerated_4-6Straight chain oxaalkylene can especially enumerate C_4-6One oxaalkylene of straight chain, can particularly enumerate formula- (CH₂)_m-O-(CH₂)_m(wherein, each numerical value m is same or different to each other, and is independently represented each other 2 or 3, for example, 2) representated by One oxaalkylene can particularly enumerate-(CH₂)₂-O-(CH₂)₂-、-(CH₂)₂-O-(CH₂)₃-、-(CH₂)₃-O-(CH₂)₃- Or-(CH₂)₂-O-(CH₂)₄-。

According to an aspect of the present invention, in the formula (I), multiple group R are same or different to each other, each independently Selected from C_1-4Linear or branched alkyl group is preferably each independently selected from methyl and ethyl, is more preferably methyl.

According to an aspect of the present invention, in the formula (I), X OH.

According to an aspect of the present invention, in the contact procedure, the organic formwork agent and first oxide The molar ratio in source (by first oxide in terms of) is generally from 0.02 to 0.5, preferably from 0.05 to 0.5, from 0.15 to 0.5 Or from 0.3 to 0.5.

According to an aspect of the present invention, in the contact procedure, as the organic formwork agent, in addition to the formula (I) except the compound representated by, can also further with the use of this field when manufacturing molecular sieve it is conventional use of other Organic formwork agent.Preferably, in the contact procedure, as the organic formwork agent, the formula (I) institute's generation is only used only The compound of table.Here, compound representated by the formula (I) can be used alone, or with the combination of arbitrary ratio Using a variety of.

According to an aspect of the present invention, in the contact procedure, first oxide source is usually tetravalence oxidation Material resource, for example can enumerate selected from silica source, titanium dioxide ge source, titanium dioxide tin source, titania source and zirconium dioxide source At least one of, preferably silica (SiO₂) source or silica source and titanium dioxide ge source combination.These first oxygen Compound source can be used alone, or is applied in combination with arbitrary ratio a variety of.When being applied in combination a variety of, any two kinds Molar ratio between first oxide source is such as from 20:200 to 35:100.As the example being applied in combination, such as can Silica source and titanium dioxide ge source is applied in combination to enumerate, at this time between the silica source and the titanium dioxide ge source Molar ratio is such as from 20:200 to 35:100.

According to an aspect of the present invention, in the contact procedure, as first oxide source, this can be used Field conventional use of any corresponding oxidation material resource for this purpose, respective metal in including but not limited to described first oxide Oxide, hydroxide, alkoxide, metal oxyacid salts, acetate, oxalates, ammonium salt, sulfate, halide salt and nitric acid Salt etc..For example, when first oxide be silica when, as first oxide source, for example, can enumerate silica solution, Thick block silica gel, ethyl orthosilicate, waterglass, white carbon black, silicic acid, silica gel or potassium silicate etc..When first oxide is two When germanium oxide, as first oxide source, for example tetraalkoxy germanium, germanium oxide or nitric acid germanium can be enumerated etc..When described When first oxide is titanium dioxide tin source, as first oxide source, for example stannic chloride, STANNOUS SULPHATE CRYSTALLINE, nitric acid tin can be enumerated Deng.When first oxide is titanium oxide, as first oxide source, for example tetraalkoxy titanium, dioxy can be enumerated Change titanium, Titanium Nitrate etc..When first oxide is zirconium dioxide, as first oxide source, for example sulphur can be enumerated Sour zirconium, zirconium chloride, zirconium nitrate etc..These first oxide sources can be used alone, or be made with the ratio combination of needs With a variety of.

According to an aspect of the present invention, in the contact procedure, second oxide source is usually trivalent oxidation Material resource, for example can enumerate selected from alumina source, oxidation boron source, iron oxide source, gallium oxide source, rare earth oxide source, indium oxide At least one of source and vanadium oxide source, preferably aluminium oxide (Al₂O₃) source.These second oxide sources can be used alone, Or it is applied in combination with arbitrary ratio a variety of.Mole when being applied in combination a variety of, between any two kind of second oxide source Frequently in this way from 30:200 to 60:150.

According to an aspect of the present invention, in the contact procedure, as second oxide source, this can be used Field conventional use of any corresponding oxidation material resource for this purpose, respective metal in including but not limited to described second oxide Oxide, hydroxide, alkoxide, metal oxyacid salts, acetate, oxalates, ammonium salt, sulfate, halide salt and nitric acid Salt etc..For example, when second oxide is aluminium oxide as second oxide source, for example aluminium chloride, sulphur can be enumerated Sour aluminium, hydrated alumina, sodium metaaluminate, Aluminum sol or aluminium hydroxide etc..When second oxide is boron oxide, as Second oxide source, for example boric acid, borate, borax, diboron trioxide can be enumerated etc..When second oxide is oxygen When changing iron, as second oxide source, for example ferric nitrate, iron chloride, iron oxide can be enumerated etc..When second oxide When for gallium oxide, as second oxide source, for example gallium nitrate, gallium sulfate, gallium oxide can be enumerated etc..When second oxygen When compound is rare earth oxide, as second oxide source, for example lanthana, neodymia, yttrium oxide, oxidation can be enumerated Cerium, lanthanum nitrate, neodymium nitrate, yttrium nitrate, Cericammoniumsulfate etc..When second oxide is indium oxide, as second oxidation Material resource, for example inidum chloride, indium nitrate, indium oxide can be enumerated etc..When second oxide be vanadium oxide when, as this second Oxide source, for example vanadium chloride, ammonium metavanadate, sodium vanadate, vanadium dioxide, vanadic sulfate can be enumerated etc..These second oxidations Material resource can be used alone, or is applied in combination with the ratio of needs a variety of.

