CN102371166A - Preparation method of binder-free ZSM-5 fluidized bed catalyst - Google Patents
Preparation method of binder-free ZSM-5 fluidized bed catalyst Download PDFInfo
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Abstract
The invention relates to a preparation method of a binder-free ZSM-5 fluidized bed catalyst and mainly solves the problem of low activity of ZSM-5 fluidized bed catalysts in the prior art. The preparation method of the binder-free ZSM-5 fluidized bed catalyst in the invention comprises the following steps of: (a) uniformly mixing a binder, a matrix material, a pore-expanding agent, a dispersant, a guiding agent and a liquid medium to form a fluid suspension; (b) carrying out high-speed shearing, dispersing, and controlling the granularity of the materials in the fluid suspension within 0.1 to 5 microns; (c) carrying out spray drying on the fluid suspension to form a microspheric catalyst precursor I; (d) roasting the microspheric catalyst precursor I at the temperature of 300-700 DEG C for 1-10 hours to obtain a catalyst precursor II; (e) putting the catalyst precursor II into template steam, and crystallizing at the temperature of 100-200 DEG C for 10-200 hours to obtain a catalyst precursor III; (f) roasting the microspheric catalyst precursor III at the temperature of 400-700 DEG C for 1-10 hours to obtain the finished product catalyst. The technical scheme greatly solves the problem and can be applied in the reaction process of producing light olefins by light oil catalytic cracking.
Description
Technical field
The present invention relates to a kind of preparation method of adhesiveless ZSM-5 fluid catalyst, particularly about a kind of preparation method of ZSM-5 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, even compression molding, intensity also is lower than 20 newton, 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 2～10 the pH value, 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, 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.
Summary of the invention
Technical problem to be solved by this invention is the lower problem of ZSM-5 fluid catalyst activity that exists in the prior art, and a kind of preparation method of new adhesiveless ZSM-5 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 adhesiveless ZSM-5 fluid catalyst may further comprise the steps:
(a) binding agent, host material, expanding agent, dispersant, directed agents 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 the microspherical catalyst precursor I;
(d) this microspherical catalyst precursor I of 300～700 ℃ of roastings 1～10 hour, obtain catalyst precarsor II;
(e) put into the template steam to catalyst precarsor II,, obtain catalyst precarsor III 100～200 ℃ of crystallization 10～200 hours;
(f) this microspherical catalyst precursor II of 400～700 ℃ of roastings I 1～10 hour, obtain the adhesiveless ZSM-5 fluid catalyst.
In the technique scheme, with the solid constituent weight percent meter of suspension, it is 20～80% for the binding agent consumption that the solid constituent of suspension is formed preferable range; The host material consumption is 10～70%; The consumption of expanding agent is 0.1～5%; The consumption of dispersant is 0.01～5%; The directed agents consumption is 0.01～4%; Wherein, the binding agent preferred version is to be selected from least a in silica sol liquid or the solid amorphous silica; The host material preferred version is to be selected from least a in kaolin, calcined kaolin, diatomite, bentonite, carclazyte or the clay; The expanding agent preferred version is to be selected from least a in methylcellulose, polyvinyl alcohol, sesbania powder, soluble starch or the CNT; The dispersant preferred version is to be selected from least a in Triammonium citrate, ammonium oxalate, ammonium carbonate or the carbonic hydroammonium, and the directed agents preferred version is at least a in oxide, hydroxide or its salt of weak acid that is selected from period of element Table I A or IIA element.
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 to be selected from least a in ammoniacal liquor, ethylenediamine, triethylamine, n-butylamine, hexamethylene diamine, 4-propyl bromide or TPAOH, tetraethyl ammonium hydroxide or the tetraethylammonium bromide.
