CN102371183B - 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 adhesive-free fluidized bed catalyst, particularly about a kind of preparation method of molecular sieve fluid bed catalyst of the reaction for preparing low-carbon olefin by catalytic pyrolysis light oil.
Background technology
Ethylene, propylene industry has very important status 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.Ethene and propylene can be used for producing plastics and other chemical products, are important Organic Chemicals, and along with 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 widely used in field of petrochemical industry 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 become catalyst to be applied to 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 higher, if adopt 100% molecular sieve as industrial catalyst, with so that the operating cost of industrial process increase.Industrial process General Requirements catalyst possesses certain shape and intensity to be adapted to industrial reactor.For fixed bed reactors, catalyst need not mobile after installing, but catalyst need possess certain crush strength, to prevent in dress agent process that catalyst is hit and damaged, and prevents from being installed in the catalyst of lower floor owing to bearing pressure and breakage.The damaged efflorescence of catalyst may cause the rising of device Pressure Drop, and 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 or turbulence in reactor, 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, selective, stability, shape and intensity simultaneously concurrently, thereby satisfies industrial process to the requirement of catalyst.
The US6509290 patent disclosure a kind of method for preparing molecular sieve catalyst, contain molecular sieve in this catalyst and grind particle and initial molecule sieve.This grinds particle mainly from the broken particle of Catalyst Production technique and reaction system recirculation.The 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, the 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 disclosure a kind of method for preparing molecular sieve catalyst, the method comprise with molecular sieve, liquid and effectively the molecular sieve catalyst of the large drying of hardening capacity be mixed together the formation slurry, 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.
Adhesive-free zeolite catalyst is exactly the active principle that the binding agent that adds in the zeolite molecular sieve catalyst forming process is changed into molecular sieve, makes not contain Binder Composition in the whole catalyst, keeps simultaneously the good intensity of catalyst.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 the activity of catalyst higher, treating capacity is larger, 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 catalyst based on binder-free zeolite molecular sieves refers in the catalyst binder content less than or equal to 5%.
General molecular sieve is the method preparation by Hydrothermal Synthesis, is Powdered, without intensity, easily runs off, even compression molding, intensity also is lower than 20 newton, can not directly use, and need to add binding agent when industry or laboratory applications and carry out extrusion or spray shaping.In the general molecular sieve based catalyst forming process, the weight that add binding agent is no less than 40% of total catalyst weight, although 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 adhesive-free fluidized bed catalyst is provided.The catalyst that the method makes has the high advantage of catalytic activity.
For addressing the above problem, the technical solution used in the present invention is as follows: a kind of preparation method of adhesive-free fluidized bed 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) the catalyst precarsor II is put into the template steam, 100～200 ℃ of crystallization 10～200 hours, obtain the catalyst precarsor III;
(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 with the finished catalyst weighing scale 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 with the finished catalyst weighing scale 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 with the finished catalyst weighing scale 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 with contained molecular sieve weighing scale 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 with contained molecular sieve weighing scale in the finished catalyst weight after the roasting, the consumption preferable range of dispersant is 0.01～10%; Adopt the middle material particular diameter preferable range of method control step (b) of high speed shear or circulating emulsion 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 kg/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 % by weight/hour; Binding agent accounts for 10～40 % by weight in the catalyst that makes; Molecular sieve accounts for 10～50 % by weight; Matrix material accounts for 10～80 % by 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 binder free characterization of catalyst means, with the contained phase of XRD test and the content of each phase, turn the pattern of the molecular sieve of the situation of crystalline substance and generation with scanning electron microscopic observation catalyst cross section binding agent.Turn brilliant after binder content by the XRD phase quantitatively and in the stereoscan photograph content of binding agent determine.The catalyst silica alumina ratio is determined 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 by adding, make each component Uniform Dispersion in the catalyst, be difficult for reuniting, after adopting emulsify at a high speed to shear, suspension is difficult for layering or precipitation, and the catalyst surface of preparing is smooth, sphericity is high, and fluid effect is better.Owing to added expanding agent in catalyst preparation process, the diffusion of catalyst is better again, and activity is higher.Because the slurry of preparation is evenly, each material asks and can combine closely, in conjunction with closely, the finished catalyst that obtains has higher scuff resistance between each phase of the catalyst of preparation, its abrasion index can reach 0.01 % by weight/hour.The present invention is also by adding crystal seed in preformed catalyst, control is suitable for alkaline environment and the material proportion of zeolite growth, make binding agent lower jointly inducing of 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 adhesive-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 turn the staggered growth of the binder free catalyst zeolite crystal grain that obtains behind the crystalline substance, intercrystalline is in conjunction with closely, so the intensity of catalyst is also higher.It is more that the present invention also has in the unit volume active site by employing, the pore volume of catalyst is larger, average pore size and porosity are larger, catalyst activity and diffusion be the binder free catalyst preferably, improved the quantity of active site in the unit volume, macroporosity can contact rapidly with active site raw material, product can diffuse out rapidly, reduced the generation of carbon distribution and other side reactions, improved the selective of low-carbon alkene, higher pore volume has also increased the appearance carbon ability of catalyst, makes catalyst activity higher, life-span is longer, has obtained preferably technique effect.
