CN101927180A - Catalyst for preparing propylene from C4 olefins, and application and regeneration method thereof - Google Patents

Catalyst for preparing propylene from C4 olefins, and application and regeneration method thereof Download PDF

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Publication number
CN101927180A
CN101927180A CN2009100872023A CN200910087202A CN101927180A CN 101927180 A CN101927180 A CN 101927180A CN 2009100872023 A CN2009100872023 A CN 2009100872023A CN 200910087202 A CN200910087202 A CN 200910087202A CN 101927180 A CN101927180 A CN 101927180A
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catalyst
propylene
oxide
silica
zeolite
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CN101927180B (en
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王定博
刘小波
马志元
王超
戴伟
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • 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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses a method for increasing yield of propylene by using C4 fraction in ethylene plants and oil plants. In order to solve the problems of catalyst stability and regeneration in the prior art for preparing propylene from C4 olefins, high-silica zeolite and silicon oxide are selected as the main components of the catalyst, and basic oxides and acidic oxides are used for modification to prepare the olefin conversion catalyst, wherein the basic oxides are preferably calcium oxide and lithium oxide, and the acidic oxides are preferably boron oxide and phosphorus oxide. After being tested, the catalyst has favorable stability, and various properties can be restored after the catalyst is regenerated. The application method of the catalyst comprises the following steps: using the mixture of raffinate I or etherified C4 as the raw material, exchanging heat, preheating, contacting with high silicon/aluminum ratio zeolite catalyst in a fixed bed adiabatic reactor to generate the reactant mixture containing ethylene and propylene, exchanging heat, cooling and separating to obtain propylene, ethylene and the like for cycle use. The invention provides an industrially available method.

