CN103785460B - 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 comprises the natural mineral matter of (a) 15% ~ 65%; The oxide of (b) 10% ~ 30%; (c) the MFI structure molecular sieve of 25% ~ 75% and the beta-molecular sieve mixture of P Modification, wherein said P Modification beta-molecular sieve, with P
2o
5meter phosphorus content accounts for 3 ~ 10 heavy %, this molecular sieve
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.The preparation method of described catalyst comprises described P Modification beta-molecular sieve to mix with natural mineral matter, electrodeless adhesive oxides and pulls an oar, spray-dired step, wherein Beta molecular screen primary powder is carried out P Modification again by the preparation method of P Modification beta-molecular sieve after temperature-programmed calcination removed template method.Described catalytic cracking catalyst is used for naphtha catalytic pyrolysis preparing and has higher productivity of low carbon olefin hydrocarbon for propylene.
Description
Technical field
The present invention relates to a kind of fluid catalyst of producing olefin hydrocarbon by catalytic pyrolysis, particularly a kind of is that raw material produces the catalyst containing beta-molecular sieve of ethene, propylene and butylene through fluidized catalytic cracking solution preocess 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.Wherein conventional 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.The ACO of the recent development developed by KBR company of the U.S. and SK Energy Co., Ltd. (KR) of Korea S
tM(AdvancedCatalyticOlefins) the proprietary catalyst developed in conjunction with Orthoflow fluid catalytic cracking reactor system and SK Energy Co., Ltd. (KR) of Korea S of technique, its proprietary catalyst is have peracidity, microballoon ZSM-5 molecular sieve catalyst that hydrothermal stability is high.
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 yield that naphtha catalytic cracking can significantly improve the conversion ratio of naphtha and ethene, propylene.
But above-mentioned ZSM-5 molecular sieve catalyst mainly improves ethene and productivity of propylene.Naphtha catalytic pyrolysis preparing is β zeolite for another catalyst that low-carbon alkene uses, and 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 beta zeolite obtained by the method.
Summary of the invention
An object of the present invention is to provide a kind of fluid catalyst of the producing olefin hydrocarbon by catalytic pyrolysis containing Beta-zeolite modified by phosphorous, and this catalyst has excellent hydrothermal stability and the productivity of low carbon olefin hydrocarbon of Geng Gao.
Two of object of the present invention is to provide preparation method and application's method of described catalyst.
The invention provides a kind of catalyst of producing olefin hydrocarbon by catalytic pyrolysis, comprise following component by weight percentage: the natural mineral matter of (a) 15% ~ 65%; The oxide of (b) 10% ~ 30%; (c) the MFI structure molecular sieve of 25% ~ 75% and the beta-molecular sieve mixture of P Modification, described P Modification beta-molecular sieve, with P
2o
5meter phosphorus content accounts for 3 ~ 10 heavy %, this molecular sieve
27in AlMASNMR, the ratio of chemical shift to be (40 ± 3) ppm resonance signal peak area and chemical shift be (54 ± 3) ppm resonance signal peak area is more than or equal to 1.
The preparation method of the beta-molecular sieve of wherein said P Modification, it is characterized in that comprising 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 to carry out the step of P Modification after removed template method again.More specifically, the preparation method of the beta-molecular sieve of described P Modification comprises the steps:
(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, calcination process at least 0.5 hour at 200-400 DEG C, then calcination process at least 0.5 hour removed template method at being warmed up to 500-800 DEG C in 2 hours at the most;
(3) introduce phosphorus-containing compound and modification is carried out to molecular sieve;
(4) calcination process at least 0.5 hour at 400 ~ 800 DEG C.
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.With catalyst total amount for benchmark, weight percent meter, in the content of butt natural mineral matter for 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 all 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%.
Described MFI structure molecular sieve is preferably one or more in HZSM-5 molecular sieve, element modified ZSM-5 molecular sieve such as phosphorus and/or rare earth modified ZSM-5 molecular sieve, ZRP molecular sieve and ZSP molecular sieve.
The preparation method of catalyst provided by the invention comprises the beta-molecular sieve mixing making beating of the predecessor of water, natural mineral matter, oxide and/or oxide, MFI structure molecular sieve and modification, then slurries is carried out spraying dry and roasting.
