CN103785459A - Catalytic cracking catalyst and preparation method thereof - Google Patents
Catalytic cracking catalyst and preparation method thereof Download PDFInfo
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- CN103785459A CN103785459A CN201210418395.8A CN201210418395A CN103785459A CN 103785459 A CN103785459 A CN 103785459A CN 201210418395 A CN201210418395 A CN 201210418395A CN 103785459 A CN103785459 A CN 103785459A
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Abstract
The invention relates to a catalytic cracking catalyst and a preparation method thereof. The catalyst is characterized by comprising, by weight, (a) 15-65% of a natural mineral, (b) 10-30% of an oxide, and (c) 25-75% of a MFI structure molecular sieve and phosphorus-containing silicon-rich beta molecular sieve mixture, wherein the phosphorus-containing silicon-rich beta molecular sieve contains 1-10 wt% (calculated as P2O5) of the phosphorus, and in the 27Al MAS NMR of the molecular sieve, a ratio of the resonance signal peak area at the chemical shift of 40+/-3 ppm to the resonance signal peak area at the chemical shift of 54+/-3 ppm is more than or equal to 1, and the sum of the resonance signal peak areas at the chemical shifts of 0+/-3 ppm and -12+/-3 ppm accounts for less than or equal to 10% of the total peak area. The preparation method comprises: mixing the natural mineral, the oxide and/or the oxide precursor, the MFI structure molecular sieve and the phosphorus-containing silicon-rich beta molecular sieve to prepare a slurry, and then adopting the prepared slurry to carry out spray drying on the catalyst so as to be used for catalytic cracking of naphtha, such that the high low-carbon olefin yield is provided.
Description
Technical field
The present invention relates to a kind of fluid catalyst of producing olefin hydrocarbon by catalytic pyrolysis, particularly a kind of catalyst of producing ethene, propylene and butylene take naphtha as raw material through fluidized catalytic cracking process.
Background technology
Ethene, propylene and butylene are very important industrial chemicals, mainly adopt in the world at present naphtha steam cracking method to produce these low-carbon alkenes.This method exists many deficiencies such as reaction temperature is high, energy consumption is large.In order to overcome these problems, carry out a large amount of catalytic pyrolysis technical research both at home and abroad, expect by the introducing of catalytic action, suitably reduce on the one hand reaction temperature, reduce coking and energy consumption, also expect on the other hand to improve yield of light olefins, regulate more neatly product to distribute.A kind of catalyst is wherein 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, under 650 ℃ of conditions of temperature, carry out the method for naphtha pyrolysis.The ACO of the recent development of being developed by KBR company of the U.S. and SK energy company of Korea S
tM(Advanced Catalytic Olefins) technique is carried out naphtha conversion in conjunction with the proprietary catalyst of Orthoflow fluid catalytic cracking reactor system and the exploitation of SK energy company of Korea S, and its proprietary catalyst is tool 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% at least one being selected from phosphorus, rare earth or alkaline earth oxide; 4) 85.0 ~ 95.0% be selected from original position synthetic containing ZSM-5 zeolite molecular sieve composition, particle size is the microballoon of 10 ~ 200 μ m.
CN102371172A discloses a kind of fluid catalyst of producing olefin hydrocarbon by catalytic pyrolysis.The composition of this catalyst comprises, by weight percentage: 1) 15.0 ~ 60.0% kaolin; 2) 10.0 ~ 30.0% at least one that are selected from silica or aluminium oxide; 3) 0.5 ~ 15.0% at least one being selected from phosphorus, rare earth or alkaline earth oxide; 4) 25.0 ~ 70.0% be selected from the synthetic ZSM-5 zeolite of employing directing agent method that crystallite dimension is 200 ~ 1000nm.This catalyst can significantly improve the yield of the conversion ratio of naphtha and ethene, propylene for naphtha catalytic cracking.
Above-mentioned ZSM-5 molecular sieve catalyst is mainly to improve ethene and productivity of 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 of above-mentioned ammonium exchange is pumped to part framework aluminum with acid treatment, make its silica alumina ratio be greater than 50; (3) the β zeolite after above-mentioned dealuminzation is mixed to 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 ℃ 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 in the catalyst that the method obtains in the time preparing low-carbon alkene for naphtha pyrolysis.
