CN103357429A - Productive propylene fluidized catalytic cracking (FCC) catalyst and preparation method thereof - Google Patents
Productive propylene fluidized catalytic cracking (FCC) catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of a productive propylene fluidized catalytic cracking (FCC) catalyst. The preparation method comprises the following steps of: mixing and pulping 530 parts by weight of H-ZSM-5 molecular sieve, 20 to 40 parts by weight of USY molecular sieve, 40 to 70 parts by weight of natural clay and 5 to 20 parts by weight of a binder for 30 to 60 minutes to obtain a mixture, wherein the adding amount of the binder is counted on the basis of silica; standing the pulped mixture for 1 to 4 hours, continuously pulping for 10 to 30 minutes, naturally drying, and drying in a drying oven at 100 to 120 DEG C for 4 to 8 hours; placing the dried product into a muffle furnace, heating to 500 to 650 DEG C, roasting for 2 to 6 hours and naturally cooling to prepare the productive propylene FCC catalyst of 100 to 200 meshes. The productive propylene FCC catalyst prepared by the method provided by the invention has the advantages of high conversion rate of heavy oil, high propylene selectivity and low yield of dry gas and coke. In addition, the preparation method of the catalyst is simple and low in cost and has good industrial application prospect.
Description
Technical field
The present invention relates to a kind of catalytic cracking (FCC) Catalysts and its preparation method, belong to oil hydrogenation catalyst catalyst preparation technical field.
Background technology
Propylene is important basic organic chemical industry raw material, and it is mainly used in synthetic its derivative such as polypropylene, acrylonitrile, expoxy propane, acrylic acid, fourth octanol, methacrylaldehyde, isopropylbenzene etc.In recent years, be subjected to the impact of polypropylene demand growth, society is day by day vigorous to the demand of propylene, the whole world all will and face the difficult problem of propylene shortage, for this reason, the petrochemical industry industrial structure is also adjusted on the increase production of propylene.
66% propylene is from hydrocarbons steam cracking device in the world at present, and 32% from the oil plant FCC apparatus, is obtained by dehydrogenating propane and other alkene conversion and cracking reaction on a small quantity.Steam cracking device is produced propylene and is only suitable in the processing lightweight material, such as natural gas, naphtha and light diesel fuel etc.Along with crude oil is more and more heavier, the yield of light oil such as naphtha reduce gradually, and the raw material imbalance between supply and demand is day by day serious; Simultaneously under 800-900 ℃ cracking temperature, the unit carbon atom Gibbs free energy of ethene is lower than propylene, and therefore no matter on reaction mechanism or thermodynamics side and considering, steam cracking all is unfavorable for the raising of Propylene Selectivity.FCC is the main processes of heavy oil lighting, reaction temperature is at 400-600 ℃, the unit carbon atom Gibbs free energy of propylene is lower than other alkene and alkane under this temperature, and under the condition of acidic catalyst catalysis, the carbonium ion reaction mechanism is deferred in the hydrocarbon cracking reaction, and propylene is one of primary product; In reaction system, add again have select the shape function MFI type molecular sieve as auxiliary agent, because this molecular sieve C in the cracked naphtha optionally
7-C
13Straight chain and short-chain branch alkene, generate the C of straight chain
3-C
5Alkene, like this, not only can improve the octane number of gasoline, and can further increase the selective of propylene.
CN1031834A discloses a kind of hydrocarbon conversion processes of preparing low-carbon olefins, the raw material that the method adopts is petroleum distillate, residual oil or the crude oil of different boiling ranges, in fluid bed or moving-burden bed reactor, use the solid acid catalyst that contains ZSM-5 molecular sieve, temperature 500-650 ℃, pressure 1.5-3.0 * 10
5Pa, weight (hourly) space velocity (WHSV) 0.2-2.0h
-1, oil ratio 2-12 condition under carry out catalytic conversion reaction.Compare with FCC and the steam pyrolysis method of routine, the method can obtain more propylene and butylene, and the total output of propylene and butylene can reach about 40%.
USP7582203B2, USP5318696 and USP4994173 disclose respectively and have added the ZSM-5 auxiliary agent to improve the method for quality of gasoline in conventional FCC catalyst, adopt these methods not having significantly to reduce the octane number that can increase gasoline under the prerequisite of gasoline yield, improving simultaneously low-carbon alkene, mainly is the productive rate of propylene and butylene.