The invention provides a kind of fluid catalyst of producing olefin hydrocarbon by catalytic pyrolysis of naphtha, described catalyst contains a kind of novel P Modification beta-molecular sieve and MFI structure molecular sieve is active component, there is more excellent hydrothermal stability and better selectivity of light olefin, there is higher ethene, propylene and butylene productive rate after hydrothermal aging, can be used for naphtha fluidized catalytic cracking.The method of producing olefin hydrocarbon by catalytic pyrolysis of naphtha provided by the invention, has higher propylene, ethene and butylene productive rate.
Detailed description of the invention
The beta-molecular sieve of P Modification of the present invention, with P
2o
5meter phosphorus content accounts for the heavy % of 3-10, preferably accounts for the heavy % of 5-9.
The beta-molecular sieve of P Modification of the present invention, its
27in AlMASNMR, chemical shift be 54 ± 3ppm resonance signal characterize four-coordination framework aluminum species, chemical shift be 40 ± 3ppm resonance signal characterize be the framework aluminum species with phosphorus coordination.Modified beta molecular sieve provided by the invention, 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, is preferably greater than or equal to 2, a value of such as 1.5 to 5.
The beta-molecular sieve preparation method of P Modification of the present invention comprises by former for beta-molecular sieve powder (the sodium form beta-molecular sieve containing organic formwork agent) in the temperature range of 200 DEG C to 800 DEG C, obtains with the step of carrying out P Modification after removed template method again through the non-overlapping temperature range process of at least two from low to high.More particularly comprise the steps:
(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) introduce phosphorus-containing compound and modification is carried out to molecular sieve;
(4) calcination process at least 0.5 hour at 400 ~ 800 DEG C.
In the beta-molecular sieve preparation method of P Modification of the present invention, in described step (1), described sodium form beta-molecular sieve is the sodium form beta-molecular sieve (as USP3,308,069, CNZL00107486.5) of conventional crystallization gained.Usually in described sodium form beta-molecular sieve (Na β), sodium content counts the heavy % of 4-6 with sodium oxide molybdena.Described 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 %.Described ammonium salt for conventional inorganic ammonium salt, can be selected from ammonium chloride, one of ammonium sulfate or ammonium nitrate or their mixture.
In preparation method provided by the invention, described step (2) be adopt low temperature to high temperature different temperatures interval treatment step (1) obtain molecular sieve, removed template method process.Described 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, described low temperature range is 200-400 DEG C, preferred 300-350 DEG C, and described high temperature range is 500-800 DEG C, preferred 500-600 DEG C.Such as, described 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 described above two temperature range process, first at least can process 1 hour at 120-180 DEG C.
In preparation method provided by the invention, introduce the product of phosphorus-containing compound to step (2) in step (3) and carry out modification.Described phosphorus-containing compound is selected from phosphoric acid, ammonium hydrogen phosphate, one of ammonium dihydrogen phosphate (ADP) or ammonium phosphate or its mixture.Preferred employing impregnation method carries out, and described dipping is pull an oar evenly by the phosphorus-containing compound aqueous solution of the molecular sieve after removed template method and amount of calculation in room temperature to 95 DEG C, dries.
The invention provides in preparation method, step (4) is beta-molecular sieve product calcination process at least 0.5 hour, preferably 0.5-8 hour at 400 ~ 800 DEG C, preferably 500-600 DEG C of P Modification step (3) obtained.Wherein said calcination process process can adopt dry roasting also can adopt wet roasting, and described wet roasting is preferably carried out under 1-100%, more preferably 100% steam atmosphere.
Described MFI structure molecular sieve and P Modification beta-molecular sieve mixture, with catalyst total amount for benchmark, according to weight percent meter, in the content of the described MFI structure molecular sieve of butt and P Modification beta-molecular sieve mixture for 25% ~ 75%, preferably 30% ~ 70%.MFI structure molecular sieve and P Modification beta-molecular sieve can mix with arbitrary proportion, and such as MFI structure molecular sieve and P Modification beta-molecular sieve mass ratio are 0.05 ~ 50:1, and being preferably 0.1 ~ 20:1, such as, is 0.1:4 ~ 4:1.The silica alumina ratio (Si/Al mol ratio) of described P Modification beta-molecular sieve is preferably 12 ~ 100.
