CN1931432A - Modified molecular sieve for catalytic cracking to prepare lower carbon olefin - Google Patents
Modified molecular sieve for catalytic cracking to prepare lower carbon olefin Download PDFInfo
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- CN1931432A CN1931432A CNA2005101031205A CN200510103120A CN1931432A CN 1931432 A CN1931432 A CN 1931432A CN A2005101031205 A CNA2005101031205 A CN A2005101031205A CN 200510103120 A CN200510103120 A CN 200510103120A CN 1931432 A CN1931432 A CN 1931432A
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- molecular sieve
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention discloses one kind of molecular sieve for catalytic cracking to prepare lower carbon olefin. By means of fast ion exchange process plus soaking process, at least two kinds of alkali earth metal are introduced into powdered hydrogen type serial ZSM molecular sieves simultaneously to obtain homogeneous alkali earth metal modified serial ZSM molecular sieves. The modification process is simple and feasible. When the modified molecular sieves are used in low temperature catalytically cracking petroleum hydrocarbon, there will be C2-C4 low carbon olefin yield obviously higher than that with un-modified molecular sieve and methane yield obviously lowered compared with the thermally cracking reaction in the same reaction degree.
Description
Technical field
The present invention relates to a kind of catalytic pyrolysis petroleum hydrocarbon that is used for and produce alkali-earth metal modified molecular sieve of low-carbon alkene and preparation method thereof.
Background technology
At present, tube furnace steam heat cracking process is mainly adopted in the production of low-carbon alkene (ethene, propylene and butylene) in the world.The ethylene yield of method acquisition surpasses 99% of total output thus.But because tube furnace exists: (1) energy consumption is big; (2) generate a large amount of waste by-product in the thermal cracking processes, cause the wasting of resources; (3) be difficult to regulate the composition of ethene and propylene; (4) problem such as heavy hydrocarbon feeds incompatibility, various countries' petrochemical industry successively begins Deep Catalytic Cracking process is attempted.
Deep Catalytic Cracking process can be divided into high temperature and low temperature pyrolyzer process.In low temperature (below 750 ℃) catalytic pyrolysis process, more is the catalyst main active component with ZSM series Si-Al molecular sieve.Is that active component is produced low-carbon alkene as patents such as EP0511013, US2002241764, EP1036133 and DE6980958T with the ZSM-5 molecular sieve.But because the acidic site that has of molecular sieve itself both be the active sites of oil pyrolysis hydrocarbon, the while is again the carbon deposition activity position, causes the stability of molecular sieve can not be satisfactory.For this reason, often on molecular sieve, introduce alkaline-earth metal and molecular sieve is carried out modification, in the hope of regulating the acidity of molecular sieve with other elements (as rare earth and phosphorus).At present, when being modified component, only use a kind of alkali earth metal with alkaline-earth metal.The method of introducing alkaline-earth metal mostly is infusion process and mechanical mixing.As disclosed technology in the patents such as CN1222558A, CN1211469A, CN1218786A and US6210562B1, the modifying element of ZSM series molecular sieve is single alkaline-earth metal, and the introducing method of metal is infusion process.In addition, the molecular sieve catalyst that uses in Deep Catalytic Cracking process carries out modification or introduce the metallic element modification by mechanical mixing in forming process by infusion process introducing metallic element more thereafter normally earlier with molecular sieve molded.
The above-mentioned modified molecular screen of mentioning is used for the catalytic pyrolysis process of low temperature, though in catalytic pyrolysis process the carbon deposit phenomenon is suppressed to some extent, has also reduced the catalytic pyrolysis activity when introducing other elements (as rare earth and phosphorus).
Summary of the invention
The purpose of this invention is to provide a kind of ZSM series molecular sieve that the catalytic pyrolysis petroleum hydrocarbon is produced the modification of low-carbon alkene that is used for.