USP5380690 and CN1093101A disclose the preparation method take the five-membered ring silica-rich zeolite of phosphorous and rare earth element as the FCC catalyst that helps active component.Hydrothermal stability and the activity stability of the catalyst of the method preparation are all higher, under 580 ℃, compare as the FCC catalyst that helps the active component preparation with the H-ZSM-5 zeolite take routine, and its conversion ratio has improved 4-7 unit, C
2-C
4The productive rate of alkene has improved 4-5 unit.
CN1354224A discloses a kind of FCC Catalysts and its preparation method of producing more propylene, and the main active component of this catalyst is high-silicon Y-Zeolite, helps active component by the compositions of mixtures of beta zeolite or modenite or ZRP zeolite.This catalyst is used for the FCC process, and when the high-quality gasoline of isoparaffin was rich in production, the productive rate of propylene and iso-butane also was improved to some extent.
CN101310858A discloses the preparation method of a kind of RFCC (RFCC) catalyst, and the main active component of this catalyst is the USY molecular sieve, and helping active component is the beta-mercerising eutectic molecular sieve of beta zeolite and modenite.Be that the RFCC catalyst of auxiliary agent is compared with adopting ZSM-5 molecular sieve, this catalyst has significantly improved heavy oil transformation rate and liquid yield in the productivity of propylene that improves RFCC.
In sum, the main method that increases at present FCC process productivity of propylene is to add to contain ZSM-5, the beta equimolecular sieve of selecting the shape function in the FCC major catalyst.But, be used at present the lower problem of ZSM-5 molecular sieve auxiliary agent ubiquity Propylene Selectivity of FCC process.And in the FCC catalyst or co-catalyst of the disclosed propylene enhancing of prior art, only paid attention to the acidity of molecular sieve and the modulation of hydrothermal stability, the pore structure of not paying close attention to molecular sieve in cracking process on the impact of product selectivity, up to the present, the relevant report of FCC process propylene enhancing productive rate, especially Propylene Selectivity not yet appears the hierarchical porous structure ZSM-5 molecular sieve is applied to.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of preparation method of producing more propylene FCC catalyst, by with ZSM-5 molecular sieve and USY molecular sieve compound obtain a kind of take the USY molecular sieve as main active component, to be rich in mesoporous multi-stage artery structure ZSM-5 molecular sieve as helping the FCC catalyst of active component.It is simple that this method for preparing catalyst has technique, characteristics with low cost.
The present invention also provides a kind of producing more propylene FCC catalyst, and it is used for the FCC process by said method preparation with this catalyst, the advantage such as have that the heavy oil transformation rate is high, Propylene Selectivity good, dry gas and coke yield are low.
For achieving the above object, the present invention at first provides a kind of preparation method of producing more propylene FCC catalyst, and it may further comprise the steps:
(1), the binding agent of the natural clay of the USY molecular sieve of the H-ZSM-5 molecular sieve of 530 weight portions, 20-40 weight portion, 40-70 weight portion and 5-20 weight portion mixed making beating 30-60min obtain mixture, the addition of binding agent is in silica;
(2), after the mixture after will pulling an oar leaves standstill 1-4h, continue making beating 10-30min, after naturally drying, dry 4-8h in 100-120 ℃ of baking oven;
(3), the product of oven dry is placed Muffle furnace, be warming up to 500-650 ℃ of roasting 2-6h, make 100-200 purpose producing more propylene catalytic cracking catalyst after naturally cooling off.