According to an aspect of the present invention, in the contact procedure, first oxide source is (with first oxidation Object is meter, such as SiO₂) with second oxide source (in terms of being by second oxide, such as Al₂O₃) molar ratio it is general For from 5 to ∞, preferably from 25 to 95, more preferably from 30 to 70.Here, indicating to be not used described when the molar ratio is ∞ Second oxide source is not deliberately introduced second oxide source into the contact procedure.

According to an aspect of the present invention, in the contact procedure, water and first oxide source are (with described first Oxide be meter) molar ratio be generally from 5 to 50, preferably from 5 to 15.

According to an aspect of the present invention, in the contact procedure, alkali source can be used, alkali source can also not used. When specially not using alkali source, required for the group X that compound representated by the formula (I) is included may be used to provide herein OH^-.Here, this field conventional use of any alkali source for this purpose can be used, including but unlimited as the alkali source In the inorganic base for taking alkali or alkaline earth metal as cation, especially sodium hydroxide and potassium hydroxide etc..These alkali sources can be with One kind is used alone, or is applied in combination with arbitrary ratio a variety of.

According to an aspect of the present invention, in the contact procedure, the alkali source is (with OH^-For meter) and first oxygen The molar ratio in compound source (in terms of being by first oxide) is generally from 0 to 1, preferably from 0.04 to 1, from 0.1 to 1, from 0.2 To 1, from 0.3 to 0.7 or from 0.45 to 0.7.

According to an aspect of the present invention, in the contact procedure, as the crystallization condition, crystallization temperature is generally From 80 DEG C to 120 DEG C, preferably from 120 DEG C to 170 DEG C or from 120 DEG C to 200 DEG C.

According to an aspect of the present invention, in the contact procedure, as the crystallization condition, crystallization time is generally At least 1 day, preferably at least 2 days, preferably from 3 days to 8 day, from 5 days to 8 day or from 4 days to 6 day.

According to an aspect of the present invention, in the manufacturing method of the molecular sieve, after contact procedure completion, Molecular sieve can be isolated as product from reaction mixture obtained by conventionally known any separate mode.? This, the zeolite product includes molecular sieve of the invention.In addition, as the separate mode, for example can enumerate to described The method that the reaction mixture of acquisition is filtered, washs and dries.

According to an aspect of the present invention, in the manufacturing method of the molecular sieve, described be filtered, washed and dried can be with It is carried out according to conventionally known in the art any mode.For concrete example, as the filtering, for example can simply it filter The reaction mixture of the acquisition.As the washing, for example it can enumerate and carry out washing using deionized water until filter liquor PH value reach 7-9, preferably 8-9.As the drying temperature, for example 40-250 DEG C, preferably 60-150 DEG C can be enumerated, as The time of the drying, for example can enumerate 8-30 hours, preferably 10-20 hours.The drying can carry out under normal pressure, can also To carry out under reduced pressure.

According to an aspect of the present invention, the manufacturing method of the molecular sieve can also include by the acquisition as needed Molecular sieve the step of being roasted (hereinafter referred to as calcination steps), to remove the organic formwork agent and moisture that may be present Deng thus to obtain the molecular sieve after roasting.In the context of the present specification, by the molecule before the roasting and after roasting Sieve molecular sieve or molecular sieve according to the present invention also referred to collectively as of the invention.

According to an aspect of the present invention, in the method for the manufacture molecular sieve, the roasting can be according to this field Conventionally known any mode carries out, for example maturing temperature is generally from 300 DEG C to 750 DEG C, preferably from 400 DEG C to 600 DEG C, and Calcining time is generally from 1 hour to 10 hour, preferably from 3 hours to 6 hour.In addition, the roasting is generally in oxygen-containing atmosphere Lower progress, such as under air or oxygen atmosphere.

According to an aspect of the present invention, the manufacturer of molecular sieve of the invention or molecular sieve according to the present invention The two (in the context of the present specification, is also referred to collectively as molecular sieve or root of the invention by any molecular sieve manufactured by method According to molecular sieve of the invention), as needed, ion exchange can also be carried out by conventionally known in the art any mode, than Such as can by ion-exchange or solution dipping method (correlation technique such as may refer to United States Patent (USP) US3140249 and US3140253 etc.), formed in include metal cation (such as Na ion or K ion depend on its and specific make Make method) other cations are replaced in whole or in part.As it is described other cation, such as can enumerate hydrogen ion, its His alkali metal ion (including K ion, Rb ion etc.), ammonium ion (including NH₄Ion, quaternary ammonium ion such as tetramethyl ammonium With tetraethyl ammonium ion etc.), alkaline-earth metal ions (including Mg ion, Ca ion), Mn ion, Zn ion, Cd ion, noble metal Ion (including Pt ion, Pd ion, Rh ion etc.), Ni ion, Co ion, Ti ion, Sn ion, Fe ion and/or rare earth Metal ion etc..

Molecular sieve according to the present invention can also be handled, to improve sial as needed by dilute acid soln etc. Than, or handled with vapor, to improve the acid resistant of molecular sieve crystal.

Molecular sieve according to the present invention has good heat/hydrothermal stability, and has bigger Kong Rong.As a result, Molecular sieve of the invention can adsorb more/bigger molecules, to show excellent absorption/catalytic performance.

Molecular sieve according to the present invention, has stronger acidity, and the quantity in the especially acid site L is more.This is existing skill The molecular sieve that art had not manufactured.As a result, molecular sieve of the invention is especially in acid catalyzed reaction with more excellent Performance.

Molecular sieve according to the present invention can be rendered as any physical form, such as powdered, graininess or molding Product shape (such as strip, trilobes etc.).These physical forms can be obtained according to conventionally known in the art any mode, and There is no particular limitation.

