CN102039172B - Binderless beta zeolite/MCM-22 symbiotic molecular sieve catalyst and preparation method thereof - Google Patents
Binderless beta zeolite/MCM-22 symbiotic molecular sieve catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of a binderless beta zeolite/MCM-22 symbiotic molecular sieve catalyst, mainly solving the problems that a traditional beta zeolite/MCM-22 symbiotic molecular sieve catalyst has lower activity in case of containing a binder and has poor strength in case of lacking a binder, and a mechanical mixture of the beta zeolite containing the binder and MCM-22 molecular sieve has lower activity. According to the technical scheme that the beta zeolite/MCM-22 symbiotic molecular sieve catalyst contains a binderless beta zeolite/MCM-22 symbiotic molecular sieve with the mol ratio of SiO2/Al2O3 of 20-200, wherein the weight content of a binder is 0-5 percent, the weight ratio of the beta zeolite to MCM-22 in the beta zeolite/MCM-22 symbiotic molecular sieve is (0.15-80): 1, and the formed catalyst has the mechanical strength of 50-180N/g, the invention favorably solves the problems, and the prepared binderless beta zeolite/MCM-22 symbiotic molecular sieve catalyst can be used in industrial production of propylene prepared by catalytically cracking naphtha.
Description
Technical field
The present invention relates to a kind of binder free β zeolite/MCM-22 coexisting molecular sieve Catalysts and its preparation method.
Background technology
Molecular sieve has good shape selective catalysis performance and absorption property owing to have evenly regular pore passage structure, bigger specific area and higher thermally-stabilised row, is applied in field of petrochemical industry widely.Because molecular sieve powder self intensity is lower, be prone to disperse to run off, can't directly be applied in use in the industry; Therefore in use need add the binding agent moulding and gain in strength, in the catalyst after the moulding, because binding agent parcel molecular sieve; Caused the effective rate of utilization of molecular sieve to descend, the duct of the molecular sieve of part is blocked, causes the specific area of catalyst lower; Activity is also lower, and again because binding agent is no regular pore passage structure, reaction raw materials and product are in catalyst diffusion difficulty; Carbon deposit has certain influence to life of catalyst easily.Be converted into the molecular sieve active principle to the binding agent in the catalyst, then can overcome above problem, improve activity of such catalysts and diffusion.
The binder free catalyst is exactly the active principle that changes into the binding agent that is added in the molecular sieve catalyst forming process in molecular sieve, makes not contain the binding agent composition in the whole catalyst, keeps the good intensity of catalyst simultaneously.General Adhesive-free Molecular Sieve catalyst refers in the catalyst weight of binder content smaller or equal to 5%.Transform or almost completely be converted into the molecular sieve composition fully owing to binding agent in the binder free catalyst; So just improved the content of molecular sieve in the per volume of catalyst; Make activity of such catalysts higher, treating capacity is bigger, simultaneously owing to no longer include binding agent in the catalyst; Solved binding agent parcel molecular sieve and reduced the effective rate of utilization of molecular sieve and the problem that binding agent stops up molecular sieve pore passage, the effective rate of utilization of molecular sieve and carbon accumulation resisting ability are improved greatly.
General coexisting molecular sieve is to prepare through the synthetic method of hydro-thermal, is Powdered, and no intensity is prone to run off, and can not directly use, and need add binding agent when industry or laboratory applications and carry out extrusion or spray shaping.In the general molecular sieve catalyst forming process, the weight that add binding agent is no less than 40% of total catalyst weight, though the moulding rear catalyst has had intensity, the effective rate of utilization of catalyst reduces, active and diffusion variation.
In the document, the general title of two kinds of molecular sieves of using of the literary style of coexisting molecular sieve is write together at present, and the centre adds one "/" expression, for example, and the coexisting molecular sieve that β zeolite and MCM-22 form, writing " β zeolite/MCM-22 coexisting molecular sieve ".