In above-mentioned preparation method provided by the invention, preferably, the H-ZSM-5 molecular sieve that adopts is to be rich in mesoporous multi-stage artery structure H-ZSM-5 molecular sieve, and the mesoporous pore volume of this multi-stage artery structure H-ZSM-5 molecular sieve is not less than 0.14cm
3/ g, mesoporous pore size is between 5-30nm.Above-mentioned multi-stage artery structure H-ZSM-5 molecular sieve can be as raw material take rectorite, under the condition that does not add the second template, (this multi-stage artery structure Na-ZSM-5 molecular sieve can be that the preparation method according to the multi-stage artery structure ZSM-5 molecular sieve that provides in the Chinese patent application of application number for 201210082420.X prepares to the synthetic multi-stage artery structure Na-ZSM-5 molecular sieve of Direct Hydrothermal crystallization, the full text of above-mentioned patent application is introduced here as a reference), and then get through ammonium exchange system, wherein, the ammonium exchange is processed and can be carried out in a conventional manner, for example two hands over the mode of two roastings.According to specific embodiments of the present invention, above-mentioned multi-stage artery structure H-ZSM-5 molecular sieve can prepare according to following steps:
The mode of a, employing high-temperature roasting is carried out activation processing to natural lamellar clay, make silicon, al composition activation in the clay, wherein, the natural lamellar clay that adopts can be one or more the mixture in kaolin, rectorite, the imvite etc., and this natural lamellar clay is preferably rectorite, and the activation temperature of activation processing may be controlled to 600-1000 ℃, soak time may be controlled to 2-6h, preferably, activation temperature is 700-900 ℃, and soak time is 3-5h;
B, will join through the natural clay of activation processing and carry out acid treatment in the acid solution, obtain mixture, can extract activated aluminum species in the natural clay by acid-treated mode, keep the lamellar structure of its activated silica; In the acid treatment process, the acid solution that adopts can be in the mineral acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid one or more, is preferably hydrochloric acid; The concentration of acid solution may be controlled to 0.2-2M; The mass ratio of acid solution and natural lamellar clay is 10-100: 1; Acid-treated temperature may be controlled to 50-90 ℃, and the time may be controlled to 1-24h;
C, waterglass, template (such as tetrapropyl amine bromide TPABr etc.) and water are joined in the mixture that step b obtains successively, make the composition of this mixture meet Na
2O: Al
2O
3: SiO
2: H
2O=(3-11): 1: (20-100): mol ratio (500-1500), Na
2O, Al
2O
3, SiO
2And H
2O represents respectively basicity, aluminium source, silicon source and water;
D, utilize the pH value of the mixture that concentration obtains step c for the sulfuric acid of 0.5-1.5M to be adjusted to 9-12, obtain reactant gel;
E, reactant gel is carried out burin-in process; This burin-in process can be carried out in confined conditions, also can carry out in the system of opening wide, and the temperature of burin-in process may be controlled to 40-90 ℃, and the time may be controlled to 6-48h; Preferably, the temperature of burin-in process may be controlled to 50-80 ℃, and the time may be controlled to 8-24h;
F, process carry out hydrothermal crystallizing through the reactant gel of burin-in process, obtain the multi-stage artery structure ZSM-5 molecular sieve; This hydrothermal crystallizing is processed and can be carried out in a conventional manner, preferably, hydrothermal crystallizing is processed and is carried out in such a way: directly reaction gel is placed autoclave to carry out hydrothermal crystallizing under uniform temperature, crystallization temperature may be controlled to 150-200 ℃, and crystallization time may be controlled to 12-72h;
G, the multi-stage artery structure ZSM-5 molecular sieve is carried out ammonium exchange process, obtain multi-stage artery structure H-ZSM-5 molecular sieve; This ammonium exchange is processed and can be carried out in a conventional manner, preferably, is the NH of 1-2M with multi-stage artery structure molecular sieve and concentration
4Cl solution mixes by 1: 10 mass ratio, then under 70 ℃ of water bath condition, exchange 4h, after filtration, washing, 8-12h dry after, be warmed up to 520 ℃ of roasting 4h with the speed of 2 ℃/min after, repeat above-mentioned steps once, namely obtain hierarchical porous structure H-ZSM-5 molecular sieve.
In above-mentioned preparation method provided by the invention, preferably, in step (1), the natural clay that adopts is one or more the mixture in kaolin, rectorite, imvite and the diatomite etc.More preferably, this natural clay is kaolin.
In above-mentioned preparation method provided by the invention, preferably, in step (1), the binding agent that adopts is one or more the mixture in boehmite, aluminium colloidal sol, Ludox, waterglass and the phosphorus aluminium colloidal sol etc.More preferably, this binding agent is Ludox.
The invention provides a kind of producing more propylene catalytic cracking catalyst, it is by above-mentioned preparation method's preparation provided by the invention.
For the lower problem of ZSM-5 molecular sieve auxiliary agent ubiquity Propylene Selectivity that is used at present the FCC process, the result that the inventor obtains by the commercial Application situation of domestic and international promoter for more propylene is investigated shows, when the ZSM-5 additive dosage accounts for the 3.0-5.0wt.% of antigravity system general reserve, in the situation that dry gas and coke yield remain unchanged substantially, productivity of propylene increases 0.8-3.5 percentage point, and selective (productivity of propylene/liquefied gas yield * 100%) of propylene only can increase about 3.0 percentage points.Therefore, increasing the selective of propylene, namely improve the content of propylene in the liquefied gas under keeping the substantially constant prerequisite of dry gas and coke yield, is the key that improves FCC process productivity of propylene and increase refinery's economic benefit.This just requires ZSM-5 molecular sieve auxiliary agent for the FCC process to have suitable acidity and pore passage structure, good hydrothermal stability, to suppress the productive rate of dry gas and coke in the FCC process, improves the selective of propylene.And in the FCC catalyst or co-catalyst of the disclosed propylene enhancing of prior art, only paid attention to the acidity of molecular sieve and the modulation of hydrothermal stability, the pore structure of not paying close attention to molecular sieve in cracking process on the impact of product selectivity, up to the present, the relevant report of FCC process propylene enhancing productive rate, especially Propylene Selectivity not yet appears the multi-stage artery structure ZSM-5 molecular sieve is applied to.
