CN103785454B - A kind of catalytic cracking catalyst and preparation method thereof - Google Patents
A kind of catalytic cracking catalyst and preparation method thereof Download PDFInfo
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Abstract
A kind of catalytic cracking catalyst and preparation method thereof, this catalyst characteristics is to comprise following component, by weight percentage: the natural mineral matter of (a) 15% ~ 65%; The oxide of (b) 10% ~ 30%; (c) the phosphorous Silicon-rich beta-molecular sieve of 25% ~ 75%, in described phosphorous Silicon-rich beta-molecular sieve, with P
2o
5meter phosphorus content accounts for 1 ~ 10 heavy %, its
27al? MAS? in NMR, the ratio of chemical shift to be 40 ± 3ppm resonance signal peak area and chemical shift be 54 ± 3ppm resonance signal peak area is more than or equal to 1, and the percentage that the resonance signal peak area sum of chemical shift to be 0 ± 3ppm and chemical shift be-12 ± 3ppm accounts for total peak area is less than or equal to 10%.Its preparation method comprises the phosphorous Silicon-rich beta-molecular sieve described in preparation, described content rich silicon molecular sieve by crystal and described natural mineral matter, oxide and/or oxide precursor is pulled an oar, spraying dry.This catalyst has for naphtha catalytic cracking, has higher productivity of low carbon olefin hydrocarbon.
Description
Technical field
The present invention relates to a kind of fluidized catalyst of producing olefin hydrocarbon by catalytic pyrolysis, particularly a kind of with phosphorous modified beta molecular sieve for being that raw material produces the fluidized catalyst of ethene, propylene and butylene through catalytic pyrolysis process with naphtha.
Background technology
Ethene, propylene and butylene are very important industrial chemicals, mainly adopt naphtha steam cracking method to produce these low-carbon alkenes at present in the world.This method also exists many deficiencies such as reaction temperature is high, energy consumption is large.In order to overcome these problems, carrying out a large amount of deep catalytic cracking technology research both at home and abroad, having expected the introducing by catalytic action, suitably reduce reaction temperature on the one hand, reduce coking and energy consumption, also expect on the other hand to improve yield of light olefins, regulate product slates more neatly.A kind of catalyst is the catalyst containing molecular sieve.
Japanese industry technology institute material, chemistry institute and Japan Chemical Industry Association's joint development with the La/ZSM-5 (10%La/ZSM-5) of load La mass fraction 10% as catalyst.By the ACO of KBR company of the U.S. and SK Energy Co., Ltd. (KR) of Korea S recent development
tM(AdvancedCatalyticOlefins) technique, its proprietary catalyst is microballoon ZSM-5 molecular sieve catalyst.
CN102371171A discloses a kind of fluid catalyst of producing olefin hydrocarbon by catalytic pyrolysis.The composition of this catalyst comprises, by weight percentage: 1) 0.5 ~ 15.0% be selected from least one in phosphorus, rare earth or alkaline earth oxide; 4) 85.0 ~ 95.0% be selected from fabricated in situ containing ZSM-5 zeolite molecular sieve composition, particle size is the microballoon of 10 ~ 200 μm.This catalyst is used for the yield that Naphtha solution can significantly improve the conversion ratio of naphtha and ethene, propylene.
CN102371172A discloses a kind of fluid catalyst of producing olefin hydrocarbon by catalytic pyrolysis.The composition of this catalyst comprises, by weight percentage: the 1) kaolin of 15.0 ~ 60.0%; 2) 10.0 ~ 30.0% at least one in silica or aluminium oxide is selected from; 3) 0.5 ~ 15.0% at least one in phosphorus, rare earth or alkaline earth oxide is selected from; 4) 25.0 ~ 70.0% the ZSM-5 zeolite that crystallite dimension is the employing directing agent method synthesis of 200 ~ 1000nm is selected from.This catalyst is used for the receipts that naphtha catalytic cracking can significantly improve the conversion ratio of naphtha and ethene, propylene
Catalyst containing ZSM-5 molecular sieve can improve the productive rate of ethene and propylene.Another conventional molecular sieve is beta-molecular sieve, can improve butylene productive rate.The method of modifying of a CN1179994A β zeolite, is made up of the following step substantially: (1) by Na β zeolite ammonium ion exchange to the Na on zeolite
2o content is less than 0.1 heavy %; (2) the β zeolite acid treatment exchanged by above-mentioned ammonium pumps part framework aluminum, makes its silica alumina ratio be greater than 50; (3) the β zeolite after above-mentioned dealuminzation is mixed post-drying with phosphoric acid or phosphate, make P on gained zeolite
2o
5amount be 2 ~ 5 heavy %; (4) by (3) step products therefrom under water vapour atmosphere in 450 ~ 650 DEG C of hydrothermal calcines 0.5 ~ 4 hour.But still there is low-carbon alkene (ethene, propylene and the butylene) problem that productive rate is not high when preparing low-carbon alkene for naphtha pyrolysis in catalyst prepared by the zeolite that the method obtains.