The preparation method of catalyst provided by the invention comprises the beta-molecular sieve mixing making beating of the predecessor of water, natural mineral matter, oxide and/or oxide, MFI structure molecular sieve and modification, then slurries is carried out spraying dry and roasting.The colloidal sol of the predecessor such as described oxide of described oxide, described oxide sol has suitable mechanical strength and abrasion resistance as binding agent to make final catalyst in catalyst preparation process, can be one or more in Ludox, Alumina gel, peptization boehmite, silicon-aluminum sol and phosphorated aluminiferous collosol.The consumption of each component makes to contain in final catalyst, with catalyst total amount for benchmark, and the natural mineral matter of 15% ~ 65%, the mixture of the oxide of 10% ~ 30% and the described MFI structure molecular sieve of 25% ~ 75% and P Modification beta-molecular sieve.
The present invention also provides a kind of method of producing olefin hydrocarbon by catalytic pyrolysis of naphtha, the method 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 catalyst of described producing olefin hydrocarbon by catalytic pyrolysis provided by the invention.Described alkene is ethene, propylene and butylene, and described naphtha is such as straight-run naphtha, and its boiling range is generally 40 ~ 180 DEG C, and catalytic condition comprises: reaction temperature is 600 ~ 750 DEG C, air speed 0.1 ~ 10h
-1, preferably pass into water vapour in course of reaction, the part by weight of steam and naphtha is for being 0.1 ~ 10:1: be such as 0.2 ~ 5:1.
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.
The beta-molecular sieve of P Modification prepares 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, then heat up (heating rate 5 DEG C/min) to 550 DEG C, calcination process 4 hours removed template methods; Add 14.6 kilograms of H
3pO
4(concentration 85 % by weight) is dissolved in 90 kg of water, dry with the molecular sieve hybrid infusion after 100 kilograms of above-mentioned roastings; Gained sample was 500 DEG C of calcination process 2 hours, and namely molecular sieve provided by the invention, is designated as B1.The physical data of sample and
27alMASNMR peak area ratio lists in table 1.
The beta-molecular sieve of P Modification prepares 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 30 minutes; Add 9.6 kilograms of (NH
3)
2hPO
4(concentration 85 % by weight) is dissolved in 90 kg of water, dry with the molecular sieve hybrid infusion after 100 kilograms of above-mentioned roastings; Gained sample calcination process 2 hours under 550 DEG C and 100% steam, namely molecular sieve provided by the invention, is designated as B2.The physical data of sample and
27alMASNMR peak area ratio lists in table 1.
The beta-molecular sieve of P Modification prepares embodiment 3
By beta-molecular sieve (Tianjin Chemist Technology Development Co., Ltd, SiO
2/ Al
2o
3=50, sodium oxide content 0.05 % by weight) 350 DEG C of calcination process 2 hours, then within 30 minutes, be warming up to 550 DEG C of calcination process, 4 hours removed template methods; Then 17 kilograms of H are added
3pO
4(concentration 85 % by weight) is dissolved in 90 kg of water, dry with the molecular sieve hybrid infusion after 100 kilograms of above-mentioned roastings; Gained sample 600 DEG C of calcination process 2 hours, i.e. molecular sieve provided by the invention, be designated as B3.The physical data of sample and
27alMASNMR peak area ratio lists in table 1.
The beta-molecular sieve of P Modification prepares embodiment 4
By Na beta-molecular sieve (Tianjin Chemist Technology Development Co., Ltd, SiO
2/ Al
2o
3=50, sodium oxide content 0.05 % by weight) 350 DEG C of calcination process 2 hours, then within 30 minutes, be warming up to 550 DEG C of calcination process, 4 hours removed template methods; Then 12.1 kilograms of H are added
3pO
4(concentration 85 % by weight) is dissolved in 90 kg of water, dry with the molecular sieve hybrid infusion after 100 kilograms of above-mentioned roastings; Gained sample is 550 DEG C and 100% steam roasting process 2 hours, and namely molecular sieve provided by the invention, is designated as B4.The physical data of sample and
27alMASNMR peak area ratio lists in table 1.
