CN1170913C - Prodn of olefins - Google Patents
Prodn of olefins Download PDFInfo
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- CN1170913C CN1170913C CNB988134624A CN98813462A CN1170913C CN 1170913 C CN1170913 C CN 1170913C CN B988134624 A CNB988134624 A CN B988134624A CN 98813462 A CN98813462 A CN 98813462A CN 1170913 C CN1170913 C CN 1170913C
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- Prior art keywords
- olefin
- effluent
- raw material
- alkene
- propylene
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-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
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- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A process for the catalytic cracking of an olefin-rich feedstock which is selective towards light olefins in the effluent, the process comprising contacting a hydrocarbon feedstock containing one or more olefins, with a MFI-type crystalline silicate catalyst having a silicon/aluminium atomic ratio of at least about 300 at an inlet temperature of from 500 to 600 DEG C, at an olefin partial pressure of from 0.1 to 2 bars and the feedstock being passed over the catalyst at an LHSV of from 10 to 30<-1> h, to produce an effluent with an olefin content of lower molecular weight than that of the feedstock.
Description
The present invention relates to the method for the hydrocarbon feed of cracking rich olefins, it has selectivity to the light olefin in the effluent.Especially optionally transform olefin(e) centent from the olefin feedstock of refinery or petrochemical unit with raw material in the effluent of redistributing generation.
The known zeolite that uses in the catalytic dewaxing of for example petroleum of people is converted into lighter product with long chain paraffins in the prior art, although this is not the purpose of dewaxing, is converted into alkene to the small part paraffinic hydrocarbons.People have known the use crystalline silicate in the method, MFI type crystalline silicate for example, the specific crystalline silicate structure type that " MFI " expression of trigram name is confirmed by the structure council (StructureCommission of the International Zeolite Association) of International Zeolite Association.The example of MFI type crystalline silicate is synthetic zeolite ZSM-5 and silicon zeolite (silicalite), and other MFI type crystalline silicate is known in the prior art.
GB-A-1323710 discloses the employing crystalline silicate catalyst, and ZSM-5 especially removes the process for dewaxing of linear paraffins and slight branched paraffin from hydrocarbon feed.US-A-4247388 also discloses and has used ZSM-5 type crystalline silicate that oil and synthetic hydrocarbon feed are carried out the method for catalytic hydrodewaxing, and similarly process for dewaxing is open in US-A-4284529 and the US-A-5614079.Catalyzer is a crystal aluminosilicate, and above-mentioned prior art document discloses the differential responses condition of using and be used for disclosed process for dewaxing of the Si/Al ratio of wide region.
GB-A-2185753 discloses the hydrocarbon feed process for dewaxing that uses the silicon zeolite catalyst, and US-A-4394251 discloses to adopt has the crystalline silicate particulate hydroconversion process that contains the aluminium shell.
Also known hydrocarbon feed, the especially paraffin that will contain straight chain and/or slight branched-chain hydrocarbon of people is selectively converted to the low molecular weight product mixture that contains a large amount of alkene in the prior art.Described in GB-A-2075045, US-A-4401555 and US-A-4309276, conversion process is undertaken by raw material is contacted with the crystalline silicate that is called the silicon zeolite, and the silicon zeolite is open in US-A-4061724.
The silicon zeolite catalyst exists different silicon/al atomic ratios and different crystallized forms.CosdenTechnology, the EP-A-0146524 of Inc and 0146525 disclose has the symmetric silicon zeolite type of oblique crystal crystalline silica and preparation method thereof.These silicate have the sial atomic ratio greater than 80.
WO-A-97/04871 discloses and has used the steam treatment mesopore zeolite, handles to improve the butylene selectivity at the catalytic pyrolysis mesolite with acidic solution subsequently.
Name is called paper (the de Lucas etc. of " dealuminzation of HZSM-5 zeolite: steam treatment is to the effect of acid and aromatization activity ", Applied Catalysis A:General 154 1997 221-240, Else vierScience B.V. publishes) disclose acetone in the presence of this dealuminated zeolite/propyl carbinol mixture and be converted into the method for hydrocarbon.
Also know the use crystalline silicate catalyst from for example US-A-4171257 people, for example ZSM-5 makes the petroleum distillate dewaxing to produce light olefin cut, for example C
3-C
4Olefin fraction.Usually, temperature of reactor reaches about 500 ℃, and reactor adopts and helps the low hydrocarbon partial pressure that petroleum distillate is converted into propylene, and dewaxing cracking alkane hydrocarbon chain causes the viscosity of raw material overhead product to reduce, but also produces small amounts of olefins from the cracked paraffinic hydrocarbons.
EP-A-0305720 discloses the method for producing gaseous olefin by the catalyzed conversion of hydrocarbon.EP-B-0347003 discloses the method that hydrocarbon feed is converted into light olefin.WO-A-90/11338 discloses C
2-C
12Paraffin conversion is petroleum chemistry raw material, especially C
2-C
4The method of alkene.US-A-5043522 and EP-A-0395345 disclose the method that is prepared alkene by the paraffinic hydrocarbons with 4 or more carbon atoms.EP-A-0511013 discloses the method for being produced alkene by the catalyzer of the steam activation of adopting phosphorous and H-ZSM-5 by hydrocarbon.US-A-4810356 discloses the method for common dewaxing treatment gas oil in the presence of the silicon zeolite catalyst.GB-A-2156845 discloses by propylene or has contained the method that the hydrocarbon mixture of propylene is produced iso-butylene.GB-A-2159833 discloses the method for producing iso-butylene by catalytic pyrolysis lightweight overhead product.
People are known to the above-mentioned crystalline silicate of enumerating in the prior art, compare with the corresponding long chain paraffinic hydrocarbons, and long-chain olefin trends towards with the faster rate cracking.
People are also known, and this conversion is unsettled in time when crystalline silicate is the catalyzer of alkene as paraffin conversion, and conversion rate descends with the increase of stream time, and this is because formed Jiao's (carbon) who is deposited on the catalyst surface.
These known methods are used for the heavy paraffins molecule is cracked into lighter molecule.Yet when needs were produced propylene, not only productive rate was low, and the stability of crystalline silicate catalyst is also low.For example, in FCC apparatus, productivity of propylene is 3.5wt% usually.By adding known ZSM-5 catalyzer so that " press for extracting juice " goes out more propylene from cleaved feed hydrocarbon raw material in FCC apparatus, the propone output of FCC apparatus can increase to 7-8wt% propylene at the most.Not only the increase of productive rate is quite little, and ZSM-5 catalyzer stability in FCC apparatus is very low.
To the increase in demand of propylene, especially produce polypropylene,
Because acryloyl derivative, especially polyacrylic growth, petrochemical industry face the main task that obtains propylene at present.The traditional method that increases production of propylene is not entirely satisfactory, and for example producing is that the additional naphtha steam cracking device of propylene of twice of ethene is the method for expensive production propylene, because raw material is very expensive, and cost of investment is very high.Petroleum naphtha is as the raw material of steam cracking device, because it is the basis that refinery is produced gasoline.Dehydrogenating propane obtains the propylene of high yield, but raw material (propane) is only cost-saved in recent years, makes the method costliness to limit the production of propylene.Can obtain propylene by FCC apparatus, but productive rate is lower, increases productive rate and be proved to be expensive and limited.Another kind is called the method for metathesis or disproportionation can produce propylene by ethene and butylene, combines with steam cracking device, and this technology is normally expensive, is worth suitable ethene as raw material because its uses with propylene.