Summary of the invention
An object of the present invention is to provide the fluid catalyst of producing olefin hydrocarbon by catalytic pyrolysis, and this catalyst has excellent hydrothermal stability and better product selectivity.
Two of object of the present invention is to provide the preparation method of described catalyst.
A catalyst for producing olefin hydrocarbon by catalytic pyrolysis, comprises following component by weight percentage: the natural mineral matter of (a) 15% ~ 65%; The oxide of (b) 10% ~ 30%; (c) the phosphorous Silicon-rich beta-molecular sieve of 25% ~ 75%; Described phosphorous Silicon-rich beta-molecular sieve, with P
2o
5meter phosphorus content accounts for 1 ~ 10 heavy %, this molecular sieve
27in AlMASNMR, the ratio that chemical shift is (54 ± 3) ppm resonance signal peak area for (40 ± 3) ppm resonance signal peak area and chemical shift is more than or equal to 1, and the percentage that the resonance signal peak area sum of chemical shift to be (0 ± 3) ppm and chemical shift be (-12 ± 3) ppm accounts for total peak area is less than or equal to 10%.
The silica alumina ratio (Si/Al) of described phosphorous Silicon-rich beta-molecular sieve (the Silicon-rich beta-molecular sieve also referred to as phosphorous) is 12-100.Its preparation method comprises by former for beta-molecular sieve powder in the temperature range of 200 DEG C to 800 DEG C, through the non-overlapping temperature range process of at least two from low to high with dealuminzation after removed template method, then carries out the step of P Modification.
Phosphorous Silicon-rich beta-molecular sieve provided by the invention, with P
2o
5meter phosphorus content accounts for the heavy % of 1-10, it is characterized in that, this molecular sieve
27in AlMASNMR, the ratio of chemical shift to be 40 ± 3ppm resonance signal peak area and chemical shift be 54ppm ± 3ppm resonance signal peak area is more than or equal to 1, and the resonance signal peak area sum of chemical shift to be 0 ± 3ppm and chemical shift be-12ppm ± 3ppm accounts for the percentage of total peak area for being less than or equal to 10%.
Phosphorous Silicon-rich beta-molecular sieve provided by the invention, with P
2o
5meter phosphorus content accounts for the heavy % of 1-10, preferably accounts for the heavy % of 1-8.
Phosphorous Silicon-rich beta-molecular sieve provided by the invention,
27in AlMASNMR, the ratio of chemical shift to be 40 ± 3ppm resonance signal peak area and chemical shift be 54ppm ± 3ppm resonance signal peak area is more than or equal to 1, is preferably greater than or equal to 2, such as, be a value in 2 to 5; The percentage that the resonance signal peak area sum of chemical shift to be 0 ± 3ppm and chemical shift be-12ppm ± 3ppm accounts for total peak area is preferably less than 10%, is preferably less than or equal to 6%, such as, be a value in 1-6%.
Above-mentioned phosphorous Silicon-rich beta-molecular sieve provided by the invention, its preparation method comprises the former powder of beta-molecular sieve in the temperature range of 200 DEG C to 800 DEG C, through the non-overlapping temperature range process of at least two from low to high to carry out the step of P Modification after removed template method again, preferred step comprises:
(1) sodium form beta-molecular sieve is exchanged the Na made on molecular sieve through ammonium
2o content is less than 0.2 heavy %;
(2) molecular sieve step (1) obtained after drying, processes at least 0.5 hour under 200-400 DEG C of temperature range, then under being warmed up to 500-800 DEG C of temperature range in 2 hours at the most, processes at least 0.5 hour removed template method;
(3) at temperature 25-100 DEG C, the product obtained by the dealumination agent solution treatment steps (2) of weight concentration 1-20%;
(4) introduce phosphorus-containing compound and modification is carried out to molecular sieve;
(5) calcination process at least 0.5 hour at 400 ~ 800 DEG C.
Preparation method provided by the invention, compared with the modifying process of existing beta-molecular sieve, the main distinction be method of modifying of the present invention be by former for beta-molecular sieve powder (the sodium form beta-molecular sieve containing organic formwork agent) after non-overlapping temperature range stage by stage process is from low to high with roasting removed template method, chemically dealumination treatment is carried out to β zeolite, then carry out P Modification.
