CN1504541A - Catalyst for preparing olefin with arene as side product by hydrocarbon catalytic cracking, preparing method and uses thereof - Google Patents
Catalyst for preparing olefin with arene as side product by hydrocarbon catalytic cracking, preparing method and uses thereof Download PDFInfo
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Abstract
A catalyst for preparing lower carbon number hydrocarbons and parallel aromatic hydrocarbons through catalytic hydrocarbon pyrolysis, comprises molecular sieve with bore diameter of 0.45-0.7 nm, nonshaped-set oxide compound and at least two modified elements from phosphor, alkaline-earth metal, lithium and tombarthite. Its preparing process comprises, (1) preparing catalyst base material from crystallization shaped molecular sieve and silicon or aluminum containing amorphous substance or aperture structure modifier through mixing modeling, (2) preparing type-H catalyst base material through sintering, (3) soaking or exchanging catalyst base material by one or more modifying solution through one-step or multistep mode, and drying and sintering for preparation of catalyst.
Description
Technical field
The present invention relates to a kind of hydrocarbon catalytic cracking and produce the catalyzer of low-carbon alkene and coproduction aromatic hydrocarbons.
The invention still further relates to above-mentioned Preparation of catalysts method.
The invention still further relates to the application in hydrocarbon catalytic cracking of above-mentioned catalyzer.
Background technology
Cracking is the important means of producing compositions such as gasoline and low-carbon alkene from the heaviness composition of oil, about 50% gasoline results from catalytic cracking process, and for the production of ethene and propylene, be difficult to develop perfect catalytic pyrolysis process, the thermo-cracking of petroleum naphtha still is in leading status always.Produce the condition of gasoline than catalytic cracking, owing to thermodynamic (al) reason, obtaining the crackate low-carbon alkene often needs to surpass 800 ℃ high temperature, is reflected in the tubular oven and carries out, material to reactor has very high requirement, and the pyroreaction energy waste is serious; The composition of the low-carbon alkene that thermal cracking processes generated is difficult to change simultaneously, and often the change product is distributed with very urgent requirement in the reality, and these problems make people constantly explore the approach of producing low-carbon alkene by catalytic pyrolysis.
Some hydrocarbon catalytic cracking system alkene catalysts of development mainly contain following several types, an acidic catalyst, basic catalyst and catalyst of transition metal oxide at present.In an acidic catalyst system, USP 4,172, and 816 with Ag-MOR/Al
2O
3Be catalyzer, reaction between 600-750 ℃, the yield of ethene and propylene reaches 42%; USP6,288,298 is the petroleum naphtha cracking catalyst with aluminium silicophosphate molecular sieve SAPO-11, and this catalyst activity is lower, and 575 ℃ of cracking light naphthar components, transformation efficiency is 39.2%, and the propylene selectivity reaches 56% in the converted product.In basic catalyst, the potassium-vanadium Vniios technology of USSR (Union of Soviet Socialist Republics) development, adopting with the potassium vanadate is active ingredient, α-Al
2O
3Be carrier, B
2O
3Deng oxide compound is the catalyzer of auxiliary agent, and at 780 ℃, under the water vapor existence condition, the yield of ethene and propylene is respectively 38% and 14.5% on this catalyzer, and the propylene/ethylene ratio is approximately 0.4.U.S. Pat P3,767,567 with CaO, any oxide compound and Al among SrO and the BaO
2O
3Carry out the catalytic cracking of petroleum naphtha as catalyzer, temperature of reaction is higher, when obtaining ethene and propylene, produces relatively large dry gas, CO and CO
2, recovery brings difficulty to product separation.In the transition metal oxide system, the Cr of Japanese Patent Publication 48-45364 report
2O
3/ Al
2O
3Naphtha cracking is had certain effect, do not have aromatic hydrocarbons to generate in the product, but can produce relatively large CO and CO
2
The aromatic hydrocarbons that an acidic catalyst catalysis hydrocarbon cracking generates is the by product that low-carbon alkene is produced, by can partly suppress the generation of aromatic hydrocarbons to the modulation of acid sites, also can promote the generation of aromatic hydrocarbons, this adjustable sex change provides possibility for the distribution of adjusting the catalytic pyrolysis product: not only can pass through producing low-carbon alkene by catalytic pyrolysis, also can obtain simultaneously certain specific alkene and aromatic hydrocarbons in crackate distributes, be implemented in coproduction aromatic hydrocarbons when producing alkene, for the later use of product provides rational products distribution.