Description of drawings
Fig. 1 is the XRD collection of illustrative plates of the adhesiveless ZSM-5 catalyst of embodiment 1 preparation
The invention will be further elaborated below by embodiment, 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, use high-speed shearing machine high speed shear 30 minutes, then add 400 gram sial molecular proportions and be 30 ZSM-5 molecular sieve, high speed shear is 30 minutes again, then adds aluminium colloidal sol 500 grams of salic 20 % by weight, continues high speed shear 30 minutes, add again 1 gram Triammonium citrate, continue high speed shear after 30 minutes, measure the granularity of this suspension with laser particle analyzer, 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 kg/hour, obtains forming microspherical catalyst precursor I.The catalyst precarsor I adopts temperature-programmed calcination, burns 3 hours at 400 ℃, and then 650 ℃ were burnt 3 hours, 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, 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, then wash 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 ZSM-5 fluidized bed catalyst.The XRD collection of illustrative plates of the catalyst that makes as shown in Figure 1, it is shown as pure ZSM-5 phase.The ESEM picture of the catalyst that makes as shown in Figure 2, it is shown as pure ZSM-5 crystal grain, has hardly the binding agent of unformed state.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 abrasion instrument measure abrasion index be 0.02 % by weight/hour.
[embodiment 2～10]
According to the method for embodiment 1, adopt batching and the preparation condition of table 1 and table 3, wherein Ludox is for containing silica 40 % by weight, and it is as shown in table 2 to make fluidized bed catalyst performance.
Table 3
[embodiment 11]
The methods of getting 200 gram embodiment 1 make fluid bed ZSM-5 catalyst, put 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 sees Table 4), the examination catalyst activity, 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 product distributes and is shown in Table 5, and obtaining the weight ethylene yield is 28%, and the propylene weight yield is 22%, diene weight total recovery is 50%.
Table 4 light oil raw material index
| Project | Data |
| Density (20 ℃) kg/m 3 | 704.6 |
| Boiling range is boiling range ℃ just | 40 |
| Whole boiling range ℃ | 160 |
| Saturated vapor pressure (20 ℃) kPa | 50.2 |
| Alkane % (% by weight) | 65.2 |
| Cycloalkane % (% by weight) | 28.4 |
| Alkene % (% by weight) | 0.2 |
| Aromatic hydrocarbons % (% by weight) | 6.2 |
Table 5
| Product distributes | 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 (1)
1. the preparation method of an adhesive-free fluidized bed catalyst, 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, then add 400 gram sial molecular proportions and be 30 ZSM-5 molecular sieve, high speed shear is 30 minutes again, then aluminium colloidal sol 500 grams that add salic 20 % by weight, continue high speed shear 30 minutes, and added again 1 gram Triammonium citrate, continue high speed shear after 30 minutes, measure the granularity of this suspension with laser particle analyzer, 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 kg/hour, obtains forming the microspherical catalyst precursor I; Catalyst precarsor I adopts temperature-programmed calcination, burns 3 hours at 400 ℃, and then 650 ℃ were burnt 3 hours, 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, 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, then wash 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 ZSM-5 fluidized bed catalyst; The XRD collection of illustrative plates of the catalyst that makes is shown as pure ZSM-5 phase; The ESEM picture of the catalyst that makes is shown as pure ZSM-5 crystal grain, has hardly the binding agent of unformed state, and the binder content of unformed state is 0.2%;
The catalyst that obtains after the roasting is measured granularity with laser particle analyzer, and its average grain diameter is 70 microns, and nitrogen adsorption desorption measurement the specific area is 310m
2/ gram, average pore size is 3.5nm, density of catalyst be at 0.8 grams per milliliter, adopt abrasion instrument mensuration abrasion index be 0.02 % by weight/hour.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102618617A CN102371183B (en) | 2010-08-23 | 2010-08-23 | Preparation method for adhesive-free fluidized bed catalyst |
| 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 |
| SG2013012976A SG187927A1 (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 |
| RU2013112852/04A RU2565599C2 (en) | 2010-08-23 | 2011-08-23 | Binder-free molecular sieve-based catalyst and method for production thereof |
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| CN107511173B (en) * | 2016-06-18 | 2020-02-07 | 中国石油化工股份有限公司 | Process for producing alkylbenzene |
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| CN101121148B (en) * | 2006-08-08 | 2010-05-12 | 中国科学院大连化学物理研究所 | Direct forming method of fluidized reaction catalyst containing molecular sieve |
| CN101259424B (en) * | 2008-03-18 | 2011-05-18 | 南京工业大学 | Preparation of toluene shape-selective disproportionation without adhesive |
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