The prepared producing more propylene FCC catalyst of method provided by the invention is as main active component take USY, with the multi-stage artery structure ZSM-5 molecular sieve for helping active component, take natural clay as matrix, be prepared from take Ludox etc. as binding agent, it has good pore passage structure, and the conventional ZSM-5 molecular sieve material that has solved present industrial application can not contain mesoporous hanging down with micropore, duct utilization rate simultaneously causes it to be applied to the low problem of Propylene Selectivity in the FCC producing more propylene process.When being applied to producing more propylene FCC catalyst provided by the invention in the production of propylene, feedstock oil at first carries out presplitting at natural clay, then carries out further cracking through USY molecular sieve and multi-stage porous ZSM-5 molecular sieve successively.The mesopore orbit that the multi-stage artery structure ZSM-5 molecular sieve has simultaneously micropore and is interconnected not only makes it have good Shape-selective, and is beneficial to contacting and reactant and the diffusion of product molecule in its duct of reactant molecule and active sites.Therefore, adopt that the producing more propylene FCC catalyst of method provided by the invention preparation has advantages of that the heavy oil transformation rate is high, Propylene Selectivity good, dry gas and coke yield be low.In addition, the preparation method of this catalyst is simple, and is with low cost, has preferably prospects for commercial application.
Description of drawings
Fig. 1 is the XRD spectra of multi-stage artery structure ZSM-5 molecular sieve;
Fig. 2 is the N of multi-stage artery structure ZSM-5 molecular sieve
2The adsorption-desorption thermoisopleth;
Fig. 3 is the graph of pore diameter distribution of multi-stage artery structure ZSM-5 molecular sieve.
The specific embodiment
Understand for technical characterictic of the present invention, purpose and beneficial effect being had more clearly, existing technical scheme of the present invention is carried out following detailed description, but but can not be interpreted as restriction to practical range of the present invention.
Among the embodiment, synthetic raw materials used in natural lamellar clay and waterglass be technical grade, other are SILVER REAGENT.
Among the embodiment, the XRD the data records with German Brooker AXS D8 Advance type X-ray diffractometer; N
2Adsorption-desorption data and mesoporous pore-size distribution are recorded by U.S.'s Mike ASAP-2020 adsorption instrument.
The present embodiment provides a kind of multi-stage artery structure ZSM-5 molecular sieve, and it prepares according to following steps:
5g is joined in the hydrochloric acid solution that 400g concentration is 0.2M through the rectorite of calcination activation, place 70 ℃ water-bath rapid stirring 4h, obtain mixture;
In said mixture, add successively 170g deionized water, 8.9g 4-propyl bromide (TPABr) and 129g waterglass, rapid stirring 5min;
The pH value of regulating mixture with sulfuric acid solution is adjusted to 10, to becoming gel state, obtains reactant gel;
Then bath temperature is risen to 80 ℃, gel is left standstill burin-in process 8h;
Then will be transferred to through the gel of burin-in process the hydrothermal crystallizing that carries out 48h in the 1L autoclave under 170 ℃ processes;
Crystallization is cooled off, filters, is washed purified product after finishing, and then puts into baking oven in 120 ℃ of dry 4-8h, with products therefrom roasting 5h in 550 ℃ of Muffle furnaces, with removed template method, namely obtains the multi-stage artery structure ZSM-5 molecular sieve again, is designated as A.
The XRD spectra of this multi-stage artery structure ZSM-5 molecular sieve as shown in Figure 1, N
2The adsorption-desorption thermoisopleth as shown in Figure 2, pore structure parameter is as shown in table 1, graph of pore diameter distribution as shown in Figure 3, as can be seen from Figure 3, the mesoporous aperture of A is 6-20nm.