Summary of the invention
The object of the present invention is to provide a kind of hydrocarbon catalytic cracking to produce the catalyzer of low-carbon alkene and aromatic hydrocarbons, this catalyzer can make hydrocarbon molecules optionally be converted into low-carbon alkene (ethene and propylene) and coproduction aromatic hydrocarbons (benzene, toluene).
Another object of the present invention is to provide the method for the above-mentioned catalyzer of preparation.
Catalyzer provided by the invention can be used in the cracking reaction of saturated or undersaturated hydrocarbon polymer.
For achieving the above object, catalyzer provided by the invention contains the molecular sieve that the aperture is the 0.45-0.7 nanometer, and molecular sieve content accounts for the 5-95wt% of catalyzer; Contain the mixture of unbodied aluminum oxide, silicon oxide or both arbitrary proportions, content accounts for the 0-90wt% of catalyzer; This catalyzer contains modifying element, is at least two kinds in phosphorus, alkaline-earth metal, lithium and the rare earth, and its content is respectively: phosphorus is that 0-wt4%, alkaline-earth metal are 0-5wt%, and lithium is 0-2wt%, and rare earth element is 0-15wt%.
The main process that the present invention prepares above-mentioned catalyzer is as follows:
1, the amorphous compound of molecular screen primary powder, silicon or aluminium and pore structure conditioning agent are mixed, add ammoniacal liquor and water and regulate mixture and become gel, pinch or extrusion prepares catalyst substrates, remove the molecular sieve template in high-temperature roasting through mixing.
2, use NH
4NO
3Solution exchanges baked molecular sieve matrix, and dry, roasting obtains H type catalyst substrates.
3, under decompression or normal pressure, to flood or exchange catalysts matrix by a step or the mode of multistep with one or more modulation solution, drying, roasting prepare catalyzer.
It is the 0.45-0.7 nanometer that the present invention prepares the used molecular sieve bore diameter scope of catalyzer, can select Si-Al molecular sieve or aluminium silicophosphate molecular sieve for use, Si-Al molecular sieve can be selected ZSM-5, ZSM-11, mordenite, Beta zeolite for use, and reasonable is ZSM-5 or ZSM-11 and both mixed crystal; Silicon phosphorus aluminium series molecular sieve can be selected SAPO-5, SAPO-11, SAPO-34 etc. for use, and reasonable is SAPO-11.Molecular sieve accounts for the 5-95wt% of catalyst substrates.
Contain unbodied silicon oxide, aluminum oxide or amorphous aluminum silicide in the catalyst substrates of the present invention's preparation, amorphous oxide accounts for the 0-90% of catalyst substrates.
The present invention prepares catalyzer and uses the pore structure conditioning agent, can adopt sodium carboxymethylcellulose pyce, gac, sesbania powder, starch or its mixture, preferred sesbania powder.
The present invention prepares catalyzer can select modifications a kind of, two or more elements for use to the modification of molecular sieve matrix.Reasonable modifying element is P, Li, alkaline-earth metal and rare earth, and preferable content is: the P amount is 0-4%, and the alkaline-earth metal amount is 0-5wt%, and the Li amount is 0-2wt%, and the rare earth element amount is 0-15wt%.Several different methods such as that modification can be adopted is synthetic, exchange, dipping, mixing.
The catalyzer of the present invention's preparation is applicable to the hydrocarbon catalytic cracking device of fixed bed, fluidized-bed and moving-bed.
The catalytic pyrolysis process that the catalyzer for preparing among the present invention is used for hydrocarbons, can make high temperature (＞800 ℃) thermal cracking processes be converted into the catalytic pyrolysis process that can carry out at lesser temps (＜700 ℃), increase the yield of split product simultaneously, in catalytic cracking to petroleum naphtha, the yield of ethene and propylene can reach 50-60% in the product, the yield of ethene, propylene and butylene can reach 55-70%, C
2And C
3Alkene and alkane yield can reach 60%-70%.
