CN101683621B - Catalyst for producing low-carbon olefins through catalytic cracking by fixed bed - Google Patents
Catalyst for producing low-carbon olefins through catalytic cracking by fixed bed Download PDFInfo
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- CN101683621B CN101683621B CN2008102236386A CN200810223638A CN101683621B CN 101683621 B CN101683621 B CN 101683621B CN 2008102236386 A CN2008102236386 A CN 2008102236386A CN 200810223638 A CN200810223638 A CN 200810223638A CN 101683621 B CN101683621 B CN 101683621B
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Abstract
The invention discloses a molecular sieve-containing catalyst for producing low-carbon olefins through catalytic cracking by a fixed bed. To solve the problem that the prior catalyst has high acid content and is easy to coke, the catalyst provided by the invention contains a molecular sieve with the aperture between 5 and 6.5, a modified component thereof and an adhesive. The modified component contains alkaline earth metal oxides, phosphorous oxides and group VIII metal oxides. When the catalyst is used for catalytic cracking, under the condition that a temperature is 200 DEG or more lower than the conventional pyrolysis temperature, compared with the pyrolysis process, the total weight yield of ethylene and propylene is improved, the yield of methane is reduced by about 6 percent, and the ratio of the propylene to the ethylene is improved by more than 1 time.
Description
Technical field
The present invention relates to a kind of catalyst of producing low-carbon alkene, more particularly, the present invention relates to a kind of catalyst that bed bioreactor catalytic pyrolysis petroleum hydrocarbon is produced low-carbon alkene that is used for fixing.
Background technology
At present, ethene is raw material with naphtha or low-carbon alkanes mainly in the world, adopts tube furnace steam heat cracking technique to produce.Although hydrocarbon vapours thermal cracking technique for producing ethylene is constantly perfect through the development of decades, because steam cracking is by means of heat activation hydrocarbons, so reaction temperature is very high.Generally, when gaseous hydrocarbon was raw material, cracking temperature was 840～870 ℃; When liquid hydrocarbon was raw material, cracking temperature was 780～840 ℃.Therefore, the limiting factor of tube furnace steam heat cracking technique production ethylene process is: (1) energy consumption is big; (2) cracking reaction stove material need use expensive special substance (nickel-chromium steel) satisfying the requirement of pyroreaction, but even so, the average life span of boiler tube is merely 6 years; (3) course of reaction receives thermal control, and products distribution is non-adjustable, can not regulate the output of different products with the market demand; (4) have a large amount of carbonizable substances (like carbon monoxide, carbon dioxide, methane and coke) and high carbonizable substance (like condensed-nuclei aromatics) to generate, resource utilization is low.
For solving the deficiency of pyrolysis technology, add catalyst in the course of reaction, under lower reaction temperature, carry out the catalytic pyrolysis petroleum hydrocarbon.Compare with the steam heat cracking technique, low-temperature catalytic pyrolysis technology (below 750 ℃) has the advantage of four aspects: (1) energy consumption is low; (2) material requires low (3) can be according to the market demand, the flexible product structure, and obtain high propylene/ethylene and compare products distribution; (4) one carbonizable substance (methane, CO, CO
2) and high carbonizable substance productive rate low, resource utilization is high.
In fixed bed reactors, carry out in the process of low-temperature catalytic pyrolysis petroleum hydrocarbon producing light olefins, more is the catalyst main active component with ZSM series Si-Al molecular sieve, and regulates the acidity of molecular sieve with modified component.Using IIA family, VA family and rare earth element like CN1565732A is that 40～80 ZSM-5 and ZSM-11 molecular sieve carry out modification to silica alumina ratio, has also added the pore structure conditioning agent simultaneously.
CN1597112A is that 35～100 HZSM-5 molecular sieve is first component with silica alumina ratio, is that second component constitutes composite catalyst with oxide.Wherein, oxide is the composite oxides that contain elements such as Fe, Cr, Mo, V, Ca, K, Al, Si.
