CN103785460A - Catalytic cracking catalyst and preparation method thereof - Google Patents
Catalytic cracking catalyst and preparation method thereof Download PDFInfo
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- CN103785460A CN103785460A CN201210419455.8A CN201210419455A CN103785460A CN 103785460 A CN103785460 A CN 103785460A CN 201210419455 A CN201210419455 A CN 201210419455A CN 103785460 A CN103785460 A CN 103785460A
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Abstract
The invention discloses a catalytic cracking catalyst and a preparation method thereof, the catalytic cracking catalyst includes (a)15%-65% of a natural mineral, (b) 10%-30% of an oxide and (c) 25%-75% of a mixture of a MFI structure molecular sieve and a phosphorus-modified beta molecular sieve; the phosphorus-modified beta molecular sieve comprises 3-10 wt% by P2O5 of phosphorus, and in the 27Al MAS NMR (Magic Angle Spinning Nuclear Magnetic Resonance) of the molecular sieve, the ratio of resonance signal peak area at the chemical shift of 40+-3ppm to resonance signal peak area at the chemical shift of 54+-3ppm is greater than or equal to 1. The preparation method of the catalyst comprises the steps of mixing and pulping of the phosphorus-modified beta molecular sieve, the natural mineral and a non-polar oxide adhesive, and spray drying, and the preparation method of the phosphorus-modified beta molecular sieve is as follows: programmed heating of beta molecular sieve raw powder to bake to remove a template agent, and then phosphorus modification. The catalytic cracking catalyst is applied to preparation of propylene by catalytic cracking of naphtha, and the low-carbon olefin production rate is higher.
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 containing beta-molecular sieve 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.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 of being developed by KBR company of the U.S. and SK energy company of Korea S
tM(Advanced Catalytic Olefins) technique is in conjunction with the proprietary catalyst of Orthoflow fluid catalytic cracking reactor system and SK energy company of Korea S exploitation, and its proprietary catalyst is to 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% 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.This catalyst can significantly improve the yield of the conversion ratio of naphtha and ethene, propylene for naphtha catalysis solution.
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.
But above-mentioned ZSM-5 molecular sieve catalyst is mainly to improve ethene and productivity of propylene.Another catalyst that naphtha catalytic pyrolysis preparing uses for low-carbon alkene is β zeolite, 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 catalyst prepared by the beta zeolite obtaining by the method in the time preparing low-carbon alkene for naphtha pyrolysis.
Summary of the invention
One of 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 by weight percentage following component: (a) 15%～65% natural mineral matter; (b) 10%～30% oxide; (c) the beta-molecular sieve mixture of 25%～75% MFI structure molecular screen and phosphorus modification, described phosphorus modified beta molecular sieve, with P
2o
5meter phosphorus content accounts for 3～10 heavy %, this molecular sieve
27in Al MAS NMR, chemical shift is that the ratio that (40 ± 3) ppm resonance signal peak area and chemical shift are (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 phosphorus modification, it is characterized in that comprising by former beta-molecular sieve powder 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.More specifically, the preparation method of the beta-molecular sieve of described phosphorus modification comprises the steps:
(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) after drying, calcination process at least 0.5 hour at 200-400 ℃, then being warmed up at least 0.5 hour removed template method of calcination process at 500-800 ℃ in 2 hours at the most for molecular sieve step (1) being obtained;
(3) introduce phosphorus-containing compound molecular sieve is carried out to modification;
(4) calcination process at least 0.5 hour at 400～800 ℃.
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, take the content of butt natural mineral matter as 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, 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.
The preparation method of catalyst provided by the invention comprises the beta-molecular sieve of the predecessor of water, natural mineral matter, oxide and/or oxide, MFI structure molecular screen and modification is mixed and pulled an oar, then slurries are sprayed 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 phosphorus modified beta molecular sieve and MFI structure molecular screen is active component, there is more excellent hydrothermal stability and better selectivity of light olefin, after hydrothermal aging, there is higher ethene, propylene and butylene productive rate, can be used for naphtha fluidisation catalytic pyrolysis.The method of producing olefin hydrocarbon by catalytic pyrolysis of naphtha provided by the invention, has higher propylene, ethene and butylene productive rate.
The specific embodiment
The beta-molecular sieve of phosphorus 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 phosphorus modification of the present invention, its
27in Al MAS NMR, chemical shift is the four-coordination framework aluminum species that 54 ± 3ppm resonance signal characterizes, chemical shift be 40 ± 3ppm resonance signal characterize be and the framework aluminum species of phosphorus coordination.Modified beta molecular sieve provided by the invention, this molecular sieve
27in AlMAS 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 1.5 to 5 value.