It is the method for propylene that EP-A-0109059 discloses the conversion of olefines that will contain 4-12 carbon atom, alkene with have crystallization and zeolite structured (for example ZSM-5 or ZSM-11), and have SiO
2/ Al
2O
3Mol ratio is equal to or less than 300 silico-aluminate contact.Specification sheets require the pure zeolite of every kg greater than the high spatial speed of 50kg/h to obtain high propylene yield, specification sheets illustrates that also common space velocity is high more, SiO
2/ Al
2O
3Mol ratio (being called the Z ratio) is low more.This specification sheets also only exemplifies at short notice the conversion of olefines method of (for example several hrs), unresolvedly guarantees catalyzer stability problem in required long period (for example at least 160 hours or several days) in industrial production.In addition, be undesirable to the requirement of high spatial speed for the industrial implementation of olefin process.
Therefore, people still need the propylene production of high yield, and this method can easily combine with oil refining or petroleum chemistry device, utilize raw material on the market than advantages of being cheap (having some surrogates on the market).
On the other hand, MFI type crystalline silicate also is the known catalysts that is used for olefin oligomerization.For example EP-A-0031675 discloses at catalyzer, and for example ZSM-5 exists the mixture that contains alkene down to be converted into the method for gasoline.To those skilled in the art, the operational condition that is used for oligomerisation reaction obviously is different from the cracked condition that is used for.Usually, in the oligomerisation reaction device, temperature is no more than about 400 ℃, and high pressure helps oligomerisation reaction.
GB-A-2156844 discloses at the isomerization method of silicon zeolite (silicalite) as the alkene of catalyzer.US-A-4579989 discloses that conversion of olefines is the method for the hydrocarbon of higher molecular weight in the presence of the silicon zeolite catalyst.US-A-4746762 discloses in the presence of crystalline silicate catalyst the light olefin upgrading and has produced rich C
5The method of+liquid hydrocarbon.US-A-5004852 discloses that to be used for conversion of olefines be the two-step approach of stop bracket gasoline, and in the first step, olefin oligomerization is C
5+ alkene.US-A-5171331 discloses the method for producing gasoline, and it is included in the siliceous crystalline molecular sieve catalyst of mesopore, and for example oligomerisation contains the C of raw material under the existence of stable silicon zeolite of silicon zeolite, halogen or zeolite
2-C
6Alkene.US-A-4414423 discloses the multistep processes that is prepared high boiling hydrocarbon by normally gaseous hydrocarbon, and first step is included in the siliceous crystalline molecular sieve catalyst of mesopore and has the normally gaseous alkene of input down.US-A-4417088 discloses the dimerization and the process for trimerization of higher olefins in the presence of the silicon zeolite.US-A-4417086 discloses the oligomerization of alkene in the presence of the silicon zeolite.GB-A-2106131 and GB-A-2106132 disclose at catalyzer, and the oligomerization of alkene was to produce high boiling hydrocarbon under for example zeolite or silicon zeolite existed.GB-A-2106533 discloses the oligomerization of gaseous olefin in the presence of zeolite or silicon zeolite.
The purpose of this invention is to provide a kind of method, compare with the method for above-mentioned prior art, this method has used the cheap alkene that exists in refinery and the petroleum chemistry device as raw material, it is catalytically conveted to light olefin, especially propylene.
Another object of the present invention provides the method for preparing propylene with high propylene yield and purity.
Another object of the present invention provides the method that can produce the alkene effluent, and described effluent is at least in the chemical grade mass range.
Another object of the present invention provides the method for producing alkene, and it has stable olefin conversion for a long time and stable product distributes.
Another object of the present invention provides the method that olefin feedstock is converted into propylene, and it has high yield on olefin basis, and does not consider the source and the composition of olefin feedstock.
The invention provides a kind of method of catalytic cracking rich olefins raw material, this method has selectivity for the light olefin in the effluent, this method comprises makes the hydrocarbon feed that contains one or more alkene and silicon/aluminum ratio contact under the olefin partial pressures of 500-600 ℃ temperature in, 0.1-2 crust at least about 300 MFI type crystalline silicate catalyst, and raw material is with 10-30h
-1LHSV produce by catalyzer and have the effluent of comparing the lower olefin component of molecular weight with raw material.
So, the present invention can provide a kind of method, wherein from oil refining, not only optionally be cracked into light olefin with the rich olefins hydrocarbon stream (product) of petroleum chemistry device, and especially being cracked into propylene, the rich olefins raw material can be 300 MFI type crystalline silicate catalyst by having specific Si/Al atomic ratio at least.The preferably commercial obtainable catalyzer of catalyzer, it does not carry out any steam treatment or dealumination process subsequently by using organic formwork agent crystallization preparation.Raw material can 500-600 ℃ temperature range, the olefin partial pressures and the 10-30h of 0.1-2 crust
-1LHSV by catalyzer, obtain propylene based on the 30-50% at least of the olefin(e) centent in the raw material.
In specification sheets, term " silicon/al atomic ratio " is meant the Si/Al atomic ratio of overall material, and it can be measured by chemical analysis.Especially for the crystalline silicate material, described Si/Al ratio not only is used for the Si/Al skeleton of crystalline silicate, but is used for whole material.
Raw material can be undiluted or be used rare gas element, for example charging behind the nitrogen dilution.Under one situation of back, the absolute pressure of raw material constitutes the dividing potential drop of hydrocarbon feed in the rare gas element.
With reference now to describing all respects of the present invention in detail,, wherein as just the accompanying drawing of giving an example :-
Accompanying drawing 1 is presented at the summation of olefin feedstock transformation efficiency, productivity of propylene and other component in the catalytic pyrolysis process of the present invention and the relation between silicon/al atomic ratio.
According to the present invention, the cracking of alkene is that the olefin cracking in hydrocarbon stream is than light olefin and selective Be cracked under the meaning of propylene and carry out. Raw material and effluent preferably have by weight substantially the same Olefin(e) centent. The olefin(e) centent of effluent is generally raw material olefin content ± 15wt%, more preferably ± and 10wt %. Raw material can comprise the hydrocarbon stream that contains alkene of any kind, and raw material can contain 10-100wt% alkene usually Hydrocarbon, in addition, more can be undiluted or dilute rear feeding with diluent, diluent optionally comprises non-alkene The hydrocarbon that belongs to. Contain olefin feedstock and especially can be that to contain carbon number be C4-C
10, more preferably carbon number is C4-C
6Positive structure and the mixture of branched-chain alkene, it is C that mixture optionally contains carbon number4-C
10Positive structure and side chain alkane and/or aromatic hydrocarbons. Contain olefin stream and usually have about 180 ℃ the boiling of pact-15-The point.
