CN102371183A - Preparation method for adhesive-free fluidized bed catalyst - Google Patents
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Abstract
The invention relates to a preparation method for an adhesive-free fluidized bed catalyst. The problem of low activity of the fluidized bed catalyst in the prior art is mainly solved. The problem is well solved by adopting the technical scheme that the preparation method for the fluidized bed catalyst comprises the following steps of: (a) uniformly mixing molecular sieve, adhesive, a matrix material, a pore expanding agent, dispersant and a liquid medium to form suspension; (b) performing high-speed shearing and dispersion, and controlling the granularity of the materials in the suspension to be between 0.1 and 5 microns; (c) performing spray drying on the suspension to form a micro-spherical catalyst precursor I; (d) roasting the micro-spherical catalyst precursor I at the temperature of between 300 and 700 DEG C for 1 to 10 hours to obtain a catalyst precursor II; (e) putting the catalyst precursor II into template steam, and crystallizing at the temperature of between 100 and 200 DEG C for 10 to 200 hours to obtain a catalyst precursor III; and (f) roasting the micro-spherical catalyst precursor III at the temperature of between 400 and 700 DEG C for 1 to 10 hours to obtain a catalyst finished product. The catalyst can be applied to the reaction process of preparing low-carbon olefin by catalytic pyrolysis of light oil.
Description
Technical field
The present invention relates to a kind of preparation method of binder free fluid catalyst, particularly about a kind of preparation method of molecular sieve fluid bed catalyst of the reaction that is used for the naphtha catalytic cracking producing light olefins.
Background technology
Ethylene, propylene industry has critical role as the tap of petrochemical industry in the national economic development.Along with the development of society, the market demand of China's ethylene, propylene sharply increases, and the import volume of ethylene, propylene and downstream product thereof increases year by year, and the home products occupation rate of market is less than half the.Ethene and propylene can be used for producing plastics and other chemical products, are important Organic Chemicals, and along with the progress and the development of modern society, its demand is increasing.Ethylene yield more than 98% comes from steam cracking technology in the world at present, and production of propylene mainly produces the joint product of ethene with steam cracking and two kinds of forms of byproduct of oil plant catalytic cracking obtain.
Molecular sieve is applied in field of petrochemical industry widely owing to have good shape selective catalysis performance and heat endurance preferably.When molecular sieve is applied to Industrial Catalysis, generally can not adopt 100% molecular sieve to be prepared into catalyst applications in industrial process.Self caking property of molecular sieve is poor, and self granularity is too tiny, is difficult to be shaped to the catalyst that directly applies to industrial process.The manufacturing cost of molecular sieve is generally than higher, if adopt 100% molecular sieve as industrial catalyst, with making the operating cost of industrial process increase.Industrial process generally requires catalyst to possess certain shape and intensity to be adapted to industrial reactor.For fixed bed reactors, catalyst need not to move after installing, but catalyst need possess certain crush strength, and to prevent in dress agent process that catalyst is hit and damaged, and the catalyst that prevents to be installed in lower floor is owing to bearing pressure and breakage.The rising that the damaged efflorescence of catalyst possibly cause device pressure to fall, reflex action may occur unusually, and the product composition changes, and is unfavorable for the goal response process.For fluidized-bed reactor; Because this constantly circulates catalyst in reactor or turbulence; Friction between catalyst granules and particle, catalyst and wall of reactor, catalyst and regenerator wall, catalyst and heat collector wall, catalyst and the conveyance conduit wall and collision all can make catalyst levigate and damaged, final form effusion reaction system with fine powder.These fine powders pollute the environment, and the use cost of catalyst is risen.Therefore, no matter be that molecular sieve is applied to fixed bed reactors, still be applied to fluidized-bed reactor, all need pass through molecular sieve and carrier material the effect formation molecular sieve catalyst composition of binding agent; This combination of molecular sieve can have catalytic activity, selectivity, stability, shape and intensity concurrently simultaneously, thereby satisfies the requirement of industrial process to catalyst.
The US6509290 patent discloses a kind of method for preparing molecular sieve catalyst, contains molecular sieve in this catalyst and grinds particle and initial molecule sieve.This grinds particle mainly from the broken particle of Catalyst Production technology and reaction system recirculation.This method comprises molecular sieve, original binding agent and filler, spray-diredly grinds particle or agglomerate and be mixed together from the non-original particle that grinds of reaction unit.This mixture is dry, form the finished product catalyst granules.In order to increase the intensity of catalyst granules, this grinds particle and is substantially free of coke.