The beta-molecular sieve preparation method of phosphorus modification of the present invention comprises that by former beta-molecular sieve powder (containing the sodium type beta-molecular sieve of organic formwork agent) 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 obtains in the temperature range of 200 ℃ to 800 ℃.More particularly comprise the steps:
(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) introduce phosphorus-containing compound molecular sieve is carried out to modification;
(4) calcination process at least 0.5 hour at 400～800 ℃.
In the beta-molecular sieve preparation method of phosphorus modification of the present invention, in described step (1), described sodium type beta-molecular sieve is the sodium type beta-molecular sieve (as USP3,308,069, CNZL00107486.5) of conventional crystallization gained.Conventionally in described sodium type beta-molecular sieve (Na β), sodium content is counted the heavy % of 4-6 with sodium oxide molybdena.Described 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 %.Described 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 preparation method provided by the invention, described 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.Described processing is in the interval of 200 ℃ to 800 ℃, in at least two non-overlapping temperature ranges from low to high, carry out, described low temperature range is 200-400 ℃, preferred 300-350 ℃, and described high temperature range is 500-800 ℃, preferred 500-600 ℃.For example, described 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 two temperature ranges described above are processed, first at least process 1 hour at 120-180 ℃.
In preparation method provided by the invention, introduce phosphorus-containing compound in step (3) product of step (2) is carried out to modification.Described phosphorus-containing compound is selected from one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) or ammonium phosphate or its mixture.Preferably adopt impregnation method to carry out, described dipping is by the phosphorus-containing compound aqueous solution of the molecular sieve after removed template method and amount of calculation in room temperature to 95 ℃ making beating evenly, dries.
The invention provides in preparation method, step (4) is that the beta-molecular sieve product of phosphorus modification that step (3) is obtained is at 400～800 ℃, preferably calcination process at least 0.5 hour at 500-600 ℃, preferred 0.5-8 hour.Wherein said calcination process process can adopt dry roasting also can adopt wet roasting, and described wet roasting is preferably at 1-100%, more preferably carry out under 100% steam atmosphere.
Described MFI structure molecular screen and phosphorus modified beta molecular sieve mixture, take catalyst total amount as benchmark, according to weight percent meter, take the content of the described MFI structure molecular screen of butt and phosphorus modified beta molecular sieve mixture as 25%～75%, preferably 30%～70%.MFI structure molecular screen and phosphorus modified beta molecular sieve can be mixed with arbitrary proportion, and for example MFI structure molecular screen and phosphorus modified beta molecular sieve mass ratio are 0.05～50:1, are preferably 0.1～20:1, for example, be 0.1:4～4:1.The silica alumina ratio (Si/Al mol ratio) of described phosphorus modified beta molecular sieve is preferably 12～100.
The preparation method of catalyst provided by the invention comprises the beta-molecular sieve of the predecessor of water, natural mineral matter, oxide and/or oxide, MFI structure molecular screen and modification is mixed and pulled an oar, then slurries are sprayed dry and roasting.The colloidal sol of for example described oxide of the predecessor of described oxide, described oxide sol in catalyst preparation process as binding agent so that final catalyst has suitable mechanical strength and abrasion resistance, can be one or more in Ludox, aluminium colloidal sol, peptization boehmite, silicon-aluminum sol and phosphorated aluminiferous collosol.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% described MFI structure molecular screen and the mixture of phosphorus modified 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, the catalyst that wherein said catalytic cracking catalyst is described producing olefin hydrocarbon by catalytic pyrolysis provided by the invention.Described alkene is ethene, propylene and butylene, and described naphtha is for example straight-run naphtha, and its boiling range is generally 40～180 ℃, and catalytic condition comprises: reaction temperature is 600～750 ℃, air speed 0.1～10h
-1, in course of reaction, preferably passing into water vapour, the part by weight of steam and naphtha is for being 0.1～10:1: be for example 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 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.
The beta-molecular sieve Preparation Example 1 of phosphorus modification
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 is 350 ℃ of calcination process 2 hours, and then heat up (5 ℃/min of heating rates) to 550 ℃, 4 hours removed template methods of calcination process; Add 14.6 kilograms of H
3pO
4(concentration 85 % by weight) are dissolved in 90 kg of water, dry with the molecular sieve hybrid infusion after 100 kilograms of above-mentioned roastings; Gained sample was 500 ℃ of calcination process 2 hours, and molecular sieve provided by the invention, is designated as B1.The physical data of sample and
27al MAS NMR peak area ratio is listed in table 1.
