CN102039164A - Method for preparing adhesive-free mordenite/beta zeolite symbiotic molecular sieve catalyst - Google Patents
Method for preparing adhesive-free mordenite/beta zeolite symbiotic molecular sieve catalyst Download PDFInfo
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Abstract
The invention relates to a method for preparing an adhesive-free mordenite/beta zeolite symbiotic molecular sieve catalyst to mainly solve the following problems: the mordenite/beta zeolite symbiotic molecular sieves prepared in the prior art contain adhesives and have complex preparation processes and higher cost; the mordenite/beta zeolite symbiotic molecular sieve catalysts have lower activity when containing adhesives; the adhesive-free mordenite/beta zeolite molecular sieves have poorer strength; and the adhesive-containing mechanical mixture of mordenite and beta zeolite has lower activity. The invention preferably solves the above problems by adopting the following technical scheme: in terms of the weight of the catalyst after forming and roasting, mixing, forming and drying 10-80% of beta zeolite, 1-20% of alkaline substances, 1-20% of compounds of aluminium and 10-80% of silicon oxide, then putting the obtained mixture into steam containing at least one template agent from ammonia water, ethylene diamine, triethylamine, n-butylamine, hexamethylene diamine, tetrapropyl ammonium bromide or tetrapropyl ammonium hydroxide and crystallizing the mixture at the temperature of 120-200 DEG C for 10-240 hours to obtain the adhesive-free mordenite/beta zeolite symbiotic molecular sieve catalyst. The adhesive-free mordenite/beta zeolite symbiotic molecular sieve catalyst prepared by the method can be used in the reaction of naphtha catalytic pyrolysis to prepare propylene.
Description
Technical field
The present invention relates to a kind of binder free mordenite/beta zeolite coexisting molecular sieve Preparation of catalysts 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, easily disperse to run off, industrially can't directly be applied in use, therefore in use needing to add the binding agent moulding gains 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, and activity is also lower, again because binding agent is no regular pore passage structure, reaction raw materials and product are in catalyst diffusion difficulty, and carbon deposit has certain influence to life of catalyst easily.Binding agent in the catalyst is converted into the active principle molecular sieve then can overcomes above problem, improve activity of such catalysts and diffusion.
The binder free catalyst is exactly the active principle that the binding agent that is added in the molecular sieve catalyst forming process is changed into molecular sieve, makes not contain the binding agent composition in the whole catalyst, keeps the good intensity of catalyst simultaneously.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 Adhesive-free Molecular Sieve catalyst refers in the catalyst weight of binder content smaller or equal to 5%.
General coexisting molecular sieve is to prepare by the synthetic method of hydro-thermal, is Powdered, and no intensity easily runs 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 by gas phase conversion at the presoma that preformed catalyst adds ZSM-5.
Chinese patent 200510028782 has reported that the present invention of small crystal grain without bonding agent modenite prepare zeolite method is a primary raw material by adopting with diatomite or white carbon, add the crystal seed directed agents, and with Ludox or sodium metasilicate as the binding agent moulding, handle the technical scheme that is converted into integrated microcrystal mordenites with organic amine mutually with the water vapour gas-solid then, mainly solve the weakness that the zeolite powder exists difficult recovery, easy inactivation and gathering in actual applications, and the adding binding agent can cause that effective surface area reduces the problem that influences with diffusion-restricted in the forming process.
Chinese patent 200510029462 has been reported the preparation method of ZSM-type molecular sieve without binding agent.By adopting content is the mixture that the former powder of 5～50 weight % binding agent silica and ZSM type molecule forms, in the aqueous solution that contains halogenation organic amine and alkyl diamine or steam, be converted into the technical scheme of integrated ZSM type molecular sieve through hydrothermal treatment consists, mainly solved and add binding agent in the molecular sieve catalyst forming process and can cause that effective surface area reduces the problem with the diffusion-restricted influence.