It is that 15～60 penta-basic cyclic molecular sieve carries out modification to silica alumina ratio that CN10720231C uses phosphorus and alkaline-earth metal and/or transition metal.Wherein said penta-basic cyclic molecular sieve is the molecular sieve of ZSM-5, ZSM-8 or ZSM-11 structure type.
CN101045212A exploitation ZSM-5 molecular sieve (silica alumina ratio is 12～100) and the compound preparation catalyst of modenite are used for fixing bed bioreactor catalytic pyrolysis naphtha producing light olefins.
Comprise silica alumina ratio in the CN101035619A molecular sieve catalyst and be 15～300 HZSM-5 molecular sieve, lamellar compound, aluminium oxide, P
2O
5, SiO
2And B
2O
3This patent has more mainly been stressed the effect of hole to catalyst performance, that is macropore is to the splitting action of mink cell focus.
When the molecular sieve silica alumina ratio is low, though high by the catalyst activity of its preparation, be used for course of reaction and be easy to carbon deposit, catalyst stability will be had a strong impact on.For guaranteeing higher alkane cracking ability, can in time handle the carbonizable substance that is deposited on the catalyst again simultaneously, often adopt fluidized-bed reactor, occur like the described catalyst of CN1915509A simultaneously.But carrying out with low-carbon alkene (referring to ethene and propylene) with fluidized-bed reactor is in the process of main purpose product, because reaction temperature is high, requires harsh to the fluid bed selection to reaching operation.Because fixed bed and fluid bed are the reaction system of differential responses characteristics, so they also have nothing in common with each other to the requirement of its catalyst.That is the two is the catalyst of two different series, can not mention in the same breath.As the catalyst needs that are used for fixing bed bioreactor satisfy the requirement of active, selectivity and stability simultaneously, and the catalyst that is used for fluidized-bed reactor is more stressed activity and mar proof.When the catalyst that will be used for fluidized-bed reactor is used for fixing bed bioreactor, will be easy to carbon deposit, can not guarantee to have enough stability.
In sum; Disclosed method for preparing catalyst has two types in fixed bed reactors catalytic pyrolysis petroleum hydrocarbon producing light olefins field: (1) is main active component with the ZSM-5 molecular sieve, is aided with metal-modified or supplies the part cracking ability of ZSM-5 molecular sieve with other active components; (2) be main active component with the ZSM-5 molecular sieve, obtain porous solid acid catalyst through pillared reaction.
Above-mentioned two kinds of methods have been considered cracking ability more when the design catalyst, and consider less to acidic zeolite and acid amount to the performance (like carbon deposit) of catalyst.When the silica alumina ratio of the used molecular sieve of catalyst in the fixed bed reactors≤300, it is acid and the acid amount is troubling to the influence of catalyst stability.Because this moment, the acid amount of molecular sieve was also bigger, the acidity of some molecular sieve is also stronger, even 650 ℃ of reactions down, activity is still very high in the course of reaction, very easy carbon deposit, thus cause rapid catalyst deactivation.
Summary of the invention
For solving above the problems of the prior art, the present invention provides a kind of catalyst that bed bioreactor catalytic pyrolysis petroleum hydrocarbon is produced low-carbon alkene that is used for fixing.This catalyst is selected high silica alumina ratio ZSM-5 molecular sieve for use, and is aided with suitable modification, has certain stability again so that catalyst has the highly active while.
The catalyst that is used for fixing a preparing low-carbon olefin by catalytically cracking of the present invention; Comprise: ZSM type molecular sieve and modified component and the adhesive of aperture for
; The silica alumina ratio of said molecular sieve is 300～1000, and said modified component comprises alkaline earth oxide, phosphorous oxides and VIII family metal oxide.
Preferably; Gross weight and weight percent content in catalyst; Said catalyst contains 10～80% molecular sieve, 20～85% adhesive, 0.01～15% alkaline earth oxide, 0.01～15% VIII family metal oxide and 0.1～15% phosphorous oxides, and the degree sum of all compositions is 100%.