The modified molecular screen that is used for catalytic cracking to prepare lower carbon olefin of the present invention makes by the method for modifying that may further comprise the steps:
1) aqueous solution that will contain at least two kinds of alkaline-earth metal ions joins in the powdery Hydrogen ZSM series molecular sieve, fully stirs, and leaves standstill then, once multiple alkaline-earth metal ions is introduced molecular sieve; Preferred fully stirring 0～2 hour was left standstill 0～2 hour;
2) the product suction filtration, drying, the roasting that step 1) are obtained obtain the modified powdery molecular sieve, machine-shaping.
The total concentration of the aqueous solution of preferred described at least two kinds of alkaline earth metal compounds is 0.01～20% (wt).
Preferred described alkaline-earth metal is calcium and magnesium.
Preferred described ZSM series molecular screening one or more mixtures in the molecular sieve of ZSM-5, ZSM-8 and ZSM-11 structure type; More preferably described ZSM series molecular sieve is the molecular sieve of ZSM-5 structure type.
The preferred high silica alumina ratio molecular sieve of described ZSM series molecular sieve is 50～500 as the silica alumina ratio of molecular sieve.
In an optimized technical scheme of the present invention, described ZSM series molecular sieve is that silica alumina ratio is the molecular sieve of 120～300 ZSM-5 structure type.
Adaptable all forming methods may be used to modified molecular screen machine-shaping of the present invention in catalyst preparation process.In the process of moulding, can add adhesive, auxiliary agent of appropriate amount etc., as silica, kaolin and bentonite etc.Those skilled in the art can determine at an easy rate.
Another object of the present invention provides the preparation method of above-mentioned modified molecular screen.
The method of modifying of molecular sieve of the present invention may further comprise the steps:
(1) preparation contains the aqueous solution of two kinds of alkaline-earth metal at least, and weight concentration is 0.01～20%;
(2) aqueous solution that will contain alkaline-earth metal ions under agitation joins in the powdery Hydrogen ZSM series molecular sieve, and the solid-liquid weight ratio is 1: 2～10;
(3) adopt fast ion exchange method+infusion process, introduce metal ion, promptly fully stirred 0～2 hour, left standstill then 0～2 hour, make mealy molecular sieve in the solution of residual metallic ion concentration, flood suction filtration;
(4) air dry is more than 10 hours, 80～150 ℃ of dryings 10～20 hours, 400～600 ℃ of roastings 1～4 hour;
Preferred described alkaline-earth metal is calcium and magnesium, and the weight ratio of two kinds of metals is 0.01～100.
In method of modifying of the present invention,, the hydrogen on solution metal ion and the molecular sieve is exchanged by abundant stirring; Mealy molecular sieve is flooded in the solution of residual metallic ion concentration; Thereby realize alkaline-earth metal ions is introduced molecular sieve, this method is referred to as fast ion exchange method+infusion process.
The present invention also can be used for the modification of ammonium type ZSM series molecular sieve.Equally, when other courses of reaction need have the modified molecular screen of homogeneity, also can use this method to molecular sieve modified.
Low-carbon alkene of the present invention refers to that carbon number is 2～4 alkene.
Molecular sieve of the present invention can be used for the catalytic pyrolysis process of naphtha and other petroleum hydrocarbon materials, is preferred for light hydrocarbon.
Molecular sieve of the present invention can carry out under common catalytic cracking reaction condition, preferably in the presence of water, and 300～750 ℃ of reaction temperatures, pressure 0.1～0.5MPa, water-oil factor 0.1～1, weight space velocity 1～15h
-1Condition under carry out catalytic cracking reaction.
Molecular sieve of the present invention is used for the catalytic cracking reaction process, and the reactor of use can be suspension bed, fluid bed or fixed bed reactors, also can be the reactor that is applicable to catalytic cracking reaction arbitrarily.
Beneficial effect of the present invention is as follows:
1, the present invention's at least two kinds of alkaline-earth metal modified molecular screens simultaneously, the weak acid amount of molecular sieve obviously improves, and acid distributes and broadens, and weak acid/total acid ratio raises; B acid/L acid ratio obviously reduces.