Description

The catalyst of preparing propylene from C 4 olefins and application thereof and renovation process
Technical field
The present invention relates to a kind of catalyst and application and renovation process for preparing low-carbon alkene, specifically, the present invention relates to a kind of catalyst and application and renovation process that ethylene plant's carbon four raffinate I or refinery casing head prepare propylene that be used for.
Background technology
Propylene is the important Organic Chemicals that is only second to ethene, along with fast development of national economy, its demand is also constantly increased.The present propylene of China situation that is in that supply falls short of demand, the method for conventional stimulation propylene more and more can not satisfy the demand in market.Hydrocarbon vapours cracking and catalytic cracking are two sources greatly of propylene, and the former can propylene enhancing by reducing cracking severity, but growth is limited in one's ability; The latter is by the improvement of aspects such as catalyst, process conditions, apparatus structure, can propylene enhancing, but confirmed it is expensive, and be limited.Lower C4 and the above olefin feedstock of C4 of added value that produces in oil plant or the ethylene plant's production process carried out processing and utilization, and producing propylene has become an emerging cracking technique.It is simple that this technology has technology, small investment, and the characteristics of instant effect are subjected to the favor of many petrochemical industry research department.
A kind of method of olefin catalytic cracking to produce propylene is proposed among patent CN1611471A and the CN1611472A, 400～600 ℃ of reaction temperatures, reaction pressure 0～0.15Mpa, the liquid phase air speed is 2～30hr -1, the former reaches the selectivity and the yield of raising purpose product propylene than the type ZSM 5 molecular sieve catalyst of (＜100) with the phosphorus modified low silicon-aluminum.At 560 ℃ and liquid phase air speed 10hr -1Condition under, propylene selectivity 53.8%, yield 38.8%.This patent relates to the catalyst modification problem of low silica-alumina ratio molecular sieve, does not use the high silica alumina ratio molecular sieve.The latter is 230～600 type ZSM 5 molecular sieve with the silica alumina ratio preferable range, and by the grain size of control ZSM type molecular sieve, the time of staying that reduces reactant and product is to reach the purpose that improves selection of catalysts and stability.At 500 ℃ and liquid phase air speed 10h -1Condition under, propene yield is greater than 30%.This patent focuses on the synthetic of molecular screen primary powder, does not add other active component and carries out modification.
Patent CN1600757 adopts the ZSM-5/ZSM-11 cocrystallization molecular sieve after ammonium ion exchange, with the performance of K, Mg, La, Ce allotment molecular sieve, is raw material with the butylene, 500～650 ℃ of reaction temperatures, and liquid phase air speed 1～50h -1Under pressure 0.01～0.8MPa, the total recovery of ethene and propylene reaches 40%～55%.The catalytic cracking reaction time is short, and the stability of catalyst is not investigated.
Patent CN1490288 adds the halogen sodium salt in the crystallization process of ZSM type molecular screen primary powder, be reaction raw materials with carbon four and carbon four above alkene, and reaction temperature is 400～600 ℃, and reaction pressure is 0～0.15MPa, liquid phase air speed 10～50hr -1, investigated of the influence of the proportioning of molecular sieve different halogen sodium salts and silica in crystallization process in more detail to catalytic cracking reaction.Lay particular emphasis on molecular sieve crystallization synthetic, the selectivity and the stability of propylene in the course of reaction is not further elaborated.
CN1274342A discloses by catalyzed conversion to contain at least a C of 20% (weight) or higher (with the weight of hydrocarbon feed) 4-C 12The straight-chain hydrocarbons of alkene is the method that raw material is produced ethene and propylene.Zeolite in the zeolite catalyst that this method is used is not contain proton, SiO substantially 2/ Al 2O 3Mol ratio is 200-5000, contain the zeolite of at least a IB family metal, intermediate pore size, the zeolite of preferred ZSM-5 family.Be reflected at 400～700 ℃ temperature, 0.1～10 atmospheric pressure and 1～1000h -1Weight hourly space velocity under carry out, the diluent gas of use comprises hydrogen, methane, steam and inert gas, can obtain to be up to 6.5% ethylene yield and 22.7% productivity of propylene, stability is not further elaborated.
CN1313268A discloses with C 2～C 5Gaseous hydrocarbon, be the method that raw material is produced ethene as natural gas, liquefied petroleum gas or catalytic cracked gas.Use in this method to contain the clay molecular sieve with layer structure catalyst, at 650～750 ℃, 1.5 * 10 5～4 * 10 5Under the condition in Pa, 0.2～1 second reaction time, can obtain stability not to be further elaborated up to 15.49% ethylene yield and 25.19% productivity of propylene.
WO 00/26163 discloses to contain C 4And C 5The mixture of alkene is a raw material, prepares the method for ethene and propylene in the presence of zeolite catalyst.The catalyst that this method is used as the aperture greater than 3.5 dusts, have the not interconnected duct of one dimension, the zeolite of pore volume between 14～28, be reflected at 200～750 ℃ temperature, 0.5～10 atmospheric pressure and 0.5～1000h -1Weight hourly space velocity under carry out, do not add other active component and carry out modification.