In preparation method provided by the invention, in said step (1), said sodium form beta-molecular sieve is the sodium form beta-molecular sieve (as USP3,308,069, CNZL00107486.5) of conventional crystallization gained.In usually said sodium form beta-molecular sieve, sodium content counts the heavy % of 4-6 with sodium oxide molybdena.Said ammonium exchanges with the process reducing sodium content, preferably according to molecular sieve: ammonium salt: H
2o=1:(0.1 ~ 1): the process that the weight ratio of (5 ~ 10) exchanges at least 0.5 hour, preferably filters after 0.5 ~ 2 hour at room temperature to 100 DEG C, such ammonium exchange process can repeat 1 ~ 4 time, to make the Na on molecular sieve
2o content is less than 0.2 heavy %.Said ammonium salt for conventional inorganic ammonium salt, can be selected from ammonium chloride, one of ammonium sulfate or ammonium nitrate or their mixture.
In phosphorous Silicon-rich beta-molecular sieve preparation method provided by the invention, said step (2) be adopt low temperature to high temperature different temperatures interval treatment step (1) obtain molecular sieve, removed template method process.Said process is in the interval of 200 DEG C to 800 DEG C, carry out in the non-overlapping temperature range of at least two from low to high, said low temperature range is 200-400 DEG C, preferred 300-350 DEG C, and said high temperature range is 500-800 DEG C, preferred 500-600 DEG C.Such as, said process is Na after being exchanged by step (1) ammonium
2the molecular sieve that O content is less than 0.2 heavy % first calcination process at least 0.5 hour at 200-400 DEG C, preferably 300-350 DEG C after the drying, preferably 1 ~ 12 hour, then in 2 hours at the most, preferably 1 hour, calcination process is warmed up under 500-800 DEG C of temperature range at least 0.5 hour, preferably 1 ~ 8 hour.In step (2), also before above-mentioned said two temperature range process, first at least can process 1 hour fully to remove moisture at 120-180 DEG C.
In phosphorous Silicon-rich beta-molecular sieve preparation method provided by the invention, said step (3) is at temperature 25-100 DEG C, the process of the product obtained by dealumination agent solution treatment steps (2).In step (2), the consumption of dealumination agent adds by required degree of dealumination experience, and the usual processing time is β zeolite 1-6 hour, and dealumination agent solution preferred weight concentration is 1-20%.Said dealumination agent is selected from organic acid (comprising ethylenediamine tetra-acetic acid, oxalic acid, citric acid, sulfosalicylic acid), inorganic acid (comprising fluosilicic acid, hydrochloric acid, sulfuric acid, nitric acid), organic and inorganic salts (comprising ammonium oxalate, ammonium fluoride, ammonium fluosilicate, ammonium fluoroborate), and chemical dealuminization process can once or several times be carried out.
In phosphorous Silicon-rich beta-molecular sieve preparation method provided by the invention, introduce the product of phosphorus-containing compound to step (3) in step (4) and carry out modification.Said phosphorus-containing compound is selected from phosphoric acid, ammonium hydrogen phosphate, one of ammonium dihydrogen phosphate (ADP) or ammonium phosphate or its mixture.Step (4) said modifying process can adopt impregnation method to carry out.Wherein said dipping can be by dealuminzation after molecular sieve and the phosphorus-containing compound aqueous solution of amount of calculation pull an oar in room temperature to 95 DEG C and evenly dry.
In phosphorous Silicon-rich beta-molecular sieve preparation method provided by the invention, step (5) is the phosphorous beta-molecular sieve product calcination process at least 0.5 hour, the preferably 0.5-8 hour at 400 ~ 800 DEG C, preferably 500-600 DEG C that step (4) are obtained.Wherein said calcination process process can adopt dry roasting also can adopt wet roasting, and said wet roasting is preferably carried out under 1-100%, more preferably 100% steam atmosphere.
Wherein said natural mineral matter such as clay, comprises one or more the mixture in kaolin, halloysite, imvite, diatomite, convex-concave rod stone, sepiolite, galapectite, hydrotalcite, bentonite and rectorite etc.With catalyst total amount for benchmark, weight percent meter, the content of natural mineral matter is 15% ~ 65%, preferably 20% ~ 55%.
Described oxide is selected from one or more the mixture in silica, aluminium oxide, zirconia, titanium oxide, amorphous aluminum silicide and aluminum phosphate material, described oxide preferably comes from its corresponding dissolved colloidal state material, such as, in Ludox, Alumina gel, peptization boehmite, silicon-aluminum sol and phosphorated aluminiferous collosol one or more.With catalyst total amount for benchmark, weight percent meter, the content of oxide is 10% ~ 30%, preferably 12% ~ 28%.