Embodiment 2
The present embodiment provides a kind of multi-stage artery structure ZSM-5 molecular sieve, it is according to the preparation of the method for embodiment 1, different is in the present embodiment, the rectorite sintering temperature is 750 ℃, and roasting time is 4h, and the pH value of reactant gel is 11, the reactant gel aging temperature is 75 ℃, ageing time is 10h, and products therefrom is designated as B, and its mesoporous pore volume is 0.18cm
3/ g, Micropore volume are 0.076cm
3/ g, mesoporous pore volume are 2.37 times of Micropore volume, and mesoporous aperture is 6-20nm.
Embodiment 3
The present embodiment provides a kind of multi-stage artery structure ZSM-5 molecular sieve, it is according to the preparation of the method for embodiment 1, different is in the present embodiment, the rectorite sintering temperature is 950 ℃, roasting time is 2h, and the pH value of reactant gel is 11, and the reactant gel ageing time is 24h, products therefrom is designated as C, and its mesoporous pore volume is 0.16cm
3/ g, Micropore volume are 0.073cm
3/ g, mesoporous pore volume are 2.18 times of Micropore volume, and mesoporous aperture is 5-19nm.
Embodiment 4
The present embodiment provides a kind of multi-stage artery structure ZSM-5 molecular sieve, and it is that different is in the present embodiment according to the preparation of the method for embodiment 1, the rectorite consumption is 12g, and concentration of hydrochloric acid is 0.6M, and the deionized water consumption is 469g, the template consumption is 23.8g, the waterglass consumption is 206.7g, and the pH value of reactant gel is 9, and reactant gel is aging under air-tight state, aging temperature is 75 ℃, ageing time is 20h, and products therefrom is designated as D, and its mesoporous pore volume is 0.14cm
3/ g, Micropore volume are 0.107cm
3/ g, mesoporous pore volume are 1.31 times of Micropore volume, and mesoporous aperture is 5-30nm.
Embodiment 5
The present embodiment provides a kind of preparation method of conventional ZSM-5 molecular sieve, and it is that different is in the present embodiment, changes rectorite into aluminum sulfate according to the preparation of the method for embodiment 1, and prepared molecular sieve is designated as E, and its mesoporous pore volume is 0.06cm
3/ g, Micropore volume are 0.11cm
3/ g, mesoporous pore volume only are 0.57 times of Micropore volume, without obvious mesoporous pore-size distribution.When pore structure parameter is as shown in table 1 for the sial that feeds intake of A and E.
Hand over two roasting PROCESS FOR TREATMENT to make the H-ZSM-5 molecular sieve according to two respectively the ZSM-5 molecular sieve of above-mentioned gained, the implementation step is as follows: be the NH of 1M with ZSM-5 molecular sieve and concentration
4Cl solution is that 1: 10 ratio is mixed in mass ratio, then exchanges 4h under 70 ℃ of water bath condition, after filtration, washing, dry 4-8h in 120 ℃ of baking ovens, speed with 2 ℃/min is warmed up to 520 ℃ of roasting 4h, repeats above step once, namely obtains the H-ZSM-5 molecular sieve.
The pore structure parameter of table 1ZSM-5 molecular sieve
| Sample | Silica alumina ratio | S BET | S Meso | S meso/S micro | V Total | V meso/V micro |
| A | 60 | 373 | 214 | 1.35 | 0.28 | 2.65 |
| |
60 | 335 | 99 | 0.42 | 0.22 | 0.95 |
Annotate: S
BET, S
MesoAnd S
MicroRepresent respectively that BET amass than table, mesoporous table and long-pending and micropore table and amass V
Total, V
MesoAnd V
MicroRepresent respectively total pore volume, mesoporous pore volume and Micropore volume
Embodiment 6
The present embodiment provides a kind of producing more propylene FCC catalyst, and it prepares by following steps:
With 50g kaolin, 25gUSY molecular sieve (Catalyst Factory, Nankai Univ production), 60g Ludox (SiO
2Content is 26wt.%), 10g multi-stage artery structure H-ZSM-5 molecular sieve-4 A and 20g deionized water mix and pull an oar into uniform sizing material, with the making beating after mixture leave standstill 1-4h after, continue making beating 10-30min, after naturally drying, dry 4-8h in 100-120 ℃ of baking oven; The product of oven dry is placed Muffle furnace, be warming up to 500-650 ℃ of roasting 2-6h, naturally make 100-200 purpose particle after the cooling, obtain the producing more propylene FCC catalyst take the multi-stage artery structure ZSM-5 molecular sieve as auxiliary agent, be designated as Cat-A-10.