In the existing patent mainly is that the modification and the preparation process of molecular sieve are studied, and does not see the relevant report about catalyst stability and regeneration.
Summary of the invention
The present invention prepares catalyst stability and the regeneration problem that the propylene technology exists in order to solve existing C 4 olefin, having proposed selection silica-rich zeolite and silica is the catalyst key component, adopting basic anhydride and acidic oxide is that modified component prepares the alkene reforming catalyst, through examination, catalyst of the present invention has good stable, can recover the various performances of catalyst through regeneration.
An object of the present invention is to provide a kind of catalyst that C 4 olefin prepares propylene that is used for, in total catalyst weight, described catalyst comprises: 75%～95% silica-rich zeolite, 5%～20% silica and 1%～10% modified component, described modified component are basic anhydride and acidic oxide.
Preferably, described silica-rich zeolite is selected from commodity ZRP by name or ZSM-5 class zeolite.
Preferably, SiO in the described silica-rich zeolite 2With Al 2O 3Mol ratio be 150～250.
Preferably, described basic anhydride are calcium oxide and/or lithia, and described acidic oxide is boron oxide or phosphorous oxide.
Another object of the present invention provides a kind of Application of Catalyst method, specifically, is not adding under the dilution component, at 450～550 ℃ of temperature, pressure 0.01～0.5MPa and weight hourly space velocity 1～30h -1Condition under, the C-4-fraction of ethylene plant's carbon four raffinate I or oil plant contacts in fixed bed adiabatic reactor with as the described catalyst of one of claim 1～4, generation contains the reactant mixture of propylene and ethene, obtain propylene through heat exchange, cooling, separation, isolated ethene and lighter component Returning reactor;
A further object of the present invention provides the renovation process of catalyst of the present invention, specifically, stops the C-4-fraction charging, and logical nitrogen/air (or water/air) is regenerated under 400～550 ℃, wherein oxygen content 1 volume %～10 volume %.
The shape of the catalyst that method of the present invention is used can be spherical, granular, strip, extrudate etc.
The used catalyst of method of the present invention adopts kneading method and immersion process for preparing to obtain, and comprises the following steps: that specifically (1) mix silica-rich zeolite, silica, extrusion aid in proportion, and that wherein silica uses is known specific area＞200m 2The high-purity silicon oxide of/g; Used extrusion aid such as sesbania powder, polyacrylamide, silica gel etc.; (2) add nitric acid behind the mixing, stir evenly the back extrusion modling, wherein the weight percent concentration of nitric acid is less than 10%; (3) 60～140 ℃ of dryings 5～20 hours, 450～650 ℃ of roastings 0.5～15 hour; (4) carrier that adopts the precursor solution impregnation steps (3) of basic anhydride to obtain, preferred calcium nitrate and the lithium nitrate solution of using, use the precursor solution of acidic oxide after the drying again, the preferred solution that uses compounds such as phosphoric acid, ammonium phosphate and boric acid, 80～150 ℃ of bakings 10 hours, burnt 4～10 hours then at 500～600 ℃.
After catalyst activity reduced, the renovation process of taking was: 1) stop carbon four chargings, reaction bed temperature is reduced to 400 ℃; 2) slowly water flowing steam/air or nitrogen/air (wherein oxygen content 1 volume %～10 volume %) make reaction bed temperature＜550 ℃; 3) check tail gas with limewash, regeneration finished when no carbon dioxide produced.
The raw material that contains C 4 olefin that method of the present invention is used can be selected from:
(1) the carbon four raffinate I of ethylene plant, the soon product after the butadiene extracting in the C-4-fraction;
(2) C-4-fraction that obtains of catalytic cracking unit;
(3) C-4-fraction (C 4 mixture that does not contain isobutene) after ethylene plant, the oil plant etherificate.
C-4-fraction (C 4 olefin content＞60%) is as raw material of the present invention after preferred use carbon four raffinate I or the etherificate; Wherein said monoolefine is the alkene that contains the straight or branched of the two keys of 4 carbon atoms and, i.e. the various isomers of butylene are as 1-butylene, suitable-the 2-butylene, anti--the 2-butylene, isobutene.
Method provided by the invention can be used as the independent method for preparing propylene, also can combine use with preparing ethylene by steam cracking and oil plant FCC apparatus.
The characteristics of molecular sieve catalyst are that active height, poor selectivity and life cycle are short, the molecular sieve catalyst of high silica alumina ratio is increasing aspect selectivity and the life cycle, but if do not add modified component, still easy knot charcoal in course of reaction, and to the poor selectivity of propylene.Processing by modified component is handled, and can reduce growing amount, the prolongation life cycle of catalyst charcoal in course of reaction, and improves the selectivity of propylene.Therefore, the present invention has the following advantages:
1, be raw material with the C 4 mixture that does not contain diolefin, do not add diluent, technology is simple, easy to operate;