Summary of the invention
One of object of the present invention is to provide the fluid catalyst of producing olefin hydrocarbon by catalytic pyrolysis, and this catalyst has the selectivity of light olefin of good hydrothermal stability and Geng Gao.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: (a) 15% ~ 65% natural mineral matter; (b) 10% ~ 30% oxide; (c) mixture of 25% ~ 75% MFI structure molecular screen and phosphorous Silicon-rich beta-molecular sieve, described phosphorous Silicon-rich beta-molecular sieve, with P
2o
5meter phosphorus content accounts for 1 ~ 10 heavy %, this molecular sieve
27in Al MAS NMR, 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 that chemical shift is (12 ± 3) ppm for (0 ± 3) ppm and chemical shift 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 (also referred to as phosphorous Silicon-rich beta-molecular sieve) is 12-100.Its preparation method comprises former beta-molecular sieve powder in the temperature range of 200 ℃ to 800 ℃, dealuminzation after at least two non-overlapping temperature ranges are from low to high processed with removed template method, then the step of carrying out phosphorus 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 Al MAS NMR, chemical shift is that 40 ± 3ppm resonance signal peak area and chemical shift are that the ratio of 54ppm ± 3ppm resonance signal peak area is more than or equal to 1, and the chemical shift percentage that to be 0 ± 3ppm and chemical shift account for total peak area for the resonance signal peak area sum of-12ppm ± 3ppm is 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 Al MAS NMR, chemical shift is that 40 ± 3ppm resonance signal peak area and chemical shift are that the ratio of 54ppm ± 3ppm resonance signal peak area is more than or equal to 1, is preferably greater than or equal to 2, for example, be a value in 2 to 5; The chemical shift percentage that to be 0 ± 3ppm and chemical shift account for total peak area for the resonance signal peak area sum of-12ppm ± 3ppm is preferably and is less than 10%, is preferably and is less than or equal to 6%, for example, be a value in 1-6%.
Above-mentioned phosphorous Silicon-rich beta-molecular sieve provided by the invention, its preparation method is to comprise that the former powder of beta-molecular sieve is in the temperature range of 200 ℃ to 800 ℃, the step of carrying out again phosphorus modification after at least two non-overlapping temperature ranges are from low to high processed with removed template method, preferred step comprises:
(1) sodium type beta-molecular sieve is made to the Na on molecular sieve through ammonium exchange
2o content is less than 0.2 heavy %;
(2) molecular sieve step (1) being obtained after drying, is processed at least 0.5 hour under 200-400 ℃ of temperature range, then under 500-800 ℃ of temperature range, processes at least 0.5 hour removed template method being warmed up in 2 hours at the most;
(3) at temperature 25-100 ℃, the product obtaining by the dealumination agent solution treatment steps (2) of weight concentration 1-20%;
(4) introduce phosphorus-containing compound molecular sieve is carried out to modification;
(5) calcination process at least 0.5 hour at 400～800 ℃.
Phosphorous Silicon-rich beta-molecular sieve preparation method of the present invention, compared with the modifying process of existing beta-molecular sieve, the main distinction is that method of modifying of the present invention is that former beta-molecular sieve powder (containing the sodium type beta-molecular sieve of organic formwork agent) is processed with after roasting removed template method through non-overlapping temperature range stage by stage from low to high, β zeolite is carried out to dealumination treatment by chemical method, then carry out phosphorus modification.
In phosphorous Silicon-rich beta-molecular sieve preparation method provided by the invention, in said step (1), the sodium type beta-molecular sieve (as USP3,308,069, CNZL00107486.5) that said sodium type beta-molecular sieve is conventional crystallization gained.In usually said sodium type beta-molecular sieve (Na beta-molecular sieve), sodium content is counted the heavy % of 4-6 with sodium oxide molybdena.Said ammonium exchanges to reduce the process of sodium content, preferably according to molecular sieve: ammonium salt: H
2o=1:(0.1～1): the weight ratio of (5～10) exchange at least 0.5 hour at room temperature to 100 ℃, the preferred process of filtering after 0.5～2 hour, such ammonium exchange process can repeat 1～4 time, so that the Na on molecular sieve
2o content is less than 0.2 heavy %.Said ammonium salt can be conventional inorganic ammonium salt, can be selected from one of ammonium chloride, ammonium sulfate or ammonium nitrate or their mixture.