The preparation method of catalyst provided by the invention comprises and being pulled an oar together with phosphorous Silicon-rich beta-molecular sieve by the precursor of natural mineral matter, oxide and/or oxide, then slurries are carried out spraying dry and roasting, the colloidal sol of described oxide precursor such as described oxide, described oxide sol can be used as binding agent and has suitable mechanical strength and abrasion resistance to make final catalyst in catalyst preparation process.The consumption of each component makes to contain in final catalyst, take total catalyst weight as benchmark, the natural mineral matter of 15% ~ 65%, the oxide of 10% ~ 30% and the phosphorous Silicon-rich beta-molecular sieve of 25% ~ 75%, preferably, the precursor of natural mineral matter, oxide and/or oxide and the consumption of phosphorous Silicon-rich beta-molecular sieve make consisting of of described catalyst: natural mineral matter content is 20 % by weight ~ 55 % by weight, the content of described phosphorous rich silicon molecular sieve by crystal is 30 % by weight ~ 70 % by weight, and the content of described oxide is 12 ~ 28 % by weight.One or more in precursor such as Ludox, Alumina gel, peptization boehmite, silicon-aluminum sol and the phosphorated aluminiferous collosol of described oxide.
The present invention also provides a kind of method of producing olefin hydrocarbon by catalytic pyrolysis of naphtha, this comprises the catalytic step in fluidized-bed reactor or riser reactor by naphtha and catalytic cracking catalyst, and wherein said catalytic cracking catalyst is the fluid catalyst of described producing olefin hydrocarbon by catalytic pyrolysis provided by the invention.Described alkene is ethene, propylene and butylene, and described naphtha is straight-run naphtha, and its boiling range is generally 40 ~ 180 DEG C, and catalytic condition comprises: reaction temperature is 600-750 DEG C, 0.1 ~ 10 second haptoreaction time, weight (hourly) space velocity (WHSV) 0.1 ~ 10h
-1, preferably pass into water vapour in course of reaction, the ratio of steam and naphtha is: 0.1 ~ 10:1, such as, be 0.2 ~ 5:1.
The invention provides a kind of fluid catalyst of producing olefin hydrocarbon by catalytic pyrolysis of naphtha, containing a kind of novel beta-molecular sieve, compared with being the catalyst prepared of active component with conventional beta-molecular sieve, there is more excellent hydrothermal stability, there is better selectivity of light olefin.The method of producing olefin hydrocarbon by catalytic pyrolysis of naphtha provided by the invention, has higher ethene, propylene and butylene productive rate.
Detailed description of the invention
The present invention is further illustrated for the following examples, but not thereby limiting the invention.
In each embodiment and comparative example, Na in each sample beta-molecular sieve
2o, Fe
2o
3, Co
2o
3, NiO, CuO, Mn
2o
3, ZnO, SnO
2, Al
2o
3, SiO
2content with x-ray fluorescence method measure (see " Petrochemical Engineering Analysis method (RIPP experimental technique) ", the volumes such as Yang Cuiding, Science Press, nineteen ninety publish).
27alMASNMR adopts BrukerAdvanceIII500MHz NMR to test, and formant spectrogram adopts integration method to calculate each peak area after carrying out swarming matching.Wherein the performance of raw materials is as follows: kaolin (Kaolin of Suzhou company, solid content 75%), (zunyi, guizhou three closes white ore deposit to galapectite, solid content 75%), rectorite (From Zhongxiang Hubei rectorite ore deposit, solid content 75%), imvite (Chaoyang City, Liaoning Province Hong Shi bentonite company, solid content 75%), boehmite (Shandong Aluminium Industrial Corp, solid content 65%), Alumina gel (Shandong catalyst branch company, alumina content is 22.5%), Ludox (Qingdao Marine Chemical Co., Ltd., silica content 25.5%, pH value 3.0), phosphorated aluminiferous collosol (P content 16%, Al content 8%, pH value is 2.0).Above content is weight percentage.
Embodiment 1
By Na beta-molecular sieve, (Shandong catalyst plant is produced, SiO
2/ Al
2o
3=25 mol ratios, sodium oxide content 4.5 % by weight, lower same) use NH
4cl solution exchanges washing to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Drying, gained sample, 350 DEG C of calcination process 2 hours, is then warming up to 550 DEG C in 40 minutes, at 550 DEG C of calcination process, 4 hours removed template methods; Get above-mentioned molecular sieve 100Kg(butt) adding water is mixed with the molecular sieve pulp of the heavy % of solid content 10, adds oxalic acid 20 kilograms in stirring, and be warming up to 80 DEG C and stir 1h, filtered water is washed till filtrate neutrality; Add 9 kilograms of H
3pO
4(concentration 85 % by weight, lower same) is dissolved in 50 kg of water, dries with molecular sieve filter cake hybrid infusion; Gained sample was 550 DEG C of calcination process 2 hours, and namely molecular sieve provided by the invention, is designated as F-1.The physical data of sample and
27alMASNMR peak area ratio lists in table 1.