In concrete preferred embodiment of the present invention, hydrocarbon feed contains the C from oil plant and steamed cracking unit4Mixture. The various raw materials of this steamed cracking unit cracking, comprise ethane, propane, butane, Naphtha, gas-oil, fuel wet goods. More particularly, hydrocarbon feed can contain from being used for mink cell focus The C that is converted into gasoline and installs than the fluid catalystic cracking in the crude refining of light product (FCC)4Heat up in a steamer Divide. Should be from the C of FCC apparatus4Cut contains the alkene of the 50wt% that has an appointment usually, and in addition, hydrocarbon feed can contain the C that comes in the comfortable crude refining for the preparation of the device of methyl tertiary butyl ether(MTBE) (MTBE)4Cut, institute State MTBE by methyl alcohol and isobutene preparation. Equally should be from the C of MTBE device4Cut contains usually The alkene of about 50wt%. These C4Divide respectively the exit fractionation at FCC or MTBE device. Hydrocarbon feed also can comprise the C from the naphtha steamed cracking unit of petrochemistry device4Cut, its mid-boiling point are about 15-180 ℃ C5-C
9The naphtha of material by steam cracking to produce, C especially4Cut. This C4Cut contains the 1,3-butadiene of 40-50% by weight, about 25% isobutene, pact usually 15% butylene (form of but-1-ene and/or but-2-ene) and about 10% normal butane and/or iso-butane. Contain alkene The hydrocarbon feed of hydrocarbon also can comprise from steamed cracking unit at Butadiene Extraction (raffinate 1) or butadiene C behind the hydrogenation4Cut.
In addition, raw material also can comprise the rich butadiene C of hydrogenation4Cut contains the C greater than 50wt% usually4Alkene. In addition, hydrocarbon feed can be included in the pure olefin feedstock for preparing in the petrochemistry device.
Contain that olefin feedstock also can comprise mild cracking naphtha (LCN) (being called in addition slight catalytically cracked gasoline (LCCS)) or from the C of steam cracker or mild cracking naphtha5Cut, the mild cracking naphtha Effluent fractionation by aforesaid FCC apparatus in crude refining. These two kinds of raw materials contain alkene Hydrocarbon in addition, contains olefin feedstock and can comprise from the moderate cracking naphtha of this FCC apparatus or from being used for The visbreaking stone that the viscosity breaking plant of the residue of vacuum distillation plant obtains in the processing crude refining Cerebrol.
Contain the mixture that olefin feedstock can comprise one or more above-mentioned raw materials.
Use in a preferred method of the invention C5Cut has obvious advantage as containing the alkene hydrocarbon feed, in any case because need to remove by the C in the gasoline of oil refining generation5Material. This is because at vapour There is C in the oil5Ozone lateral reactivity and the photochemical activity of resulting gasoline have been increased. Using slightly In the situation of pressure naphtha as the raw material that contains alkene, the olefin(e) centent of remaining gasoline fraction reduces, from And the photochemical activity of reduction steam pressure and gasoline.
When transforming the mild cracking naphtha, the method according to this invention can be produced C2-C
4Alkene, C4Cut is enrichment alkene very, isobutene especially, and it is the interested raw material of MTBE device. Work as conversion C4During cut, produce on the one hand C2-C
3Alkene produces the C that mainly contains isoalkene on the other hand5-C
6Alkene. Remaining C4Cut is rich in butane, iso-butane especially, it is the alkyl plant raw material interested of PETROLEUM PROCESSING, in alkyl plant by C3And C5The mixture production of raw material is used for the alkane of gasoline The base compound. The C that mainly contains isomeric olefine5-C
6Cut is that the sense of production tert pentyl methyl ether (TAME) is emerging The interest raw material.
The inventor is surprised to find, the method according to this invention, and olefin feedstock is cracking optionally To redistribute the olefin(e) centent of the effluent Raw that generates. Thereby selecting catalyst and process conditions exist The method has specific productive rate for the specific alkene in the raw material on the olefin basis. Usually, selective catalysis Thereby agent and process conditions the method on olefin basis has same high productive rate to propylene, and is former with alkene The source of material is for example from the C of FCC apparatus4Cut, from the C of MTBE device4Cut, mild cracking naphtha or from the C of mild cracking naphtha5Cuts etc. are irrelevant. On the basis of existing technology This is very beyond expectation. Be generally pact based on the olefin(e) centent of raw material based on the productivity of propylene of alkene 30-50%. The weight that productive rate take alkene as basic specific alkene is defined as alkene in the effluent divided by by The initial total olefin content of weighing scale. For example, for the raw material that contains 50wt% alkene, if effluent Containing the 20wt% propylene, is 40% based on the productivity of propylene of alkene. This can with the actual yield phase of product Contrast, the actual yield of product is defined as the product weight of generation divided by the weight of raw material. According to the present invention Preferred aspect, the alkane that comprises in raw material and aromatic hydrocarbons only transform a little.
According to a preferred aspect of the present invention, the crystallization silicic acid that comprises MFI family for the catalyst of olefin cracking Salt, it can be any other silicate in zeolite, silicon zeolite or this family.
Crystalline silicate preferably has hole or passage and the high silicon/al atomic ratio of 10 oxygen ring definition.
Crystalline silicate is based on the XO connected to one another by sharing oxonium ion
4The microporous crystalline inorganic polymer of tetrahedron skeleton, wherein X can be trivalent (for example aluminium, boron ...) or tetravalence (germanium for example, silicon ...).The crystalline structure of crystalline silicate is by the particular order definition of the network of the tetrahedron element that wherein links together.The size of crystalline silicate hole opening is by the number of tetrahedron element or the cationic character decision that forms required Sauerstoffatom and exist in the hole.They have the unique combination of following character: high internal surface area, the uniform hole with one or more discrete size; Ion-exchange capacity; Good thermostability; With the ability that is adsorbed with organic compounds.Because the hole dimension of these crystalline silicates is similar to the interested organic molecule of many reality, the turnover of their control reactants and product obtains specific selectivity in catalyzed reaction.Crystalline silicate with MFI structure has bidirectional crossed pore system, and this system has following bore dia: along the straight hole road of [010]: 0.53-0.56nm with along the sinusoidal duct of [100]: 0.51-0.55nm.
Crystalline silicate catalyst has textural property and chemical property, uses under special reaction condition, thereby catalytic pyrolysis is carried out easily.Different reaction paths can take place on catalyzer.At the about 500-600 of temperature in ℃, more preferably 520-600 ℃, more preferably 540-580 ℃ is the 0.1-2 crust with olefin partial pressures, and under the most preferably from about non-pressurized preferred processing condition, the transfer of olefinic double bonds can easily realize in the raw material, causes double-bond isomerization.In addition, this isomerization trends towards reaching thermodynamic(al)equilibrium.Propylene can be for example catalytic pyrolysis by hexene or heavy olefins raw material directly produce.Olefins by catalytic cracking can be regarded as and comprised through the process of bond rupture generation than short molecule.
It is about 300 that the high silicon/al atomic ratio of catalyzer is preferably greater than, thereby catalyzer has low relatively acidity.The intensity and the density of acid position are directly related on hydrogen transfer reactions and the catalyzer, and this reaction preferably is suppressed avoiding forming coke in olefin process, thereby reduction catalyzer stability in time.This hydrogen transfer reactions trends towards producing saturate, paraffinic hydrocarbons for example, and unsettled diolefine of intermediate and cycloolefin, and aromatic hydrocarbons, they all are unfavorable for being cracked into light olefin.Cycloolefin is the precursor of aromatic hydrocarbons and class coke molecule, and especially at solid acid, promptly acidic solid catalyst exists down.The acidity of catalyzer can contact with ammonia by making catalyzer, and ammonia is adsorbed on the acid position of catalyzer, ammonia desorption at high temperature subsequently, and the amount that is determined at the residual ammonia on the catalyzer by differential thermal weight analysis method is determined.Preferred silicon/aluminum ratio is 300-1000, most preferably 300-500.