Molecular sieve according to the present invention can be used in combination, thus to obtain combination of molecular sieve with other materials.As this A little other materials, for example active material and non-active material can be enumerated.As the active material, for example synthesis can be enumerated Zeolite and natural zeolite etc. as the non-active material (commonly referred to as binder), for example can enumerate clay, carclazyte, silicon Glue and aluminium oxide etc..These other materials can be used alone, or is applied in combination with arbitrary ratio a variety of.As institute The dosage of other materials is stated, can be not particularly limited directly referring to the conventional amount used of this field.

Alkylation according to the present invention, with the molar ratio computing of silica and aluminium oxide, the silica alumina ratio of previous molecular sieve Preferably 30~150, more preferably 40~120.

Alkylation according to the present invention, the catalyst is preferably by the binder group of molecular sieve above-mentioned and surplus At.In terms of the quality of catalyst, the mass fraction of catalyst is 15%~95%, preferably 40%~80%.

Alkylation according to the present invention, the binder are preferably silica and/or aluminium oxide.

Alkylation according to the present invention, a kind of suitable preparation method of catalyst are as follows: by molecular screen primary powder above-mentioned and glue Predecessor (silicon compound and/or aluminium compound), nitric acid and the deionized water kneading extruded moulding of agent are tied, at 550 DEG C after drying Left and right roasts in air, removed template method, is exchanged 1~2 time at 70 DEG C~90 DEG C with ammonium salt aqueous solution, then washed, dry It is dry, in 500 DEG C~600 DEG C roasting deamination 1~5 hour to get catalyst.

Alkylation according to the present invention, the suitable preparation method of catalyst of another kind are as follows: by molecular screen primary powder above-mentioned in 550 DEG C or so roast in air, removed template method, are exchanged 1~2 time at 70 DEG C~90 DEG C with ammonium salt aqueous solution, then through washing Wash, dry, in 500 DEG C~600 DEG C roasting deamination 1~5 hour, then (silicon compound and/or calorize are closed with the predecessor of binder Object), nitric acid and deionized water kneading extruded moulding, 1~5 hour is roasted after dry in 450 DEG C~550 DEG C to get catalyst.

The predecessor of alkylation according to the present invention, the binder can close for silicon-containing compound and/or containing calorize Object, wherein silicon-containing compound can be selected from one of silica solution, methyl orthosilicate and ethyl orthosilicate or a variety of；Aluminum contained compound It can be selected from one of boehmite, SB powder, Aluminum sol and aluminium isopropoxide or a variety of.When using silicon-containing compound and contain When the mixture of aluminium compound, in terms of the gross mass of silica and aluminium oxide, the silicon-containing compound and aluminum contained compound it is mixed The mass ratio for closing object and previous molecular sieve is 10:95 to 40:60, preferably 15:85 to 30:70；Wherein, with silica and oxidation The ratio of the molar ratio computing of aluminium, silicon-containing compound and aluminum contained compound is 1:1 to 1:2.

Alkylation according to the present invention, the ethylene raw used are refinery catalytic cracking dry for pure ethylene, containing ethylene Gas (optimal ethylene volume fraction be 10%~60%) and plant catalytic containing ethylene crack dry gas, and (optimal ethylene volume fraction is One or more of 10%~60%).Catalytic cracking (FCC) and catalytic pyrolysis are important petroleum refining process, these add The useless tail gas (FCC dry gas and catalytic pyrolysis dry gas etc.) that work process generates is referred to as catalysis drying gas.Catalysis drying gas is in addition to containing ethylene Outside, there are also a small amount of C₃H₆, H₂, CH₄, C₂H₆, C₃H₈, CO, CO₂, H₂O,H₂The components such as S.The dry gas is into must be through before reactor Purification is crossed to deviate from sour gas, alkali nitrogen and water, wherein sour gas includes hydrogen sulfide and carbonyl sulfur, and alkali nitrogen includes ammonia and its His basic nitrogen compound.

Alkylation according to the present invention, alkylation reaction condition can be with are as follows: 140 DEG C of temperature~280 DEG C, preferably 160 DEG C~250 DEG C；Reaction pressure is 1MPa~4MPa, preferably 1.2Pa~3.6MPa；The molar ratio of benzene and ethylene is 1:1 in charging ~12:1, preferably benzene alkene ratio are 4:1~12:1；Weight (hourly) space velocity (WHSV) in terms of ethylene is 0.1h^-1~0.8h^-1, preferably 0.1h^-1~ 0.5h^-1。

Alkylation according to the present invention, the reactor for being alkylated reaction can be, but not limited to be fixed bubbling bed Reactor, fixed trickle bed reactor or paste state bed reactor, preferably fixed bubbling bed reactor.Using fixed bubbling bed reaction When device, ethylene and the benzene endfeed all under reactor, reaction product are drawn from top.When using fixed trickle bed reactor, second Alkene is fed from reactor bottom, and benzene is in the middle part of reactor or top is fed, and reaction product is drawn from reactor bottom.

The present invention is illustrated using embodiment in further detail below, however, the present invention is not limited to these examples.

In the context of the present specification, it is included in embodiment below and comparative example, using Netherland, PANalytical Corporation equipment carries out XRD test.Test condition: Cu target, K α radiation, Ni filter plate, tube voltage 40kV, tube current 40mA, scanning range are 2-50 °.

In the context of the present specification, it is included in embodiment below and comparative example, using FEI Co., the U.S. Quanta 200F (20kv) type scanning electron microscope.Test condition: suspension method sample preparation is used, sieve sample 0.01g is put Enter 2mL vial.Dispersed with dehydrated alcohol, shaken well, takes a drop with dropper, drip on diameter 3mm specimen screen, it is to be dried Afterwards, it is placed in sample injector, is inserted into Electronic Speculum and is observed.It is described observation can be used 10,000 times enlargement ratio or 50,000 times Enlargement ratio.In addition, observing molecular sieve under 50,000 times of enlargement ratio, an observation visual field is randomly selected, the observation is calculated The average value of the average value of the sum of effective diameter of whole molecular sieve crystals and the sum of height in the visual field.Repeat the operation total 10 It is secondary.Using the average value of the sum of 10 average value as effective diameter and height.