Composite molecular screen, coexisting molecular sieve or the mixed crystal molecular sieve of existing report all needs synthetic back of molecular sieve or adding crystal seed directed agents hydro-thermal synthetic, and building-up process is very complicated comparatively.Synthesizing flokite/beta zeolite coexisting the molecular sieve of report all is to be prepared from by the synthetic method of hydro-thermal at present.Add crystal seed or template agent in the building-up process, the complicated and pollution again of preparation method.
Directly the method for preparing binder free mordenite/beta zeolite coexisting molecular sieve catalyst can be optimized preparation process, avoids the preparation process complicated problems, has tangible economic worth and social value.
At present, binder free composite molecular screen and preparation method thereof does not appear in the newspapers, and prepares the technology of binder free composite molecular screen and does not appear in the newspapers yet by adding single crystal seed.Therefore, binder free mordenite/beta zeolite coexisting molecular sieve catalyst does not have report as yet yet, is that crystal seed or directed agents prepare binder free mordenite/beta zeolite coexisting molecular sieve report is not more arranged by single molecular sieve.
Summary of the invention
Technical problem to be solved by this invention is that the mordenite/beta zeolite coexisting molecular sieve of prior art for preparing contains that binding agent, preparation process complexity, cost are higher, the relatively poor and lower problem of mechanical impurity activity that contains the modenite and the β zeolite of binding agent of activity mordenite/beta zeolite coexisting molecular sieve intensity lower, that do not contain binding agent when containing binding agent in the mordenite/beta zeolite coexisting molecular sieve catalyst, and a kind of new method for preparing binder free mordenite/beta zeolite coexisting molecular sieve catalyst is provided.It is simple that this method has preparation process, and cost is lower, environmental protection, and it is higher to have catalytic activity with the catalyst of this method preparation in addition, simultaneously also advantage of higher of mechanical strength.
For addressing the above problem, the technical solution used in the present invention is as follows: a kind of binder free mordenite/beta zeolite coexisting molecular sieve Preparation of catalysts method may further comprise the steps:
A) catalyst weight meter, after the compound of the β zeolite 10～80%, 0.2～20% alkaline matter, 0.5～20% aluminium and 10～80% the silica 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) thing I places to put into and contains at least a template agent steam that is selected from ammoniacal liquor, ethylenediamine, triethylamine, n-butylamine, hexamethylene diamine, 4-propyl bromide or TPAOH, carries out obtaining binder free mordenite/beta zeolite coexisting molecular sieve catalyst precarsor after crystallization is handled 10～240 hours at 120～200 ℃;
C) precursor 400～700 ℃ of following roastings 1～10 hour, obtains binder free mordenite/beta zeolite coexisting molecular sieve catalyst through super-dry;
Wherein, in the catalyst weight behind the shaping and roasting, template agent is 5～300%, the SiO of β zeolite
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 IA or IIA element; The compound of aluminium is selected from least a in the hydroxide of the hydrous oxide of oxide, aluminium of aluminium salt, aluminium or aluminium.
SiO in the prepared mordenite/beta zeolite coexisting molecular sieve in the technique scheme
2/ Al
2O
3Preferable range is 20～120; 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 compound amount preferable range of aluminium is 1～10%; The consumption preferable range of β zeolite is 20～70%; The consumption preferable range of alkaline matter is 1～10%; The consumption preferable range of silica is 15～70%; The consumption preferable range of organic amine is 10～100%; The crystallization temperature preferable range is 140～180 ℃, and the crystallization time preferable range is 20～100 hours; The SiO of mordenite/beta zeolite coexisting molecular sieve
2/ Al
2O
3The mol ratio preferable range is 20～60, and wherein weight of binder content preferable range is 0～5%, and more preferably scope is 0.1～2%; The weight ratio preferable range of modenite and β zeolite is 0.5～80: 1 in the mordenite/beta zeolite coexisting molecular sieve, the crush strength preferable range of the binder free catalyst that makes be 60～150 newton/.