At present the binder free catalyst of report has the binder free beta-zeolite molecular sieve, is to make through gas phase conversion at the presoma that preformed catalyst adds the β zeolite.
Document (Wei Yongsheng etc., synthetic MCM-22 molecular sieve of dynamic method and sign thereof are printed during chemical industry, the 20th the 2nd phase of volume, 2006) is a template with hexamethylene imine HMI, adopts dynamic hydrothermal crystallization method to synthesize the MCM-22 zeolite molecular sieve.Adopt XRD to characterize it is carried out material phase analysis, adopt ammonia desorption-temperature programmed desorption NH-TPD method to characterize its acid matter, the result shows: be prone to generate mixed crystal, too high β zeolite and the MCM-49 zeolite of then mainly generating of basicity in the building-up process.
Existing composite molecular screen, coexisting molecular sieve or the mixed crystal molecular sieve of reporting all need be synthetic synthetic back of molecular sieve or adding crystal seed directed agents hydro-thermal, and building-up process is very complicated and pollution again comparatively.
The method that directly prepares binder free β zeolite/MCM-22 coexisting molecular sieve catalyst can be optimized preparation process, avoids preparing the process complicated problems, has tangible economic worth and social value.
Summary of the invention
One of technical problem to be solved by this invention is the relatively poor and lower problem of mechanical impurity activity that contains the β zeolite and the MCM-22 molecular sieve of binding agent of activity β zeolite/MCM-22 coexisting molecular sieve intensity lower, that do not contain binding agent when containing binding agent in existing β zeolite/MCM-22 coexisting molecular sieve catalyst, and a kind of new binder free β zeolite/MCM-22 coexisting molecular sieve catalyst is provided.It is higher that this catalyst has catalytic activity, and the while mechanical strength is advantage of higher also.Two of technical problem to be solved by this invention provides a kind of new corresponding preparation method of the catalyst with one of technical solution problem.
For one of solving the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of binder free β zeolite/MCM-22 coexisting molecular sieve catalyst, contain SiO
2/ Al
2O
3Mol ratio is β zeolite/MCM-22 coexisting molecular sieve of 20～200, and wherein weight of binder content 0～5%; The weight ratio of β zeolite and MCM-22 is 0.15～80: 1 in β zeolite/MCM-22 coexisting molecular sieve, the mechanical strength of binding agent be 50～180 newton/.
The SiO of β zeolite/MCM-22 coexisting molecular sieve in the technique scheme
2/ Al
2O
3The mol ratio preferable range is 40～100; Wherein weight of binder content preferable range is 0.2～2%; The weight ratio preferable range of β zeolite and MCM-22 is 0.2～5: 1 in β zeolite/MCM-22 coexisting molecular sieve, the catalyst strength preferable range behind the shaping and roasting that makes be 70～150 newton/.
For solve the problems of the technologies described above two, the technical scheme that the present invention adopts is following: above-mentioned binder free β zeolite/MCM-22 coexisting molecular sieve Preparation of catalysts method may further comprise the steps:
A) in the catalyst weight behind the shaping and roasting; After the compound of the β zeolite/MCM-22 coexisting molecular sieve 10～80%, 0.1～10% alkaline matter, 0～20% aluminium and 10～80% silica mixing, moulding, the drying; Obtain preformed catalyst precursor mixture I, wherein among the mixture I compound weight content of aluminium less than the weight content of silica;
B) mixture I is placed to put into to contain be selected from tetraethylammonium bromide, tetraethyl ammonium hydroxide or hexamethylene imine template steam; Carry out crystallization after 20～300 hours at 110-190 ℃, obtain binder free β zeolite/MCM-22 coexisting molecular sieve catalyst precarsor;
C) catalyst precarsor 400～700 ℃ of following roastings 1～10 hour, obtains binder free β zeolite/MCM-22 coexisting molecular sieve catalyst through super-dry;
Wherein, in the catalyst weight behind the shaping and roasting, template agent is 5～300%, as the SiO of the β zeolite/MCM-22 coexisting molecular sieve of crystal seed
2/ Al
2O
3Mol ratio is 20～100; Alkaline matter is selected from least a in oxide, hydroxide or its salt of weak acid of I A in the periodic table of elements or II A element; The compound of aluminium is selected from least a in the hydroxide of hydrous oxide or aluminium of oxide, aluminium of aluminium salt, aluminium.