The beta-molecular sieve of P Modification prepares embodiment 5
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, gained sample, 150 DEG C of calcination process 2 hours, is then warming up to 350 DEG C of calcination process 2 hours for 30 minutes, then within 40 minutes, is warming up to 550 DEG C of calcination process, 4 hours removed template methods; Add 10g (NH
3)
2hPO
4(concentration 85 % by weight) is dissolved in 90 kg of water, dries with the molecular sieve hybrid infusion after 100 kilograms of above-mentioned roastings; Gained sample 550 DEG C of calcination process 2 hours, i.e. molecular sieve provided by the invention.Be designated as B5.The physical data of sample and
27alMASNMR peak area ratio lists in table 1.Use the physical data of MFI structure molecular sieve (being catalyst asphalt in Shenli Refinery of China Petrochemical Industry product) and consumption to list in table 2.Kind and the consumption of the kind of natural mineral matter and consumption, binding agent are listed in table 3 and table 4 respectively.
The following examples illustrate Catalysts and its preparation method provided by the invention, wherein the performance of raw materials is as follows: kaolin (Kaolin of Suzhou company, solid content 75 % by weight), (zunyi, guizhou three closes white ore deposit to galapectite, solid content 75 % by weight), rectorite (From Zhongxiang Hubei rectorite ore deposit, the heavy % of solid content 75), imvite (Chaoyang City, Liaoning Province Hong Shi bentonite company, solid content 75 % by weight), boehmite (Shandong Aluminium Industrial Corp, solid content 65 % by weight, concentration 31 % by weight hydrochloric acid peptization is first used before using, described hydrochloric acid with in the mol ratio of the boehmite of aluminium oxide for 0.20), Alumina gel (Shandong catalyst branch company, alumina content is 22.5 % by weight), Ludox (Qingdao Marine Chemical Co., Ltd., silica content 25.5 % by weight, pH value 3.0), phosphorated aluminiferous collosol (P content 16 % by weight, Al content 8 % by weight, pH value is 2.0).
Embodiment 1-5
By the beta-molecular sieve of natural mineral matter, MFI structure molecular sieve, 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, sintering temperature is 500 DEG C, roasting time is 2 hours, obtains catalyst C1-C5 provided by the invention.Use the physical data of P Modification beta-molecular sieve, consumption and
27alMASNMR peak area ratio lists in table 1.
Comparative example 1
Prepare phosphorous beta-molecular sieve according to the method for CN1179994A: by 100g(butt) Na beta-molecular sieve (with embodiment 1 Na used beta-molecular sieve) join in the ammonium sulfate of 2 liter of 4 heavy % 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, refilters, and is phosphoric acid and the 3g boehmite (Al of 85% heavy % by filter cake and 14g concentration
2o
3the heavy % of content 67) mixture that forms mixes, 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, be designated as DB1.By the beta-molecular sieve DB1 of natural mineral matter, MFI structure molecular sieve, 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, roasting, sintering temperature is 500 DEG C, roasting time is 2 hours, obtains catalyst D1 provided by the invention.
Comparative example 2
According to the method for embodiment 1, said Na beta-molecular sieve (with embodiment 1 Na beta-molecular sieve used) is processed, but do not carry out calcination process before P Modification, obtain comparative example 2 molecular sieve DB2.By the beta-molecular sieve DB2 of natural mineral matter, MFI structure molecular sieve, 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, sintering temperature is 500 DEG C, roasting time is 2 hours, obtains catalyst D2 provided by the invention.
Comparative example 3
By Na beta-molecular sieve NH
4cl solution exchanges washing to Na
2o content, lower than 0.2 % by weight, filters to obtain filter cake; Drying, gained sample is at 550 DEG C of calcination process, 4 hours removed template methods; Add 14 kilograms of H
3pO
4(concentration 85%) is dissolved in 90 kg of water, dries with the molecular sieve hybrid infusion after 100 kilograms of above-mentioned roastings; Gained sample 550 DEG C of calcination process 2 hours, i.e. molecular sieve provided by the invention.The physical data of sample and
27alMASNMR peak area ratio lists in table 1
Comparative example 3
According to the method Kaolinite Preparation of Catalyst of embodiment 1, unlike the B1 molecular sieve described in the ZRP molecular sieve replacement by equivalent, obtain catalyst D3.