One of feature of the present invention is that crystalline silicate catalyst has high silicon/aluminum ratio, and stable conversion of olefines can be finished based on the high productivity of propylene of the 30-50% of alkene, and with the source of olefin feedstock with form irrelevant.This height ratio has reduced the acidity of catalyzer, thereby increases the stability of catalyzer.
Not only needs obtain high productivity of propylene based on alkene according to the present invention, and need to obtain C in effluent
3Highly purified propylene in the material, the alkene of high percentage ratio is cracked into alkene in raw material, rather than is cracked into paraffinic hydrocarbons or aromatic hydroxy compound.Propylene preferably has at least 93% purity, and is preferred, in the raw material at least by weight 85% olefin cracking be alkene or exist as initial alkene.In addition, catalyzer of the present invention preferably also has high stability in cracking process, and promptly catalyzer can be owing to the coke by ashamed deposition or formation on catalyzer reduces activity.The inventor finds that the formation of this coke causes catalyzer obviously to descend with the ability of high productivity of propylene cracking olefin in time.According to the present invention, by the MFI type crystalline silicate catalyst that has at least about silicon/al atomic ratio of 300 is provided, and, in cracking process, can obtain all these required results in conjunction with required processing parameters such as temperature and pressures.
Found that various preferred catalyst of the present invention demonstrates high stability,, can obtain stable productivity of propylene in for example up to 10 days especially at several days.This makes the olefin cracking process to carry out continuously in two parallel " waving " reactors, and when one of them reactor is operated, another reactor then carries out the regeneration of catalyzer.Catalyzer of the present invention is also several times renewable, and catalyzer still is handiness, and this is because it can be used in the different sources and various raw materials with different composition of cracking from oil refining or petroleum chemistry device, no matter is pure or mixture.
In catalytic pyrolysis process, select processing condition highly selective to propylene to be provided, stablize olefin conversion and stable olefin product distribution in effluent for a long time.This purpose is by using low sour density catalyzer (being high Si/Al atomic ratio) and realizing in conjunction with low pressure, high temperature in and short contacting time, all these processing parameters are interrelated, and total accumulative effect (for example higher pressure can be offset or compensation by higher temperature in) is provided.Select processing condition to be unfavorable for forming the hydrogen transfer reactions of paraffinic hydrocarbons, aromatic hydrocarbons and burnt precursor.Therefore process conditions adopts high spatial speed, low pressure and high reaction temperature.LHSV is preferably 10-30h
-1, olefin partial pressures is preferably the 0.1-2 crust, and more preferably 0.5-1.5 clings to, and especially preferred olefin partial pressures is normal pressure (i.e. 1 crust).Hydrocarbon feed is preferably to be enough to the main entrance pressure charging of raw material by reactor.Hydrocarbon feed can be undiluted or at rare gas element, for example dilutes charging in the nitrogen.Total absolute pressure in the reactor is the 0.5-10 crust.The inventor finds to adopt low olefin partial pressures, and for example normal pressure trends towards being reduced in the generation of hydrogen transfer reactions in the cracking process, it thereby reduced the possibility that the coking that trends towards making catalyst stability to descend forms.The cracking of alkene is 500-600 ℃ in the temperature in of raw material preferably, more preferably 520-600 ℃, more preferably 540-580 ℃, usually carries out under about 560 ℃-570 ℃.
Catalytic pyrolysis process can carry out in fixed-bed reactor, moving-burden bed reactor or fluidized-bed reactor.Typical fluidized-bed reactor is the FCC type of reactor of the fluid catalystic cracking that is used to refine oil.Typical moving-burden bed reactor is the reactor of continuous catalytic reforming type, and as mentioned above, this process can be used pair of parallel " to wave " reactor to carry out continuously.
Because catalyzer for a long time, demonstrates high stability to conversion of olefines at least 10 days usually, the frequency of catalyst regeneration is low.More particularly, catalyzer has the life-span above 1 year.
Behind catalytic pyrolysis process, reactor effluent input fractionator is isolated required alkene by effluent.When catalytic pyrolysis process is used to produce propylene, contain the C of at least 93% propylene
3Cut is by fractionation, and purifying to be to remove all contaminants then, and for example S-contained substance, arsine etc. are greater than C
3Heavier alkene capable of circulation.
According to various aspects of the invention, in cracking process, not only can adopt various olefin feedstock, and by selecting suitable process conditions and special catalyst, the may command olefin process distributes optionally to produce specific alkene in the effluent that generates.
For example according to main aspect of the present invention.Rich olefins logistics from oil refining or petroleum chemistry device is cracked into light olefin, especially propylene.The light ends of effluent, i.e. C
2And C
3Cut can contain and surpass 95% alkene.The abundant purifying of this cut quilt is to constitute the chemical grade olefin feedstock.The inventor finds that in the method the productivity of propylene based on alkene is the 30-50% based on the olefin(e) centent of raw material, and described raw material contains one or more C
4Or above alkene.In the method, effluent is compared with raw material has different alkene distributions, but total olefin content is substantially the same.
In another embodiment, method of the present invention is by C
5Olefin feedstock produces C
2-C
3Alkene.Catalyzer is that silicon/aluminum ratio is at least 300 crystalline silicate, and processing condition are that temperature in is 500-600 ℃, and olefin partial pressures is the 0.1-2 crust, and LHSV is 10-30h
-1, produce and contain as C
2-C
3The alkene effluent of at least 40% olefin(e) centent that alkene exists.
Another preferred embodiment of the present invention provides by the lightweight pressure naphtha and produces C
2-C
3The method of alkene.Lightweight pressure naphtha and silicon/aluminum ratio contain as C at least 300 crystalline silicate catalyst contact by the cracking generation
2-C
3The alkene effluent of at least 40% olefin(e) centent that alkene exists.In the method, processing condition comprise that temperature in is 500-600 ℃, and olefin partial pressures is the 0.1-2 crust, and LHSV is 10-30h
-1
All respects of the present invention illustrate with reference to following non-limiting example.
Embodiment 1
In this embodiment, the raw material that contains the 1-hexene is pressed and about 25h with about 580 ℃ temperature in, non-pressurized outlet hydrocarbon
-1LHSV input reactor in the presence of ZSM-5 type catalyzer, this catalyzer can be purchased with trade(brand)name ZEOCAT P2-2 by the CU Chemie Ueticon AG company of Switzerland.Commercially available catalyzer does not carry out any steam treatment or dealumination process subsequently by using organic formwork agent crystallization preparation.Catalyzer has the silicon/al atomic ratio of 50,200,300 and 490 variation.The crystallographic dimension of each catalyzer is the 2-5 micron, and particle size is the 35-45 order.Carry out many tests, for every test, the composition of measuring effluent is to produce the indication for the summation of every kind of alkene, saturates and aromatic hydrocarbons in the different Si/Al atomic ratio numerical value effluents.Result's explanation in accompanying drawing 1 that these tests obtain after producing 5 hours.Accompanying drawing 1 be presented at after the olefins by catalytic cracking process of the present invention the productive rate of propylene, 1-in the effluent the alkene olefin feedstock the percentage ratio transformation efficiency and in effluent the summation of saturates, alkene and aromatic hydrocarbons.Improve the test that the Si/Al atomic ratios are done for 4, with the C of effluent
3The purified propylene that the scale of the propylene in the material shows is 70%, 91%, 93% and 97%.