In the technique scheme, I A major element preferred version is selected from least a in sodium or the potassium, and II A element preferred version is selected from least a in magnesium or the calcium; The salt of weak acid preferred version is selected from least a in carbonate, oxalates or the citrate; In the catalyst weight behind the shaping and roasting, the consumption preferable range of β zeolite/MCM-22 coexisting molecular sieve is 20～70%; The consumption preferable range of alkaline matter is 0.5%～5%; The compound amount preferable range of aluminium is 2～15%; The consumption preferable range of silica is 15～70%; Template agent is 10～100%.The crystallization temperature preferable range is 120～170 ℃, and the crystallization time preferable range is 20～100 hours; In the catalyst weight behind the shaping and roasting, preferred version is also to contain 0.1～2% the expanding agent at least a in sesbania powder, methylcellulose or the soluble starch that is selected among the preformed catalyst precursor mixture I.
It is strip solid cylindrical, that diameter is 0.5～2mm that shape after the catalyst precarsor mixture I extrusion is generally tangent plane, is broken into every grain length degree after the drying and is 5 millimeters short cylindrical shape catalyst bar, is convenient to change brilliant and handles and examination.Catalyst mechanical strength among the present invention is calculated by this shape measure.Catalyst precarsor mixture I also can make cellular as required, clover shape, hollow tubular or shape such as spherical, and its strength criterion is meter in addition.
In the characterization method of binder free catalyst, with the contained thing of XRD test mutually and the content of each thing phase, change the pattern of molecular sieve of situation and the generation of crystalline substance with the scanning electron microscopic observation binding agent.Change brilliant back binder content through the XRD thing mutually quantitatively and in the stereoscan photograph content of binding agent confirm.The catalyst silica alumina ratio is confirmed with chemico-analytic method.The strength test method of catalyst is the crushing strength of the catalyst after test roasting on the pressure testing machine; Every of the catalyst of surveying is of a size of 1.5 millimeters of diameters; 5 millimeters of length; Be disposed across on the testing machine, suffered maximum pressure when measuring catalyst breakage is got its mean value after testing 10 catalyst crushing strengths.
The present invention is through adding β zeolite/MCM-22 coexisting molecular sieve crystal seed in preformed catalyst; Put into the template steam of specific suitable β zeolite/MCM-22 coexisting molecular sieve growth; Control is suitable for the alkaline environment and the material proportion of MCM-22 and β zeolite growth simultaneously; Make binding agent under the inducing of crystal seed; Molecular sieve active ingredient be can change into, simultaneously in the control environment of template steam and alkalescence, MCM-22 molecular sieve or β zeolite seed crystal and can nucleating growth also can be induced in the binding agent; Therefore binding agent can be transformed into the coexisting molecular sieve active principle through the method for gas phase conversion, obtains binder free type β zeolite/MCM-22 coexisting molecular sieve catalyst.The content of binding agent can reach below 0.5% in the binder free type β zeolite/MCM-22 coexisting molecular sieve catalyst that makes; Even do not contain binding agent; All β zeolite/MCM-22 coexisting molecular sieve in the catalyst; Improve the content of coexisting molecular sieve in the per volume of catalyst like this, improved activity of such catalysts.In addition and since change β zeolite/MCM-22 binder free coexisting molecular sieve thing of obtaining behind the crystalline substance mutually between staggered growth, ins conjunction with tightr, so the intensity of catalyst is also higher, on average crushing strength can reach 180 newton/.The β zeolite that makes/MCM-22 coexisting molecular sieve catalyst can be used in the reaction of naphtha catalytic pyrolysis preparing propylene, and the diene weight yield of ethylene, propylene can reach more than 53%, has obtained better technical effect.