2, reaction temperature is lower, and catalyst system therefor anti-coking performance and regenerability are good, and life cycle is long;
3, catalyst is silica-rich zeolite and some oxides, and preparation method and renovation process are simple.
4, under the same conditions, light components such as ethene recycle the back productivity of propylene increases.
Description of drawings
Fig. 1 is the schematic flow sheet of Application of Catalyst of the present invention.
1 heat exchanger, 2 heating furnaces, 3 reactors, 4 coolers, 5 compressors, 6 oil absorb and take off ethylene column, 7 stabilizers.
The specific embodiment
Below in conjunction with accompanying drawing Application of Catalyst method of the present invention is described.
Catalyst is packed in the insulation fix bed reactor 3 into logical N 2Behind the leak test, open heating furnace 2 heating, temperature is led to carbon four after being raised to assigned temperature.Carbon four enters heating furnace 2 and reactor 3, and product enters oil through heat exchanger 1 and cooler 4, compressor 5 and absorbs and take off ethylene column 6, and gas phase recycles, liquid phase enters stabilizer 7, the gas phase air inlet divides device can get propylene, and liquid phase is returned tower 6, and the unnecessary gasoline of doing is handled.
Below example will illustrate further the present invention, but not thereby limiting the invention.
Embodiment 1 preparation catalyst A
With 85g ZSM-5 molecular sieve (SiO 2/ Al 2O 3＞200), 15g silica and 2g sesbania powder mix; Add the phosphoric acid of 80ml 5% behind the mixing, be squeezed into the cylindrical type of 2mm after stirring evenly, and cut into 2～3mm; 80 ℃ and 120 ℃ dry 10 hours respectively, 580 ℃ of calcinings 6 hours down, take out and be cooled to room temperature then, it is standby to put into drier.Zhi Bei catalyst is labeled as catalyst A by this way.
Embodiment 2 preparation catalyst B
With 75g ZSM-5 molecular sieve (SiO 2/ Al 2O 3＞200), 10g silica, 10g calcium oxide, 2g boron oxide and 2g sesbania powder mix the nitric acid of adding 80ml 5% behind the mixing.Other method of operating is identical with embodiment 1.Zhi Bei catalyst is labeled as catalyst B by this way.
Embodiment 3 preparation catalyst C
With 75g ZRP molecular sieve (SiO 2/ Al 2O 3＞200), 10g silica, 10g calcium oxide, 2g lithia and 2g sesbania powder mix adding 80ml 5% phosphoric acid behind the mixing.Other method of operating is identical with embodiment 1.Zhi Bei catalyst is labeled as catalyst C by this way.
Comparative Examples 1 preparation catalyst D
The catalyst A of getting the 30g moulding is dissolved with 10 gram calcium nitrate, 1 gram lithium nitrate solution dipping with 20ml respectively, be dissolved with 2 gram BAS dippings with 20ml again behind the airing, respectively 80 ℃ and 120 ℃ of dryings 10 hours, after 6 hours, it is standby to put into drier 580 ℃ of calcinings behind the airing.Zhi Bei catalyst is labeled as catalyst D by this way.
Embodiment 4
In the small stationary bed bioreactor, be raw material with the C 4 mixture after the etherificate, use catalyst A, B, C and D, at pressure 0.1MPa and carbon quadruple amount air speed 10h -1Under react, under the differential responses temperature, the productivity of propylene of reaction 10 hours the time listed in table 1.
The consisting of of raw material (wt%) wherein:
Iso-butane 0.11, normal butane 22.84, anti--2-butylene 32.31,1-butylene 26.65, isobutene 0.12, suitable-2-butylene 18.24.
Reactor is the stainless steel tube of internal diameter Φ 16mm, wall thickness 2mm, interior dress 25ml catalyst, and the particle diameter of catalyst is about 2.0mm * 3.0mm.
Embodiment 5
In reactor feed, add ethene.
With C 4 mixture after the etherificate and ethene is raw material, uses catalyst D, at pressure 0.1MPa, carbon quadruple amount air speed 10h -1Under react, the amount that produces when using catalyst D among ethylene feed amount and the embodiment 4 is identical, under the differential responses temperature, the productivity of propylene of reaction in the time of 10 hours is listed in table 1
The stability and the regeneration test of embodiment 6 catalyst
In temperature is that 500 ℃, pressure are that 0.1MPa, carbon quadruple amount air speed are 10h -1Condition under, with 240 hours inner catalysts table 2 that the results are shown in to the C 4 olefin conversion reaction.
Step is as follows during catalyst regeneration: 1) stop carbon four chargings, reaction bed temperature is reduced to 400 ℃; 2) slowly blowing air and water vapour make reaction bed temperature＜550 ℃; 3) check tail gas with limewash, regeneration finished when no carbon dioxide produced.Use the catalyst after regenerating, carry out the evaluating catalyst test, result of the test is listed in table 3.
Table 1 productive rate (wt%) of propylene during 10h under the differential responses temperature
Figure B2009100872023D0000061
The stability test result of table 2. catalyst D
Reaction time (h) 24 48 72 96 120 144 168 192 216 240
Productivity of propylene (wt%) 37.85 37.78 37.77 37.51 37.49 37.33 37.28 37.20 36.92 36.86
C 4 olefin conversion ratio % 76.99 75.76 74.92 74.86 74.51 73.58 73.17 72.68 71.31 70.39
Result of the test after the table 3. catalyst D regeneration
Reaction time (h) 24 48 72 96 120 144 168 192 216 240
Productivity of propylene (wt%) 37.76 37.59 37.60 37.33 37.12 37.23 37.18 37.10 36.67 36.51
C 4 olefin conversion ratio % 75.85 75.65 74.82 73.96 73.37 72.86 72.51 70.98 70.61 70.35