Said molecular sieve is ZSM-5, ZSM-8 or ZSM-11 type more preferably, the silica alumina ratio of molecular sieve more preferably 320～600.
Said alkali earth metal is preferably Ca and/or Mg, and VIII family metal is preferably at least a among Fe, Co and the Ni.
Said adhesive is preferably silica, aluminium oxide or their mixture.
Alkaline-earth metal and VIII family metal preferably use water soluble salt and under mild acid conditions soluble salt, like nitrate, phosphate, oxalates, chloride and acetate.Said phosphorous oxides is preferably from phosphoric acid and phosphate, or other water-soluble substanceses, like diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) etc.
Under following condition, use catalyst of the present invention to carry out catalytic cracking reaction: 550～700 ℃ of temperature, pressure 0～0.3MPa, water-oil factor 0.1～3, weight space velocity 1～20h
-1Said oil is meant petroleum hydrocarbon, naphtha etc. for example, preferred C
4～C
8Alkane or its mixture and naphtha.
Low-carbon alkene of the present invention is meant that carbon number is 2～4 alkene, more particularly, is meant ethene, propylene and butylene.
The introducing method of modified component is a conventional method in the catalyst of the present invention, like ion-exchange, infusion process and mixing method etc.
The shaping of catalyst method is a conventional method, extrusion method for example commonly used.Be about to molecular sieve and adhesive and mix extruded moulding, 100 ℃ of dry 10h, 560 ℃ of roasting 4h.In addition, also can use other forming methods (like spray drying process).
When carrying out modification, or earlier mealy molecular sieve is carried out ion-exchange, add moulding such as adhesive then, or earlier molecular sieve and adhesive etc. is mixed moulding, carry out ion-exchange again with ion-exchange.Usually, earlier water miscible slaine water dissolving, will be placed this aqueous solution by quid pro quo then in the ion exchange process, in the scope of normal temperature～95 ℃, stir certain hour, filtration, drying is being higher than roasting under the decomposition temperature of salt.The operating parameter of concrete operations step is decided according to the character of molecular sieve and the requirement of final catalyst performance.This field Preparation of Catalyst personnel have certain understanding to this, so repeat no more.
When introducing modified component, earlier molecular sieve and adhesive etc. is mixed aftershaping with infusion process.After processes such as drying, roasting, article shaped is placed in the solution (often be its aqueous solution, also can be the solution of other solvents when specific (special) requirements is arranged) that contains impregnated thing, normal temperature stops after 1～10 hour down, filters drying, roasting.
When carrying out modification with mixing method, material (like slaine) the dissolving back (also can not dissolving) of intending modification is even with mechanical mixture such as molecular sieve and adhesives, moulding, drying is being higher than roasting under the decomposition temperature of salt.
Phosphorus has stabilization to framework of molecular sieve aluminium.Especially under the reaction condition that high-temperature vapor exists, the existence of phosphorus can postpone the speed that framework of molecular sieve aluminium comes off, thereby makes molecular sieve catalyst have stable acidity and active.Therefore, the modified component of molecular sieve catalyst is often selected phosphorus for use, especially for the high silica alumina ratio molecular sieve.But phosphorus itself has certain acidity and reactivity, causes as active site some undesirable reactions taking place at the position that phosphorus exists, like hydrogen transfer reaction.For this reason, add alkaline-earth metal in the catalyst of the present invention, suppress hydrogen transfer reaction and take place to regulate the acidity of catalyst.The VIII family metal oxide has dehydrogenation functionality, thereby under reaction condition, helps the generation of low-carbon alkene.The synergy of these components makes catalyst have higher propylene and yield of ethene, by the accessory substance C of hydrogen transfer reaction generation
1～C
3The alkane productive rate is low.Simultaneously, reaction condition is gentle.