In the context of the present specification, it is included in embodiment below and comparative example, using U.S. Varian^UNITY INOVA 500MHz type nuclear magnetic resonance chemical analyser.Test condition: being popped one's head in using solid double resonance, Φ 4mm ZrO₂Rotor.Experiment Parameter: test temperature is room temperature, scanning times nt=5000, pulse width pw=3.9 μ s, spectrum width sw=31300Hz, observing nuclear Resonant frequency Sfrq=125.64MHz, sampling time at=0.5s, chemical shift calibrate δ_TMS=0, delay time d1= 4.0s, mode of uncoupling dm=nny (inverted gated decoupling), deuterated chloroform lock field.

In the context of the present specification, it is included in embodiment below and comparative example, using Rigaku motor strain 3013 type Xray fluorescence spectrometer of family name commercial firm.Test condition: tungsten target, excitation voltage 40kV, excitation current 50mA.Experimentation: After sample tabletting on Xray fluorescence spectrometer, emit fluorescence, the atom of wavelength of fluorescence λ and element under x-ray bombardment There are following relationships between ordinal number Z: λ=K (Z-S)^-2, K is constant, as long as being measured to the wavelength X of fluorescence, so that it may determine this kind Element.With the intensity of scintillation counter and proportional counter measurement each element characteristic spectral line, carries out element and quantitatively or semi-quantitatively divide Analysis.

In the context of the present specification, it is included in embodiment below and comparative example, all medicaments and raw material were both Can be commercially available, it can also be manufactured according to existing knowledge.

In the context of the present specification, it is included in embodiment below and comparative example, total specific surface area of molecular sieve, Kong Rong and bore dia are measured according to following analysis method.

Equipment: Micromeritic ASAP2010 static state n2 absorption apparatus

Measuring condition: being placed in sample processing system for sample, is evacuated to 1.33 × 10 at 350 DEG C^-2Pa, heat-insulation pressure keeping 15h purifies sample.At -196 DEG C of liquid nitrogen temperature, absorption of measurement purification sample under the conditions of not pressing P/P0 on year-on-year basis to nitrogen Amount and desorption rate, obtain adsorption-desorption isothermal curve.Then total specific surface area is calculated using two parameter BET formula, taken than pressing P/ The adsorbance below of P0 ≈ 0.98 is the Kong Rong of sample, with the distribution of BJH model calculated hole diameters.

In the context of the present specification, be included in embodiment below and comparative example, dilute ethylene using pure ethylene with Nitrogen is formulated, and the volume fraction of ethylene is 15%.

In the context of the present specification, be included in embodiment below and comparative example, using bubbling bed reactor into The process of the dilute ethylene liquid phase legal system ethylbenzene of row.Reactor is stainless steel tubular type isothermal reaction pipe, internal diameter 12mm, catalyst loading 8mL, benzene and ethylene (including dilute ethylene) are introduced by reaction bottom of the tube.

Conversion of ethylene and ethylbenzene selectivity are calculated by following equation:

Conversion of ethylene XE=(second in ethylene moles-gas discharge in the molal quantity of ethylene in charging-liquid discharging Alkene molal quantity)/charging in ethylene molal quantity × 100%

The molar fraction of ethylbenzene selectivity SEB=ethylbenzene/(molar fraction of 1- benzene) × 100%

Embodiment 1

The manufacture of template A1:

15g (0.087mol) 4-methyl hexamethylene diamine is added in 500ml there-necked flask, 250ml isopropanol is added, drips at room temperature Add 18.8g (0.087mol) Isosorbide-5-Nitrae-dibromobutane, be added dropwise after 15min, be warming up to reflux, solution is gradually become by colorless and transparent At white opacity, 200ml acetic acid second is added into reaction solution after tracking raw material fully reacting with high performance liquid chromatography (HPLC) Ester, flow back 1h, filters after cooling, and obtained solid is successively washed with ethyl acetate, ether, obtains white solid product 30g, is 1,1, 6,6- tetramethyl -1,6- diaza twelve-ring -1,6- dibromo salts (n 4, m 6, the compound that R is methyl, X is Br), phase To molecular weight be 388.2,273.7 DEG C of fusing point,¹HNMR spectrogram chemical shift (300MHz, CDCl₃)δ1.50(t,4H),1.90 (t,8H),3.14(s,12H),3.40(t,8H)。

The manufacture of template B1: the Br in template A1 is replaced by OH using ion-exchange；Ion exchange resin is Strong-basicity styrene series anion exchange resin, working solution are the template A1 aqueous solution of 15m%, and operation temperature is 25 DEG C, work The mass ratio for making liquid and ion exchange resin is 1:3；Flow velocity is 3 drops/sec；Solution after exchange is removed water with Rotary Evaporators, It is the compound that n is 4, m 6, R are methyl, X is OH in formula (I) up to product, relative molecular weight 262.2, purity is 99.21%, bromine content 0.79m%.