In phosphorous Silicon-rich beta-molecular sieve preparation method provided by the invention, said step (2) is the molecular sieve that adopts low temperature to obtain to the interval treatment step of different temperatures (1) of high temperature, the process of removed template method.Said processing is in the interval of 200 ℃ to 800 ℃, in at least two non-overlapping temperature ranges from low to high, carry out, said low temperature range is 200-400 ℃, preferred 300-350 ℃, and said high temperature range is 500-800 ℃, preferred 500-600 ℃.For example, said processing is by Na after the exchange of step (1) ammonium
2the molecular sieve that O content is less than 0.2 heavy % after dry first 200-400 ℃, preferred calcination process at least 0.5 hour at 300-350 ℃, preferably 1～12 hour, then 2 hours at the most, be preferably warmed up under 500-800 ℃ of temperature range calcination process in 1 hour at least 0.5 hour, preferably 1～8 hour.In step (2), also can, before above-mentioned said two temperature ranges are processed, first at least process 1 hour fully to remove moisture at 120-180 ℃.
In phosphorous Silicon-rich beta-molecular sieve preparation method provided by the invention, said step (3) is at temperature 25-100 ℃, the process of the product obtaining by dealumination agent solution treatment steps (2).In step (2), the consumption of dealumination agent is to add by required dealuminzation degree experience, and the processing time is β zeolite 1-6 hour conventionally, 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 phosphorus-containing compound in step (4) product of step (3) is carried out to modification.Said phosphorus-containing compound is selected from one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) or ammonium phosphate or its mixture.The said modifying process of step (4) can adopt impregnation method to carry out.Wherein said dipping can be that the phosphorus-containing compound aqueous solution of the molecular sieve after dealuminzation and amount of calculation is evenly dried in room temperature to a 95 ℃ making beating.
In phosphorous Silicon-rich beta-molecular sieve preparation method provided by the invention, step (5) is phosphorous beta-molecular sieve product calcination process at least 0.5 hour, the preferred 0.5-8 hour at 400～800 ℃, preferred 500-600 ℃ that step (4) is obtained.Wherein said calcination process process can adopt dry roasting also can adopt wet roasting, and said wet roasting is preferably at 1-100%, more preferably carry out under 100% steam atmosphere.
In catalyst provided by the invention, wherein said natural mineral matter comprises one or more the mixture in kaolin, halloysite, imvite, diatomite, convex-concave rod stone, sepiolite, galapectite, hydrotalcite, bentonite and rectorite etc.Take catalyst total amount as benchmark, weight percent meter, the content of natural mineral matter is 15% ~ 65%, preferably 20% ~ 55%.
In catalyst provided by the invention, 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, for example, in Ludox, aluminium colloidal sol, peptization boehmite, silicon-aluminum sol and phosphorated aluminiferous collosol one or more.Take catalyst total amount as benchmark, weight percent meter, the content of oxide is 10% ~ 30%, preferably 12% ~ 28%.
Described MFI structure molecular screen is preferably one or more in HZSM-5 molecular sieve, element modified for example phosphorus of ZSM-5 molecular sieve and/or rare earth modified ZSM-5 molecular sieve, ZRP molecular sieve and ZSP molecular sieve.
Described MFI structure molecular screen and phosphorous Silicon-rich beta-molecular sieve mixture, take catalyst total amount as benchmark, weight percent meter, described mixture content is 25% ~ 75%, preferably 30% ~ 70%.MFI structure molecular screen and phosphorus modified beta molecular sieve can be mixed with arbitrary proportion, and preferably MFI structure molecular screen/phosphorous Silicon-rich beta-molecular sieve mass ratio is 0.05 ~ 50:1, is preferably 0.1:4 ~ 4:1.