2, because the present invention is to carry out under the powdery condition uniformly, obviously comparing with existing method of modifying (flooding under at completed state) to the modification of molecular sieve, after the modified molecular screen moulding of gained of the present invention, its performance has homogeneity from inside to outside.
3, because modified molecular screen of the present invention adopts fast ion exchange+immersion process for preparing, so the hydrogen that is exchanged by alkaline-earth metal should be positioned at the position of easier disengaging molecular sieve, so alkaline-earth metal ions concentration surperficial at molecular sieve and the aperture is higher than in the hole.
4, the preparation method of modified molecular screen of the present invention is simple, easy to operate.
5, modified molecular screen of the present invention can be starkly lower than under the temperature of thermal cracking and big raw material treating capacity under catalytic pyrolysis naphtha and other petroleum hydrocarbon materials, and can improve yield of light olefins significantly.
During with modified molecular screen low-temperature catalytic pyrolysis petroleum hydrocarbon of the present invention, compare, can obviously improve the yield of low-carbon alkene (carbon number is 2～4) with using unmodified molecular sieve.
During with modified molecular screen low-temperature catalytic pyrolysis petroleum hydrocarbon of the present invention, compare, can obviously reduce the methane yield with the heat scission reaction of same reaction degree.
Description of drawings
Fig. 1 carries out the device schematic flow sheet of catalytic pyrolysis for using molecular sieve of the present invention.
1 raw material control valve, 2 preheaters, 3 reactors, 4 chillers, 5 condensation separators, 6 valves
7 wet gas flow meters
Illustrate that below in conjunction with accompanying drawing use molecular sieve of the present invention carries out catalytic thermal cracking method.
Fixed-bed tube reactor 3 is installed logical N
2Behind the leak test, heating is treated to open raw material control valve 1 after temperature rises to assigned temperature, and feedstock oil and water enter reactor 3 after preheater 2 preheatings gasification.Product after chiller 4 and condensation separator 5 condensations and cooling, gas-liquid separation.Get the gas sample at regular intervals, analyze its composition with gas chromatograph.The cumulative volume of gas measures with wet gas flow meter 7.Behind the reaction certain hour, open valve 6, collect accumulation liquid sample.Weigh.Calculate productive rate.
Embodiments of the invention and Comparative Examples are all carried out in small-sized tubular fixed-bed reactor.Reactor is a quartz ampoule, internal diameter 10mm, long 300mm.The built-in external diameter of reactor is 4mm, and length is the Thermal couple casing pipe of 200mm.Raw materials used is Yanshan Mountain naphtha, and the boiling range scope is 49～188 ℃.
The specific embodiment
Below example will illustrate further the present invention, but not thereby limiting the invention.
Embodiment 1
Preparation contains the calcium nitrate and the magnesium nitrate aqueous solution 50g of 2.5% (weight) respectively.Under agitation this liquid is added to rapidly in the 10g powdery HZSM-5 molecular sieve (Hunan Jianchang Petrochemical Co., Ltd's production).Stirred 1 hour under the room temperature, left standstill 1 hour.Suction filtration.Normal temperature was placed 20 hours down.120 ℃ dry 10 hours down, 580 ℃ of roastings 4 hours.Add 5 gram silica, extruded moulding, 120 ℃ of dryings 10 hours, 580 ℃ of roastings 4 hours.Be ground to 20～40 orders, be used for cracking reaction.
Molecular sieve after the modification characterizes the ratio of its B acid and L acid with infrared spectrometer, and pyridine is a probe molecule; Levy its strong acid and weak acid amount with full-automatic chemical absorption instrument, pyridine is a probe molecule.Characterization result sees Table 1.
The catalytic pyrolysis appreciation condition is: filling modified molecular screen 1 gram in the fixed bed reactors, and 685 ℃ of reaction temperatures, water weight of oil ratio is 1, the feed weight air speed is 12 hours
-1Get the gas sample every 0.5hr and analyze its composition.Reaction result and gas phase primary product productive rate see Table 2.