The catalyzer of the present invention preparation not only is applicable to the catalytic pyrolysis process of hydrocarbons such as the alkane, naphthenic hydrocarbon, alkene of single hydrocarbons-single positive structure or isomery, and be applicable to the cracking of the petroleum fractions such as petroleum naphtha, gasoline, diesel oil of the multiple hydrocarbon mixture of hydrocarbon mixture-comprise, be specially adapted to comprise the cracking of the petroleum naphtha and the gasoline of paraffinic hydrocarbons, naphthenic hydrocarbon and aromatic hydrocarbons.
The relatively-stationary thermodynamics products distribution that produces in the contrast high temperature pyrolysis, the catalyzer of the present invention's preparation shows the selectivity of product of flexibility and changeability in cracking process, not only can highly selective produce alkene, also can be when producing alkene coproduction aromatic hydrocarbons.The activity of such catalysts center can need in addition modulation by actual product, can suppress the aromatic hydrocarbons in the product, is primary product (yield of ethene and propylene is 50-60%) with the low-carbon alkene; Also can suitably promote the generation of aromatization, coproduction aromatic hydrocarbons (yield of ethene+propylene+aromatic hydrocarbons is 60-80%) when producing alkene.
Embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1: the preparation of catalyzer 1
Former powder (the SiO of ZSM-5 molecular screen primary powder (aperture 0.51 * 0.55 nanometer, 0.53 * 0.56 nanometer) that contains synthetic template
2/ Al
2O
3=70) with silicon sol and aluminium colloidal sol (amorphous aluminum silicide SiO
2/ Al
2O
3=3) mixing moulding, template is removed in high-temperature roasting in the oven dry back, and is ground into 20-40 molecules of interest sieve matrix granule, and molecular sieve content is 85% in the matrix.Matrix granule is exchanged with ammonium nitrate solution at 80 ℃, and the exchange back obtains H type molecular sieve matrix particle 550 ℃ of following roastings.To molecular sieve matrix exchange modified component H
3PO
4Solution is prepared into catalyzer after oven dry, the roasting, and X fluorescence spectrometry P content is 4.2wt%.
Embodiment 2: the preparation of catalyzer 2
ZSM-5 molecular screen primary powder (the SiO that contains synthetic template
2/ Al
2O
3=45) with the silicon sol (SiO that contains 25wt%
2) mixing moulding, template is removed in high-temperature roasting in the oven dry back, and is ground into 20-40 molecules of interest sieve matrix granule, and molecular sieve content is 80% in the matrix.Matrix granule is exchanged with ammonium nitrate solution at 80 ℃, and the exchange back obtains H type molecular sieve matrix particle 550 ℃ of following roastings.To molecular sieve matrix exchange modified component La (NO
3)
3And H
3PO
4Solution is prepared into catalyzer after oven dry, the roasting, and X fluorescence spectrometry P content is 4.5wt%, and La content is 7.4wt%.
Embodiment 3: the preparation of catalyzer 3
ZSM-5 molecular screen primary powder (the SiO that contains synthetic template
2/ Al
2O
3=86) with the silicon sol (SiO that contains 25wt%
2) mixing moulding, template is removed in high-temperature roasting in the oven dry back, and is ground into 20-40 molecules of interest sieve matrix granule, and molecular sieve content is 80% in the matrix.Matrix granule is exchanged with ammonium nitrate solution at 80 ℃, and the exchange back obtains H type molecular sieve matrix particle 550 ℃ of following roastings.To molecular sieve matrix exchange modified component La (NO
3)
3And H
3PO
4And Li (NO
3)
3Solution is prepared into catalyzer after oven dry, the roasting, and X fluorescence spectrometry P content is 1.7wt%, and La content is 7.5wt%, and Li content is 0.8wt%.