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, test the contained thing phase and the content of each thing phase, use the pattern of the molecular sieve of brilliant situation of scanning electron microscopic observation binding agent commentaries on classics and generation with XRD.Change brilliant back binder content determine by the XRD thing mutually quantitatively and in the stereoscan photograph content of binding agent determine.The catalyst silica alumina ratio is determined 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 by adding single crystal seed β zeolite in preformed catalyst, put into the template agent steam of specific suitable modenite growth, control is suitable for the alkaline environment and the material proportion of modenite and β zeolite growth simultaneously, make binding agent under the inducing of β zeolite seed crystal, can change into β zeolite active ingredient, simultaneously in the control environment of template agent steam and alkalescence, also can induce the modenite crystal seed in the binding agent, and can nucleating growth, therefore binding agent can be transformed into the coexisting molecular sieve active principle by the method for gas phase conversion, obtain binder free type mordenite/beta zeolite coexisting molecular sieve catalyst, reach the purpose of simple environmental protection.The content of binding agent can reach below 1% in the binder free type mordenite/beta zeolite coexisting molecular sieve catalyst that makes, even do not contain binding agent, all the mordenite/beta zeolite 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.Owing to change staggered growth between the binder free coexisting molecular sieve thing phase that obtains behind the crystalline substance,,, can reach more than 180 newton so the intensity of catalyst is also higher in conjunction with tightr.The 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 54.5%, has obtained better technical effect.
Description of drawings
Fig. 1 is the XRD figure spectrum of the binder free mordenite/beta zeolite coexisting molecular sieve catalyst of embodiment 1 preparation.
Fig. 2 is the ESEM picture of the binder free mordenite/beta zeolite coexisting molecular sieve catalyst of embodiment 1 preparation.
Below by specific embodiment the present invention being done a nearly step sets forth.
The specific embodiment
[embodiment 1]
Get SiO
2/ Al
2O
3Mol ratio is 40 β zeolite 60 grams, adding quality percentage composition 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, agent bar moulding then, preformed catalyst was 80 ℃ of oven dry 3 hours, putting into the moisture and hexamethylene diamine mass ratio of inner bag bottom then is 200 milliliters autoclave of 1: 1 mixed solution 40 grams, catalyst does not contact with liquid water, put into baking oven after the autoclave sealing, 180 ℃ 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 400 ℃ of roastings of Muffle furnace internal program intensification 2 hours, 550 ℃ of roastings 3 hours make binder free mordenite/beta zeolite coexisting molecular sieve catalyst, and wherein the weight percentage of modenite is 35.7%, the β zeolite content is 63.3%, and the withstand voltage broken intensity of detecting catalyst sample is 160 newton.。The XRD figure of the catalyst that makes is composed as shown in Figure 1, and it is shown as the thing phase of mordenite/beta zeolite.The ESEM picture of the catalyst that makes as shown in Figure 2, it is shown as the mixture of ball-type modenite crystal grain and β zeolite grain, 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 be 20,40,60,80 and 100 β zeolite as crystal seed, other condition is constant, it is as shown in table 1 that raw material is formed proportioning, 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, add soluble starch, sesbania powder or methylcellulose, it is as shown in table 1 that raw material is formed proportioning, mixing and stirring, extruded moulding is made binder free mordenite/beta zeolite 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 binder free mordenite/beta zeolite coexisting molecular sieve catalyst, it with concentration 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 mordenite/beta zeolite 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 sees Table 3), the examination activity of such catalysts is that 12 millimeters fixed bed reactors normal pressure is checked and rated down with diameter, 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, and after reaction half an hour, product distributes and to see Table 4, and feed stock conversion is 94.5%, and obtaining the ethene mass yield is 29.5%, and the propylene mass yield is 24%, and diene quality total recovery is 54.5%.