The US6153552 patent research a kind of method for preparing molecular sieve catalyst; This method comprises molecular sieve and alumina sol is mixed together; This alumina sol prepares in solution and remains under the pH value of 2-10, and this mixture of spray-drying and high-temperature roasting makes wear-resistant catalyst.
The CN1791463 patent discloses a kind of method for preparing molecular sieve catalyst, and this method comprises that the molecular sieve catalyst with molecular sieve, liquid and effective big drying of hardening capacity is mixed together the formation slurry, and roasting behind dry this slurry forms wear-resistant catalyst.
Although more existing patents have related to the preparation method of fluid catalyst, the scuff resistance of fluid catalyst is lower, needs further to improve.
The binder free zeolite catalyst is exactly the active principle that changes into the binding agent that is added in the zeolite 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.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 binder free zeolite molecular sieve catalyst refers in the catalyst binder content smaller or equal to 5%.
General molecular sieve is to prepare through the synthetic method of hydro-thermal, is Powdered, and no intensity is prone to run off, even compression molding, intensity also is lower than 20 newton, 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.
Summary of the invention
Technical problem to be solved by this invention is the low problem of fluid catalyst catalytic activity that exists in the prior art, and a kind of preparation method of new binder free fluid catalyst is provided.The catalyst that this method makes has the high advantage of catalytic activity.
For addressing the above problem, the technical scheme that the present invention adopts is following: a kind of preparation method of binder free fluid catalyst may further comprise the steps:
(a) molecular sieve, binding agent, host material, expanding agent, dispersant and liquid medium are uniformly mixed to form suspension;
(b) high speed shear, dispersion, control suspension in raw meal particle size between 0.1～5um;
(c) this suspension of spray-drying forms microspherical catalyst precursor I;
(d) this microspherical catalyst precursor I of 300～700 ℃ of roastings 1～10 hour, obtain the catalyst precarsor II;
(e) put into the template steam to the catalyst precarsor II,, obtain the catalyst precarsor III 100～200 ℃ of crystallization 10～200 hours;
(f) this microspherical catalyst precursor III of 400～700 ℃ of roastings 1～10 hour, obtain finished catalyst.
In the technique scheme, the molecular sieve preferred version is for being selected from least a in ZSM-5, ZSM-23, ZSM-11, modenite, Y zeolite, β zeolite, MCM-22, MCM-49, MCM-56, ZSM-5/ modenite, ZSM-5/ β zeolite, ZSM-5/Y, MCM-22/ modenite, ZSM-5/Magadiite, ZSM-5/ β zeolite/modenite, ZSM-5/ β zeolite/Y zeolite or ZSM-5/Y zeolite/modenite of molecular screening; The crystal particle diameter preferable range of molecular sieve is between 0.1～5um, and the density preferable range of molecular sieve is at 0.5～2 grams per milliliter, and in the finished catalyst weight after the roasting, the molecular sieve content preferable range is 10～60%; The binding agent preferred version is to be selected from least a in Ludox or the aluminium colloidal sol, and in the finished catalyst weight after the roasting, the binder content preferable range is 2～50%; The host material preferred version is to be selected from least a in kaolin, calcined kaolin, diatomite, bentonite or the carclazyte, and in the finished catalyst weight after the roasting, the matrix material content preferable range is 10～50%; The expanding agent preferred version is to be selected from least a in methylcellulose, polyvinyl alcohol, sesbania powder, soluble starch or the CNT, and in contained molecular sieve weight in the finished catalyst weight after the roasting, the consumption preferable range of expanding agent is 0.1～10%; The dispersant preferred version is to be selected from least a in Triammonium citrate, ammonium oxalate, ammonium carbonate or the carbonic hydroammonium, and in contained molecular sieve weight in the finished catalyst weight after the roasting, the consumption preferable range of dispersant is 0.01～10%; The middle material particular diameter preferable range of method control step (b) that adopts high speed shear or circulating emulsion is between 0.1～2um; (a) step suspension solids content preferable range is 10～50%; The spray shaping condition is 180～300 ℃ of inlet temperatures, 100～160 ℃ of outlet temperatures, and 5000～15000 rev/mins of centrifugal rotational speeds, exit whirlwind pressure reduction is 0.5～1.0KPa, charging rate is 0.5～5 kilogram/hour; The catalyst of spray-drying preparation is through after the high-temperature roasting; The average grain diameter of particle is between 50～90um, and specific area is between 100～300, and average pore size is between 1～20nm; Density between 0.6～1.2 grams per milliliter, abrasion index 0.01～1.2 weight %/hour; Binding agent accounts for 10～40 weight % in the catalyst that makes; Molecular sieve accounts for 10～50 weight %; Matrix material accounts for 10～80 weight %.The template preferred version is at least a for being selected from ammoniacal liquor, ethylenediamine, triethylamine, n-butylamine, hexamethylene diamine, 4-propyl bromide or TPAOH, tetraethyl ammonium hydroxide, tetraethylammonium bromide or the hexamethylene imine.