The embodiment of the present invention use the physical data of P Modification beta-molecular sieve, consumption and
27alMASNMR peak area ratio lists in table 1.Use the physical data of MFI structure molecular sieve and consumption to list in table 2.Kind and the consumption of the kind of natural mineral matter and consumption, binding agent are listed in table 3 and table 4 respectively.Spray-dired exhaust temperature, sintering temperature and time list in table 5.
Table 1
Table 2
Table 3
| Test number | Natural mineral matter kind | Consumption, kilogram |
| Embodiment 1 | Rectorite and kaolin | Rectorite 40, kaolin 40 |
| Embodiment 2 | Galapectite | 53.3 |
| Embodiment 3 | Cover holder soil | 26.7 |
| Embodiment 4 | Kaolin | 13.3 |
| Comparative example 1 | Rectorite and kaolin | Rectorite 40, kaolin 40 |
| Comparative example 2 | Rectorite and kaolin | Rectorite 40, kaolin 40 |
| Comparative example 3 | Rectorite and kaolin | Rectorite 40, kaolin 40 |
Table 4
Table 5
| Embodiment is numbered | Catalyst is numbered | Spraying dry exhaust temperature/DEG C | Sintering temperature/DEG C | Roasting time/h |
| Embodiment 1 | C1 | 180 | 500 | 1 |
| Embodiment 2 | C2 | 170 | 500 | 1.5 |
| Embodiment 3 | C3 | 180 | 500 | 1 |
| Embodiment 4 | C4 | 175 | 500 | 2 |
| Comparative example 1 | D1 | 180 | 500 | 1.5 |
| Comparative example 2 | D2 | 170 | 500 | 1 |
| Comparative example 3 | D3 | 175 | 500 | 2 |
Embodiment 5
The present embodiment illustrates and adopts catalyst provided by the invention to be used in naphtha catalytic cracking, for the impact of hydrothermal stability and selectivity of light olefin.
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.Feedstock oil is straight-run naphtha, initial boiling point 45.5 DEG C, and the end point of distillation 166.5 DEG C specifically forms in table 6.Reaction result is 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 |
It is weight percentage composition in table 6
Table 7
| Catalyst | C1 | C2 | C3 | C4 | D1 | D2 | D3 |
| Conversion ratio/% | 37.8 | 40.6 | 45.3 | 49.2 | 35.4 | 35.6 | 34.9 |
| Ethylene yield/% | 6.88 | 7.15 | 8.79 | 8.96 | 6.44 | 6.56 | 6.32 |
| Productivity of propylene/% | 12.76 | 14.68 | 15.81 | 15.54 | 11.15 | 11.17 | 11.03 |
| Butylene productive rate/% | 6.09 | 7.16 | 7.90 | 8.69 | 5.86 | 5.89 | 5.54 |
| Ethene+propylene+butylene productive rate % | 25.73 | 28.99 | 32.50 | 33.19 | 23.45 | 23.62 | 22.89 |
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.
From table 7, data can find out that modified molecular screen provided by the invention has good activity stability and selectivity of light olefin.Compared with comparative example, the catalyst that is active component with MFI structure molecular sieve and P Modification beta-molecular sieve provided by the invention, while improving cracking hydrocarbon ability, effectively improve the selectivity of light olefin of crackate, the productive rate of ethene, propylene and butylene has raising by a relatively large margin.
Claims (14)
1. a catalyst for producing olefin hydrocarbon by catalytic pyrolysis of naphtha, composed as follows by weight percentage:
The natural mineral matter of (a) 15% ~ 65%;
The oxide of (b) 10% ~ 30%;
The MFI structure molecular sieve of (c) 25% ~ 75% and the mixture of P Modification beta-molecular sieve; Described P Modification beta-molecular sieve, with P
2o
5meter phosphorus content accounts for 3 ~ 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;
Described natural mineral matter be selected from 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, amorphous aluminum silicide one or more.
2. according to catalyst according to claim 1, it is characterized in that, in described MFI structure molecular sieve and the mixture of P Modification beta-molecular sieve, the weight ratio of MFI structure molecular sieve and P Modification beta-molecular sieve is 0.1:4 ~ 4:1.