Embodiment 2
Preparation contains the calcium nitrate and the magnesium nitrate aqueous solution 50g of 2% (weight) respectively, and other step and condition are together
Embodiment 1.
The catalytic pyrolysis appreciation condition is with embodiment 1.Molecular sieve characterization result after the modification sees Table 1.Reaction result and gas phase primary product productive rate see Table 2.
Embodiment 3
Calcium nitrate and magnesium nitrate aqueous solution 50g that preparation contains 0.14% (weight) respectively left standstill 3 hours.Normal temperature was placed 24 hours down.Preparation process and other condition are with embodiment 1.
The catalytic pyrolysis appreciation condition is with embodiment 1.Molecular sieve characterization result after the modification sees Table 1.Reaction result and gas phase primary product productive rate see Table 2.
Embodiment 4
Preparation contains calcium nitrate, magnesium nitrate and the strontium nitrate aqueous solution 50g of 0.14% (weight) respectively, and normal temperature was placed 30 hours down.Preparation process and other condition are with embodiment 1.
The catalytic pyrolysis appreciation condition is with embodiment 1.Reaction result and gas phase primary product productive rate see Table 2.
Comparative Examples 1
120 ℃ in HZSM-5 molecular sieve dry 10 hours down, 550 ℃ of roastings 4 hours.Compressing tablet is ground to 20～40 orders, is used for cracking reaction.
The catalytic pyrolysis appreciation condition is: unmodified molecular sieve 1 gram of filling in the fixed bed reactors.In addition, all same embodiment of other reaction conditions.The molecular sieve characterization result sees Table 1.Reaction result and gas phase primary product productive rate see Table 2.
Comparative Examples 2
In same reactor, do not add catalyst, carry out thermal cracking.Appreciation condition is: 780 ℃ of reaction temperatures, inlet amount be with the embodiment condition, all same embodiment of remaining reaction condition.Reaction result and gas phase primary product productive rate see Table 2.
Table 1
| B acid/L acid | Strong acid acid amount (mmol/g) | Weak acid acid amount (mmol/g) | Weak acid/total acid | |
| Embodiment 1 embodiment 2 embodiment 3 Comparative Examples 1 | 2.09 2.82 3.08 9.30 | 1.73 3.06 2.43 2.88 | 10.16 20.69 12.82 10.16 | 0.85 0.87 0.84 0.78 |
Table 2
| Factor of created gase (wt%) | Primary product productive rate (wt%) | |||||
| Methane | Ethene | Propylene | Butylene | C 2 ＝～C 4 ＝ | ||
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 Comparative Examples 1 Comparative Examples 2 | 46.27 50.95 48.29 50.36 39.49 45.63 | 2.19 2.98 2.36 2.98 1.95 6.44 | 10.00 11.33 9.81 10.57 7.59 17.64 | 18.14 18.31 18.08 17.79 14.62 10.99 | 6.04 6.18 6.35 6.40 5.88 4.65 | 34.18 35.82 34.24 34.76 28.10 33.28 |
As can be seen from Table 2, compare with unmodified molecular sieve, the weight yield of modified molecular screen of the present invention ethene+propylene+butylene in catalytic pyrolysis process is significantly improved.Compare with thermal cracking, can be issued to better reaction result being lower than nearly 100 ℃ condition.
Claims (11)
1. modified molecular screen that is used for catalytic cracking to prepare lower carbon olefin is characterized in that making by the method for modifying that may further comprise the steps:
1) aqueous solution that will contain at least two kinds of alkaline-earth metal ions joins in the powdery Hydrogen ZSM series molecular sieve, fully stirs, and leaves standstill then, once multiple alkaline-earth metal ions is introduced molecular sieve;
2) the product suction filtration, drying, the roasting that step 1) are obtained obtain the modified powdery molecular sieve, machine-shaping.