With catalyst Cat-A-10 behind 800 ℃ of hydrothermal treatment consists 10h, (its character is as shown in table 2) reacts at the small fixed flowing bed device take Daqing atmospheric residue as raw material, and reaction condition is: loaded catalyst 50g, 560 ℃ of reaction temperatures, mass space velocity 12h
-1, oil ratio 10: 1.Acquired results is as shown in table 3, adopts the producing more propylene FCC catalyst Cat-A-10 take multi-stage artery structure ZSM-5 molecular sieve A as auxiliary agent, and resulting productivity of propylene and Propylene Selectivity are respectively 13.57wt.% and 41.12%.Compare with Cat-E-10 in the Comparative Examples, its productivity of propylene and Propylene Selectivity have increased respectively 1.59 and 3.50 percentage points.
The character of table 2 Daqing atmospheric residue
| Feedstock oil | Daqing atmospheric residue |
| Density (20 ℃), kg/m 3 | 913.00 |
| Viscosity (80 ℃), mm 2/s | 47.43 |
| Carbon residue, wt.% | 4.30 |
| Mean molecule quantity, g/mol | 577 |
| Element forms, wt.% | |
| C | 86.77 |
| H | 12.87 |
| Four components, wt.% | |
| Saturated hydrocarbons | 57.08 |
| Aromatic hydrocarbons | 27.61 |
| Resin and asphalt | 15.31 |
Annotate: four components refer to saturated hydrocarbons, aromatic hydrocarbons, resin and asphalt.
Embodiment 7
The present embodiment provides a kind of producing more propylene FCC catalyst, and it prepares by following steps:
With 50g kaolin, 20g USY molecular sieve (Catalyst Factory, Nankai Univ production), 60g Ludox (SiO
2Content is 26wt.%), 15g multi-stage artery structure H-ZSM-5 molecular sieve-4 A and 20g deionized water mix and pull an oar into uniform sizing material, with the making beating after mixture leave standstill 1-4h after, continue making beating 10-30min, after naturally drying, dry 4-8h in 100-120 ℃ of baking oven; The product of oven dry is placed Muffle furnace, be warming up to 500-650 ℃ of roasting 2-6h, naturally make 100-200 purpose particle after the cooling, obtain the producing more propylene FCC catalyst take the multi-stage artery structure ZSM-5 molecular sieve as auxiliary agent, be designated as Cat-A-15.
With catalyst Cat-A-15 behind 800 ℃ of hydrothermal treatment consists 10h, take Daqing atmospheric residue as raw material (its character is as shown in table 2), react at the small fixed flowing bed device, reaction condition such as embodiment 1, the result shows, its productivity of propylene and Propylene Selectivity are respectively 14.17wt.% and 42.57%.
Embodiment 8
With 50g kaolin, 30gUSY molecular sieve (Catalyst Factory, Nankai Univ production), 60g Ludox (SiO
2Content is 26wt.%), 5g multi-stage artery structure H-ZSM-5 molecular sieve-4 A and 20g deionized water mix and pull an oar into uniform sizing material, with the making beating after mixture leave standstill 1-4h after, continue making beating 10-30min, after naturally drying, dry 4-8h in 100-120 ℃ of baking oven; The product of oven dry is placed Muffle furnace, be warming up to 500-650 ℃ of roasting 2-6h, naturally make 100-200 purpose particle after the cooling, obtain the producing more propylene FCC catalyst take the multi-stage artery structure ZSM-5 molecular sieve as auxiliary agent, be designated as Cat-A-5.
With catalyst Cat-A-5 behind 800 ℃ of hydrothermal treatment consists 10h, take Daqing atmospheric residue as raw material (its character is as shown in table 2), react at the small fixed flowing bed device, reaction condition such as embodiment 1, the result shows, its productivity of propylene and Propylene Selectivity are respectively 11.44wt.% and 39.07%.
Embodiment 9
With 50g kaolin, 25gUSY molecular sieve (Catalyst Factory, Nankai Univ production), 60g Ludox (SiO
2Content is 26wt.%), 10g multi-stage artery structure H-ZSM-5 molecular sieve B and 20g deionized water mix and pull an oar into uniform sizing material, with the making beating after mixture leave standstill 1-4h after, continue making beating 10-30min, after naturally drying, dry 4-8h in 100-120 ℃ of baking oven; The product of oven dry is placed Muffle furnace, be warming up to 500-650 ℃ of roasting 2-6h, naturally make 100-200 purpose particle after the cooling, obtain the producing more propylene FCC catalyst take the multi-stage artery structure ZSM-5 molecular sieve as auxiliary agent, be designated as Cat-B-10.