3. according to catalyst according to claim 1, it is characterized in that, the silica of described MFI structure molecular sieve and alumina molar ratio are 15-300, and the silica alumina ratio of described P Modification beta-molecular sieve is 12-100.
4. according to catalyst according to claim 1, it is characterized in that, with P in described P Modification beta-molecular sieve
2o
5meter phosphorus content accounts for the heavy % of 5-9.
5. according to catalyst according to claim 1, it is characterized in that, the ratio of described 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.
6. the preparation method of catalyst described in any one of Claims 1 to 5, comprise the described P Modification beta-molecular sieve of preparation, by the step of described P Modification beta-molecular sieve, MFI structure molecular sieve, natural mineral matter, described oxide and/or oxide precursor thing and water mixing making beating, spraying dry and roasting; The method of wherein said preparation described P Modification beta-molecular sieve comprises by former for beta-molecular sieve powder 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 to adopt impregnation method after removed template method again.
7. a preparation method for catalyst described in any one of Claims 1 to 5, comprising:
(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) dipping introducing phosphorus-containing compound carries out modification to molecular sieve;
(4) calcination process at least 0.5 hour at 400 ~ 800 DEG C; Obtained described P Modification beta-molecular sieve;
(5) obtained P Modification beta-molecular sieve is mixed with MFI structure molecular sieve, natural mineral matter, oxide precursor pull an oar, spraying dry.
8. in accordance with the method for claim 7, it is characterized in that, it is according to molecular sieve that the ammonium described in step (1) exchanges: ammonium salt: H
2o=1:(0.1-1): the weight ratio of (5-10) exchanges, filters at room temperature to 100 DEG C, and this process is at least carried out once; Described ammonium salt is selected from the mixture of one or more in ammonium chloride, ammonium sulfate and ammonium nitrate.
9. in accordance with the method for claim 7, it is characterized in that, the process that phosphorus-containing compound described in step (3) carries out modification to molecular sieve adopts impregnation method to carry out, described impregnation method is pull an oar evenly by the phosphorus-containing compound aqueous solution of the molecular sieve after removed template method and amount of calculation in room temperature to 95 DEG C, dries.
10. according to the method described in claim 7 or 9, it is characterized in that, described phosphorus-containing compound is selected from phosphoric acid, ammonium hydrogen phosphate, one of ammonium dihydrogen phosphate (ADP) or ammonium phosphate or its mixture.
11. in accordance with the method for claim 7, it is characterized in that, described oxide precursor is one or more in Ludox, Alumina gel, peptization boehmite, silicon-aluminum sol and phosphorated aluminiferous collosol.
12. according to the method for claim 7, and it is characterized in that, the calcination process process described in step (4) is carried out under 1-100% steam atmosphere.
13. 1 kinds of naphtha catalytic crackings produce the method for low-carbon alkene, comprise the step of being reacted by the catalyst exposure described in naphtha and any one of claim 1 ~ 6.
14. in accordance with the method for claim 13, it is characterized in that, described catalytic temperature is 600 ~ 750 DEG C, and weight (hourly) space velocity (WHSV) is 0.1 ~ 10h
-1.
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| CN112473732B (en) * | 2019-09-12 | 2023-05-05 | 中国石油化工股份有限公司 | Catalytic cracking catalyst for producing propylene and preparation method and application method thereof |
| TW202146336A (en) * | 2020-04-13 | 2021-12-16 | 大陸商中國石油化工科技開發有限公司 | Phosphorus-containing/phosphorus-modified zsm-5 molecular sieve, pyrolysis additive and pyrolysis catalyst containing same, preparation method therefor and application thereof |
| CN114505093B (en) * | 2020-10-28 | 2023-08-08 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent and preparation method and application thereof |
| CN114715910B (en) * | 2021-01-05 | 2023-05-05 | 中国石油化工股份有限公司 | Phosphorus and metal modified ZSM-5 molecular sieve and preparation method thereof |
| CN115518678B (en) * | 2021-06-24 | 2023-11-10 | 中国石油化工股份有限公司 | Light hydrocarbon catalytic cracking catalyst and preparation method and application thereof |
| CN114904566B (en) * | 2022-05-31 | 2024-04-23 | 山东京博石油化工有限公司 | Fluidized bed light hydrocarbon catalytic cracking catalyst and preparation method and application thereof |
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