Description of drawings
Fig. 1 is the XRD figure spectrum of the binder free β zeolite/MCM-22 coexisting molecular sieve catalyst of embodiment 1 preparation;
Fig. 2 is the ESEM picture of the binder free β zeolite/MCM-22 coexisting molecular sieve catalyst of embodiment 1 preparation.
Through embodiment the present invention is done further elaboration below.
The specific embodiment
[embodiment 1]
Get β zeolite/MCM-22 coexisting molecular sieve 60 grams, the adding weight percentage is 40% Ludox 40 grams and aluminum sulfate 16 grams, after the mixing and stirring; 10 milliliters of sodium hydroxide solutions that add 1 mol again, mixing and stirring, the moulding of agent bar then; Preformed catalyst is 80 ℃ of oven dry 3 hours, put into then the inner bag bottom moisture with the hexamethylene imine weight ratio be 200 milliliters autoclave of 1: 1 mixed solution 40 gram, catalyst does not contact with liquid water; Put into baking oven after the autoclave sealing, 165 ℃ of crystallization were taken out after 60 hours, washed then 2 times; Put into 120 ℃ of oven dry of baking oven 3 hours; Putting into the 400 ℃ of roastings 2 hours that heat up of Muffle furnace internal program, 550 ℃ of roastings 3 hours make binder free β zeolite/MCM-22 coexisting molecular sieve catalyst.The XRD figure spectrum of the catalyst that makes is as shown in Figure 1; It is shown as the thing phase of β zeolite/MCM-22 coexisting molecular sieve; Wherein the weight percentage of β zeolite is 69.0%, and MCM-22 content is 30.0%, the withstand voltage broken intensity of detecting catalyst sample be 150 newton/.The ESEM picture of the catalyst that makes is as shown in Figure 2, and it is shown as the mixture of ball-type β zeolite grain and sheet MCM-22 crystal grain, and the binder content of unformed state is 1%.
[embodiment 2～6]
According to the method for embodiment 1, get SiO respectively
2/ Al
2O
3Mol ratio is that β zeolite/MCM-22 coexisting molecular sieve of 20,40,60,80 and 100 is as crystal seed; Other condition is constant, and it is as shown in table 1 that raw material is formed proportioning, and the binder free catalyst that makes is as shown in table 2.
[embodiment 7～13]
Method according to embodiment 1; Other condition is constant, in forming process, adds soluble starch, sesbania powder or methylcellulose, and it is as shown in table 1 that raw material is formed proportioning; Mixing and stirring; Extruded moulding is processed binder free β zeolite/MCM-22 coexisting molecular sieve catalyst by the method for embodiment 1 again, and the result is as shown in table 2.
[embodiment 14]
Method according to embodiment 1 makes the binder free catalyst; Use concentration is 5% ammonium nitrate solution; It in the solid-to-liquid ratio of catalyst and ammonium nitrate solution 1: 10 ratio; 90 ℃ of exchanges three times, 550 ℃ of roastings made the binder free β zeolite/MCM-22 coexisting molecular sieve catalyst of Hydrogen after 3 hours then.The component that adopts Shanghai Gaoqiao petro-chemical corporation to produce is C
4～C
10Light oil be raw material (the raw material physical index is seen table 3), the examination activity of such catalysts, using diameter is 12 millimeters fixed bed reactors normal pressure examination down, range of reaction temperature is 650 ℃, reaction pressure is 0.02MPa, mass space velocity is 1 hour
-1, water/feedstock oil mass ratio is 1: 1, the reaction half an hour after, products distribution is seen table 4, feed stock conversion is 93%, the ethene mass yield is 27.0%, the propylene mass yield is 26%, diene quality total recovery is 53%.