With catalyst Cat-B-10 behind 800 ℃ of hydrothermal treatment consists 10h, take Daqing atmospheric residue as raw material (its character is as shown in table 2), react at the small fixed flowing bed device, reaction condition such as embodiment 1, the result shows, its productivity of propylene and Propylene Selectivity are respectively 14.02% and 40.53%.
With 50g kaolin, 25gUSY molecular sieve (Catalyst Factory, Nankai Univ production), 60g Ludox (SiO
2Content is 26wt.%), 10g multi-stage artery structure H-ZSM-5 molecular sieve C and 20g deionized water mix and pull an oar into uniform sizing material, with the making beating after mixture leave standstill 1-4h after, continue making beating 10-30min, after naturally drying, dry 4-8h in 100-120 ℃ of baking oven; The product of oven dry is placed Muffle furnace, be warming up to 500-650 ℃ of roasting 2-6h, naturally make 100-200 purpose particle after the cooling, obtain the producing more propylene FCC catalyst take the multi-stage artery structure ZSM-5 molecular sieve as auxiliary agent, be designated as Cat-C-10.
With catalyst Cat-C-10 behind 800 ℃ of hydrothermal treatment consists 10h, take Daqing atmospheric residue as raw material (its character is as shown in table 2), react at the small fixed flowing bed device, reaction condition such as embodiment 1, the result shows, its productivity of propylene and Propylene Selectivity are respectively 12.06% and 41.63%.
Embodiment 11
With 50g kaolin, 20gUSY molecular sieve (Catalyst Factory, Nankai Univ production), 60g Ludox (SiO
2Content is 26wt.%), 15g multi-stage artery structure H-ZSM-5 molecular sieve D and 20g deionized water mix and pull an oar into uniform sizing material, with the making beating after mixture leave standstill 1-4h after, continue making beating 10-30min, after naturally drying, dry 4-8h in 100-120 ℃ of baking oven; The product of oven dry is placed Muffle furnace, be warming up to 500-650 ℃ of roasting 2-6h, naturally make 100-200 purpose particle after the cooling, obtain the producing more propylene FCC catalyst take the multi-stage artery structure ZSM-5 molecular sieve as auxiliary agent, be designated as Cat-D-15.
With catalyst Cat-D-15 behind 800 ℃ of hydrothermal treatment consists 10h, take Daqing atmospheric residue as raw material (its character is as shown in table 2), react at the small fixed flowing bed device, reaction condition such as embodiment 1, the result shows, its productivity of propylene and Propylene Selectivity are respectively 13.47% and 43.67%.
Comparative Examples
With 50g kaolin, 25gUSY molecular sieve (Catalyst Factory, Nankai Univ production), 60g Ludox (SiO
2Content is 26wt.%), 10g conventional H-ZSM-5 micro porous molecular sieve E and 20g deionized water mix and pull an oar into uniform sizing material, the mixture after the making beating is left standstill 1-4h after, continue making beating 10-30min, after naturally drying, dry 4-8h in 100-120 ℃ of baking oven; The product of oven dry is placed Muffle furnace, be warming up to 500-650 ℃ of roasting 2-6h, naturally make 100-200 purpose particle after the cooling, obtain the FCC catalyst, be designated as Cat-B-10.
Behind 800 ℃ of hydrothermal treatment consists 10h, (its character is as shown in table 2) reacts at the small fixed flowing bed device take Daqing atmospheric residue as raw material with catalyst Cat-E-10, reaction condition such as embodiment 1, and its result is as shown in table 3.The result shows, its productivity of propylene and Propylene Selectivity are respectively 11.98wt.% and 37.62%.
Table 3 small fixed flowing bed catalyst reaction result
| Product distribution (wt.%) | Cat-A-10 | Cat-E-10 |
| Dry gas | 8.27 | 7.95 |
| Ethene | 3.40 | 2.91 |
| Propylene | 13.57 | 11.98 |
| Liquefied gas | 33.00 | 31.85 |
| Gasoline | 31.10 | 31.38 |
| Diesel oil | 12.28 | 12.59 |
| Heavy oil | 6.49 | 6.75 |
| Coke | 8.75 | 9.27 |
| Amount to | 100 | 100 |
| Liquid is received | 82.88 | 82.56 |
| Conversion ratio | 81.23 | 80.66 |
| Propylene Selectivity (%) | 41.12 | 37.62 |
Can find out by contrast, the resulting productivity of propylene of producing more propylene FCC catalyst and the Propylene Selectivity that adopt embodiment 6-11 to provide are all high than the catalyst that Comparative Examples provides, this illustrates that producing more propylene FCC catalyst provided by the present invention has the advantages such as the heavy oil transformation rate is high, Propylene Selectivity is good, and the conventional ZSM-5 molecular sieve material that has solved present industrial application can not contain mesoporous hanging down with micropore, duct utilization rate simultaneously causes it to be applied to the lower problem of Propylene Selectivity in the FCC producing more propylene process.