The preparation method of catalyst provided by the invention comprise by natural mineral matter, oxide with or the precursor of oxide pull an oar together with phosphorous Silicon-rich beta-molecular sieve, MFI structure molecular screen, then slurries are sprayed and be dried and roasting, the colloidal sol of for example oxide of described oxide precursor, described oxide sol in catalyst preparation process as binding agent so that final catalyst has suitable mechanical strength and abrasion resistance.The consumption of each component makes to contain in final catalyst, take catalyst total amount as benchmark, and 15% ~ 65% natural mineral matter, 10% ~ 30% oxide and 25% ~ 75% phosphorous Silicon-rich beta-molecular sieve.One or more in described oxide precursor for example Ludox, aluminium colloidal sol, peptization boehmite, silicon-aluminum sol and phosphorated aluminiferous collosol.
The present invention also provides a kind of method of producing olefin hydrocarbon by catalytic pyrolysis, be included in fluidized-bed reactor or in riser reactor hydrocarbon ils is contacted with catalyst, described catalyst is described catalyst provided by the invention, described hydrocarbon ils is naphtha, the temperature of described contact is 600 ~ 750 ℃, and agent oil weight (hourly) space velocity (WHSV) is 0.1 ~ 10h
-1, in course of reaction, preferably passing into water vapour, water weight of oil ratio is that 0.1 ~ 10:1 is for example 0.2 ~ 5:1.The boiling range of described naphtha is generally 40 ~ 180 ℃, for example, can be straight-run naphtha.
The fluid catalyst of producing olefin hydrocarbon by catalytic pyrolysis provided by the invention has more excellent hydrothermal stability, has higher productivity of low carbon olefin hydrocarbon.Described catalyst, for naphtha fluidisation catalytic pyrolysis, has higher yield of light olefins, and ethene, propylene and butylene yield significantly improve.
The specific embodiment
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 molecule sieve
2o, Fe
2o
3, Co
2o
3, NiO, CuO, Mn
2o
3, ZnO, SnO
2, Al
2o
3, SiO
2content for x-ray fluorescence method measure (referring to " Petrochemical Engineering Analysis method (RIPP experimental technique) ", the volumes such as Yang Cuiding, Science Press, nineteen ninety publish).
27al MAS NMR adopts Bruker Advance III 500MHz NMR to test, and formant spectrogram carries out adopting integration method to calculate each peak area after 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%), aluminium colloidal sol (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-mentioned 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 with) use NH
4the exchange of Cl solution is washed to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Dry, gained sample, 350 ℃ of calcination process 2 hours, is then warming up to 550 ℃ for 40 minutes, in 4 hours removed template methods of 550 ℃ of calcination process; Get above-mentioned molecular sieve 100Kg(butt) adding water is mixed with the molecular sieve pulp of solid content 10 heavy %, adds 20 kilograms of oxalic acid in stirring, is warming up to 80 ℃ and stirs 1h, and filtered water is washed till filtrate neutrality; Add 9 kilograms of H
3pO
4(the heavy % of concentration 85) is dissolved in 50 kg of water, dry with molecular sieve filter cake hybrid infusion; Gained sample was 550 ℃ of calcination process 2 hours, and molecular sieve provided by the invention, is designated as F-1.The physical data of sample and
27al MAS NMR peak area ratio is listed in table 1.
Natural mineral matter, MFI structure molecular screen, phosphorous Silicon-rich beta-molecular sieve F-1, binding agent colloidal sol and water are mixed to making beating, the slurries that obtain are spray dried to diameter mainly at the particle of 40-150 micron and in 500 ℃ of roastings 1 hour, obtain catalyst C1 provided by the invention.The physical data of the phosphorous Silicon-rich beta-molecular sieve that uses, consumption and
27al MAS NMR peak area ratio is listed in table 1.The kind of the kind of MFI structure molecular screen, natural mineral matter and consumption, binding agent and consumption are listed in respectively in table 2 and table 3, table 4.