For the commercial catalysts of silicon/al atomic ratio of about 200-300, the productive rate of alkene and be lower than 85% and 30% desirable value respectively in the effluent based on the productive rate of the propylene of alkene.Purified propylene also is lower than 93% industrial required numerical value.This explanation need rise than to surpassing 300 the Si/Al atom of commercially available catalyzer by aforesaid steam treatment and dealuminzation and aforesaid dealuminzation.In contrast, when adopting this steam treatment and dealumination process, the Si/Al that obtains is than preferably only greater than 180, with obtain in effluent required olefin(e) centent, based on the productivity of propylene and the purified propylene of alkene.Without the Si/Al atomic ratio of steam treatment and the pretreated commercially available catalyzer of dealuminzation greater than about 300 o'clock, be alkene at least about 85% olefin cracking in the raw material or exist as starting olefin.Therefore, greater than 300, raw material and effluent have by weight olefin(e) centent in fact to following degree at the Si/Al atomic ratio, promptly by weight the olefin(e) centent of raw material and effluent separately ± the 15wt% scope in.In addition, be at least about at 300 o'clock at the Si/Al of this commercial untreated catalyzer that obtains atomic ratio, based on the productive rate of the propylene of alkene for by weight at least about 30%.Be about at 490 o'clock at the Si/Al of the untreated catalyzer that is purchased atomic ratio, the olefin(e) centent of effluent is greater than about 90% weight of the olefin(e) centent of raw material, based on the productive rate of the propylene of alkene near 40%.
Embodiment 2
In this embodiment, the various different crystalline silicates that will have a MFI type of Different Silicon/al atomic ratio are used for the catalytic pyrolysis of olefin feedstock.MFI silicate contains ZSM-5 type zeolite, especially commercial with trade(brand)name H-ZSM-5 by the PQ Corporation of Southpoint of company, P.O.Box 840, Valley Forge, the zeolite that PA 19482-0840, USA obtain.The granular size of crystalline silicate is the 35-45 order, without anticipating modification.
Crystalline silicate is packed in the tubular reactor, be heated to about 530 ℃, subsequently with 1g hexene injecting reactor in 60 seconds.Rate of injection WHSV is 20h
-1, agent weight of oil ratio is 3.Cracking process carries out under the outlet hydrocarbon pressure (normal pressure) of 1 crust.
Table 1 shows the productive rate of various components in the effluent of representing with wt% and the amount of the coke that produces on the catalyzer in tubular reactor.
As can be seen,, on catalyzer, form tangible coking degree for crystalline silicate with low Si/Al atomic ratio, this thereby will cause catalyzer less stable in time when being used for the catalytic pyrolysis process of alkene.In contrast, as can be seen for the crystalline silicate catalyst with high silicon/al atomic ratio, this embodiment is about 350, does not form coking on catalyzer, causes the high stability of catalyzer.
As can be seen, for high Si/Al atomic ratio (350) catalyzer, be about 28.8 based on the productivity of propylene of alkene in the effluent, apparently higher than the productivity of propylene of two tests using low Si/Al atomic ratio.Therefore as can be seen, in producing the process of other alkene, use olefins by catalytic cracking catalyzer to increase productivity of propylene based on alkene with high silicon/al atomic ratio.
Also find to increase the formation that the Si/Al atomic ratio has reduced propane.
Comparing embodiment 1 and 2
In these comparing embodiments, what be purchased does not carry out steam treatment and is used to contain the catalytic pyrolysis of the raw material of butylene by the silicon zeolite catalyst that dealumination process is carried out in extracting.
In catalytic pyrolysis process, the raw material that contains butylene has illustrated composition among table 2a and the 2b.
Catalytic pyrolysis process is at 545 ℃ temperature in, non-pressurized outlet hydrocarbon pressure and 30h
-1Carry out under the LHSV.
Table 2a and 2b are presented at the classification detailed catalogue of the propylene, iso-butylene and the n-butene quantity that exist in the effluent.
In comparing embodiment 1, catalyzer contains the silicon zeolite of silicon/aluminum ratio about 120, and crystal size is the 4-6 micron, and surface-area (BET) is 399m
2/ g.The silicon zeolite is pressed, washs and keeps 35-45 purpose part.Catalyzer does not carry out any steam treatment and takes out the aluminium process, in comparing embodiment 2, catalyzer contain with comparing embodiment 1 in identical initial silicon zeolite, it is in the atmosphere of 72vol% steam and 28vol% nitrogen, steam treatment is 48 hours under 550 ℃ and normal pressure, but takes out the aluminium process.The result is shown in respectively among table 2a and the 2b.
As can be seen, catalyzer does not demonstrate stability from comparing embodiment 1 and comparing embodiment 2, and in other words, the ability of catalyst cracking process reduces in time.Can believe that this is because form coke at catalyst surface, this is because catalyzer adopts low silicon/al atomic ratio, causes the high relatively tart result of catalyzer.
For comparing embodiment 1, paraffinic hydrocarbons, for example propane have also obviously been formed.
Embodiment 3
In this embodiment, the raw material that contains described in the table 3 the 1-butylene raw material of forming exports hydrocarbon partial pressure and about 23h at about 560 ℃ feed(raw material)inlet temperature, normal pressure in the presence of the same catalyst described in the embodiment 1
-1Raw material LHSV input reactor.As catalyzer used among the embodiment 1, the silicon/al atomic ratio of this catalyzer is 300.In embodiment 1, catalyzer is commercially available, by using organic formwork agent crystallization preparation, does not carry out any steam treatment or dealumination process subsequently.The crystallographic dimension of every kind of catalyzer and granular size as described in example 1 above, produced 40 hours and produce 112 hours after measure the composition of effluent, the explanation in table 3 of the analytical results of effluent.Table 3 shows the catalyzer with 300 silicon/al atomic ratio, and catalytic pyrolysis process has high stability having optionally for the propylene in the effluent.Therefore, after producing 40 hours, propylene accounts for the 18.32wt% of effluent, and after 112 hours, propylene accounts for the 18.19wt% of effluent, and after 162 hours, propylene accounts for the 17.89wt% of effluent.This is presented at and reached 5 days and not obviously reduction of the propylene content in the effluent in the long duration above 3 days.3 days time is common circulation or the recovery time that is used for fixing two parallel " waving " reactors of a type.The result of comparing embodiment 1 relatively after the result of embodiment 3 after 112 hours and 162 hours can be respectively with 97 hours and 169 hours.For comparing embodiment 1, catalyzer was a quite stable in 97 hours, compare with initial volume, the content of propylene descends about 1.1% in the effluent, but between 97 hours and 169 hours, stability obviously descends, and does not have this situation for embodiment 3 in the corresponding time of 112 hours and 162 hours.