Table 2
Table 3 light oil raw material index
| 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 |
[embodiment 15]
Get the binder free type mordenite/beta zeolite that obtains among the embodiment 1, method by embodiment 14 is made hydrogen type catalyst, get 100 grams, with concentration is that 300 milliliters of the ammonium hydrogen phosphates of 0.5 mol flooded modification 4 hours at 95 ℃, then sample is taken out 120 ℃ of oven dry 3 hours,, obtain the binder free type mordenite/beta zeolite coexisting molecular sieve catalyst of phosphorus modification again 650 ℃ of roastings 3 hours, method according to embodiment 14 is checked and rated, and the results are shown in Table 5.
[embodiment 16]
Get binder free type mordenite/beta zeolite coexisting molecular sieve catalyst 100 grams of the phosphorus modification that obtains among the embodiment 15, with concentration is that 300 milliliters of the ammonium hydrogen phosphates of 0.2 mol flooded modification 4 hours at 95 ℃, then sample is taken out 120 ℃ of oven dry 3 hours, again 650 ℃ of roastings 3 hours, obtain the binder free type ZSM-5/ beta zeolite coexisting molecular sieve catalyst of lanthanum and phosphorus modification, method according to embodiment 14 is checked and rated, and the results are shown in Table 5.
[comparative example 1]
Preparing silica alumina ratio by the method for Chinese patent CN1647856A is 40 mordenite/beta zeolite mixed crystal molecular sieve, method by embodiment 14 is made hydrogen type molecular sieve, then mixed crystal molecular sieve direct tablet compressing, break into pieces, sieve, 20～40 purpose catalyst granules that do not contained binding agent, put into fixed bed reactors, press the method examination of embodiment 14, the results are shown in Table 5.
[comparative example 2]
Preparing silica alumina ratio by the method for Chinese patent CN1647856A is 40 mordenite/beta zeolite mixed crystal molecular sieve, method by embodiment 14 is made hydrogen type molecular sieve, and then according to the method extruded moulding of embodiment 1, obtain containing the mordenite/beta zeolite mixed crystal molecular sieve catalyst of binding agent, put into fixed bed reactors, press the method examination of embodiment 14, the results are shown in Table 5.
[comparative example 3]
The silica alumina ratio of getting the production of Shanghai petrochemical industry research institute is 40 modenite, method by embodiment 14 is made hydrogen type molecular sieve, then the modenite direct tablet compressing, break into pieces, sieve, 20～40 purpose catalyst granules that do not contained binding agent, put into fixed bed reactors, press the method examination of embodiment 14, the results are shown in Table 5.
[comparative example 4]
The silica alumina ratio of getting the production of Shanghai petrochemical industry research institute is 40 β zeolite, method by embodiment 14 is made hydrogen type molecular sieve, then β zeolite direct tablet compressing, break into pieces, sieve, 20～40 purpose catalyst granules that do not contained binding agent, put into fixed bed reactors, press the method examination of embodiment 14, the results are shown in Table 5.
[comparative example 5]
The silica alumina ratio that Shanghai petrochemical industry research institute produces is 40 modenite, method by embodiment 14 is made hydrogen type molecular sieve, method by embodiment 14 is made hydrogen type molecular sieve, and then according to the method extruded moulding of embodiment 1, obtain containing the ZSM-5 molecular sieve catalyst of binding agent, put into fixed bed reactors, press the method examination of embodiment 14, the results are shown in Table 5.
[comparative example 6]
The silica alumina ratio of getting the production of Shanghai petrochemical industry research institute is 40 β zeolite, method by embodiment 14 is made hydrogen type molecular sieve, make hydrogen type molecular sieve by the method for embodiment 14 then, and then according to the method extruded moulding of embodiment 1, obtain containing the beta zeolite coexisting molecular sieve catalyst of binding agent, put into fixed bed reactors, press the method examination of embodiment 14, the results are shown in Table 5.