Embodiment 2
By Na beta-molecular sieve, (Shandong catalyst plant is produced, SiO
2/ Al
2o
3=25) use NH
4the exchange of Cl solution is washed to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Dry, gained sample, 350 ℃ of calcination process 2 hours, is then warming up to 4 hours removed template methods of 550 ℃ of calcination process for 40 minutes; Get above-mentioned molecular sieve 100 kilograms (butts) and add water and be mixed with the molecular sieve pulp of solid content 10 heavy %, add 10 kilograms of fluosilicic acid (concentration 30%) in stirring, be warming up to 60 ℃ and stir 1h, filtered water is washed till filtrate neutrality; Add 10 kilograms of (NH
3)
2hPO
4(the heavy % of concentration 85) is dissolved in 90 kg of water, dry with above-mentioned molecular sieve filter cake hybrid infusion; Gained sample was 550 ℃ of calcination process 2 hours, and molecular sieve provided by the invention, is designated as F-2.The physical data of sample and
27al MAS NMR peak area ratio is listed in table 1.
Natural mineral matter, MFI structure molecular screen, phosphorous Silicon-rich beta-molecular sieve F-2, binding agent and water are mixed to making beating, the slurries that obtain are spray dried to diameter mainly at the particle of 40-150 micron roasting (500 ℃ roasting 1.5 hours), obtain catalyst C2 provided by the invention.The physical data of the phosphorous Silicon-rich beta-molecular sieve that uses, consumption and
27al MAS NMR peak area ratio is listed in table 1.The kind of the kind of MFI structure molecular screen, natural mineral matter and consumption, binding agent and consumption are listed in respectively in table 2 and table 3, table 4.
Embodiment 3
By Na beta-molecular sieve, (Shandong catalyst plant is produced, SiO
2/ Al
2o
3=25) use NH
4the exchange of Cl solution is washed to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Dry, gained sample, 350 ℃ of calcination process 2 hours, is then warming up to 4 hours removed template methods of 550 ℃ of calcination process for 40 minutes; Get above-mentioned molecular sieve 100 kilograms (butts) and add water and be mixed with the molecular sieve pulp of solid content 10 heavy %, add 2 kilograms of ammonium fluosilicates in stirring, be warming up to 60 ℃ and stir 1h, filtered water is washed till filtrate neutrality; Add 14 kilograms of H
3pO
4(concentration 85 % by weight) are dissolved in 90 kg of water, dry with above-mentioned molecular sieve filter cake hybrid infusion; Gained sample is at 550 ℃ of calcination process 2 hours, i.e. molecular sieve F-3 provided by the invention.The physical data of sample and
27al MAS NMR peak area ratio is listed in table 1.
Natural mineral matter, MFI structure molecular screen, phosphorous Silicon-rich beta-molecular sieve F-3, binding agent and water are mixed to making beating, the slurries that obtain are spray dried to diameter mainly at the particle of 40-150 micron roasting (500 ℃ roasting 1 hour), obtain catalyst C3 provided by the invention.The physical data of the phosphorous Silicon-rich beta-molecular sieve that uses, consumption and
27al MAS NMR peak area ratio is listed in table 1.The kind of the kind of MFI structure molecular screen, natural mineral matter and consumption, binding agent and consumption are listed in respectively in table 2 and table 3, table 4.
Embodiment 4
By Na beta-molecular sieve, (Shandong catalyst plant is produced, SiO
2/ Al
2o
3=25) use NH
4the exchange of Cl solution is washed to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Dry, gained sample, 350 ℃ of calcination process 2 hours, is then warming up to 4 hours removed template methods of 550 ℃ of calcination process for 40 minutes; Get above-mentioned molecular sieve 100 kilograms (butts) and add water and be mixed with the molecular sieve pulp of solid content 10 heavy %, add 30 kilograms of ammonium oxalate in stirring, be warming up to 60 ℃ 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 ℃ of calcination process 2 hours, and molecular sieve provided by the invention, is designated as F-4.The physical data of sample and
27al MAS NMR peak area ratio is listed in table 1.