Claims (8)
1. the preparation method of a producing more propylene catalytic cracking catalyst, it may further comprise the steps:
(1), the binding agent of the natural clay of the USY molecular sieve of the H-ZSM-5 molecular sieve of 530 weight portions, 20-40 weight portion, 40-70 weight portion and 5-20 weight portion mixed making beating 30-60min obtain mixture, the addition of described binding agent is in silica;
(2), after the mixture after will pulling an oar leaves standstill 1-4h, continue making beating 10-30min, after naturally drying, in 100-120 ℃ of baking oven, dry 4-8h;
(3), the product of oven dry is placed Muffle furnace, be warming up to 500-650 ℃ of roasting 2-6h, make 100-200 purpose producing more propylene catalytic cracking catalyst after naturally cooling off.
2. preparation method according to claim 1, wherein, described H-ZSM-5 molecular sieve is to be rich in mesoporous multi-stage artery structure H-ZSM-5 molecular sieve, the mesoporous pore volume of this multi-stage artery structure H-ZSM-5 molecular sieve is not less than 0.14cm
3/ g, mesoporous aperture is 5-30nm.
3. preparation method according to claim 2, wherein, described multi-stage artery structure H-ZSM-5 molecular sieve is take rectorite as raw material, under the condition that does not add the second template, the multi-stage artery structure Na-ZSM-5 molecular sieve that the Direct Hydrothermal crystallization is synthetic, and then get through ammonium exchange system.
4. preparation method according to claim 1, wherein, described natural clay is one or more the mixture in kaolin, rectorite, imvite and the diatomite.
5. preparation method according to claim 4, wherein, described natural clay is kaolin.
6. preparation method according to claim 1, wherein, described binding agent is one or more the mixture in boehmite, aluminium colloidal sol, Ludox, waterglass and the phosphorus aluminium colloidal sol.
7. preparation method according to claim 6, wherein, described binding agent is Ludox.
8. producing more propylene catalytic cracking catalyst, it is by each described preparation method's preparation of claim 1-7.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107282099A (en) * | 2017-06-29 | 2017-10-24 | 李瑛� | Assistant for calalytic cracking of voluminous isomery low-carbon alkene and its preparation method and application |
| CN111036288A (en) * | 2018-10-11 | 2020-04-21 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN111036281A (en) * | 2018-10-11 | 2020-04-21 | 中国石油天然气股份有限公司 | Catalytic cracking auxiliary agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4994173A (en) * | 1984-07-05 | 1991-02-19 | Mobil Oil Corporation | Method of adding zsm-5 containing catalyst to fluid bed catalytic cracking units |
| CN101310858A (en) * | 2007-05-21 | 2008-11-26 | 北京化工大学 | Heavy oil catalytic cracking catalyst |
-
2012
- 2012-03-28 CN CN201210085604.1A patent/CN103357429B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4994173A (en) * | 1984-07-05 | 1991-02-19 | Mobil Oil Corporation | Method of adding zsm-5 containing catalyst to fluid bed catalytic cracking units |
| CN101310858A (en) * | 2007-05-21 | 2008-11-26 | 北京化工大学 | Heavy oil catalytic cracking catalyst |
Non-Patent Citations (1)
| Title |
|---|
| LIU HAIYAN，ET AL: "In-situ Synthesis and Catalytic Properties of ZSM-5/Rectorite Composites as Propylene Boosting Additive in Fluid Catalytic Cracking Process", 《CHINESE JOURNAL OF CHEMICAL ENGINEERING》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107282099A (en) * | 2017-06-29 | 2017-10-24 | 李瑛� | Assistant for calalytic cracking of voluminous isomery low-carbon alkene and its preparation method and application |
| CN107282099B (en) * | 2017-06-29 | 2020-01-07 | 李瑛� | Catalytic cracking auxiliary agent for producing high-yield isomeric low-carbon olefin, and preparation method and application thereof |
| CN111036288A (en) * | 2018-10-11 | 2020-04-21 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN111036281A (en) * | 2018-10-11 | 2020-04-21 | 中国石油天然气股份有限公司 | Catalytic cracking auxiliary agent and preparation method thereof |
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