Comparing embodiment 3
In this comparing embodiment, commercially available silicon/al atomic ratio is the catalytic pyrolysis that 25 ZSM-5 catalyzer is used to contain the raw material of butylene.In this catalytic pyrolysis process, the raw material that contains butylene has the composition described in table 4.
Catalytic pyrolysis process is pressed and 50h at 560 ℃ temperature in, normal pressure outlet hydrocarbon
-1The condition of LHSV under carry out.
Selecting catalyst and processing condition, especially high spatial speed are to simulate disclosed corresponding catalyst and condition among the above-mentioned EP-A-0109059.
Catalytic pyrolysis process carried out nearly 40 hours, the composition of results of regular determination effluent after the continuous time of on-stream time (TOS).The composition of effluent after the specific on-stream time, and the explanation in table 4 of corresponding butylene transforming degree.
As can be seen from Table 4, when the ZSM-5 catalyzer with low silicon/al atomic ratio of about 25 is used in combination with high spatial speed, EP-A-0109059 illustrates that this is important for obtaining high productivity of propylene, therefore, although productivity of propylene can be sufficiently high to produce about 16wt% propylene in effluent, this occurs in and goes into operation about 15-20 hour, and after this, productivity of propylene descends rapidly.This explanation is as the low silicon/al atomic ratio of employing in the disclosed method among the EP-A-0109059 and in conjunction with high spatial speed, and catalyst stability is very low.
Table 1
Productive rate/wt%
Propane propylene gas # coke
H-ZSM-5[25] 28 5.8 59.3 4.35
H-ZSM-5[40] 19.8 10 60.4 1.44
H-ZSM-5[350] 1.8 28.8 63.8 0
# gas=H
2, C
2-C
4Alkene and paraffinic hydrocarbons
Table 2a
Comparing embodiment 1 unmodified silicon zeolite (Si/Al=120)
T
Inlet(℃) 549
LHSV(h
-1) 30
TOS(h) 5 97 169
Raw material flows out logistics and goes out the thing effluent
N-butene transformation efficiency (%) 85.20 79.90 55.90
C
1 P1 0.00 0.41 0.21 0.10
C
2 P2 0.00 0.51 0.17 0.00
O2 0.00 8.64 4.97 0.90
C
3 P3 0.30 3.80 1.61 0.40
O3 0.10 20.36 19.25 8.48
C
4 iP4 31.10 31.57 29.92 30.71
nP4 12.80 13.27 13.03 13.06
iO4 3.70 5.14 6.70 13.46
nO4 51.00 7.76 9.96 22.43
C
5 iP5+nP5+cp5 0.00 0.93 1.19 0.50
iO5+nO5+cO5 0.20 4.11 6.69 6.98
C6 C6+ 0.80 3.50 6.30 2.99
Total amount 100.00 100.00 100.00 100.00
Alkene O2-O5 55.00 46.01 47.57 52.24
Paraffinic hydrocarbons P1-P5 44.20 50.49 46.13 44.77
Other and unknown material 0.80 3.50 6.30 2.99
Total 100.00 100.00 100.00 100.00
Table 2b
The silicon zeolite of comparing embodiment 2 steam treatment
T
Inlet(℃) 549
LHSV(h
-1)?29.6
TOS(h) 16 72
Raw material flows out logistics and goes out thing
N-butene transformation efficiency 73.10 70.10
C
1 P1 0.00 0.20 0.10
C
2 P2 0.00 0.10 0.00
O2 0.00 2.73 1.71
C
3 P3 0.10 0.40 0.30
O3 0.30 17.89 14.27
C
4 iP4 33.40 33.87 33.16
nP4 9.70 10.11 10.15
iO4 2.40 10.11 10.75
nO4 53.20 14.47 15.99
C
5 iP5+nP5+cP5 0.50 0.51 0.50
iO5+nO5+cO5 0.10 7.18 8.54
C
6 C6+ 0.30 2.43 4.52
Total amount 100.00 100.00 100.00
Alkene O2-O5 56.00 52.38 51.26
Paraffinic hydrocarbons 43.70 45.19 44.22
Other and unknown material 0.30 2.43 4.52
Total amount 100.00 100.00 100.00
Table 3
Embodiment 3
Silicon zeolite (Si/Al=300)
T
Inlet(℃) 560
LHSV(h
-1) 23
TOS(h) 40 112 162
Raw material flows out logistics and goes out the thing effluent
N-butene transformation efficiency (%) 82.01 79.94 77.54
C
1 P1 0.01 0.31 0.25 0.20
C
2 P2 0.00 0.41 0.33 0.27
O2 0.00 5.51 4.81 4.14
C
3 P3 0.22 2.02 1.54 1.23
O3 0.06 18.32 18.19 17.89
D3 0.01 0.00 0.00 0.00
C
4 iP4 29.40 29.26 28.45 28.15
nP4 15.41 15.76 16.40 16.35
iO4 2.55 6.03 6.80 7.51
nO4 52.15 9.38 10.46 11.72
D4 0.03 0.09 0.09 0.10
C
5 iP5 0.07 0.40 0.34 0.31
nP5 0.00 0.21 0.18 0.15
cP5 0.00 0.41 0.35 0.30
iO5 0.09 3.31 3.65 4.01
nO5 0.00 1.73 1.89 2.06
cO5 0.00 0.20 0.20 0.20
D5 0.00 0.14 0.14 0.13
C
6 iP6 0.00 0.04 0.03 0.02
nP6 0.00 0.06 0.05 0.05
cP6 0.00 0.43 0.34 0.27
iO6 0.00 0.73 0.73 0.72
nO6 0.01 1.50 1.37 1.24
cO6 0.00 0.06 0.06 0.06
D6 0.00 0.00 0.00 0.00
A6 0.00 0.61 0.59 0.57
iP7 0.00 0.07 0.06 0.05
nP7 0.00 0.00 0.00 0.00
cP7 0.00 0.21 0.18 0.14
iO7 0.00 0.17 0.20 0.19
nO7 0.00 0.08 0.08 0.07
cO7 0.00 0.33 0.23 0.19
D7 0.00 0.00 0.00 0.00
A7 0.00 1.06 0.94 0.77
iP8 0.00 0.09 0.09 0.09
nP8 0.00 0.00 0.00 0.00
cP8 0.00 0.03 0.01 0.01
iO8 0.00 0.00 0.00 0.00
nO8 0.00 0.00 0.00 0.00
cO8 0.00 0.00 0.00 0.00
A8 0.00 1.03 0.95 0.83
Total amount 100.00 100.00 100.00 100.00
Paraffinic hydrocarbons (P) 45.10 49.70 48.60 47.59
Alkene (O) 54.86 47.37 48.68 50.00
Diolefine (D) 0.04 0.23 0.23 0.24
Aromatic hydrocarbons (A) 0.00 2.70 2.49 2.17
Total amount 100.00 100.00 100.00 100.00
Table 4
Comparing embodiment 3
ZSM5(Si/Al＝25)
T
Inlet(℃) 560
LHSV(h-1) 50
TOS(h) 0.22 4.35 9.50 14.67 20.80 26.88 32.05 39.98
Raw material flows out logistics and goes out logistics and go out logistics and go out logistics and go out logistics and go out logistics and go out the thing effluent
Butene conversion 93.59 88.88 82.58 76.71 67.29 55.85 43.02 28.04
C
1 P1 0.02 3.69 2.02 0.85 0.34 0.17 0.12 0.09 0.06
C
2 P2 0.00 5.48 2.23 0.94 0.52 0.23 0.12 0.07 0.03
O2 0.00 4.29 6.26 6.92 5.32 3.36 1.88 1.07 0.37
C
3 P3 0.34 28.07 16.97 9.22 3.64 1.65 0.98 0.62 0.55
O3 0.12 6.05 9.36 12.81 15.99 16.04 13.09 10.03 5.48
D3 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
C
4 iP4 32.04 12.31 23.44 26.54 33.90 33.72 33.84 32.22 33.72
nP4 12.65 6.25 10.52 13.69 13.58 13.89 13.82 13.99 13.51
iO4 2.22 1.37 2.39 3.74 4.99 6.17 8.35 10.60 12.31