[embodiment 15]
Get the binder free type β zeolite/MCM-22 coexisting molecular sieve that obtains among the embodiment 1, process hydrogen type catalyst, get 100 grams by the method for embodiment 14; Using concentration is that 300 milliliters of the ammonium hydrogen phosphates of 0.5 mol flooded modification 4 hours at 95 ℃; Take out sample 120 ℃ of oven dry 3 hours then,, obtain the binder free type β zeolite/MCM-22 coexisting molecular sieve catalyst of phosphorus modification again 650 ℃ of roastings 3 hours; Method according to embodiment 14 is checked and rated, and the result sees table 5.
[embodiment 16]
Get binder free type β zeolite/MCM-22 coexisting molecular sieve catalyst 100 grams of the phosphorus modification that obtains among the embodiment 15; Using concentration is that 300 milliliters of the ammonium hydrogen phosphates of 0.2 mol flooded modification 4 hours at 95 ℃; Take out sample 120 ℃ of oven dry 3 hours then,, obtain the binder free type β zeolite/MCM-22 coexisting molecular sieve catalyst of lanthanum and phosphorus modification again 650 ℃ of roastings 3 hours; Method according to embodiment 14 is checked and rated, and the result sees table 5.
Table 2
| Embodiment | The SiO of gained binder free β zeolite/MCM-22 coexisting molecular sieve 2/Al 2O 3 | MCM-22 content (weight %) in gained binder free β zeolite/MCM-22 coexisting molecular sieve | β zeolite content (weight %) in gained binder free β zeolite/MCM-22 coexisting molecular sieve | Binder content (weight %) in the gained binder free catalyst | Gained binder free catalyst strength (newton /) |
| Embodiment 3 | 24 | 25.5 | 74.0 | 0.5 | 174 |
| Embodiment 4 | 62 | 35.4 | 63.5 | 1.1 | 125 |
| Embodiment 5 | 80 | 38.5 | 59.5 | 3.0 | 80 |
| Embodiment 6 | 120 | 1.9 | 98.1 | 0 | 175 |
| Embodiment 7 | 180 | 7.3 | 91.4 | 1.3 | 165 |
| Embodiment 8 | 105 | 23.4 | 75.4 | 1.2 | 140 |
| Embodiment 9 | 56 | 10.6 | 84.4 | 5.0 | 50 |
| Embodiment 10 | 200 | 86.6 | 11.5 | 1.9 | 90 |
| Embodiment 11 | 35 | 83.2 | 16.6 | 0.2 | 185 |
| Embodiment 12 | 163 | 75.5 | 24.1 | 0.4 | 160 |
| Embodiment 13 | 42 | 87.5 | 10.9 | 1.6 | 80 |
[comparative example 1]
Preparing silica alumina ratio by the method for Chinese patent CN101279880A is β zeolite/MCM-22 coexisting molecular sieve mixed crystal molecular sieve of 40; Method by embodiment 14 is processed hydrogen type molecular sieve; Then mixed crystal molecular sieve direct tablet compressing, break into pieces, sieve, do not contained 20～40 purpose catalyst granules of binding agent, put into fixed bed reactors; Press the method examination of embodiment 14, the result sees table 5.
[comparative example 2]
Preparing silica alumina ratio by the method for Chinese patent CN101279880A is β zeolite/MCM-22 coexisting molecular sieve mixed crystal molecular sieve of 40; Method by embodiment 14 is processed hydrogen type molecular sieve; And then, obtain containing the β zeolite/β zeolite mixed crystal molecular sieve catalyst of binding agent according to the method extruded moulding of embodiment 1, put into fixed bed reactors; Press the method examination of embodiment 14, the result sees table 5.