Claims (6)

1. a C 4 olefin prepares the catalyst of propylene, it is characterized in that in total catalyst weight, described catalyst comprises: 75%～95% silica-rich zeolite, 5%～20% silica and 1%～10% modified component, described modified component are basic anhydride and acidic oxide.
2. catalyst as claimed in claim 1 is characterized in that, described silica-rich zeolite is selected from commodity ZRP by name or ZSM-5 class zeolite.
3. catalyst as claimed in claim 1 is characterized in that, SiO in the described silica-rich zeolite 2With Al 2O 3Mol ratio be 150～250.
4. catalyst as claimed in claim 1 is characterized in that, described basic anhydride are calcium oxide and/or lithia, and described acidic oxide is boron oxide or phosphorous oxide.
5. as the described Application of Catalyst of one of claim 1～4, it is characterized in that, do not adding under the dilution component, at 450～550 ℃ of temperature, pressure 0.01～0.5MPa and weight hourly space velocity 1～30h -1Condition under, the C-4-fraction of ethylene plant's carbon four raffinate I or oil plant contacts in fixed bed adiabatic reactor with as the described catalyst of one of claim 1～4, generation contains the reactant mixture of propylene and ethene, obtain propylene through heat exchange, cooling, separation, ethene and lighter component Returning reactor.
6. as the renovation process of the described catalyst of one of claim 1～4, it is characterized in that, stop the C-4-fraction charging, logical nitrogen/air (or water/air) is regenerated under 400～550 ℃, wherein oxygen content 1 volume %～10 volume %.
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Cited By (5)

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CN102872902A (en) * 2011-07-12 2013-01-16 中国石油化工股份有限公司 Catalytic cracking assistant for propylene yield increase
CN103506151A (en) * 2012-06-15 2014-01-15 中国石油化工股份有限公司 Catalyst for preparation of sec-butyl acetate from C4 olefins
CN107739291A (en) * 2017-10-20 2018-02-27 山西沸石科技有限公司 A kind of method that FCC gasoline modification produces chemical products simultaneously
CN113304779A (en) * 2020-02-27 2021-08-27 中国石油化工股份有限公司 Carbon tetraolefin cracking propylene yield-increasing catalyst containing all-silicon mesoporous microspheres and preparation method and application thereof
WO2022207884A1 (en) 2021-04-01 2022-10-06 Synthos Dwory 7 Spolka Z Ograniczona Odpowiedzialnoscia Spolka Jawna Adiabatically conducted process for the production of 1,3-butadiene from mixtures of ethanol and acetaldehyde with catalyst regeneration

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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
CN1235845C (en) * 2003-10-27 2006-01-11 中国石油化工股份有限公司 Method for producing propene for olefin catalytic cracking
CN100443453C (en) * 2005-09-07 2008-12-17 中国石油化工股份有限公司 Method of preparing propylene and ethylene by catalytic cracking olefin
CN101172247B (en) * 2006-10-31 2010-05-19 中国石油化工股份有限公司 Catalyst for production of propylene and ethylene with carbon alkatetraenes, regeneration and uses thereof

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Publication number Priority date Publication date Assignee Title
CN102872902A (en) * 2011-07-12 2013-01-16 中国石油化工股份有限公司 Catalytic cracking assistant for propylene yield increase
CN103506151A (en) * 2012-06-15 2014-01-15 中国石油化工股份有限公司 Catalyst for preparation of sec-butyl acetate from C4 olefins
CN103506151B (en) * 2012-06-15 2016-02-24 中国石油化工股份有限公司 C 4 olefin prepares 2-butyl acetate catalyst
CN107739291A (en) * 2017-10-20 2018-02-27 山西沸石科技有限公司 A kind of method that FCC gasoline modification produces chemical products simultaneously
CN107739291B (en) * 2017-10-20 2021-12-07 山西沸石科技有限公司 Method for modifying FCC gasoline and producing chemical products simultaneously
CN113304779A (en) * 2020-02-27 2021-08-27 中国石油化工股份有限公司 Carbon tetraolefin cracking propylene yield-increasing catalyst containing all-silicon mesoporous microspheres and preparation method and application thereof
CN113304779B (en) * 2020-02-27 2023-04-11 中国石油化工股份有限公司 Carbon tetraolefin cracking propylene yield-increasing catalyst containing all-silicon mesoporous microspheres and preparation method and application thereof
WO2022207884A1 (en) 2021-04-01 2022-10-06 Synthos Dwory 7 Spolka Z Ograniczona Odpowiedzialnoscia Spolka Jawna Adiabatically conducted process for the production of 1,3-butadiene from mixtures of ethanol and acetaldehyde with catalyst regeneration

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