nO4 52.16 2.11 3.66 5.74 7.67 11.62 15.65 20.39 26.82
D4 0.05 0.03 0.06 0.09 0.11 0.10 0.04 0.05 0.06
C
5 iP5 0.25 0.87 1.10 1.11 0.59 0.44 0.34 0.34 0.23
nP5 0.00 0.39 0.56 0.54 0.31 0.18 0.10 0.06 0.02
cP5 0.00 0.12 0.24 0.39 0.31 0.19 0.10 0.05 0.01
iO5 0.12 0.62 1.17 2.08 2.89 4.19 4.87 4.81 3.29
nO5 0.01 0.32 0.61 1.09 1.50 2.17 2.53 2.51 1.73
cO5 0.00 0.05 0.07 0.11 0.13 0.15 0.12 0.09 0.05
D5 0.00 0.04 0.05 0.07 0.08 0.10 0.11 0.13 0.13
C
6 iP6 0.00 0.09 0.15 0.14 0.06 0.02 0.01 0.00 0.00
nP6 0.00 0.04 0.07 0.09 0.04 0.06 0.04 0.02 0.01
cP6 0.00 0.11 0.24 0.46 0.35 0.15 0.06 0.03 0.01
iO6 0.00 0.13 0.26 0.53 0.78 0.87 0.62 0.42 0.19
nO6 0.01 5.05 3.93 3.06 1.98 1.44 1.12 0.93 0.66
cO6 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.05 0.03
D6 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
A6 0.00 4.37 2.31 1.28 0.59 0.46 0.41 0.35 0.20
C
7 iP7 0.00 0.03 0.06 0.08 0.08 0.07 0.06 0.04 0.02
nP7 0.00 0.01 0.01 0.01 0.01 0.01 0.00 0.00 0.00
cP7 0.00 0.03 0.09 0.19 0.18 0.11 0.06 0.03 0.01
iO7 0.00 0.01 0.05 0.14 0.22 0.30 0.30 0.26 0.14
nO7 0.00 0.01 0.02 0.06 0.08 0.11 0.11 0.10 0.06
cO7 0.00 0.03 0.10 0.21 0.30 0.33 0.25 0.17 0.09
D7 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
A7 0.00 11.10 6.83 4.15 1.72 0.79 0.38 0.21 0.06
C
8 iP8 0.00 0.01 0.01 0.03 0.05 0.07 0.07 0.08 0.04
nP8 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
cP8 0.00 0.00 0.01 0.02 0.02 0.02 0.02 0.02 0.02
iO8 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
nO8 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
cO8 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
A8 0.00 6.88 5.12 3.58 1.63 0.77 0.38 0.21 0.07
Total amount 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00
Paraffinic hydrocarbons 45.29 57.53 57.72 54.31 53.99 50.97 49.72 47.65 48.25
Alkene 54.64 20.05 27.90 36.52 41.88 46.81 48.95 51.41 51.23
Diolefine 0.07 0.07 0.11 0.16 0.19 0.20 0.15 0.17 0.19
Aromatic hydrocarbons 0.00 22.35 14.26 9.01 3.94 2.02 1.17 0.76 0.33
Total amount 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00
Paraffinic hydrocarbons=P
Alkene=O
Diolefine=D
Aromatic hydrocarbons=A
Claims (23)
1, a kind of have the optionally method of catalytic pyrolysis rich olefins hydrocarbon feed for the light olefin in the effluent, and this method comprises that the MFI type crystalline silicate catalyst that makes the hydrocarbon feed that contains one or more alkene and silicon/al atomic ratio 300-1000 is 500-600 ℃ temperature in, 10
4-2 * 10
5Contact under the olefin partial pressures of handkerchief (0.1-2 crust), raw material is with 10-30h
-1LHSV by catalyzer, produce and have the alkene composition effluent lower than the olefin hydrocarbon molecules amount in the raw material.
2, the process of claim 1 wherein that catalyzer by using organic formwork agent crystallization preparation, does not carry out any steam treatment or dealumination process subsequently.
3, the method for claim 2, wherein catalyzer comprises ZSM-5 type catalyzer.
4, the method for any one in the claim 1～3, wherein raw material contains C
4-C
10Hydrocarbon.
5, the method for any one in the claim 1～3, wherein this method has selectivity to propylene in the effluent, thus effluent is rich in propylene.
6, the method for claim 4, wherein this method has selectivity to propylene in the effluent, thus effluent is rich in propylene.
7, the method for claim 5, wherein propylene accounts for the C that exists in the effluent
3At least 93% of compound.
8, the method for claim 6, wherein propylene accounts for the C that exists in the effluent
3At least 93% of compound.
9, the method for claim 5, wherein the productivity of propylene based on alkene that obtains of catalytic pyrolysis is 30-50%.
10, the method for any one in the claim 6～8, wherein the productivity of propylene based on alkene that obtains of catalytic pyrolysis is 30-50%.
11, the method for any one in the claim 1～3, described catalytic cracking method make the olefin cracking in the raw material form more light-weight alkene, wherein by weight, the olefin(e) centent in raw material and the effluent each other ± 15% in.
12, the method for claim 4, described catalytic cracking method make the olefin cracking in the raw material form more light-weight alkene, wherein by weight, the olefin(e) centent in raw material and the effluent each other ± 15% in.
13, the method for claim 5, described catalytic cracking method make the olefin cracking in the raw material form more light-weight alkene, wherein by weight, the olefin(e) centent in raw material and the effluent each other ± 15% in.
14, the method for any one in the claim 6～9, described catalytic cracking method make the olefin cracking in the raw material form more light-weight alkene, wherein by weight, the olefin(e) centent in raw material and the effluent each other ± 15% in.
15, the method for claim 10, described catalytic cracking method make the olefin cracking in the raw material form more light-weight alkene, wherein by weight, raw material and effluent olefin(e) centent be each other ± 15% in.
16, the method for any one in the claim 1～3, wherein temperature in is 540-580 ℃.
17, the method for claim 4, wherein temperature in is 540-580 ℃.
18, the method for claim 5, wherein temperature in is 540-580 ℃.
19, the method for any one in the claim 6～9, wherein temperature in is 540-580 ℃.
20, the method for claim 10, wherein temperature in is 540-580 ℃.
21, the method for claim 11, wherein temperature in is 540-580 ℃.
22, claim 12 or 13 method, wherein temperature in is 540-580 ℃.