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,, each component is evenly disperseed through adding at least a dispersant in Triammonium citrate, ammonium oxalate, ammonium carbonate or the carbonic hydroammonium; 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; Owing in catalyst preparation process, added at least a expanding agent in methylcellulose, polyvinyl alcohol, sesbania powder, soluble starch or the CNT, the diffusion of catalyst is better again, and is active higher.Because the slurry of preparation is evenly, can combine closely between each material, the alternate combination of each thing of the catalyst of preparation is tight, and the finished catalyst that obtains has higher scuff resistance, its abrasion index can reach 0.01 weight %/hour.Among the present invention also through the suitable material proportion of control, uses the oxide that is selected from period of element Table I A or IIA element, hydroxide perhaps at least a in its salt of weak acid be directed agents, in the template steam; Material is converted into ZSM-5 binder free catalyst, and the content of binding agent can reach below 2% in the binder free type zeolite catalyst that makes, and does not even contain binding agent; Be zeolite all in the catalyst, in the unit volume, the molecular sieve content in the catalyst is higher; Therefore; The active site number of unit volume inner catalyst is also more, so the adhesiveless ZSM-5 molecular sieve catalyst is active higher, 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
Fig. 2 is the ESEM picture 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 Ludox 500 grams of silicon oxide-containing 40 weight % then, continued high speed shear 30 minutes; Add 1 gram Triammonium citrate again, sodium carbonate 2 grams continued 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 the microspherical catalyst precursor I.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, 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 appearance mensuration 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 an adhesiveless ZSM-5 fluid catalyst may further comprise the steps:
(a) binding agent, host material, expanding agent, dispersant, directed agents 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 the microspherical catalyst precursor I;
(d) this microspherical catalyst precursor I of 300～700 ℃ of roastings 1～10 hour, obtain catalyst precarsor II;
(e) put into the template steam to catalyst precarsor II,, obtain catalyst precarsor III 100～200 ℃ of crystallization 10～200 hours;
(f) this microspherical catalyst precursor II of 400～700 ℃ of roastings I 1～10 hour, obtain the adhesiveless ZSM-5 fluid catalyst.
2. the preparation method of adhesiveless ZSM-5 fluid catalyst according to claim 1 is characterized in that the solid constituent weight percent meter with suspension,
The binding agent consumption is 20～80%;
The host material consumption is 10～70%;
The consumption of expanding agent is 0.1～5%;
The consumption of dispersant is 0.01～5%;
The directed agents consumption is 0.01～5%;
Wherein, binding agent is to be selected from least a in silica sol liquid or the solid amorphous silica; Host material is to be selected from least a in kaolin, calcined kaolin, diatomite, bentonite, carclazyte or the clay; Expanding agent is to be selected from least a in methylcellulose, polyvinyl alcohol, sesbania powder, soluble starch or the CNT; Dispersant is to be selected from least a in Triammonium citrate, ammonium oxalate, ammonium carbonate or the carbonic hydroammonium, and directed agents is at least a in oxide, hydroxide or its salt of weak acid that is selected from period of element Table I A or IIA element.
3. the preparation method of adhesiveless ZSM-5 fluid catalyst according to claim 2 is characterized in that I A element is selected from least a in sodium or the potassium; The IIA element is selected from least a in magnesium or the calcium; Salt of weak acid is selected from least a in disulfate, sulphite, bisulfites, phosphate, the hydrophosphate.
4. the preparation method of adhesiveless ZSM-5 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.
5. the preparation method of adhesiveless ZSM-5 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.
6. the preparation method of adhesiveless ZSM-5 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 %.
7. the preparation method of adhesiveless ZSM-5 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 the TPAOH; Wherein, in the weight of the catalyst precarsor II behind the shaping and roasting, template agent is 5～200%.
8. the preparation method of adhesiveless ZSM-5 fluid catalyst according to claim 1, the crystallization temperature that it is characterized in that catalyst precarsor II is 120～180 ℃, crystallization time 10～200 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102962012A (en) * | 2012-11-21 | 2013-03-13 | 陕西煤化工技术工程中心有限公司 | Inert agent for fluidized bed as well as preparation and use methods thereof |
| CN103120857A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Solid-liquid separation method of nanometer material |
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| CN103120857A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Solid-liquid separation method of nanometer material |
| CN103120857B (en) * | 2011-11-18 | 2015-08-12 | 中国石油化工股份有限公司 | The solid-liquid separating method of nano material |
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Application publication date: 20120314 |