By natural mineral matter, phosphorous Silicon-rich beta-molecular sieve F-1, binding agent colloidal sol and water mixing making beating, the slurries obtained are spray dried to diameter mainly at the particle of 40-150 micron and roasting, sintering temperature is 500 DEG C, and roasting time is 1 hour, obtains catalyst C1 provided by the invention.Use the physical data of phosphorous Silicon-rich beta-molecular sieve, consumption and
27alMASNMR peak area ratio lists in table 1.Kind and the consumption of the kind of natural mineral matter and consumption, binding agent are listed in table 2 and table 3 respectively.
Embodiment 2
By Na beta-molecular sieve, (Shandong catalyst plant is produced, SiO
2/ Al
2o
3=25) NH is used
4cl solution exchanges washing to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Drying, gained sample, 350 DEG C of calcination process 2 hours, is then warming up to 550 DEG C of calcination process, 4 hours removed template methods for 40 minutes; Get 100 kilograms, above-mentioned molecular sieve (butt) to add water and be mixed with the molecular sieve pulp of the heavy % of solid content 10, add fluosilicic acid (concentration 30%) 10 kilograms in stirring, be warming up to 60 DEG C and stir 1h, filtered water is washed till filtrate neutrality; Add 10 kilograms of (NH
3)
2hPO
4(concentration 85 % by weight) is dissolved in 90 kg of water, dry with above-mentioned molecular sieve filter cake hybrid infusion; Gained sample was 550 DEG C of calcination process 2 hours, and namely molecular sieve provided by the invention, is designated as F-2.The physical data of sample and
27alMASNMR peak area ratio lists in table 1.
By natural mineral matter, phosphorous Silicon-rich beta-molecular sieve F-2, binding agent colloidal sol and water mixing making beating, the slurries obtained are spray dried to diameter mainly at the particle of 40-150 micron and roasting, sintering temperature is 500 DEG C, and roasting time is 1.5 hours, obtains catalyst C2 provided by the invention.Use the physical data of phosphorous Silicon-rich beta-molecular sieve, consumption and
27alMASNMR peak area ratio lists in table 1.Kind and the consumption of the kind of natural mineral matter and consumption, binding agent are listed in table 2 and table 3 respectively.
Embodiment 3
By Na beta-molecular sieve, (Shandong catalyst plant is produced, SiO
2/ Al
2o
3=25) NH is used
4cl solution exchanges washing to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Drying, gained sample, 350 DEG C of calcination process 2 hours, is then warming up to 550 DEG C of calcination process, 4 hours removed template methods for 40 minutes; Get 100 kilograms, above-mentioned molecular sieve (butt) to add water and be mixed with the molecular sieve pulp of the heavy % of solid content 10, add ammonium fluosilicate 2 kilograms in stirring, be warming up to 60 DEG C and stir 1h, filtered water is washed till filtrate neutrality; Add 14 kilograms of H
3pO
4(concentration 85 % by weight) is dissolved in 90 kg of water, dry with above-mentioned molecular sieve filter cake hybrid infusion; Gained sample 550 DEG C of calcination process 2 hours, i.e. molecular sieve F-3 provided by the invention.The physical data of sample and
27alMASNMR peak area ratio lists in table 1.
By natural mineral matter, phosphorous Silicon-rich beta-molecular sieve F-3, binding agent colloidal sol and water mixing making beating, the slurries obtained are spray dried to diameter mainly at the particle of 40-150 micron and roasting, sintering temperature is 500 DEG C, and roasting time is 1 hour, obtains catalyst C3 provided by the invention.Use the physical data of phosphorous Silicon-rich beta-molecular sieve, consumption and
27alMASNMR peak area ratio lists in table 1.Kind and the consumption of the kind of natural mineral matter and consumption, binding agent are listed in table 2 and table 3 respectively.
Embodiment 4
By Na beta-molecular sieve, (Shandong catalyst plant is produced, SiO
2/ Al
2o
3=25) NH is used
4cl solution exchanges washing to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Drying, gained sample, 350 DEG C of calcination process 2 hours, is then warming up to 550 DEG C of calcination process, 4 hours removed template methods for 40 minutes; Get 100 kilograms, above-mentioned molecular sieve (butt) to add water and be mixed with the molecular sieve pulp of the heavy % of solid content 10, add ammonium oxalate 30 kilograms in stirring, be warming up to 60 DEG C and stir 1h, filtered water is washed till filtrate neutrality; Add 6 kilograms of NH
3h
2pO
4be dissolved in 90 kg of water, dry with above-mentioned molecular sieve filter cake hybrid infusion; Gained sample was 550 DEG C of calcination process 2 hours, and namely molecular sieve provided by the invention, is designated as F-4.The physical data of sample and
27alMASNMR peak area ratio lists in table 1.