[comparative example 7]
The silica alumina ratio of getting the production of Shanghai petrochemical industry research institute is 40 modenite, silica alumina ratio is 40 β zeolite, be mixed into mechanical impurity at 1: 1 according to weight ratio, method by embodiment 14 is made hydrogen type molecular sieve, and then, obtain containing the modenite of binding agent and the catalyst of β zeolite mechanical impurity according to the method extruded moulding of embodiment 1, put into fixed bed reactors, press the method examination of embodiment 14, the results are shown in Table 5.
Table 4
| Product is formed | Product weight yield (%) |
| Methane | 4.5 |
| Ethane | 6.8 |
| Ethene | 29.5 |
| Propane | 6.3 |
| Propylene | 24.0 |
| Butane | 8.8 |
| Butylene | 7.4 |
| Carbon five above cuts | 8.1 |
| Other | 4.6 |
Table 5
Claims (7)
1. binder free mordenite/beta zeolite coexisting molecular sieve Preparation of catalysts method may further comprise the steps:
A) the catalyst weight meter after the roasting, after the compound of the β zeolite 10～80%, 0.2～20% alkaline matter, 0.5～20% 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) thing I places to put into and contains at least a template agent steam that is selected from ammoniacal liquor, ethylenediamine, triethylamine, n-butylamine, hexamethylene diamine, 4-propyl bromide or TPAOH, carries out obtaining binder free mordenite/beta zeolite coexisting molecular sieve catalyst precarsor after crystallization is handled 10～240 hours at 120～200 ℃;
C) precursor 400～700 ℃ of following roastings 1～10 hour, obtains binder free mordenite/beta zeolite coexisting molecular sieve catalyst through super-dry;
Wherein, in the catalyst weight behind the shaping and roasting, template agent is 5～300%, the SiO of β zeolite
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 or IIA element; The compound of aluminium is selected from least a in the hydroxide of the hydrous oxide of oxide, aluminium of aluminium salt, aluminium or aluminium.
2. binder free mordenite/beta zeolite coexisting molecular sieve Preparation of catalysts method according to claim 1 is characterized in that I A element is selected from least a in sodium or the potassium, and 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.
3. binder free mordenite/beta zeolite coexisting molecular sieve Preparation of catalysts method according to claim 1 is characterized in that in the catalyst weight behind the shaping and roasting consumption of molecular sieve is 15～70%; The consumption of alkaline matter is 0.5～10%; The consumption of the compound of aluminium is 2～15%; The consumption of silica is 15～70%; Template agent is 10～100%.
4. binder free mordenite/beta zeolite coexisting molecular sieve Preparation of catalysts method according to claim 1 is characterized in that crystallization temperature is 140-180 ℃, and crystallization time is 20～100 hours.
5. binder free mordenite/beta zeolite coexisting molecular sieve Preparation of catalysts method 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, the soluble starch that is selected among the preformed catalyst precursor mixture I.
6. binder free mordenite/beta zeolite coexisting molecular sieve Preparation of catalysts method according to claim 1 is characterized in that the SiO of prepared mordenite/beta zeolite coexisting molecular sieve
2/ Al
2O
3Be 20～120, wherein weight of binder content 0～5%; The weight ratio of modenite and β zeolite is 0.2～100: 1 in the mordenite/beta zeolite coexisting molecular sieve, the catalyst strength behind the shaping and roasting be 50～200 newton/.
7. binder free mordenite/beta zeolite coexisting molecular sieve Preparation of catalysts method according to claim 6, it is characterized in that in the catalyst weight behind the shaping and roasting weight of binder content is 0.1～2% in the binder free mordenite/beta zeolite coexisting molecular sieve catalyst that makes.
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| CN100384735C (en) * | 2005-08-15 | 2008-04-30 | 中国石油化工股份有限公司 | Method for preparing ZSM-5 zeolite in small crystal grain without bonding agent |
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| CN114471691B (en) * | 2020-10-26 | 2023-08-04 | 中国石油化工股份有限公司 | Beta/mercerized composite crystalline phase zeolite catalyst and preparation method and application thereof |
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