Beneficial effect of the present invention is following:
1, react being lower than under the condition of conventional thermal cracking temperature >=200 ℃, the yield of ethene and propylene is higher than thermal cracking.
2, the odds ratio thermal cracking of propylene/ethylene improves more than 1 times.
3, the methane yield reduces nearly 6 percentage points than the thermal cracking processes under the equal cracking degree.
4, compare with unmodified molecular sieve catalyst, under identical or close reaction condition, the weight yield of ethene and propylene improves 5%.
The specific embodiment
Following embodiment will explain further the present invention, but therefore not limit the present invention.
Embodiments of the invention carry out in small-sized tubular fixed-bed reactor.
Embodiment 1
Preparation of Catalyst: 30g HSZM-5 molecular sieve (silica alumina ratio=360) mixes with the 10g aluminium oxide, mediates extruded moulding.Drying was 10 hours under 100 ℃, 560 ℃ of following roastings 4 hours.Article shaped impregnated in the aqueous solution that contains diammonium hydrogen phosphate, cobalt nitrate, magnesium nitrate 2 hours, filter, drying had been higher than under the decomposition temperature of above-mentioned salt roasting 4 hours.In the weight percent content of catalyst, contain 70.73% molecular sieve, 25.00% adhesive, 3.94% magnesia, 0.10% cobalt oxide and 0.23% phosphorous oxides in the final catalyst that obtains.
In small-sized tubular fixed-bed reactor, estimate the catalyst of preparation.Appreciation condition is: the weight space velocity of naphtha is 1h
-1, reaction temperature is 650 ℃, and pressure is normal pressure, and water oil feed weight ratio is 1.Reaction result is seen table 1.
Embodiment 2
Preparation of Catalyst: shaping of catalyst is with embodiment 1.Article shaped impregnated in the aqueous solution that contains diammonium hydrogen phosphate, cobalt nitrate, magnesium nitrate and calcium nitrate, 2 hours, to filter, drying had been higher than under the decomposition temperature of above-mentioned salt roasting 4 hours.In the weight percent content of catalyst, contain 73.41% molecular sieve, 22.30% adhesive, 1.57% magnesia, 2.37% calcium oxide, 0.10% cobalt oxide and 0.25% phosphorous oxides in the final catalyst that obtains.
The evaluating catalyst condition is with embodiment 1.Reaction result is seen table 1.
Embodiment 3
Preparation of Catalyst: the shaping of catalyst method is with embodiment 1.Article shaped impregnated in the aqueous solution that contains diammonium hydrogen phosphate, cobalt nitrate, magnesium nitrate and calcium nitrate, 2 hours, to filter, drying had been higher than under the decomposition temperature of above-mentioned salt roasting 4 hours.In the weight percent content of catalyst, contain 73.41% molecular sieve, 22.45% adhesive, 1.52% magnesia, 2.35% calcium oxide, 0.05% cobalt oxide and 0.22% phosphorous oxides in the final catalyst that obtains.
The evaluating catalyst condition is with embodiment 1.Reaction result is seen table 1.
Comparative Examples 1
Use identical oil product, on industrial analogue means, carry out heat scission reaction, catalyst-free, cracking condition are 860 ℃.Reaction result is seen table 1.
Comparative Examples 2
Preparation of Catalyst: the shaping of catalyst method is with embodiment 1.As comparing, this catalyst is the article shaped of molecular sieve and aluminium oxide, does not do any further modification and handles.
The evaluating catalyst condition is with embodiment 1.Reaction result is seen table 1.
Comparative Examples 3
Preparation of Catalyst: the preparation method is with embodiment 1.In order to compare, HSZM-5 molecular sieve silica alumina ratio is 200, and catalyst is formed with embodiment 1.Appreciation condition is with embodiment 1.Reaction result is seen table 1.