By natural mineral matter, phosphorous Silicon-rich beta-molecular sieve F-4, binding agent colloidal sol and water mixing making beating, the slurries obtained are spray dried to diameter mainly at the particle of 40-150 micron and roasting, sintering temperature is 500 DEG C, and roasting time is 2 hours, obtains catalyst C4 provided by the invention.Use phosphorous Silicon-rich beta-molecular sieve, boehmite wherein 31 % by weight hydrochloric acid peptizations, the mol ratio of described hydrochloric acid and the boehmite remembered with aluminium oxide for 0.20, physical data, consumption and
27alMASNMR peak area ratio lists in table 1.Kind and the consumption of the kind of natural mineral matter and consumption, binding agent are listed in table 2 and table 3 respectively.
Comparative example 1
Prepare phosphorous beta-molecular sieve according to the method for CN1179994A: by 100g(butt) Na beta-molecular sieve join in the ammonium sulfate of the heavy % of 2000ml4 in 90 DEG C stir exchange 1h, exchange again once with same method after filtration, filter, the fluosilicic acid H of filter cake and 3 heavy %
2siF
6solution 500ml reacts 2h at 60 DEG C, refilter, be that the mixture that the phosphoric acid of 85% heavy % and 3g boehmite (the heavy % of Al2O3 content 67) form mixes by filter cake and 14g concentration, after drying in 110 DEG C in an oven, put into tubular type muffle furnace with 550 DEG C at logical steam roasting 2h, the weight space velocity of water flowing steam is 2h
-1, obtain comparative example 1 molecular sieve and be designated as DF-1.
By the beta-molecular sieve DF-2 of natural mineral matter, P Modification, binding agent colloidal sol and water mixing making beating, the slurries obtained are spray dried to diameter mainly at the particle of 40-150 micron and roasting (500 DEG C roasting 1.5 hours), obtain catalyst D1.Use the physical data of P Modification beta-molecular sieve, consumption and
27alMASNMR peak area ratio lists in table 1.Kind and the consumption of the kind of natural mineral matter and consumption, binding agent are listed in table 2 and table 3 respectively.Spray-dired temperature, sintering temperature and time list in table 4.
Comparative example 2
By the method process of Na beta-molecular sieve according to embodiment 1, but do not carry out taking out aluminium process before P Modification, obtain comparative example 2 molecular sieve, be designated as DF-2.
By the beta-molecular sieve DF-2 of natural mineral matter, P Modification, binding agent colloidal sol and water mixing making beating, the slurries obtained are spray dried to diameter mainly at the particle of 40-150 micron and roasting (500 DEG C roasting 1 hour), obtain catalyst D2.Use the physical data of P Modification beta-molecular sieve, consumption and
27alMASNMR peak area ratio lists in table 1.Kind and the consumption of the kind of natural mineral matter and consumption, binding agent are listed in table 2 and table 3 respectively.Spray-dired temperature, sintering temperature and time list in table 4.The composition of catalyst D2 is listed in table 5.
Comparative example 3
By beta-molecular sieve NH
4cl solution exchanges washing to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Drying, 550 DEG C of calcination process, 4 hours removed template methods; Get above-mentioned molecular sieve 100g(butt) adding water is mixed with the molecular sieve pulp of the heavy % of solid content 10, adds oxalic acid 20g in stirring, and be warming up to 80 DEG C and stir 1h, filtered water is washed till filtrate neutrality; Add 9gH
3pO
4(concentration 85 % by weight) is dissolved in 50g water, dries with molecular sieve filter cake hybrid infusion; Gained sample was 550 DEG C of calcination process 2 hours, and namely contrast molecular sieve provided by the invention, is designated as DF-3.
The physical data of sample and
27alMASNMR peak area ratio lists in table 1.