2. modified molecular screen as claimed in claim 1 is characterized in that in described step 1), fully stirs 0～2 hour, leaves standstill 0～2 hour.
3. modified molecular screen as claimed in claim 1, the total concentration that it is characterized in that the aqueous solution of described at least two kinds of alkaline earth metal compounds are 0.01～20% (wt).
4. modified molecular screen as claimed in claim 1 is characterized in that described alkaline-earth metal is calcium and magnesium.
5. modified molecular screen as claimed in claim 1 is characterized in that the molecular sieve of described ZSM series molecular screening from ZSM-5, ZSM-8 and ZSM-11 structure type.
6. modified molecular screen as claimed in claim 5 is characterized in that described ZSM series molecular sieve is the molecular sieve of ZSM-5 structure type.
7. modified molecular screen as claimed in claim 1 is characterized in that the silica alumina ratio of described ZSM series molecular sieve is 20～500.
8. modified molecular screen as claimed in claim 1 is characterized in that described ZSM series molecular sieve is that silica alumina ratio is the molecular sieve of 70～300 ZSM-5 structure type.
9. the described preparation method who is used for the modified molecular screen of catalytic cracking to prepare lower carbon olefin of one of claim 1-8, it may further comprise the steps:
The aqueous solution that will contain at least two kinds of alkaline-earth metal ions joins in the powdery Hydrogen ZSM series molecular sieve, adopts fast ion exchange+infusion process, fully stirs 0～2 hour, leaves standstill 0～2 hour; Suction filtration, drying, roasting then once introduced molecular sieve with multiple alkaline-earth metal ions; Mealy molecular sieve machine-shaping with modification.
10. preparation method as claimed in claim 9 is characterized in that the weight ratio of the aqueous solution of described Hydrogen ZSM series molecular sieve and alkaline including earth metal ion is 1: 2～10.
11. preparation method as claimed in claim 9 is characterized in that described alkaline earth metal compounds is its nitrate, chloride or sulfate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101670296B (en) * | 2009-10-19 | 2011-05-25 | 浙江大学 | Catalyst used for low carbon olefin preparation by using oxygenated chemical, and preparation method thereof |
| CN116462208A (en) * | 2023-03-29 | 2023-07-21 | 河北欣芮再生资源利用有限公司 | Method for preparing ZSM-5 molecular sieve by using catalytic cracking dead catalyst |
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| US4288647A (en) * | 1980-03-10 | 1981-09-08 | Mobil Oil Corporation | Shape selective reactions with alkaline earth-modified zeolite catalysts |
| JPH06192134A (en) * | 1992-12-25 | 1994-07-12 | Asahi Chem Ind Co Ltd | Method for converting light hydrocarbon |
| CN1072031C (en) * | 1997-09-17 | 2001-10-03 | 中国石油化工总公司 | Preparation method for penta-basic cyclic molecular sieve composite |
| NO321464B1 (en) * | 1997-09-17 | 2006-05-15 | Res Inst Petroleum Processing | Composition containing a pentasil-type molecular sieve, and its preparation and use |
| CN1163302C (en) * | 2000-08-29 | 2004-08-25 | 中国石油化工集团公司 | Alkali-earth metal modified selective disproportionation catalyst of toluene |
| CN1189434C (en) * | 2002-12-11 | 2005-02-16 | 中国石油化工股份有限公司 | Process of catalytically cracking C4 and above olefin to produce propylene |
| US7141529B2 (en) * | 2003-03-21 | 2006-11-28 | Chevron U.S.A. Inc. | Metal loaded microporous material for hydrocarbon isomerization processes |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101670296B (en) * | 2009-10-19 | 2011-05-25 | 浙江大学 | Catalyst used for low carbon olefin preparation by using oxygenated chemical, and preparation method thereof |
| CN116462208A (en) * | 2023-03-29 | 2023-07-21 | 河北欣芮再生资源利用有限公司 | Method for preparing ZSM-5 molecular sieve by using catalytic cracking dead catalyst |
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