Embodiment 2

The manufacture of template C1

10g (0.058mol) 4-methyl hexamethylene diamine is added in 500ml there-necked flask, 250ml isopropanol is added, drips at room temperature Add 16.6g (0.058mol) 1,9- dibromo nonane, be added dropwise after 15min, be warming up to reflux, solution is gradually become by colorless and transparent At white opacity, 200ml acetic acid second is added into reaction solution after tracking raw material fully reacting with high performance liquid chromatography (HPLC) Ester, flow back 1h, filters after cooling, and obtained solid is successively washed with ethyl acetate, ether, obtains white solid product 25g, is 1,1,8, 8- tetramethyl -1,8- diaza seventeen-ring -1,8- dibromo salt ((n 9, m 6, the compound that R is methyl, X is Br)), phase It is 458.4 to molecular weight,¹The chemical shift of HNMR spectrogram (300MHz, CDCl3) δ 1.51 (t, 14H), 1.92 (t, 8H), 3.16 (s,12H),3.40(t,8H)。

The manufacture of template D1: the Br in template C1 is replaced by OH using ion-exchange；Ion exchange resin is Strong-basicity styrene series anion exchange resin, working solution are the template C1 aqueous solution of 15m%, and operation temperature is 25 DEG C, work The mass ratio for making liquid and ion exchange resin is 1:3；Flow velocity is 3 drops/sec；Solution after exchange is removed water with Rotary Evaporators, It is the compound that n is 9, m 6, R are methyl, X is OH in formula (I) up to product, relative molecular weight 332.4, purity is 99.8% compound, bromine content 0.2m%.

Embodiment 3

The manufacture of template A2: [2- (N, N- the dimethylaminoethyl)] ether of 15g (0.094mol) two is added in two-mouth bottle, 100mL isopropanol is added, 1, the 3- dibromopropane of 9.5g (0.047mol) is added dropwise under 25 DEG C of stirrings, is added dropwise, is warming up to Reflux temperature, flow back 30min, and solution becomes white opacity by colourless, then reacts 12h at a reflux temperature, is cooled to 25 DEG C, adds The ethyl acetate stirring 15min for entering 50mL forms white opacity liquid, filtering, and obtained solid is washed with ethyl acetate, obtains product 13.2g is the compound that n is 1, m 2, R are methyl, X is Br in formula (I).Its fusing point is 250.3 DEG C, purity 99.9m%, Relative molecular weight is 362.2,1H-NMR spectrogram chemical shift (300MHZ, internal standard TMS, solvent C DCl₂) δ (ppm) are as follows: 1.49 (2H, m), 2.27 (4H, m), 2.36 (4H, t), 2.53 (4H, t), 3.47 (4H, t).

The manufacture of template B2: the Br in template A2 is replaced by OH using ion-exchange；Ion exchange resin is Strong-basicity styrene series anion exchange resin, working solution are the template A2 aqueous solution of 15m%, and operation temperature is 25 DEG C, work The mass ratio for making liquid and ion exchange resin is 1:3；Flow velocity is 3 drops/sec；Solution after exchange is removed water with Rotary Evaporators, Up to product, be n is 1, m 2, R are methyl in formula (I), X be OH, relative molecular weight 236.2, purity be 98.2m%'s Compound.Its bromine content is 0.79m%.

Embodiment 4

The manufacture of template C2: by n in method manufacture formula (I) of template A2 in embodiment III-1 be 6, m 2, R are Methyl, the compound that X is Br, the difference is that, 1,3- dibromo is replaced with 1,8-, bis- bromooctane of 12.78g (0.047mol) Propane.Test obtains 17.6g product, and fusing point is 288.2 DEG C, relative molecular weight 432.2, purity 99.9m%, 1H-NMR Spectrogram chemical shift (300MHZ, internal standard TMS, solvent C DCl₂) δ (ppm) are as follows: 1.29 (2H, s), 1.39 (2H, m), 1.43 (2H, S), 2.27 (2H, m), 2.36 (2H, m), 2.55 (2H, m), 3.63 (4H, m).

The manufacture of template D2: the Br in template C2 is replaced by OH using ion-exchange；Ion exchange resin is Strong-basicity styrene series anion exchange resin, working solution are the template C2 aqueous solution of 15m%, and operation temperature is 25 DEG C, work The mass ratio for making liquid and ion exchange resin is 1:3；Flow velocity is 3 drops/sec；Solution after exchange is removed water with Rotary Evaporators, It is that n is 6, m 2, R are methyl, X OH, relative molecular weight 306.2, purity are 99.5m% chemical combination in formula (I) up to product Object.Its bromine content is 0.2m%.

Embodiment 5

1.23g sodium metaaluminate is added in the Teflon container of 45mL, 1.925g template B2 is added, 9g silicon is then added Colloidal sol (Qingdao Marine Chemical Co., Ltd., industrial goods, SiO₂Content is that 30%), still aging 1h is sufficiently mixed, wherein each group The molar ratio divided are as follows: SiO₂/Al₂O₃=35, H₂O/SiO₂=7.1, template B/SiO₂=0.15, NaOH/SiO₂=0.12.It will Said mixture is fitted into the steel autoclave with Teflon liner of 45mL and covers and seal, and autoclave is placed in rotation In convection oven, revolving speed is set as 20rpm, is warming up to 150 DEG C after reacting 1 day at 120 DEG C and reacts 5 days.Take out autoclave simultaneously So that it is rapidly cooled to room temperature, mixture is separated on the supercentrifuge of 5000rpm, collects solid, filled with deionized water Divide washing, to get product after drying 5 hours at 100 DEG C.

The scanning electron microscope (SEM) photograph of the product is shown in Fig. 1, and clearly visible molecular sieve has the crystal morphology of hexa-prism in figure, and Effective diameter is 1200nm, is highly 1000nm, ratio of height to diameter 0.833.By measurement, total specific surface area of the molecular sieve is 558m²/ g, Kong Rongwei 0.51ml/g.The XRD diagram of product is shown in Fig. 2.The silica alumina ratio of product is 36.38.

Embodiment 6

0.134g sodium metaaluminate is added in the Teflon container of 45mL, 1.81g template B1 is added, stirs 30 minutes extremely Uniformly, 3g thick block silica gel (Qingdao Marine Chemical Co., Ltd., industrial goods, SiO is then added₂98.05%) and 6.3g content is Deionized water, stirring are sufficiently mixed for 5 minutes, wherein the molar ratio of each component are as follows: SiO₂/Al₂O₃=25, H₂O/SiO₂=7, template Agent B/SiO₂=0.16, OH^-/SiO₂=0.31.