Natural mineral matter, MFI structure molecular screen, phosphorous Silicon-rich beta-molecular sieve F-4, binding agent colloidal sol and water are mixed to making beating, 36 % by weight peptizations for boehmite wherein, wherein 36 % by weight hydrochloric acid: the weight ratio of the boehmite of remembering take aluminium oxide is as 0.2, the slurries that obtain are spray dried to diameter mainly at the particle of 40-150 micron roasting (500 ℃ roasting 2 hours), obtain catalyst C4 provided by the invention.The physical data of the phosphorous Silicon-rich beta-molecular sieve that uses, consumption and
27al MAS NMR peak area ratio is listed in table 1.The kind of the kind of MFI structure molecular screen, natural mineral matter and consumption, binding agent and consumption are listed in respectively in table 2 and table 3, table 4.
Comparative example 1
Prepare phosphorous beta-molecular sieve according to the method for CN1179994A: by 100g(butt) Na beta-molecular sieve joins in the ammonium sulfate of 2000ml 4 heavy % and stirs exchange 1h in 90 ℃, after filtration, exchange again once with same method, filter the fluosilicic acid H of filter cake and 3 heavy %
2siF
6solution 500ml reacts 2h at 60 ℃, refilters, and be phosphoric acid and the 3g boehmite (Al of 85% heavy % by filter cake and 14g concentration
2o
3the heavy % of content 67) mixture of composition mixes, in baking oven after 110 ℃ of oven dry, put into tubular type muffle furnace with 550 ℃ 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.
The beta-molecular sieve DF-2 of natural mineral matter, phosphorus modification, MFI structure molecular screen, binding agent colloidal sol and water are mixed to making beating, the slurries that obtain are spray dried to diameter mainly at the particle of 40-150 micron roasting (500 ℃ roasting 1.5 hours), obtain catalyst D1.The physical data of the phosphorus modified beta molecular sieve that uses, consumption and
27al MAS NMR peak area ratio is listed in table 1.The kind of the kind of natural mineral matter and consumption, binding agent and consumption are listed in respectively in table 2 and table 3.Comparative example 2
Na beta-molecular sieve in embodiment 1, according to the method processing of embodiment 1, but was not taken out to aluminium processing before phosphorus modification, obtain comparative example 2 molecular sieves, be designated as DF-2.
The beta-molecular sieve DF-2 of natural mineral matter, phosphorus modification, MFI structure molecular screen, binding agent colloidal sol and water are mixed to making beating, the slurries that obtain are spray dried to diameter mainly at the particle of 40-150 micron roasting (500 ℃ roasting 1 hour), obtain catalyst D2.The physical data of the phosphorus modified beta molecular sieve that uses, consumption and
27al MAS NMR peak area ratio is listed in table 1.The kind of the kind of MFI structure molecular screen, natural mineral matter and consumption, binding agent and consumption are listed in respectively in table 2, table 3 and table 4.
Spray-dired exhaust temperature, sintering temperature and time list in table 5.
Comparative example 3
By beta-molecular sieve NH
4the exchange of Cl solution is washed to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Dry, 4 hours removed template methods of 550 ℃ of calcination process; Get above-mentioned molecular sieve 100g(butt) adding water is mixed with the molecular sieve pulp of solid content 10 heavy %, adds oxalic acid 20g in stirring, is warming up to 80 ℃ and stirs 1h, and filtered water is washed till filtrate neutrality; Add 9gH
3pO
4(concentration 85 % by weight) are dissolved in 50g water, dry with molecular sieve filter cake hybrid infusion; Gained sample was 550 ℃ of calcination process 2 hours, and contrast molecular sieve provided by the invention, is designated as DF-3.
The physical data of sample and
27al MAS NMR peak area ratio is listed in table 1.