Table 1
Table 2
| Catalyst is numbered | Natural mineral matter kind | Consumption, kilogram |
| C1 | Rectorite and kaolin | Rectorite 40, kaolin 40 |
| C2 | Galapectite | 53.3 |
| C3 | Cover holder soil | 26.7 |
| C4 | Kaolin | 13.3 |
| D1 | Rectorite and kaolin | Rectorite 40, kaolin 40 |
| D2 | Rectorite and kaolin | Rectorite 40, kaolin 40 |
Table 3
Table 4
| Catalyst is numbered | Spraying dry exhaust temperature/DEG C | Sintering temperature/DEG C | Roasting time/h |
| C1 | 180 | 500 | 1 |
| C2 | 170 | 500 | 1.5 |
| C3 | 180 | 500 | 1 |
| C4 | 175 | 500 | 2 |
| D1 | 180 | 500 | 1.5 |
| D2 | 170 | 500 | 1 |
Embodiment 5
By sample obtained to above-described embodiment and comparative example in 820 DEG C, evaluate on fluidized bed plant after the process in aging 17 hours of 100% steam, appreciation condition is reaction temperature 650 DEG C, and weight space velocity is 1.0 hours
-1, oil inlet quantity 1.56g, water and weight of oil are than being 4:1, and feedstock oil is straight-run naphtha, initial boiling point 45.5 DEG C, the end point of distillation 166.5 DEG C, specifically forms in table 5.Reaction result is in table 6.
Table 5
| Carbon number | N-alkane | Isoparaffin | Alkene | Cycloalkane | Aromatic hydrocarbons |
| 2 | 0.02 | 0.00 | 0.00 | 0.00 | 0.00 |
| 3 | 0.21 | 0.00 | 0.00 | 0.00 | 0.00 |
| 4 | 0.95 | 0.20 | 0.02 | 0.00 | 0.00 |
| 5 | 2.24 | 1.16 | 0.03 | 0.55 | 0.00 |
| 6 | 3.89 | 2.47 | 0.03 | 5.28 | 0.60 |
| 7 | 5.98 | 3.08 | 0.04 | 10.55 | 1.86 |
| 8 | 7.24 | 5.36 | 0.00 | 10.77 | 5.36 |
| 9 | 6.57 | 4.53 | 0.00 | 9.80 | 2.43 |
| 10 | 2.10 | 3.90 | 0.00 | 1.27 | 0.26 |
| 11 | 0.19 | 0.88 | 0.00 | 0.04 | 0.01 |
| 12 | 0.01 | 0.03 | 0.00 | 0.00 | 0.00 |
| Amount to | 29.40 | 21.61 | 00.12 | 38.24 | 10.52 |
It is weight percentage composition in table 5
Table 6
Wherein said productive rate is that benchmark obtains with feedstock.
Output (the weight)/naphtha feed amount (weight) × 100% of products collection efficiency=product
Conversion ratio is the productive rate sum of productive rate, hydrogen and the coke that in molecule, carbon number is less than or equal to the hydrocarbon products of 4.
6 data as can be seen from table, modified molecular screen provided by the invention has good activity stability and productivity of low carbon olefin hydrocarbon.Compared with comparative example, the catalyst that is active component with phosphorous Silicon-rich beta-molecular sieve provided by the invention, while improving cracking hydrocarbon ability, effectively improve the productivity of low carbon olefin hydrocarbon of crackate, the productive rate of ethene, propylene and butylene productive rate has raising by a relatively large margin.
Claims (17)
1. a producing olefin hydrocarbon by catalytic pyrolysis of naphtha catalyst, composed of the following components by weight percentage:
The natural mineral matter of (a) 15% ~ 65%;
The oxide of (b) 10% ~ 30% and;
C the phosphorous Silicon-rich beta-molecular sieve of () 25% ~ 75%, described phosphorous Silicon-rich beta-molecular sieve, with P
2o
5meter phosphorus content accounts for 1 ~ 10 heavy %, this molecular sieve
27in AlMASNMR, the ratio of chemical shift to be 40 ± 3ppm resonance signal peak area and chemical shift be 54 ± 3ppm resonance signal peak area is more than or equal to 1, and the percentage that the resonance signal peak area sum of chemical shift to be 0 ± 3ppm and chemical shift be-12 ± 3ppm accounts for total peak area is less than 10%;
Described natural mineral matter comprise kaolin, imvite, diatomite, convex-concave rod stone, sepiolite, galapectite, hydrotalcite, bentonite and rectorite in one or more; Described oxide be selected from silica, aluminium oxide, zirconia, titanium oxide and amorphous aluminum silicide one or more.
2. catalyst according to claim 1, is characterized in that, with P in described phosphorous Silicon-rich beta-molecular sieve
2o
5meter phosphorus content accounts for the heavy % of 1-8.
3. catalyst according to claim 1, is characterized in that, described phosphorous Silicon-rich beta-molecular sieve, said
27in AlMASNMR, the ratio of chemical shift to be 40 ± 3ppm resonance signal peak area and chemical shift be 54ppm ± 3ppm resonance signal peak area is more than or equal to 2.
4. catalyst according to claim 1, is characterized in that, described phosphorous Silicon-rich beta-molecular sieve, said
27in AlMASNMR, the resonance signal peak area sum of chemical shift to be 0 ± 3ppm and chemical shift be-12ppm ± 3ppm accounts for the percentage of total peak area for being less than or equal to 6%.