Said mixture is fitted into the steel autoclave with Teflon liner of 45mL and covers and seal, autoclave is put It is placed in the convection oven of rotation, revolving speed is set as 20rpm, reacts 5 days at 150 DEG C.It takes out autoclave and cools down it rapidly To room temperature, mixture is separated on the supercentrifuge of 5000rpm, collects solid, sufficiently washed with deionized water, 100 To get product DEG C after dry 5 hours.

The scanning electron microscope (SEM) photograph of the product is shown in Fig. 3, and clearly visible molecular sieve has the crystal morphology of hexa-prism in figure.By Measurement, total specific surface area of the molecular sieve are 523m²/ g, Kong Rongwei 0.356ml/g.XRF analysis Si/Al as the result is shown₂= 23.The XRD diagram of the product is shown in Fig. 4.

Embodiment 7

6.975g template D1 is added in the Teflon container of 45mL, sodium metaaluminate 0.296g is added, stirred 30 minutes To uniform, 3g thick block silica gel (Qingdao Marine Chemical Co., Ltd., industrial goods, SiO is then added₂Content is 98%, Al₂O₃Content For 0.253%).Still aging 1h is sufficiently mixed, wherein the molar ratio of each component are as follows: SiO₂/Al₂O₃=201, H₂O/SiO₂= 5.8, template D/SiO₂=0.15, NaOH/SiO₂=0.05.

Said mixture is fitted into the steel autoclave with Teflon liner of 45mL and covers and seal, autoclave is put It is placed in the convection oven of rotation, revolving speed is set as 20rpm, is warming up to 160 DEG C after reacting 1 day at 120 DEG C and reacts 5 days.It takes out Autoclave simultaneously makes it be rapidly cooled to room temperature, and mixture is separated on the supercentrifuge of 5000rpm, collects solid, spends Ionized water sufficiently washs, to get product after drying 5 hours at 100 DEG C.

The scanning electron microscope (SEM) photograph of the product is shown in Fig. 5, and clearly visible molecular sieve has the crystal morphology of hexa-prism in figure.By Measurement, total specific surface area of the molecular sieve are 564m²/ g, Kong Rongwei 0.394ml/g.The XRD diagram of product is shown in Fig. 6.XRF analysis Molecular sieve Si/Al as the result is shown₂=203.

Embodiment 8

0.735g sodium metaaluminate is added in the Teflon container of 45mL, 8.024g template B2 is added, 3g is then added Thick block silica gel (Qingdao Marine Chemical Co., Ltd., industrial goods, SiO₂Content is that 98.05%), still aging 1h is sufficiently mixed, The molar ratio of middle each component are as follows: SiO₂/Al₂O₃=80, H₂O/SiO₂=7.5, template B/SiO₂=0.15.By said mixture It is fitted into the steel autoclave with Teflon liner of 45mL and covers and seal, autoclave is placed in the convection oven of rotation In, revolving speed is set as 20rpm, is warming up to 150 DEG C after reacting 1 day at 120 DEG C and reacts 5 days.It takes out autoclave and makes it rapidly It is cooled to room temperature, mixture is separated on the supercentrifuge of 5000rpm, collect solid, sufficiently washed with deionized water, 100 DEG C after drying 5 hours to get product.

The scanning electron microscope (SEM) photograph of the product is shown in Fig. 7, and clearly visible molecular sieve has the crystalline substance of flat prism-shaped or oblate column in figure Bodily form looks.By measurement, total specific surface area of the molecular sieve is 482m²/ g, Kong Rongwei 0.346ml/g.XRF analysis result is aobvious Show Si/Al₂=84.The XRD diagram of product is shown in Fig. 8.

Embodiment 9

0.132g sodium metaaluminate is added in the Teflon container of 45mL, 8.731g template D2 is added, 3g is then added Thick block silica gel (Qingdao Marine Chemical Co., Ltd., industrial goods, SiO₂Content is that 98.05%), still aging 1h is sufficiently mixed, The molar ratio of middle each component are as follows: SiO₂/Al₂O₃=60, H₂O/SiO₂=8, template D/SiO₂=0.15.Said mixture is filled Enter in the steel autoclave with Teflon liner of 45mL and cover and seal, autoclave is placed in the convection oven of rotation, Revolving speed is set as 20rpm, is warming up to 150 DEG C after reacting 1 day at 120 DEG C and reacts 4 days.It takes out autoclave and is rapidly cooled to it Room temperature separates mixture on the supercentrifuge of 5000rpm, collects solid, is sufficiently washed with deionized water, at 100 DEG C To get product after 5 hours dry.

The scanning electron microscope (SEM) photograph of the product is shown in Fig. 9, and clearly visible molecular sieve has the crystalline substance of flat prism-shaped or oblate column in figure Bodily form looks.By measurement, total specific surface area of the molecular sieve is 452m²/ g, Kong Rongwei 0.385ml/g.XRF analysis result is aobvious Show Si/Al₂=62.

Embodiment 10

Molecular sieve is prepared according to the method for embodiment 5, the difference is that only, the dosage of silica solution is 10g, final products Si/Al₂=42.

Embodiment 11

Molecular screen primary powder (silica alumina ratio 42, calcination loss 15%) and 31.25g prepared by 88g embodiment 10 intends thin water Aluminium stone (aluminum oxide mass fraction 80%) is uniformly mixed, and appropriate nitric acid and deionized water is added, and it is dry to mediate extruded moulding Temperature programming is to 540 DEG C afterwards, roasts 5 hours, then exchanges 2 times with 80 DEG C of ammonia of 0.5mol/L ammonium nitrate solution, and 2 hours every time, It dries 12 hours, 550 DEG C and roasts 3 hours through washing, 90 DEG C again, catalyst A is made.