[comparative example 3]
The silica alumina ratio of getting the production of Oil of Shanghai Petrochemical Company research institute is 40 MCM-22 molecular sieve; Method by embodiment 14 is processed hydrogen type molecular sieve; Then MCM-22 molecular sieve direct tablet compressing, break into pieces, sieve, do not contained 20～40 purpose catalyst granules of binding agent, put into fixed bed reactors; Press the method examination of embodiment 14, the result sees table 5.
[comparative example 4]
The silica alumina ratio of getting the production of Oil of Shanghai Petrochemical Company research institute is 40 β zeolite; Method by embodiment 14 is processed hydrogen type molecular sieve; Then β zeolite direct tablet compressing, break into pieces, sieve, do not contained 20～40 purpose catalyst granules of binding agent, put into fixed bed reactors; Press the method examination of embodiment 14, the result sees table 5.
[comparative example 5]
The silica alumina ratio that Oil of Shanghai Petrochemical Company research institute produces is 40 MCM-22 molecular sieve; Method by embodiment 14 is processed hydrogen type molecular sieve,, and then according to the method extruded moulding of embodiment 1; Obtain containing the MCM-22 molecular sieve catalyst of binding agent; Put into fixed bed reactors, press the method examination of embodiment 14, the result sees table 5.
[comparative example 6]
The silica alumina ratio of getting the production of Oil of Shanghai Petrochemical Company research institute is 40 β zeolite; Method by embodiment 14 is processed hydrogen type molecular sieve; And then, obtain containing the beta-zeolite catalyst of binding agent according to the method extruded moulding of embodiment 1, put into fixed bed reactors; Press the method examination of embodiment 14, the result sees table 5.
[comparative example 7]
The silica alumina ratio of getting the production of Oil of Shanghai Petrochemical Company research institute is 40 β zeolite, and silica alumina ratio is 40 MCM-22 molecular sieve, is mixed into mechanical impurity at 1: 1 according to weight ratio; Method by embodiment 14 is processed hydrogen type molecular sieve; And then, obtain containing the β zeolite of binding agent and the catalyst of MCM-22 mechanical impurity according to the method extruded moulding of embodiment 1, put into fixed bed reactors; Press the method examination of embodiment 14, the result sees table 5.
Table 3
| Project | Data |
| Density (20 ℃) kilogram/rice 3 | 704.6 |
| Boiling range is boiling range ℃ just | 40 |
| Whole boiling range ℃ | 160 |
| Saturated vapor pressure (20 ℃) kPa | 50.2 |
| Alkane % (weight %) | 65.2 |
| Cycloalkane % (weight %) | 28.4 |
| Alkene % (weight %) | 0.2 |
| Aromatic hydrocarbons % (weight %) | 6.2 |
Table 4
| Products distribution | Product weight yield (%) |
| Methane | 5.1 |
| Ethane | 7.2 |
| Ethene | 28.0 |
| Propane | 7.0 |
| Propylene | 24.0 |
| Butane | 8.9 |
| Butylene | 7.7 |
| Carbon five above cuts | 8.5 |
| Other | 3.6 |
Table 5
| Embodiment | Catalyst strength (newton /) | Yield of ethene (weight %) | Propene yield (weight %) | Diene yield (weight %) | React 0.5 hour conversion ratio (%) |
| Embodiment 15 | 143 | 27.5 | 25 | 52.5 | 97 |
| Embodiment 16 | 138 | 26.0 | 25.0 | 51 | 95 |
| Comparative example 1 | 30 | 23 | 22 | 45 | 86 |
| Comparative example 2 | 80 | 22 | 21 | 43 | 84 |
| Comparative example 3 | 32 | 19 | 21 | 40 | 80 |
| Comparative example 4 | 31 | 20 | 19 | 39 | 79 |
| Comparative example 5 | 75 | 22 | 22 | 44 | 85 |
| Comparative example 6 | 65 | 22 | 20 | 42 | 81 |
| Comparative example 7 | 68 | 21 | 22 | 43 | 82 |
Claims (7)
1. binder free β zeolite/MCM-22 coexisting molecular sieve catalyst contains SiO
2/ Al
2O
3Mol ratio is β zeolite/MCM-22 coexisting molecular sieve of 20～200, and wherein weight of binder content is 0～5%; The weight ratio of β zeolite and MCM-22 is 0.15～80: 1 in β zeolite/MCM-22 coexisting molecular sieve, is of a size of 1.5 millimeters of diameters with every of catalyst, 5 millimeters meters of length, the mechanical strength of preformed catalyst be 50～180 newton/.