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 scanning electron microscopic observation catalyst cross section 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 mercury injection method test is adopted in catalyst pore volume, average pore size and porosity test.
In the technical scheme of the present invention, be selected from least a dispersant in Triammonium citrate, ammonium oxalate, ammonium carbonate or the carbonic hydroammonium, each component is evenly disperseed through adding; Be difficult for reuniting; After adopting emulsify at a high speed to shear, suspension is difficult for layering or deposition, and the catalyst surface of preparing is smooth; Sphericity is high, and fluid effect is better.Owing in catalyst preparation process, added expanding agent, the diffusion of catalyst is better again, and is active higher.Because the slurry of preparation is evenly, each material asks and can combine closely that the alternate combination of each thing of the catalyst of preparation is tight, the finished catalyst that obtains has higher scuff resistance, its abrasion index can reach 0.01 weight %/hour.Also through in preformed catalyst, adding crystal seed, control is suitable for the alkaline environment and the material proportion of zeolite growth in the present invention, makes binding agent inducing jointly down at zeolite seed crystal and alkali ion; In the environment of water vapour, can carry out nucleation and growth, binding agent changes into zeolite active ingredient; Obtain the binder free zeolite catalyst; Molecular sieve content is higher in its unit volume, and therefore, active site is also more.The content of binding agent can reach below 2% in the binder free type zeolite catalyst that makes; Even not containing binding agent, all is zeolite in the catalyst, owing to change the staggered growth of the binder free catalyst zeolite crystal grain that obtains behind the crystalline substance; Intercrystalline combines closely, so the intensity of catalyst is also higher.It is more that the present invention also has in the unit volume active site through employing, and the pore volume of catalyst is bigger, and average pore size and porosity are bigger; Catalyst activity and diffusion be the binder free catalyst preferably, has improved the quantity of active site in the unit volume, and macroporosity can contact raw material with active site rapidly; Product can diffuse out rapidly, has reduced the generation of carbon distribution and other side reactions, has improved the selectivity of low-carbon alkene; Higher pore volume has also increased the appearance carbon ability of catalyst; Make catalyst activity higher, the life-span is longer, has obtained better technical effect.
Description of drawings
Fig. 1 is the XRD figure spectrum of the adhesiveless ZSM-5 catalyst of embodiment 1 preparation
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
The specific embodiment
[embodiment 1]
Take by weighing 500 gram kaolin and sesbania powder 2 grams, after mixing, add 2000 gram distilled water; With high-speed shearing machine high speed shear 30 minutes, add 400 gram sial molecular proportions then and be 30 ZSM-5 molecular sieve, high speed shear is 30 minutes again; Add aluminium colloidal sol 500 grams of salic 20 weight % then, continued high speed shear 30 minutes, add 1 gram Triammonium citrate again; Continue high speed shear after 30 minutes, with the granularity of this suspension of laser particle analyzer mensuration, its average grain diameter is 2 microns.Use the spray dryer spray shaping, the spray shaping condition is: 240 ℃ of inlet temperatures, and 120 ℃ of outlet temperatures, 10000 rev/mins of centrifugal rotational speeds, exit whirlwind pressure reduction is 0.7KPa, charging rate is 1 kilogram/hour, obtains forming microspherical catalyst precursor I.The catalyst precarsor I adopts temperature-programmed calcination, burns 3 hours at 400 ℃, and 650 ℃ were burnt 3 hours then, obtains the preformed catalyst precursor II after the roasting.