On bubbling bed reaction evaluating device, it is anti-that dilute ethylene liquid phase legal system ethylbenzene is catalyzed using the catalyst A of 20~40 mesh It answers, dilute ethylene concentration is 15%, is formulated using pure ethylene and nitrogen.Loaded catalyst 2g, benzene alkene ratio are 12, reaction temperature 200 DEG C, reaction pressure 3.5MPa of degree, the weight (hourly) space velocity (WHSV) of ethylene are 0.32h^-1。

Reaction result is shown in Table 1.

Embodiment 12

Prepare catalyst according to the method for embodiment 11, the difference is that only: molecular sieve used is that embodiment 8 is made It makes.Catalyst B is made.

Dilute ethylene liquid phase legal system ethylbenzene reaction is carried out using the method for embodiment 11, the difference is that only: using catalysis Agent B, reaction temperature are 250 DEG C, and the weight (hourly) space velocity (WHSV) of ethylene is 0.15h^-1。

Reaction result is shown in Table 1.

Embodiment 13

Prepare catalyst according to the method for embodiment 11, the difference is that only: molecular sieve used is that embodiment 9 is made It makes.Catalyst C is made.

The reaction of pure ethylene liquid phase legal system ethylbenzene is carried out using the alkylation reaction condition of embodiment 11, the difference is that making With catalyst C, reaction temperature is 150 DEG C, reaction pressure 1.5MPa, and the weight (hourly) space velocity (WHSV) of ethylene is 0.3h^-1。

Reaction result is shown in Table 1.

Embodiment 14

Molecular screen primary powder (silica alumina ratio 42, calcination loss 15%) temperature programming prepared by 100g embodiment 10 is to 540 DEG C, it roasts 5 hours, then exchanges 2 times in 80 DEG C of ammonia with 0.5mol/L ammonium nitrate solution, 2 hours every time, then through washing, 90 DEG C It roasts 3 hours within drying 12 hours, 550 DEG C, the molecular sieve of Hydrogen is made；Take the molecular sieve and 66.67g silica solution (two of 60g Hydrogen Siliconoxide mass score 30%) and 66.67g Aluminum sol (aluminum oxide mass fraction 30%) be uniformly mixed, appropriate nitre is added Acid and deionized water, temperature programming roasts 3 hours obtained catalyst D to 540 DEG C after mediating extruded moulding, drying.

On bubbling bed reaction evaluating device, using the catalyst D catalysis pure ethylene and benzene liquid phase legal system second of 20~40 mesh Benzene reaction, loaded catalyst 2g, benzene alkene is than 12, and 200 DEG C of reaction temperature, the weight (hourly) space velocity (WHSV) of reaction pressure 3.5MPa, ethylene is 0.32h^-1。

Reaction result is shown in Table 1.

Embodiment 15

Using the catalyst D prepared in embodiment 14.

The reaction of pure ethylene liquid phase legal system ethylbenzene is carried out using the alkylation reaction condition of embodiment 14, the difference is that instead Answering temperature is 250 DEG C, and for benzene alkene than 6, the weight (hourly) space velocity (WHSV) of ethylene is 0.32h^-1。

Reaction result is shown in Table 1.

Embodiment 16

Using catalyst A prepared in embodiment 11.

The reaction of pure ethylene liquid phase legal system ethylbenzene is carried out using the alkylation reaction condition of embodiment 14, the difference is that making With catalyst A, reaction temperature is 180 DEG C, and benzene alkene is than 9, reaction pressure 2.0MPa, and the weight (hourly) space velocity (WHSV) of ethylene is 0.50h^-1。

Reaction result is shown in Table 1.

Table 1

As it can be seen from table 1 the method for ethylene provided by the invention and producing phenylethane from alkylation of benzene, ethylene with higher turns Rate and good ethylbenzene selectivity.

Although a specific embodiment of the invention is described in detail with attached drawing above in conjunction with the embodiments, It should be pointed out that the scope of protection of the present invention is not limited by these specific embodiments, but by claims Lai It determines.Those skilled in the art can carry out these embodiments in the range of not departing from technical idea and purport of the invention Change appropriate, and the embodiment after these changes is obviously also included within protection scope of the present invention.

Claims

1. a kind of method of benzene and preparing ethylbenzene by liquid phase alkylation of ethylene, including the presence in alkylation reaction condition and catalyst Under, make ethylene and benzene haptoreaction, which is characterized in that contain a kind of molecular sieve in the catalyst, which has formula " the Signal representated by the second oxide of monoxide " or formula " first oxide the second oxide organic formwork agent water " Property chemical composition, wherein the molar ratio of first oxide and second oxide be from 5 to ∞ (preferably from 30 to 150, More preferably from 40 to 120)；First oxide is selected from silica, germanium dioxide, stannic oxide, titanium dioxide and dioxy Change at least one of zirconium (the preferably combination of silica or silica and germanium dioxide), second oxide to be selected from At least one of aluminium oxide, boron oxide, iron oxide, gallium oxide, rare earth oxide, indium oxide and vanadium oxide (preferably aoxidize Aluminium)；The molar ratio of water and first oxide is from 5 to 50 (preferably from 5 to 15)；The organic formwork agent and described first The molar ratio of oxide is from 0.02 to 0.5 (preferably from 0.05 to 0.5, from 0.15 to 0.5 or from 0.3 to 0.5), and is had There is X-ray diffraction pattern substantially as shown in the table,

2. according to the method for claim 1, which is characterized in that the ethylene raw used is pure ethylene, the refinery containing ethylene Catalytic cracked dry gas (optimal ethylene volume fraction is 10%~60%) and the plant catalytic containing ethylene crack dry gas (optimal ethylene One or more of volume fraction is 10%~60%).