Embodiment 4: the preparation of catalyzer 4
Former powder (the SiO of ZSM-5 molecular sieve (aperture 0.51 * 0.55 nanometer, 0.53 * 0.56 nanometer) that contains synthetic template
2/ Al
2O
3=86) with the silicon sol (SiO that contains 25wt%
2) and pore structure conditioning agent sesbania powder mixing moulding, template is removed in high-temperature roasting in the oven dry back, and is ground into 20-40 molecules of interest sieve matrix granule, and molecular sieve content is 75% in the matrix.Matrix granule is exchanged with ammonium nitrate solution at 80 ℃, and the exchange back obtains H type molecular sieve matrix particle 550 ℃ of following roastings.To molecular sieve matrix exchange modified component La (NO
3)
3And H
3PO
4Solution is prepared into catalyzer after oven dry, the roasting, and X fluorescence spectrometry P content is 1.4wt%, and La content is 2.8wt%.
Embodiment 5: the preparation of catalyzer 5
The ZSM-5 molecular screen primary powder that contains synthetic template is removed template in high-temperature roasting, exchanges with ammonium nitrate solution at 80 ℃, and the exchange back obtains H type molecular sieve 550 ℃ of following roastings, exchange modified component Mg (NO
3)
2Solution is prepared into catalyzer after oven dry, the roasting, sieves out 20-40 purpose particle behind the compressing tablet, and X fluorescence spectrometry Mg content is 1.9wt%.
Embodiment 6
Carry out the catalytic cracking reaction of petroleum naphtha on fixed-bed reactor, petroleum naphtha is C
4-C
9Hydrocarbon polymer, composition is as shown in table 1, with catalyzer 1 among the embodiment 1 as catalyzer, reaction conditions: 650 ℃ of temperature, naphtha feed air speed 2, H
2O/ oil=1.4 (quality), N
2The atmosphere reaction, adopt online gas-chromatography to finish the products distribution analysis, the products distribution such as the table 1 of reaction:
The composition of table 1 petroleum naphtha
| Composition | Content (Wt%) |
| Normal paraffin | 30.82 |
| Isoparaffin | 20.63 |
| Naphthenic hydrocarbon | 33.79 |
| Alkene | 8.39 |
| Aromatic hydrocarbon | 3.61 |
| Oxide compound | 0.23 |
| Greater than C14 | 0.10 |
| Other | 2.43 |
Products distribution:
| Product | Productive rate (%) |
| Methane | 6.30 |
| Ethene | 29.51 |
| Ethane | 7.18 |
| Propylene | 23.37 |
| Propane | 5.12 |
| Butane | 1.66 |
| Butylene | 5.76 |
| Benzene | 5.45 |
| Toluene | 8.18 |
| Dimethylbenzene | 4.59 |
Embodiment 7
Carry out the catalytic cracking reaction of petroleum naphtha on fixed-bed reactor, as catalyzer, reaction conditions is with catalyzer 1 among the embodiment 1: 650 ℃ of temperature, naphtha feed air speed 2, H
2O/ oil=1.4 (quality), the products distribution of reaction such as following table:
| Product | Productive rate (%) |
| Methane | 4.59 |
| Ethene | 31.11 |
| Ethane | 5.88 |
| Propylene | 29.77 |
| Propane | 4.23 |
| Butane | 1.06 |
| Butylene | 6.10 |
| Benzene | 3.77 |
| Toluene | 5.08 |
| Dimethylbenzene | 4.06 |
Embodiment 8
Carry out the catalytic cracking reaction of normal hexane on fixed-bed reactor, as catalyzer, reaction conditions is with embodiment 6 with catalyzer 2 among the embodiment 2, the products distribution of reaction such as following table:
| Transformation efficiency (%) | 100 |
| Productive rate (%) | |
| Methane | 10.48 |
| Ethene | 28.85 |
| Ethane | 11.51 |
| Propylene | 17.86 |
| Propane | 6.84 |
| Butane | 2.55 |
| Butylene | 1.77 |
| Benzene | 8.15 |
| Toluene | 9.21 |
| Dimethylbenzene | 2.45 |
Embodiment 9
