CN102039157B - Non-binder MCM-22 molecular sieve catalyst and preparation method thereof - Google Patents
Non-binder MCM-22 molecular sieve catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of a non-binder MCM-22 molecular sieve catalyst. In the invention, the problems that the existing MCM-22 molecular sieve catalyst with the binder has lower activity and the non-binder MCM-22 molecular sieve has lower strength are solved mainly. The technical scheme in the invention comprises the following steps: the non-binder MCM-22 molecular sieve catalyst is adopted, wherein the molar ratio of SiO2 to Al2O3 is 20-200, the weight content of the binder is 0-5% and the mechanical strength of each particle of the formed catalyst is 50-180N. The problems can be better solved and the prepared non-binder MCM-22 molecular sieve catalyst can be used in the industrial production of propylene through catalytic cracking of naphtha.
Description
Technical field
The present invention relates to a kind of binder free MCM-22 molecular sieve catalyst and preparation method thereof.
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 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.
At present the binder free catalyst of report has the adhesiveless ZSM-5 molecular sieve, is to make through gas phase conversion at the presoma that preformed catalyst adds ZSM-5.
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 MCM-22 molecular sieve and the MCM-49 zeolite of then mainly generating of basicity in the building-up process.
The method that directly prepares binder free MCM-22 molecular sieve catalyst can be optimized preparation process, avoids preparing the process complicated problems, has tangible economic worth and social value.
Binder free MCM-22 molecular sieve catalyst does not have report as yet.
Summary of the invention
One of technical problem to be solved by this invention is lower, the relatively poor problem of MCM-22 molecular sieve intensity that do not contain binding agent of activity when containing binding agent in the existing MCM-22 molecular sieve catalyst, and a kind of new binder free MCM-22 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 MCM-22 molecular sieve catalyst, contain SiO
2/ Al
2O
3Mol ratio is 20～200 MCM-22 molecular sieve, and wherein weight of binder content 0～5%; The mechanical strength of the catalyst behind the shaping and roasting be 50～180 newton/.
The SiO of MCM-22 molecular sieve in the technique scheme
2/ Al
2O
3The mol ratio preferable range is 20～100, and wherein weight of binder content preferable range is 0.2～2%, 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: the preparation method of above-mentioned binder free MCM-22 molecular sieve catalyst may further comprise the steps:
A) in the catalyst weight behind the shaping and roasting; After the compound of the MCM-22 molecular sieve 10～80%, 0.1～10% alkaline matter, 0～20% aluminium and 10～80% the silica binder mixed-forming 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 contain hexamethylene imine template steam, carry out crystallization after 20～300 hours, obtain binder free MCM-22 molecular sieve catalyst precursor at 110-190 ℃;
C) catalyst precarsor 400～700 ℃ of following roastings 1～10 hour, obtains binder free MCM-22 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 MCM-22 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 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 MCM-22 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 140～180 ℃, 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 crystal seed MCM-22 molecular sieve in preformed catalyst; Put into the template steam of specific suitable MCM-22 molecular sieve growth; Control is suitable for the alkaline environment and the material proportion of MCM-22 molecular sieve growth simultaneously, makes binding agent under the inducing of crystal seed, can change into molecular sieve active ingredient; Simultaneously in the control environment of template steam and alkalescence; Also can induce MCM-22 molecular sieve or crystal seed and can nucleating growth in the binding agent, so binding agent can be transformed into MCM-22 molecular sieve active principle through the method for gas phase conversion, obtain binder free type MCM-22 molecular sieve catalyst.The content of binding agent can reach below 0.5% in the binder free type MCM-22 molecular sieve catalyst that makes; Even do not contain binding agent; All be the MCM-22 molecular sieve in the catalyst, improved the content of molecular sieve in the per volume of catalyst like this, improved activity of such catalysts.In addition and since change the binder free MCM-22 molecular sieve thing that obtains 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 binder free MCM-22 molecular sieve catalyst that makes 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 MCM-22 molecular sieve catalyst of embodiment 1 preparation;
Fig. 2 is the ESEM picture of the binder free MCM-22 molecular sieve catalyst of embodiment 1 preparation.
Through embodiment the present invention is done further elaboration below.
The specific embodiment
[embodiment 1]
Get SiO
2/ Al
2O
3Mol ratio is 20 MCM-22 molecular sieve 60 grams, and 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 MCM-22 molecular sieve catalyst.The XRD figure of the catalyst that makes spectrum is as shown in Figure 1, and it is shown as the thing phase of MCM-22 molecular sieve, and wherein the weight percentage of MCM-22 molecular sieve is 98.5%, 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 sheet MCM-22 crystal grain, and the binder content of unformed state is 1.5%.
[embodiment 2～6]
According to the method for embodiment 1, get SiO respectively
2/ Al
2O
3Mol ratio is that 20,60,100,140 and 200 MCM-22 molecular sieve 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 MCM-22 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; Using concentration is 5% ammonium nitrate solution, is 1: 10 ratio in the solid-to-liquid ratio of catalyst and ammonium nitrate solution, exchanges three times at 90 ℃; 550 ℃ of roastings made the binder free MCM-22 molecular sieve catalyst of Hydrogen after 3 hours then.The component that adopts Shanghai Gaoqiao petro-chemical corporation to produce is that the light oil of C4～C10 is raw material (the raw material physical index is seen table 3), the examination activity of such catalysts, and the use diameter is 12 millimeters fixed bed reactors normal pressure examination down; Range of reaction temperature is 650 ℃, and reaction pressure is 0.02MPa, and 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 92%; The ethene mass yield is 27.0%, and the propylene mass yield is 25%, and diene quality total recovery is 52%.