23, the method for claim 14, wherein temperature in is 540-580 ℃.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP97121376.4 | 1997-12-05 | ||
| EP97121376A EP0921176A1 (en) | 1997-12-05 | 1997-12-05 | Production of olefins |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1284110A CN1284110A (en) | 2001-02-14 |
| CN1170913C true CN1170913C (en) | 2004-10-13 |
Family
ID=8227743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB988134624A Expired - Fee Related CN1170913C (en) | 1997-12-05 | 1998-12-07 | Prodn of olefins |
Country Status (11)
| Country | Link |
|---|---|
| EP (2) | EP0921176A1 (en) |
| JP (1) | JP4048458B2 (en) |
| KR (1) | KR20010032810A (en) |
| CN (1) | CN1170913C (en) |
| AT (1) | ATE244288T1 (en) |
| AU (1) | AU1430299A (en) |
| DE (1) | DE69816114T2 (en) |
| ES (1) | ES2202911T3 (en) |
| TW (1) | TW491889B (en) |
| WO (1) | WO1999029802A1 (en) |
| ZA (1) | ZA9811082B (en) |
Families Citing this family (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0921180A1 (en) * | 1997-12-05 | 1999-06-09 | Fina Research S.A. | Production of olefins |
| EP1061116A1 (en) * | 1999-06-16 | 2000-12-20 | Fina Research S.A. | Production of olefins |
| EP1063274A1 (en) * | 1999-06-17 | 2000-12-27 | Fina Research S.A. | Production of olefins |
| EP1365004A1 (en) * | 2002-05-23 | 2003-11-26 | ATOFINA Research | Production of olefins |
| EP1396481A1 (en) * | 2002-08-14 | 2004-03-10 | ATOFINA Research | Production of olefins |
| GB0414442D0 (en) * | 2004-06-28 | 2004-07-28 | Borealis As | Zeolite catalysts |
| JP4774812B2 (en) * | 2005-06-03 | 2011-09-14 | 三菱化学株式会社 | Propylene production method |
| EP2039427A1 (en) * | 2007-09-12 | 2009-03-25 | Total Petrochemicals Research Feluy | Cracking of olefins on phosphorus modified molecular sieves |
| EP2175991A1 (en) * | 2007-07-31 | 2010-04-21 | Total Petrochemicals Research Feluy | Cracking of olefins on phosphorus modified molecular sieves. |
| WO2009016155A2 (en) | 2007-07-31 | 2009-02-05 | Total Petrochemicals Research Feluy | Use of phosphorus modified molecular sieves in conversion of organics to olefins |
| EP2082802A1 (en) | 2008-01-25 | 2009-07-29 | Total Petrochemicals Research Feluy | Process for obtaining a catalyst composite |
| EP2082803A1 (en) | 2008-01-25 | 2009-07-29 | Total Petrochemicals Research Feluy | Process for obtaining catalyst composites comprising MeAPO and their use in conversion of organics to olefins |
| EP2082801A1 (en) | 2008-01-25 | 2009-07-29 | Total Petrochemicals Research Feluy | Process for obtaining modified molecular sieves |
| EP2108637A1 (en) | 2008-04-11 | 2009-10-14 | Total Petrochemicals Research Feluy | Process to make olefins from ethanol. |
| EP2108635A1 (en) | 2008-04-11 | 2009-10-14 | Total Petrochemicals Research Feluy | Process to make olefins from ethanol |
| EP2143700A1 (en) | 2008-06-25 | 2010-01-13 | Total Petrochemicals Research Feluy | Process to make olefins from oxygenates |
| US8137631B2 (en) | 2008-12-11 | 2012-03-20 | Uop Llc | Unit, system and process for catalytic cracking |
| US8246914B2 (en) | 2008-12-22 | 2012-08-21 | Uop Llc | Fluid catalytic cracking system |
| US8889076B2 (en) | 2008-12-29 | 2014-11-18 | Uop Llc | Fluid catalytic cracking system and process |
| EP2336272A1 (en) | 2009-12-15 | 2011-06-22 | Total Petrochemicals Research Feluy | Debottlenecking of a steam cracker unit to enhance propylene production. |
| BR112013002360A2 (en) | 2010-08-03 | 2016-05-24 | Total Res & Technology Feluy | combined process to make cellefins from an isobutanol |
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| EA028645B1 (en) | 2011-08-03 | 2017-12-29 | Тотал Ресерч & Технолоджи Фелай | Method for making a catalyst comprising a phosphorus modified zeolite and use of said zeolite |
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| CN111116289B (en) * | 2018-10-30 | 2022-12-09 | 中国石油化工股份有限公司 | Energy expanding method for olefin catalytic cracking device |
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| US12071389B2 (en) | 2022-09-29 | 2024-08-27 | Totalenergies Onetech | Gas to olefins processes with coproduction of hydrogen |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0109059B1 (en) * | 1982-11-10 | 1987-07-15 | MONTEDIPE S.p.A. | Process for converting olefins having 4 to 12 carbon atoms into propylene |
| CA1209121A (en) * | 1983-07-12 | 1986-08-05 | Guenter H. Kuehl | Preparation of zeolite zsm-12 |
| US5171921A (en) * | 1991-04-26 | 1992-12-15 | Arco Chemical Technology, L.P. | Production of olefins |
-
1997
- 1997-12-05 EP EP97121376A patent/EP0921176A1/en not_active Withdrawn
-
1998
- 1998-12-03 ZA ZA9811082A patent/ZA9811082B/en unknown
- 1998-12-04 TW TW087120161A patent/TW491889B/en not_active IP Right Cessation
- 1998-12-07 WO PCT/BE1998/000187 patent/WO1999029802A1/en not_active Application Discontinuation
- 1998-12-07 ES ES98958122T patent/ES2202911T3/en not_active Expired - Lifetime
- 1998-12-07 KR KR1020007006128A patent/KR20010032810A/en active Search and Examination
- 1998-12-07 JP JP36197398A patent/JP4048458B2/en not_active Expired - Fee Related
- 1998-12-07 AU AU14302/99A patent/AU1430299A/en not_active Abandoned
- 1998-12-07 DE DE69816114T patent/DE69816114T2/en not_active Expired - Lifetime
- 1998-12-07 EP EP98958122A patent/EP1036133B1/en not_active Expired - Lifetime
- 1998-12-07 AT AT98958122T patent/ATE244288T1/en active
- 1998-12-07 CN CNB988134624A patent/CN1170913C/en not_active Expired - Fee Related
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| DE69816114T2 (en) | 2004-07-15 |
| WO1999029802A1 (en) | 1999-06-17 |
| DE69816114D1 (en) | 2003-08-07 |
| EP1036133A1 (en) | 2000-09-20 |
| EP1036133B1 (en) | 2003-07-02 |
| AU1430299A (en) | 1999-06-28 |
| ZA9811082B (en) | 1999-06-07 |
| JP4048458B2 (en) | 2008-02-20 |
| EP0921176A1 (en) | 1999-06-09 |
| ES2202911T3 (en) | 2004-04-01 |
| JPH11246869A (en) | 1999-09-14 |
| TW491889B (en) | 2002-06-21 |
| ATE244288T1 (en) | 2003-07-15 |
| CN1284110A (en) | 2001-02-14 |
| KR20010032810A (en) | 2001-04-25 |
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