Carry out the catalytic cracking reaction of hexanaphthene on fixed-bed reactor, as catalyzer, reaction conditions is with embodiment 6 with catalyzer 2 among the embodiment 2, the products distribution of reaction such as following table:
| Transformation efficiency (%) | 93.11 |
| Productive rate (%) | |
| Methane | 3.6 |
| Ethene | 23.21 |
| Ethane | 3.02 |
| Propylene | 24.59 |
| Propane | 3.61 |
| Butane | 4.86 |
| Butylene | 2.15 |
| Benzene | 8.60 |
| Toluene | 14.10 |
| Dimethylbenzene | 5.37 |
Embodiment 10
Carry out the catalytic cracking reaction of petroleum naphtha on fixed-bed reactor, as catalyzer, reaction conditions is with embodiment 6 with catalyzer 2 among the embodiment 2, the products distribution of reaction such as following table:
| Product | Productive rate (%) |
| Methane | 5.8 |
| Ethene | 22.41 |
| Ethane | 5.62 |
| Propylene | 23.29 |
| Propane | 4.18 |
| Butane | 1.75 |
| Butylene | 7.73 |
| Benzene | 6.75 |
| Toluene | 8.64 |
| Dimethylbenzene | 4.00 |
Embodiment 11
Carry out the catalytic cracking reaction of petroleum naphtha on fixed-bed reactor, as catalyzer, reaction conditions is with catalyzer 2 among the embodiment 2: 650 ℃ of temperature, and naphtha feed air speed 2 does not adopt diluent gas, the products distribution of reaction such as following table:
| Product | Productive rate (%) |
| Methane | 11.88 |
| Ethene | 20.48 |
| Ethane | 10.23 |
| Propylene | 13.91 |
| Propane | 4.06 |
| Butane | 0.68 |
| Butylene | 2.85 |
| Benzene | 11.27 |
| Toluene | 16.12 |
| Dimethylbenzene | 6.70 |
Embodiment 12
Carry out the catalytic cracking reaction of petroleum naphtha on fixed-bed reactor, as catalyzer, reaction conditions is with catalyzer 2 among the embodiment 2: 650 ℃ of temperature, naphtha feed air speed 2, H
2O/ oil=0.45 (quality), the products distribution of reaction such as following table:
| Product | Productive rate (%) |
| Methane | 4.84 |
| Ethene | 27.52 |
| Ethane | 6.34 |
| Propylene | 27.24 |
| Propane | 5.02 |
| Butane | 1.26 |
| Butylene | 7.6 |
| Benzene | 3.88 |
| Toluene | 6.23 |
| Dimethylbenzene | 3.89 |
Embodiment 13
Carry out the catalytic cracking reaction of petroleum naphtha on fixed-bed reactor, as catalyzer, reaction conditions is with embodiment 7 with catalyzer 2 among the embodiment 2, the products distribution of reaction such as following table:
| Product | Productive rate (%) |
| Methane | 3.67 |
| Ethene | 23.47 |
| Ethane | 3.97 |
| Propylene | 31.41 |
| Propane | 3.06 |
| Butane | 1.35 |
| Butylene | 7.91 |
| Benzene | 2.92 |
| Toluene | 3.76 |
| Dimethylbenzene | 4.90 |
Embodiment 14
Carry out the catalytic cracking reaction of petroleum naphtha on fixed-bed reactor, as catalyzer, reaction conditions is with catalyzer 2 among the embodiment 2: 600 ℃ of temperature, naphtha feed air speed 2, H
2O/ oil=1.4 (quality), the products distribution of reaction such as following table:
| Product | Productive rate (%) |
| Methane | 2.14 |
| Ethene | 20.45 |
| Ethane | 5.01 |
| Propylene | 25.9 |
| Propane | 6.86 |
| Butane | 2.38 |
| Butylene | 10.10 |
| Benzene | 1.76 |
| Toluene | 4.07 |
| Dimethylbenzene | 5.09 |
Embodiment 15
Carry out the catalytic cracking reaction of petroleum naphtha on fixed-bed reactor, as catalyzer, reaction conditions is with catalyzer 2 among the embodiment 2: 700 ℃ of temperature, naphtha feed air speed 2, H
2O/ oil=1.4 (quality), the products distribution of reaction such as following table:
| Product | Productive rate (%) |
| Methane | 7.01 |
| Ethene | 25.76 |
| Ethane | 4.48 |
| Propylene | 27.6 |
| Propane | 3.6 |
| Butane | 1.28 |
| Butylene | 8.99 |
| Benzene | 5.18 |
| Toluene | 5.49 |
| Dimethylbenzene | 3.27 |
Embodiment 16