2. binder free β zeolite according to claim 1/MCM-22 coexisting molecular sieve catalyst is characterized in that the SiO of contained β zeolite/MCM-22 coexisting molecular sieve
2/ Al
2O
3Mol ratio is 40～100; Wherein weight of binder content 0.2～2%; The weight ratio of β zeolite and MCM-22 is 0.2～5: 1 in β zeolite/MCM-22 coexisting molecular sieve; Every with catalyst is of a size of 1.5 millimeters of diameters, 5 millimeters meters of length, the mechanical strength of preformed catalyst be 70～150 newton/.
3. the described binder free β zeolite of claim 1/MCM-22 coexisting molecular sieve Preparation of catalysts method may further comprise the steps:
A) in the catalyst weight behind the shaping and roasting; After the compound of the β zeolite/MCM-22 coexisting molecular sieve 10～80%, 0.1～10% alkaline matter, 0～20% aluminium and 10～80% silica mixing, moulding, the drying; Obtain preformed catalyst precursor mixture I, wherein among the mixture I compound weight content of aluminium less than the weight content of silica;
B) mixture I is placed to put into to contain be selected from tetraethylammonium bromide, tetraethyl ammonium hydroxide or hexamethylene imine template steam; Carry out crystallization after 20～300 hours at 110-190 ℃, obtain binder free β zeolite/MCM-22 coexisting molecular sieve catalyst precarsor;
C) catalyst precarsor 400～700 ℃ of following roastings 1～10 hour, obtains binder free β zeolite/MCM-22 coexisting molecular sieve catalyst through super-dry;
Wherein, in the catalyst weight behind the shaping and roasting, template agent is 5～300%, as the SiO of the β zeolite/MCM-22 coexisting molecular sieve of crystal seed
2/ Al
2O
3Mol ratio is 20～100; Alkaline matter is selected from least a in oxide, hydroxide or its salt of weak acid of I A in the periodic table of elements or II A element; The compound of aluminium is selected from least a in the hydroxide of hydrous oxide or aluminium of oxide, aluminium of aluminium salt, aluminium.
4. binder free β zeolite according to claim 3/MCM-22 coexisting molecular sieve Preparation of catalysts method is characterized in that I A element is selected from least a in sodium or the potassium; II A element is selected from least a in magnesium or the calcium; Salt of weak acid is selected from least a in carbonate, oxalates or the citrate.
5. binder free β zeolite according to claim 3/MCM-22 coexisting molecular sieve Preparation of catalysts method is characterized in that in the catalyst weight behind the shaping and roasting consumption of β zeolite/MCM-22 coexisting molecular sieve is 20～70%; The consumption of alkaline matter is 0.5%～5%; The compound amount of aluminium is 2～15%; The consumption of silica is 15～70%; Template agent is 10～100% of a shaping and roasting rear catalyst weight.
6. binder free β zeolite according to claim 3/MCM-22 coexisting molecular sieve Preparation of catalysts method is characterized in that crystallization temperature is 120-170 ℃; Crystallization time is 20～100 hours.
7. binder free β zeolite according to claim 3/MCM-22 coexisting molecular sieve Preparation of catalysts method; It is characterized in that in the catalyst weight behind the shaping and roasting, also contain 0.1～2% the expanding agent at least a in sesbania powder, methylcellulose or the soluble starch that is selected among the preformed catalyst precursor mixture I.
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