The beta-molecular sieve Preparation Example 2 of phosphorus modification
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 30 minutes; Add 9.6 kilograms of (NH
3)
2hPO
4(concentration 85 % by weight) are 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 ℃ and 100% steam, molecular sieve provided by the invention, is designated as B2.The physical data of sample and
27al MAS NMR peak area ratio is listed in table 1.
The beta-molecular sieve Preparation Example 3 of phosphorus modification
By beta-molecular sieve (Tianjin Chemist Technology Development Co., Ltd, SiO
2/ Al
2o
3=50, sodium oxide content 0.05 % by weight) 350 ℃ of calcination process 2 hours, then within 30 minutes, be warming up to 4 hours removed template methods of 550 ℃ of calcination process; Then add 17 kilograms of H
3pO
4(concentration 85 % by weight) are dissolved in 90 kg of water, dry with the molecular sieve hybrid infusion after 100 kilograms of above-mentioned roastings; Gained sample is 600 ℃ of calcination process 2 hours, i.e. molecular sieve provided by the invention, and, be designated as B3.The physical data of sample and
27al MAS NMR peak area ratio is listed in table 1.
The beta-molecular sieve Preparation Example 4 of phosphorus modification
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 ℃ of calcination process 2 hours, then within 30 minutes, be warming up to 4 hours removed template methods of 550 ℃ of calcination process; Then add 12.1 kilograms of H
3pO
4(concentration 85 % by weight) are dissolved in 90 kg of water, dry with the molecular sieve hybrid infusion after 100 kilograms of above-mentioned roastings; Gained sample is processed 2 hours at 550 ℃ and 100% steam roasting, and molecular sieve provided by the invention, is designated as B4.The physical data of sample and
27al MAS NMR peak area ratio is listed in table 1.
The beta-molecular sieve Preparation Example 5 of phosphorus modification
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, gained sample, 150 ℃ of calcination process 2 hours, is then warming up to 350 ℃ of calcination process 2 hours for 30 minutes, then within 40 minutes, is warming up to 4 hours removed template methods of 550 ℃ of calcination process; Add 10g (NH
3)
2hPO
4(concentration 85 % by weight) are dissolved in 90 kg of water, dry with the molecular sieve hybrid infusion after 100 kilograms of above-mentioned roastings; Gained sample is at 550 ℃ of calcination process 2 hours, i.e. molecular sieve provided by the invention.Be designated as B5.The physical data of sample and
27al MAS NMR peak area ratio is listed in table 1.Physical data and the consumption of the MFI structure molecular screen that uses (being catalyst asphalt in Shenli Refinery of China Petrochemical Industry product) are listed in table 2.The kind of the kind of natural mineral matter and consumption, binding agent and consumption are listed in respectively in table 3 and table 4.
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, before use, first use concentration 31 % by weight hydrochloric acid peptizations, described hydrochloric acid with the mol ratio take the boehmite of aluminium oxide as 0.20), aluminium colloidal sol (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
The beta-molecular sieve of natural mineral matter, MFI structure molecular screen, phosphorus modification, binding agent colloidal sol and water are mixed to making beating, the slurries that obtain are spray dried to diameter mainly in particle the roasting of 40-150 micron, sintering temperature is 500 ℃, roasting time is 2 hours, obtains catalyst C1-C5 provided by the invention.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.
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 beta-molecular sieve used) joins in the ammonium sulfate of 2 liter of 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, be designated as DB1.The beta-molecular sieve DB1 of natural mineral matter, MFI structure molecular screen, phosphorus modification, 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, sintering temperature is 500 ℃, roasting time is 2 hours, obtains catalyst D1 provided by the invention.
Comparative example 2
According to the method for embodiment 1, the Na beta-molecular sieve of said use (with embodiment 1 Na beta-molecular sieve used) is processed, but before phosphorus modification, do not carried out calcination process, obtain comparative example 2 molecular sieve DB2.The beta-molecular sieve DB2 of natural mineral matter, MFI structure molecular screen, phosphorus modification, binding agent colloidal sol and water are mixed to making beating, the slurries that obtain are spray dried to diameter mainly in particle the roasting of 40-150 micron, sintering temperature is 500 ℃, roasting time is 2 hours, obtains catalyst D2 provided by the invention.
Comparative example 3
By Na 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, gained sample is at 4 hours removed template methods of 550 ℃ of calcination process; 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 is at 550 ℃ of calcination process 2 hours, i.e. molecular sieve provided by the invention.The physical data of sample and
27al MAS NMR peak area ratio is listed in table 1
Comparative example 3
According to the method Kaolinite Preparation of Catalyst of embodiment 1, different is to replace described B1 molecular sieve with the ZRP molecular sieve of equivalent, obtains catalyst D3.