Carry out the catalytic cracking reaction of petroleum naphtha on fixed-bed reactor, as catalyzer, reaction conditions is with catalyzer 2 among the embodiment 2: 650 ℃ of temperature, naphtha feed air speed 1, H
2O/ oil=1.4 (quality), the products distribution of reaction such as following table:
| Product | Productive rate (%) |
| Methane | 3.40 |
| Ethene | 23.01 |
| Ethane | 4.67 |
| Propylene | 29.72 |
| Propane | 4.07 |
| Butane | 1.97 |
| Butylene | 8.86 |
| Benzene | 2.5 |
| Toluene | 3.85 |
| Dimethylbenzene | 5.02 |
Embodiment 17
Carry out the catalytic cracking reaction of petroleum naphtha on fixed-bed reactor, as catalyzer, reaction conditions is with catalyzer 1 among the embodiment 1: 650 ℃ of temperature, naphtha feed air speed 3, H
2O/ oil=1.4 (quality), the products distribution of reaction such as following table:
| Product | Productive rate (%) |
| Methane | 3.72 |
| Ethene | 23.76 |
| Ethane | 5.25 |
| Propylene | 28.74 |
| Propane | 4.74 |
| Butane | 1.41 |
| Butylene | 8.78 |
| Benzene | 2.5 |
| Toluene | 4.18 |
| Dimethylbenzene | 4.50 |
Embodiment 18
Carry out the catalytic cracking reaction of gasoline on fixed-bed reactor, gasoline is C
4-C
10Hydrocarbon polymer, composition is as shown in table 2, as catalyzer, reaction conditions is with embodiment 7 with catalyzer 2 among the embodiment 2, the products distribution such as the table 2 of reaction:
The composition of table 2 gasoline
| Composition | Content (Wt%) |
| Normal paraffin | 2.38 |
| Isoparaffin | 25.42 |
| Naphthenic hydrocarbon | 4.84 |
| Alkene | 49.71 |
| Aromatic hydrocarbon | 10.18 |
| Oxide compound | 7.45 |
Products distribution:
| Product | Productive rate (%) |
| Methane | 4.79 |
| Ethene | 26.23 |
| Ethane | 1.72 |
| Propylene | 23.64 |
| Propane | 0.79 |
| Butane | 0.0 |
| Butylene | 1.03 |
| Benzene | 6.87 |
| Toluene | 6.98 |
| Dimethylbenzene | 2.31 |
Embodiment 19
Carry out the catalytic cracking reaction of petroleum naphtha on fixed-bed reactor, as catalyzer, reaction conditions is with embodiment 6 with catalyzer 3 among the embodiment 3, the products distribution of reaction such as following table:
| Product | Productive rate (%) |
| Methane | 5.66 |
| Ethene | 23.27 |
| Ethane | 5.87 |
| Propylene | 27.60 |
| Propane | 4.41 |
| Butane | 1.83 |
| Butylene | 7.49 |
| Benzene | 7.28 |
| Toluene | 7.22 |
| Dimethylbenzene | 2.0 |
Embodiment 20
Carry out the catalytic cracking reaction of petroleum naphtha on fixed-bed reactor, as catalyzer, reaction conditions is with embodiment 7 with catalyzer 4 among the embodiment 4, the products distribution of reaction such as following table:
| Product | Productive rate (%) |
| Methane | 5.55 |
| Ethene | 32.18 |
| Ethane | 5.64 |
| Propylene | 26.11 |
| Propane | 3.19 |
| Butane | 1.26 |
| Butylene | 3.61 |
| Benzene | 4.65 |
| Toluene | 6.33 |
| Dimethylbenzene | 4.18 |
Embodiment 21
Carry out the catalytic cracking reaction of petroleum naphtha on fixed-bed reactor, as catalyzer, reaction conditions is with embodiment 7 with catalyzer 5 among the embodiment 5, the products distribution of reaction such as following table:
| Product | Productive rate (%) |
| Methane | 5.01 |
| Ethene | 23.46 |
| Ethane | 5.98 |
| Propylene | 25.97 |
| Propane | 6.00 |
| Butane | 2.03 |
| Butylene | 8.78 |
| Benzene | 4.04 |
| Toluene | 6.57 |
| Dimethylbenzene | 5.40 |
Claims (10)
1, a kind of hydrocarbon catalytic cracking is produced the catalyzer of low-carbon alkene and coproduction aromatic hydrocarbons, it is characterized in that catalyzer contains the molecular sieve that the aperture is the 0.45-0.7 nanometer, and molecular sieve content accounts for the 5-95wt% of catalyzer.