Table 1
Table 2
Table 3
| Catalyst numbering | 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 4
Table 5
| Catalyst numbering | Spraying dried tail gas temperature/℃ | Sintering temperature/℃ | 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
The sample that above-described embodiment and comparative example are made is evaluated after within aging 17 hours, processing in 820 ℃, 100% steam on fluidized bed plant, and appreciation condition is 650 ℃ of reaction temperatures, and weight space velocity is 1.0 hours
-1, oil inlet quantity 1.56g, water is with weight of oil than being 4:1, feedstock oil is normal top straight-run naphtha, 45.5 ℃ of initial boiling points, 166.5 ℃ of the end points of distillation, specifically form in table 6.Reaction evaluating the results are shown in Table 7.
Table 6
| 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 |
Composition is weight percentage in table 6
Table 7
| Catalyst | C1 | C2 | C3 | C4 | D1 | D2 |
| Conversion ratio/% by weight | 38.7 | 41.5 | 46.8 | 51.6 | 36.2 | 36.5 |
| Ethylene yield/% by weight | 6.90 | 7.24 | 8.94 | 9.15 | 6.72 | 6.81 |
| Productivity of propylene/% by weight | 13.68 | 14.75 | 16.98 | 18.64 | 12.22 | 12.63 |
| Butylene productive rate/% by weight | 6.67 | 7.78 | 8.33 | 9.03 | 5.58 | 5.85 |
| (ethene+propylene+butylene) productive rate/% by weight | 27.25 | 29.77 | 34.25 | 36.82 | 24.52 | 25.29 |
Wherein said productive rate obtains take raw material charging as benchmark.
Output (the weight)/naphtha feed amount (weight) × 100% of products collection efficiency=product
Conversion ratio is the productive rate sum that in molecule, carbon number is less than or equal to productive rate, hydrogen and the coke of 4 hydrocarbon products.
As seen from Table 7, modified molecular screen provided by the invention has good activity stability and productivity of low carbon olefin hydrocarbon.Compare with comparative example, catalyst take MFI structure molecular screen and phosphorous Silicon-rich beta-molecular sieve as active component provided by the invention, in 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 and selectively all have raising by a relatively large margin.
Claims (19)
1. a catalyst for producing olefin hydrocarbon by catalytic pyrolysis, comprises following component by weight percentage:
(a) 15% ~ 65% natural mineral matter;
(b) 10% ~ 30% oxide and;
(c) 25% ~ 75% MFI structure molecular screen and phosphorous Silicon-rich beta-molecular sieve, described phosphorous Silicon-rich beta-molecular sieve, with P
2o
5meter phosphorus content accounts for 1 ~ 10 heavy %, this molecular sieve
27in Al MAS NMR, chemical shift is that 40 ± 3ppm resonance signal peak area and chemical shift are that the ratio of 54 ± 3ppm resonance signal peak area is more than or equal to 1, and chemical shift is that the percentage that resonance signal peak area sum that 0 ± 3ppm and chemical shift are-12 ± 3ppm accounts for total peak area is less than or equal to 10%.
2. catalyst according to claim 1, is characterized in that described natural mineral matter comprises one or more in kaolin, halloysite, imvite, diatomite, convex-concave rod stone, sepiolite, galapectite, hydrotalcite, bentonite and rectorite etc.; Described oxide is selected from one or more in silica, aluminium oxide, zirconia, titanium oxide, amorphous aluminum silicide.
3. according to the described catalyst of claim 1, in the MFI structure molecular screen described in it is characterized in that and the mixture of phosphorus modified beta molecular sieve, MFI structure molecular screen and phosphorus modified beta molecular sieve weight ratio are 0.1:4 ~ 4:1.
4. catalyst according to claim 1, is characterized in that, in described phosphorous Silicon-rich beta-molecular sieve with P
2o
5meter phosphorus content accounts for the heavy % of 1-8.
5. catalyst according to claim 1, is characterized in that, described phosphorous Silicon-rich beta-molecular sieve is said
27in Al MAS NMR, chemical shift is that 40 ± 3ppm resonance signal peak area and chemical shift are that the ratio of 54ppm ± 3ppm resonance signal peak area is more than or equal to 2.
6. catalyst according to claim 1, is characterized in that, described phosphorous Silicon-rich beta-molecular sieve is said
27in Al MAS NMR, the chemical shift percentage that to be 0 ± 3ppm and chemical shift account for total peak area for the resonance signal peak area sum of-12ppm ± 3ppm is for being less than or equal to 6%.