The embodiment of the present invention use phosphorus modified beta molecular sieve physical data, consumption and
27al MAS NMR peak area ratio is listed in table 1.The physical data of MFI structure molecular screen and the consumption of using listed in table 2.The kind of the kind of natural mineral matter and consumption, binding agent and consumption are listed in respectively in table 3 and table 4.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 numbering | Catalyst numbering | Spraying dried tail gas temperature/℃ | Sintering temperature/℃ | 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 explanation adopts catalyst provided by the invention for naphtha catalytic cracking, for the impact of hydrothermal stability and selectivity of light olefin.
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 4:1 with weight of oil ratio.Feedstock oil is straight-run naphtha, 45.5 ℃ of initial boiling points, and 166.5 ℃ of the end points of distillation, specifically form 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 in table 6, is weight percentage composition
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 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.
From table 7, data can find out that modified molecular screen provided by the invention has good activity stability and selectivity of light olefin.Compare with comparative example, catalyst take MFI structure molecular screen and phosphorus modified beta molecular sieve as active component provided by the invention, the selectivity of light olefin that has effectively improved crackate in improving cracking hydrocarbon ability, the productive rate of ethene, propylene and butylene has raising by a relatively large margin.
Claims (15)
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;
(c) mixture of 25%～75% MFI structure molecular screen and phosphorus modified beta molecular sieve; Described phosphorus modified beta molecular sieve, with P
2o
5meter phosphorus content accounts for 3～10 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.
2. catalyst according to claim 1, is characterized in that described natural mineral matter is selected from 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 are 0.1:4～4:1 to weight ratio.
4. according to the described catalyst of claim 1, it is characterized in that the silica of described MFI structure molecular screen and alumina molar ratio are 15-300, the silica alumina ratio of described phosphorus modified beta molecular sieve is 12-100.
5. according to catalyst claimed in claim 1, it is characterized in that, in described phosphorus modified beta molecular sieve with P
2o
5meter phosphorus content accounts for the heavy % of 5-9.
6. according to the molecular sieve of claim 1, wherein, described 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.
7. the preparation method of catalytic cracking catalyst described in claim 1～6 any one, comprise the described phosphorus modified beta molecular sieve of preparation, described phosphorus modified beta molecular sieve, MFI structure molecular screen, natural mineral matter, described oxide and/or oxide precursor thing and water are mixed to the step of the dry and roasting of making beating, spraying; The method of the described phosphorus modified beta molecular sieve of wherein said preparation comprises former beta-molecular sieve powder 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.
8. a preparation method for catalytic cracking catalyst described in claim 1～6 any one, comprising:
(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) introduce phosphorus-containing compound molecular sieve is carried out to modification;
(4) calcination process at least 0.5 hour at 400～800 ℃; Make described phosphorus modified beta molecular sieve;
(5) obtained phosphorus modified beta molecular sieve is mixed to making beating with MFI structure molecular screen, natural mineral matter, oxide precursor, spraying is dry.
9. in accordance with the method for claim 8, it is characterized in that, the described ammonium exchange of step (1) is according to molecular sieve: ammonium salt: H
2o=1:(0.1-1): the exchange at room temperature to 100 ℃ of weight ratio (5-10), filter, this process is at least carried out once.Described ammonium salt is preferably selected from one or more the mixture in ammonium chloride, ammonium sulfate and ammonium nitrate.
10. in accordance with the method for claim 8, it is characterized in that, the process that the described phosphorus-containing compound of step (3) carries out modification to molecular sieve is to adopt impregnation method to carry out, described impregnation method is by the phosphorus-containing compound aqueous solution of the molecular sieve after removed template method and amount of calculation in room temperature to 95 ℃ making beating evenly, dries.
11. according to the method described in claim 8 or 10, it is characterized in that, described phosphorus-containing compound is selected from one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) or ammonium phosphate or its mixture.
12. in accordance with the method for claim 8, it is characterized in that, described oxide precursor can be one or more in Ludox, aluminium colloidal sol, peptization boehmite, silicon-aluminum sol and phosphorated aluminiferous collosol.
13. according to the method for claim 8, it is characterized in that, the described calcination process process of step (4) is to carry out under 1-100% steam atmosphere.
14. 1 kinds of naphtha catalytic crackings are produced the method for low-carbon alkene, comprise the catalytic step of Cracking catalyst described in naphtha and claim 1～7 any one.
15. in accordance with the method for claim 14, it is characterized in that, described catalytic temperature is 600～750 ℃, and weight (hourly) space velocity (WHSV) is 0.1～10h
-1.
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| 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 |
| CN114904566A (en) * | 2022-05-31 | 2022-08-16 | 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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