5. described catalyst according to claim 1, is characterized in that the silica alumina ratio of described phosphorous Silicon-rich beta-molecular sieve is 12-100.
6. the preparation method of catalyst described in any one of Claims 1 to 5, comprises the phosphorous Silicon-rich beta-molecular sieve described in preparation, described phosphorous rich silicon molecular sieve by crystal and described natural mineral matter, oxide and/or oxide precursor is pulled an oar, spraying dry; The preparation method of wherein said phosphorous Silicon-rich beta-molecular sieve comprises the former powder of beta-molecular sieve in the temperature range of 200 DEG C to 800 DEG C, carries out the step of P Modification through the non-overlapping temperature range process of at least two from low to high with dealuminzation, again dipping after removed template method.
7. described method for preparing catalyst according to claim 6, it is characterized in that, the preparation process of described phosphorous Silicon-rich beta-molecular sieve is as follows:
(1) sodium form beta-molecular sieve is exchanged the Na made on molecular sieve through ammonium
2o content is less than 0.2 heavy %;
(2) molecular sieve step (1) obtained after drying, processes at least 0.5 hour under 200-400 DEG C of temperature range, then under being warmed up to 500-800 DEG C of temperature range in 2 hours at the most, processes at least 0.5 hour removed template method;
(3) at temperature 25-100 DEG C, the product obtained by dealumination agent solution treatment steps (2);
(4) dipping introducing phosphorus-containing compound carries out modification to molecular sieve;
(5) calcination process at least 0.5 hour at 400 ~ 800 DEG C.
8. according to method for preparing catalyst according to claim 7, wherein, said ammonium exchanges is according to molecular sieve: ammonium salt: H
2o=1:(0.1 ~ 1): the process that the weight ratio of (5 ~ 10) is filtered exchange at least 0.5 hour at room temperature to 100 DEG C after, this process is at least carried out once.
9. according to the method for catalyst preparing according to claim 7, wherein, said phosphorus-containing compound is selected from phosphoric acid, ammonium hydrogen phosphate, one of ammonium dihydrogen phosphate (ADP) or ammonium phosphate or its mixture.
10. according to method for preparing catalyst according to claim 7, it is characterized in that before step (2), the product of step (1) is at least processed 1 hour at 120-180 DEG C.
11. according to method for preparing catalyst according to claim 7, and wherein, said dealumination agent is selected from organic acid, inorganic acid, organic salt or inorganic salts, and said step (3) is carried out once or carried out several times.
12. according to method for preparing catalyst according to claim 11, wherein, said organic acid is selected from ethylenediamine tetra-acetic acid, oxalic acid, citric acid or sulfosalicylic acid, said inorganic acid is selected from fluosilicic acid, hydrochloric acid, sulfuric acid or nitric acid, said organic salt is ammonium oxalate, and said inorganic salts are ammonium fluoride, ammonium fluosilicate or ammonium fluoroborate.
13. according to method for preparing catalyst according to claim 7, and wherein, said dealumination agent, its weight concentration is 1-20%.
14. according to method for preparing catalyst according to claim 7, wherein, the said modification of said step (4) adopts impregnation method to carry out, and said impregnation method is pull an oar evenly by the phosphorus-containing compound aqueous solution of the molecular sieve after dealuminzation and amount of calculation in room temperature to 95 DEG C, dries.
15. according to method for preparing catalyst according to claim 7, and wherein, the said calcination process process of step (5) is roasting under steam atmosphere.
16. according to method for preparing catalyst according to claim 7, it is characterized in that, described natural mineral matter is clay, and described oxide precursor is one or more in aluminum phosphate, Alumina gel, peptization boehmite, Ludox, silicon-aluminum sol and phosphorated aluminiferous collosol.
The method of 17. 1 kinds of producing olefin hydrocarbon by catalytic pyrolysis, comprise hydrocarbon ils and catalyst exposure in a fluidized bed reactor or in riser reactor, it is characterized in that, described catalyst is the catalyst described in any one of Claims 1 to 5, described hydrocarbon ils is naphtha, the temperature of described contact is 600-750 DEG C, and weight (hourly) space velocity (WHSV) is 0.1 ~ 10h
-1.
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| CN1105646A (en) * | 1994-06-29 | 1995-07-26 | 中国石油化工总公司抚顺石油化工研究院 | Beta zeolite and preparing method thereof |
| CN1179994A (en) * | 1996-10-11 | 1998-04-29 | 中国石油化工总公司 | Beta zeolite modification method |
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| CN1179994A (en) * | 1996-10-11 | 1998-04-29 | 中国石油化工总公司 | Beta zeolite modification method |
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