2, catalyzer as claimed in claim 1 is characterized in that, described molecular sieve is Si-Al molecular sieve or aluminium silicophosphate molecular sieve.
3, catalyzer as claimed in claim 2 is characterized in that, described Si-Al molecular sieve is ZSM-5, ZSM-11, mordenite or Beta zeolite; Silicon phosphorus aluminium series molecular sieve is SAPO-5, SAPO-11 or SAPO-34.
As claim 2 or 3 described catalyzer, it is characterized in that 4, described Si-Al molecular sieve is ZSM-5 or ZSM-11 and both mixed crystal; Described aluminium silicophosphate molecular sieve is SAPO-11.
5, catalyzer as claimed in claim 1 is characterized in that catalyzer contains unbodied oxide component, is the mixture of aluminum oxide, silicon oxide or both arbitrary proportions, and content accounts for the 0-90wt% of catalyzer.
6, catalyzer as claimed in claim 1, it is characterized in that catalyzer contains modifying element, be at least two kinds in phosphorus, alkaline-earth metal, lithium and the rare earth, its content is respectively: phosphorus is that 0-4wt%, alkaline-earth metal are 0-5wt%, lithium is 0-2wt%, and rare earth element is 0-15wt%.
7, a kind of method for preparing the described catalyzer of claim 1, its key step is:
A) amorphous compound of molecular screen primary powder, silicon or aluminium and pore structure conditioning agent are mixed, add ammoniacal liquor and water and regulate mixture and become gel, pinch or extrusion prepares catalyst substrates, remove the molecular sieve template in high-temperature roasting through mixing;
B) use NH
4NO
3Solution exchanges baked molecular sieve matrix, and dry, roasting obtains H type catalyst substrates;
C) under decompression or normal pressure, to flood or exchange catalysts matrix by a step or the mode of multistep with one or more modulation solution, drying, roasting prepare catalyzer.
8, method as claimed in claim 4 is characterized in that, used pore structure conditioning agent can be sodium carboxymethylcellulose pyce, gac, sesbania powder, starch or its mixture, with the ratio of catalyzer be 0.2-10wt%.
As claim 7 or 8 described methods, it is characterized in that 9, described pore structure conditioning agent is the sesbania powder.
10, the application of the described catalyzer of claim 1 in the cracking hydrocarbon reaction, be applicable to the process that catalysis scission reaction saturated or undersaturated hydrocarbon polymer is produced alkene and coproduction aromatic hydrocarbons, but the cracking of reaction raw materials such as catalytic naphtha, gasoline, diesel oil is particularly useful for the hydrocarbon catalytic cracking of petroleum naphtha and gasoline fraction.
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| WO2007019797A1 (en) * | 2005-08-15 | 2007-02-22 | China Petroleum & Chemical Corporation | Fludized bed catalyst for catalytic pyrolyzing |
| WO2008028343A1 (en) | 2006-08-31 | 2008-03-13 | China Petroleum & Chemical Corporation | A process for catalytic converting hydrocarbons |
| WO2008034299A1 (en) | 2006-08-31 | 2008-03-27 | China Petroleum & Chemical Corporation | A catalyst for converting hydrocarbons |
| US20110127193A1 (en) * | 2005-08-15 | 2011-06-02 | China Petroleum & Chemical Corporation | Catalyst for Catalytic Cracking Fluidized Bed |
| CN101759199B (en) * | 2008-12-25 | 2011-11-02 | 中国石油化工股份有限公司 | Silicon and phosphorus modified ZSM-5 molecular sieve and preparation method thereof |
| CN102942954A (en) * | 2012-11-16 | 2013-02-27 | 中国石油大学(华东) | Double-reaction-pipe heavy-oil alkaline catalytic cracking and gasification coupling technology |
| TWI508779B (en) * | 2013-06-21 | 2015-11-21 | Inst Nuclear Energy Res Atomic Energy Council | A method for manufacturing gasoline catalyst |
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