3. according to the method for claim 1, which is characterized in that the catalyst by binder (preferably aluminium oxide and/or Silica) and molecular sieve composition (preferably in terms of the quality of catalyst, the mass fraction of the molecular sieve is 15%~ 95%).

4. according to the method for claim 3, which is characterized in that the catalyst is made by following methods: by the molecule Original powder and silicon-containing compound and/or aluminum contained compound, nitric acid and deionized water kneading and compacting are sieved, in air in 450 after drying DEG C~550 DEG C of burning-off templates, it is then swapped in 80 DEG C~90 DEG C of ammonium salt aqueous solution, finally at 500 DEG C~600 DEG C Roasting deamination 1 hour~5 hours to get catalyst；Wherein, the silicon-containing compound be selected from silica solution, methyl orthosilicate and One of ethyl orthosilicate is a variety of, and the aluminum contained compound is selected from boehmite, SB powder, Aluminum sol and aluminium isopropoxide One of or it is a variety of；The ammonium salt is selected from one of ammonium nitrate, ammonium chloride and ammonium sulfate or a variety of.

5. according to the method for claim 4, which is characterized in that using the mixture of silicon-containing compound and aluminum contained compound, Molar ratio of the two in terms of silica and aluminium oxide is 1:1 to 1:2.

6. according to the method for claim 1, which is characterized in that this method fixed bubbling bed reactor (optimal ethylene and Benzene is fed from reactor lower part, and reaction product is drawn from reactor top), fixed trickle bed reactor or paste state bed reactor Middle progress；And/or

The alkylation reaction condition are as follows: 150 DEG C~280 DEG C of reaction temperature, reaction pressure 1MPa~4MPa, benzene and ethylene Molar ratio is 1:1~15:1, and the weight (hourly) space velocity (WHSV) in terms of ethylene is 0.1h^-1~0.8h^-1(preferred alkylation conditions are as follows: reaction temperature The molar ratio of 160 DEG C~250 DEG C, reaction pressure 1.2MPa~3.6MPa of degree, benzene and ethylene is 3:1~12:1, in terms of ethylene Weight (hourly) space velocity (WHSV) is 0.1h^-1~0.5h^-1)。

7. a kind of method of benzene and preparing ethylbenzene by liquid phase alkylation of ethylene, including the presence in alkylation reaction condition and catalyst Under, make ethylene and benzene haptoreaction, which is characterized in that the catalyst contains a kind of molecular sieve, and the molecular sieve is by following methods It is made: making the first oxide source, the second oxide source, optional alkali source, organic formwork agent and water contact under crystallization condition, with Obtain the molecular sieve；Wherein, optionally, include the steps that the molecular sieve for roasting the acquisition；The organic formwork agent packet Containing compound representated by lower formula (I),

Wherein, group R₁And R₂It is same or different to each other, is each independently selected from C_3-12Linear chain or branched chain alkylidene and C_3-12Straight chain Or branch oxaalkylene, preferably it is each independently selected from C_3-12Straight-chain alkyl-sub and C_3-12Straight chain oxaalkylene, or preferably One of them is selected from C_3-12Linear chain or branched chain alkylidene, another is selected from C_3-12Linear chain or branched chain alkylidene and C_3-12Straight chain or branch Chain oxaalkylene, more preferably one of them is selected from C_3-12Straight-chain alkyl-sub, another is selected from C_3-12Straight-chain alkyl-sub and C_3-12Directly Chain oxaalkylene, particularly preferably one of them is selected from C_3-12Straight-chain alkyl-sub, another is selected from C_4-6Straight-chain alkyl-sub and C_4-6 Straight chain oxaalkylene (preferably C_4-6One oxaalkylene of straight chain, more preferably-(CH₂)_m-O-(CH₂)_m, wherein each numerical value m is each other It is identical or different, it is independently represented each other 2 or 3)；Multiple group R are same or different to each other, and are each independently selected from C_1-4Straight chain Or branched alkyl, it is preferably each independently selected from methyl and ethyl, is more preferably methyl；X is OH.

8. according to the method for claim 7, which is characterized in that the ethylene raw used is pure ethylene, the refinery containing ethylene Catalytic cracked dry gas (optimal ethylene volume fraction is 10%~60%) and the plant catalytic containing ethylene crack dry gas (optimal ethylene One or more of volume fraction is 10%~60%).

9. according to the method for claim 7, which is characterized in that the catalyst is by binder (aluminium oxide and/or oxidation Silicon) and molecular sieve composition (preferably in terms of the quality of catalyst, the mass fraction of the molecular sieve is 10%~95%).

10. according to the method for claim 9, which is characterized in that the catalyst is made by following methods: by the molecule Original powder and silicon-containing compound and/or aluminum contained compound, nitric acid and deionized water kneading and compacting are sieved, in air in 450 after drying DEG C~550 DEG C of burning-off templates, it is then swapped in 80 DEG C~90 DEG C of ammonium salt aqueous solution, finally at 500 DEG C~600 DEG C Roasting deamination 1 hour~5 hours to get catalyst；Wherein, the silicon-containing compound be selected from silica solution, methyl orthosilicate and One of ethyl orthosilicate is a variety of, and the aluminum contained compound is selected from boehmite, SB powder, Aluminum sol and aluminium isopropoxide One of or it is a variety of；The ammonium salt is selected from one of ammonium nitrate, ammonium chloride and ammonium sulfate or a variety of.

11. according to the method for claim 10, which is characterized in that use the mixing of silicon-containing compound and aluminum contained compound Object, molar ratio of the two in terms of silica and aluminium oxide are 1:1 to 1:2.

12. according to the method for claim 7, which is characterized in that this method fixed bubbling bed reactor (optimal ethylene and Benzene is fed from reactor lower part, and reaction product is drawn from reactor top), fixed trickle bed reactor or paste state bed reactor Middle progress；And/or