The preformed catalyst precursor II of 200 grams after the roastings, put into the inner bag of autoclave, the inner bag bottom contains 50 gram water and 50 gram ethylenediamines, and the centre is separated with screen cloth; Catalyst is put on the screen cloth, and catalyst does not contact with liquid water, puts into baking oven after the autoclave sealing; 180 ℃ of crystallization were taken out after 80 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 the adhesiveless ZSM-5 fluid catalyst.The XRD figure spectrum of the catalyst that makes is as shown in Figure 1, and it is shown as pure ZSM-5 thing phase.The ESEM picture of the catalyst that makes is as shown in Figure 2, and it is shown as pure ZSM-5 crystal grain, has the binding agent of unformed state hardly.The binder content of unformed state is 0.2%.
The catalyst that obtains after the roasting is measured granularity with laser particle analyzer; Its average grain diameter is 70 microns, and nitrogen adsorption desorption measurement the specific area is the 310m2/ gram, and average pore size is 3.5nm; Density of catalyst is at 0.8 grams per milliliter, adopt the abrasion appearance measure abrasion index be 0.02 weight %/hour.
[embodiment 2～10]
According to the method for embodiment 1, adopt the batching and the preparation condition of table 1 and table 3, wherein Ludox is for containing silica 40 weight %, and it is as shown in table 2 to make the fluid catalyst performance.
Table 3
[embodiment 11]
The method of getting 200 gram embodiment 1 makes fluid bed ZSM-5 catalyst, puts into internal diameter and be 50 millimeters fluidized-bed reactor, and 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 4), the examination activity of such catalysts, range of reaction temperature is 680 ℃, reaction pressure is 0.02MPa, weight space velocity is 1 hour
-1, water/feedstock oil weight ratio is 1: 1 time examination, and products distribution sees shown in the table 5 that obtaining the weight ethylene yield is 28%, and the propylene weight yield is 22%, and diene weight total recovery is 50%.
Table 4 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 |
Table 5
| Products distribution | Product weight yield (%) |
| Methane | 5.5 |
| Ethane | 7.6 |
| Ethene | 28.0 |
| Propane | 7.1 |
| Propylene | 22.0 |
| Butane | 8.2 |
| Butylene | 8.4 |
| Carbon five above cuts | 9.3 |
| Other | 3.9 |
Claims (8)
1. the preparation method of a binder free fluid catalyst may further comprise the steps:
(a) molecular sieve, binding agent, host material, expanding agent, dispersant and liquid medium are uniformly mixed to form suspension;
(b) high speed shear, dispersion, control suspension in raw meal particle size between 0.1～5um;
(c) this suspension of spray-drying forms microspherical catalyst precursor I;
(d) this microspherical catalyst precursor I of 300～700 ℃ of roastings 1～10 hour, obtain the catalyst precarsor II;
(e) put into the template steam to the catalyst precarsor II,, obtain the catalyst precarsor III 100～200 ℃ of crystallization 10～200 hours;
(f) this microspherical catalyst precursor III of 400～700 ℃ of roastings 1～10 hour, obtain finished catalyst.
2. the preparation method of binder free fluid catalyst according to claim 1 is characterized in that at least a in ZSM-5, ZSM-23, ZSM-11, modenite, Y zeolite, β zeolite, MCM-22, MCM-49, MCM-56, ZSM-5/ modenite, ZSM-5/ β zeolite, ZSM-5/Y, MCM-22/ modenite, ZSM-5/Magadiite, ZSM-5/ β zeolite/modenite, ZSM-5/ β zeolite/Y zeolite or ZSM-5/Y zeolite/modenite of molecular screening; The crystal particle diameter of molecular sieve is between 0.1～5um, and the density of molecular sieve is at 0.5～2 grams per milliliter, and in the finished catalyst weight after the roasting, molecular sieve content is 10～60%.
3. the preparation method of binder free fluid catalyst according to claim 1 is characterized in that binding agent is to be selected from least a in Ludox or the aluminium colloidal sol, and in the finished catalyst weight after the roasting, binder content is 2～50%; Host material is to be selected from least a in kaolin, calcined kaolin, diatomite, bentonite, carclazyte or the clay, and in the finished catalyst weight after the roasting, matrix material content is 10～50%.
4. the preparation method of binder free fluid catalyst according to claim 1; It is characterized in that expanding agent is to be selected from least a in methylcellulose, polyvinyl alcohol, sesbania powder, soluble starch or the CNT; In contained molecular sieve weight in the finished catalyst weight after the roasting, the consumption of expanding agent is 0.1～5%; Dispersant is to be selected from least a in Triammonium citrate, ammonium oxalate, ammonium carbonate or the carbonic hydroammonium, and in contained molecular sieve weight in the finished catalyst weight after the roasting, the consumption of dispersant is 0.01～5%.