Table 1 Naphtha Pyrolysis Reaction result
Can find out from table 1; Catalyst provided by the invention is in catalytic pyrolysis naphtha preparing low carbon olefin hydrocarbon; Following characteristics are arranged: (1) is compared with industrial analogue means thermal cracking processes, can improve ethene+propylene weight yield than thermal cracking processes being lower than under 200 ℃ the condition.Simultaneously, the methane yield reduces at least 6 percentage points, and the ratio of propylene/ethylene improves more than 1 times; (2) compare with unmodified molecular sieve catalyst, under identical or close reaction condition, the gross weight yield of ethene and propylene improves 5 percentage points; (3) be lower than 300 molecular sieve with silica alumina ratio and compare, under identical modified condition, the diene yield improves, and the methane yield reduces.
Claims (4)
1. catalyst that is used for fixing a preparing low-carbon olefin by catalytically cracking; It is characterized in that; Said catalyst comprises ZSM type molecular sieve and modified component and the adhesive of aperture for
; The silica alumina ratio of said molecular sieve is 300～1000, and said modified component comprises alkaline earth oxide, phosphorous oxides and VIII family metal oxide; Gross weight and weight percent content in catalyst; Said catalyst contains 10～80% molecular sieve, 20～85% adhesive, 0.01～15% alkaline earth oxide, 0.01～15% VIII family metal oxide and 0.1～15% phosphorous oxides, and the percentage by weight sum of all compositions is 100%.
2. the catalyst that is used for fixing a preparing low-carbon olefin by catalytically cracking as claimed in claim 1 is characterized in that, said molecular sieve is ZSM-5, ZSM-8 or ZSM-11 type, and the silica alumina ratio of molecular sieve is 320～600.
3. the catalyst that is used for fixing a preparing low-carbon olefin by catalytically cracking as claimed in claim 1 is characterized in that, said alkaline-earth metal is Ca and/or Mg, and VIII family metal is at least a among Fe, Co and the Ni.
4. the catalyst that is used for fixing a preparing low-carbon olefin by catalytically cracking as claimed in claim 1 is characterized in that, said adhesive is silica, aluminium oxide or their mixture.
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| CN2008102236386A CN101683621B (en) | 2008-09-28 | 2008-09-28 | Catalyst for producing low-carbon olefins through catalytic cracking by fixed bed |
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|---|---|---|---|
| CN2008102236386A CN101683621B (en) | 2008-09-28 | 2008-09-28 | Catalyst for producing low-carbon olefins through catalytic cracking by fixed bed |
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| CN101683621A CN101683621A (en) | 2010-03-31 |
| CN101683621B true CN101683621B (en) | 2012-01-25 |
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| CN103418423B (en) * | 2012-05-22 | 2016-06-22 | 中国石油化工股份有限公司 | Arene isomerization catalyst and preparation method |
| CN103586067B (en) * | 2013-07-09 | 2017-02-08 | 中国科学院过程工程研究所 | Method for synthesizing acrylic acid by aqueous formaldehyde solution and acetic acid |
| SG11202001243UA (en) | 2017-08-28 | 2020-03-30 | Saudi Arabian Oil Co | Chemical looping processes for catalytic hydrocarbon cracking |
| CN113548677B (en) * | 2020-04-24 | 2023-02-17 | 中国石油化工股份有限公司 | Composite modified molecular sieve, preparation method thereof, catalytic cracking catalyst, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1796498A (en) * | 2004-12-28 | 2006-07-05 | 中国石油化工股份有限公司 | Cracking auxiliary agent for increasing production of propylene |
| CN101035619A (en) * | 2004-09-10 | 2007-09-12 | Sk株式会社 | Solid acid catalyst for producing light olefins and process using the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101035619A (en) * | 2004-09-10 | 2007-09-12 | Sk株式会社 | Solid acid catalyst for producing light olefins and process using the same |
| CN1796498A (en) * | 2004-12-28 | 2006-07-05 | 中国石油化工股份有限公司 | Cracking auxiliary agent for increasing production of propylene |
Non-Patent Citations (1)
| Title |
|---|
| JP特开平6-199707A 1994.07.19 |
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