Table 2
| Embodiment | The SiO of gained binder free MCM-22 molecular sieve 2/Al 2O 3 | MCM-22 molecular sieve content (weight %) in the gained binder free catalyst | Binder content (weight %) in the gained binder free catalyst | Gained binder free catalyst strength (newton /) |
| Embodiment 3 | 22 | 99.5 | 0.5 | 174 |
| Embodiment 4 | 82 | 98.9 | 1.1 | 125 |
| Embodiment 5 | 110 | 97.0 | 3.0 | 80 |
| Embodiment 6 | 146 | 100.0 | 0 | 175 |
| Embodiment 7 | 220 | 98.7 | 1.3 | 165 |
| Embodiment 8 | 300 | 98.8 | 1.2 | 140 |
| Embodiment 9 | 56 | 95.0 | 5.0 | 50 |
| |
82 | 98.1 | 1.9 | 90 |
| Embodiment 11 | 360 | 99.8 | 0.2 | 185 |
| Embodiment 12 | 63 | 99.6 | 0.4 | 160 |
| Embodiment 13 | 400 | 98.4 | 1.6 | 80 |
[embodiment 15]
Get the binder free type MCM-22 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 MCM-22 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 MCM-22 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 MCM-22 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.
[comparative example 1]
Preparing silica alumina ratio by the method for Chinese patent CN101279880A is 40 MCM-22 molecular sieve; 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 40 MCM-22 molecular sieve molecular sieve; Method by embodiment 14 is processed hydrogen type molecular sieve; And then, obtain containing the MCM-22 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.
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 | 27.0 |
| Propane | 7.0 |
| Propylene | 25.0 |
| Butane | 8.8 |
| Butylene | 7.8 |
| Carbon five above cuts | 8.4 |
| Other | 3.7 |
Table 5
| Embodiment | Catalyst strength (newton /) | Yield of ethene (weight %) | Propene yield (weight %) | Diene yield (weight %) | React 0.5 hour conversion ratio (%) |
| Embodiment 15 | 140 | 27.0 | 26 | 53.0 | 96 |
| Embodiment 16 | 135 | 25.0 | 26.0 | 51.0 | 94 |
| Comparative example 1 | 32 | 22 | 22 | 44 | 85 |
| Comparative example 2 | 81 | 21 | 22 | 43 | 82 |
Claims (6)
1. a binder free MCM-22 molecular sieve catalyst contains SiO
2/ Al
2O
3Mol ratio is 20～200 MCM-22 molecular sieve, and wherein weight of binder content is 0～5%; Every with surveyed catalyst is of a size of 1.5 millimeters of diameters, 5 millimeters meters of length, the mechanical strength of preformed catalyst be the mechanical strength of 50～180 a newton/preformed catalyst be 50～180 newton/;
The preparation method of binder free MCM-22 molecular sieve catalyst may further comprise the steps:
A) in the catalyst weight behind the shaping and roasting; After the compound of the MCM-22 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 put into contain hexamethylene imine template steam, carry out crystallization after 20～300 hours, obtain binder free MCM-22 molecular sieve catalyst precursor at 120-190 ℃;
C) catalyst precarsor 400～700 ℃ of following roastings 1～10 hour, obtains binder free MCM-22 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 MCM-22 molecular sieve of crystal seed
2/ Al
2O
3Mol ratio is 20～200; Alkaline matter is selected from least a in oxide, hydroxide or its salt of weak acid of IA in the periodic table of elements or IIA 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; The Adhesive-free Molecular Sieve catalyst refers in the catalyst weight of binder content smaller or equal to 5%.
2. binder free MCM-22 molecular sieve catalyst according to claim 1 is characterized in that the SiO of contained MCM-22 molecular sieve
2/ Al
2O
3Mol ratio is 20～100, and weight of binder content is 0.2～2%, wherein, is of a size of 1.5 millimeters of diameters with every of surveyed catalyst, 5 millimeters meters of length, the mechanical strength of preformed catalyst be 70～150 newton/.
3. binder free MCM-22 molecular sieve catalyst according to claim 1 is characterized in that the IA element is selected from least a in sodium or the potassium, and the IIA 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.
4. binder free MCM-22 molecular sieve catalyst according to claim 1 is characterized in that in the catalyst weight behind the shaping and roasting consumption of MCM-22 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.
5. binder free MCM-22 molecular sieve catalyst according to claim 1 is characterized in that crystallization temperature is 140-180 ℃; Crystallization time is 20～100 hours.
6. binder free MCM-22 molecular sieve catalyst according to claim 1; 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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| CN107511163B (en) * | 2016-06-18 | 2020-11-03 | 中国石油化工股份有限公司 | Molecular sieve catalyst, preparation method and application |
| CN107512727B (en) * | 2016-06-18 | 2021-02-09 | 中国石油化工股份有限公司 | Preparation method of binder-free MWW structure molecular sieve |
| CN107511173B (en) * | 2016-06-18 | 2020-02-07 | 中国石油化工股份有限公司 | Process for producing alkylbenzene |
| CN112354557B (en) * | 2020-11-16 | 2023-03-24 | 华东师范大学 | Preparation method and application of integral titanium zeolite catalyst |
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| CN101563159A (en) * | 2006-12-21 | 2009-10-21 | 埃克森美孚化学专利公司 | A catalyst composition, the method of manufacturing, and the process of use thereof in aromatics alkylation |
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| US5039640A (en) * | 1986-07-29 | 1991-08-13 | Mobil Oil Corp. | Catalyst composition for octane improvement in catalytic cracking |
| CN1105906A (en) * | 1994-01-29 | 1995-08-02 | 复旦大学 | Hydrophobic silicon zeolite adsorbent without cohesive agent and its preparation |
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