5. the preparation method of binder free fluid catalyst according to claim 1 is characterized in that (a) step suspension solids content is 10～50%; The middle material particular diameter of method control step (b) that adopts high speed shear or circulating emulsion is between 0.1～2um.
6. the preparation method of binder free fluid catalyst according to claim 1; It is characterized in that the spray-drying condition is 180～350 ℃ of inlet temperatures; 100～180 ℃ of outlet temperatures; 5000～15000 rev/mins of centrifugal rotational speeds, exit whirlwind pressure reduction is 0.5～1.0KPa, charging rate is 0.5～5 kilogram/hour.
7. the preparation method of binder free fluid catalyst according to claim 1, the catalyst that it is characterized in that the spray-drying preparation is through after the high-temperature roasting, and the average grain diameter of particle is between 50～90um, and specific area is at 100～300m
2Between/the g, average pore size between 1～20nm, density between 0.6～1.2 grams per milliliter, abrasion index 0.01～1.2 weight %/hour; In the weight of the finished catalyst after the roasting, binder content is 10～40 weight % in the catalyst that makes; Molecular sieve is 10～50 weight %; Matrix material accounts for 10～80 weight %.
8. the preparation method of binder free fluid catalyst according to claim 1, it is at least a to it is characterized in that template is selected from ammoniacal liquor, ethylenediamine, triethylamine, n-butylamine, hexamethylene diamine, 4-propyl bromide or TPAOH, tetraethyl ammonium hydroxide, tetraethylammonium bromide or the hexamethylene imine; Wherein, in the weight of the catalyst precarsor II behind the shaping and roasting, template agent is 5～200%.
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| CN2010102618617A CN102371183B (en) | 2010-08-23 | 2010-08-23 | Preparation method for adhesive-free fluidized bed catalyst |
| SG2013012976A SG187927A1 (en) | 2010-08-23 | 2011-08-23 | Non-adhesive molecular sieve catalyst and preparation method therefor |
| RU2013112852/04A RU2565599C2 (en) | 2010-08-23 | 2011-08-23 | Binder-free molecular sieve-based catalyst and method for production thereof |
| US13/818,295 US9861969B2 (en) | 2010-08-23 | 2011-08-23 | Binderless molecular sieve catalyst and a preparation method thereof |
| PCT/CN2011/001408 WO2012024896A1 (en) | 2010-08-23 | 2011-08-23 | Non-adhesive molecular sieve catalyst and preparation method therefor |
| BR112013004126-9A BR112013004126B1 (en) | 2010-08-23 | 2011-08-23 | BAND-FREE MOLECULAR SIECE CATALYST AND METHOD FOR PREPARING THE SAME |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104226364A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Preparation method of molecular sieve fluidized bed catalyst |
| CN107511173A (en) * | 2016-06-18 | 2017-12-26 | 中国石油化工股份有限公司 | The production method of alkylbenzene |
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| CN1704163A (en) * | 2004-05-28 | 2005-12-07 | 中国石油化工股份有限公司 | Molecular screen microspherical catalyst |
| CN101121148A (en) * | 2006-08-08 | 2008-02-13 | 中国科学院大连化学物理研究所 | Direct forming method of fluidized reaction catalyst containing molecular sieve |
| CN101259424A (en) * | 2008-03-18 | 2008-09-10 | 南京工业大学 | Preparation of toluene shape-selective disproportionation without adhesive |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1704163A (en) * | 2004-05-28 | 2005-12-07 | 中国石油化工股份有限公司 | Molecular screen microspherical catalyst |
| CN101121148A (en) * | 2006-08-08 | 2008-02-13 | 中国科学院大连化学物理研究所 | Direct forming method of fluidized reaction catalyst containing molecular sieve |
| CN101259424A (en) * | 2008-03-18 | 2008-09-10 | 南京工业大学 | Preparation of toluene shape-selective disproportionation without adhesive |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104226364A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Preparation method of molecular sieve fluidized bed catalyst |
| CN104226364B (en) * | 2013-06-17 | 2016-08-24 | 中国石油化工股份有限公司 | The method preparing molecular sieve fluid bed catalyst |
| CN107511173A (en) * | 2016-06-18 | 2017-12-26 | 中国石油化工股份有限公司 | The production method of alkylbenzene |
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