7. according to the described catalyst of claim 1, it is characterized in that the described catalyst according to claim 1, the silica and the alumina molar ratio that it is characterized in that described MFI structure molecular screen are 15-300, and the silica alumina ratio of phosphorous Silicon-rich beta-molecular sieve is 12-100.
8. the preparation method of catalyst described in claim 1 ~ 7 any one, the method comprises: prepare phosphorous Silicon-rich beta-molecular sieve, natural mineral matter, oxide and/or oxide precursor, MFI structure molecular screen and described phosphorous Silicon-rich beta-molecular sieve are mixed with to slurries, then by dry prepared slurries spraying; The preparation method of wherein said phosphorous Silicon-rich beta-molecular sieve comprises that the former powder of beta-molecular sieve is in the temperature range of 200 ℃ to 800 ℃, dealuminzation, the step of carrying out again phosphorus modification after the non-overlapping temperature ranges of from low to high at least two are processed with removed template method.
9. described method for preparing catalyst according to Claim 8, is characterized in that, the preparation process of described phosphorous Silicon-rich beta-molecular sieve is as follows:
((1) makes the Na on molecular sieve by sodium type beta-molecular sieve through ammonium exchange
2o content is less than 0.2 heavy %;
(2) molecular sieve step (1) being obtained after drying, is processed at least 0.5 hour under 200-400 ℃ of temperature range, then under 500-800 ℃ of temperature range, processes at least 0.5 hour removed template method being warmed up in 2 hours at the most;
(3) at temperature 25-100 ℃, the product obtaining by dealumination agent solution treatment steps (2);
(4) introduce phosphorus-containing compound molecular sieve is carried out to modification;
(5) calcination process at least 0.5 hour at 400～800 ℃.
10. according to method for preparing catalyst claimed in claim 9, wherein, said ammonium exchange is according to molecular sieve: ammonium salt: H
2o=1:(0.1～1): the weight ratio of (5～10) process that exchange was filtered after at least 0.5 hour at room temperature to 100 ℃, this process is at least carried out once.
11. methods of preparing according to catalyst claimed in claim 9, wherein, said phosphorus-containing compound is selected from one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) or ammonium phosphate or its mixture.
12. according to method for preparing catalyst claimed in claim 9, it is characterized in that in step (2) before, the product of step (1) at least being processed 1 hour at 120-180 ℃.
13. according to method for preparing catalyst claimed in claim 9, 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.
14. according to the method for preparing catalyst described in claim 13, 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, and said organic salt is selected from ammonium oxalate, ammonium fluoride, ammonium fluosilicate or ammonium fluoroborate.
15. according to method for preparing catalyst claimed in claim 9, wherein, said dealumination agent, its weight concentration is 1-20%.
16. according to method for preparing catalyst claimed in claim 9, wherein, the said modification of said step (4) adopts impregnation method to carry out, and said impregnation method is by the phosphorus-containing compound aqueous solution of the molecular sieve after dealuminzation and amount of calculation in room temperature to 95 ℃ making beating evenly, dries.
17. according to method for preparing catalyst claimed in claim 9, and wherein, the said calcination process process of step (5) is roasting under steam atmosphere.
18. method for preparing catalyst claimed in claim 8, it is characterized in that, described oxide and/or oxide precursor are one or more of silica, aluminium oxide, zirconia, titanium oxide, amorphous aluminum silicide and aluminum phosphate, aluminium colloidal sol, peptization boehmite, Ludox, silicon-aluminum sol, phosphorated aluminiferous collosol.
The method of 19. 1 kinds of producing olefin hydrocarbon by catalytic pyrolysis, be included in fluidized-bed reactor or in riser reactor hydrocarbon ils is contacted with catalyst, it is characterized in that, described catalyst is the catalyst described in claim 1 ~ 7 any one, described hydrocarbon ils is naphtha, the temperature of described contact is 600-750 ℃, and agent oil weight (hourly) space velocity (WHSV) is 0.1 ~ 10h
-1.
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