CN101454260A

CN101454260A - Method for commercially obtaining propene

Info

Publication number: CN101454260A
Application number: CNA2007800197253A
Authority: CN
Inventors: M·舒伯特; U·米勒; C·齐奈尔; F·泰驰; S·克罗内; F·西蒙; J·帕斯特尔
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2006-03-29
Filing date: 2007-03-22
Publication date: 2009-06-10
Also published as: KR20080114821A; EP2001825A1; BRPI0710208A2; WO2007113118A1; RU2008142555A

Abstract

The invention relates to a method for commercially obtaining propene from a gas flow containing propene and at least one additional hydrocarbon. Said method comprises the following steps; (a) the gas flow is brought into contact with an adsorber containing a porous metalorganic framework material containing at least one at least bidentate organic compound which is co-ordinately bound to at least one metal ion, said adsorber being charged with propene; and (b) the propene is released from the adsorber charged with the propene. The invention further relates to the use of a porous metalorganic framework material for commercially obtaining propene from a gas flow containing propene and at least one additional hydrocarbon.

Description

Obtain the commercial run of propylene

The present invention relates to a kind of from the air-flow that contains propylene and at least a other hydrocarbon the commercial run of separation of propylene and the purposes that porous metal organic frameworks is used for separation of propylene.

Propylene is a kind of important product, for example as producing polyacrylic raw material.

Propylene is similar to its homology alkene, only is present on a small quantity in Sweet natural gas or the crude oil.So the method for direct production propylene does not have economic implications by separating from natural origin.

But, many commercial runs are arranged, wherein particularly form the mixture of propane and propylene earlier, for example by dehydrogenating propane, fluidized catalytic cracking or steam cracking, MTO (methyl alcohol is to alkene) etc.So, in all methods, must from the hydrocarbon product mixture, isolate propylene.This also is applicable to by olefin metathesis reactions produces propylene.Before this separation many purification step must be arranged.

A kind of possible separation method is distillation, but since particularly the boiling point of propane and propylene similar (according to , under 1 crust, be 5.7K; Under 5 crust is 6.1K), and need highly purified propylene, so need a large amount of theoretical trays, therefore be complicated and expensive.

It is a kind of that to be better than the method that distillatory is used for separation of propylene be absorption.

Being used for technical scale is zeolite from the conventional sorbent material of the gaseous mixture separation of propylene that contains propylene and other hydrocarbon (particularly propane).

These methods based on zeolite are described in F.A.Da Silva etc., Int.Eng.Chem.Res.40 (2001), 5758-5774; F.A.Da Silva etc., AlChe Journal 47 (2001), 341-357 and C.A.Grande etc., Int.Eng.Chem.Res.44 (2005) is among the 8815-8829.

Although existing sorbent systems still needs to provide a kind of improving one's methods of novel sorbents of using in the prior art.Particularly, required high temperature has problems in the absorption of the transformation on zeolite.Exist diffusion problem, zeolite to have lower specific surface area when in addition, having known the use zeolite.In addition, use these sorbent materials can only to reach " polymkeric substance rank " purity and (will wish higher productivity (mol (H*m with very high cost ³)).In addition, wish under low pressure to adsorb, expensive compression is carried out in the materials flow that contains propylene because can save in this case.For example, dehydrogenating propane carries out in the low pressure range of 0.1-5 crust.

Therefore, the purpose of this invention is to provide the novel sorbents of improving one's methods that can be used for the industrial separation propylene.

This purpose by a kind of from the air-flow that contains propylene and at least a other hydrocarbon the commercial run of separation of propylene realize that this method may further comprise the steps:

(a) described air-flow is contacted with the sorbent material that contains porous metal organic frameworks, obtain the sorbent material of load propylene, wherein said porous metal organic frameworks comprises at least a organic compound of bidentate at least with at least a metallic ion coordination,

(b) sorbent material from the load propylene discharges propylene.

Have been found that and use porous metal organic frameworks to make it possible to industrial separation propylene especially effectively.

The ratio of propylene in air-flow can have various values, and this major part depends on the source of air-flow.But based on the parts by volume total amount meter of propylene and one or more other hydrocarbon, the ratio of contained propylene is a particularly important in air-flow, and especially when having propane, this is the subject matter that is separated into because of hydrocarbon, particularly propane and propylene.Other composition of air-flow can use the sorbent material of choosing other wantonly to replace porous metal organic frameworks to separate in the former when appropriate step.In addition, other method, for example distillation also can be used for this purpose.

Except propylene, described air-flow contains at least a other hydrocarbon.Usually comprise multiple other hydrocarbon in addition.According to the source of air-flow, at least a other hydrocarbon except that propylene can have different character.Equally, the content of described other hydrocarbon depends on the source of air-flow usually.

Particularly, described at least a hydrocarbon is a propane.

Other hydrocarbon is C particularly ₁-C ₄Alkane, for example methane, ethane, propane, normal butane, uncle's butane; C ₂-C ₄Alkene, for example ethene, 1-butylene, 2-butylene; C ₂-C ₄Alkynes, for example acetylene, propine, ethyl acetylene, 2-butyne; And propadiene compounds.In addition, higher hydrocarbon also may reside in the gaseous mixture.

Preferably, described air-flow contains the propylene of 5-95 volume %, based on the volume ratio summation meter of the propylene in air-flow and one or more other hydrocarbon.

The ratio of propylene is more preferably 10-95 volume %, further more preferably 30-95 volume %, more preferably 50-95 volume % again, more preferably 70-95 volume %, particularly 90-95 volume % again.In addition, preferably the propylene absolute content in air-flow also meets these values.

In preferred embodiments, air-flow is the product materials flow from the optional purification of production of propylene technology.

These product materials flows contain propylene and other homology alkane, particularly propane usually, and alkene and other gaseous state composition, but they can be removed by simple purification step.An example from production of propylene technology and this product materials flow composition that can remove by purification is a vaporous water, and it can be removed by the conventional drying agent or by compression condensation and cooling suitably.Another example is a carbonic acid gas, and it can be removed by simple gas sweetening.Other example is acetylene and propadiene compounds, and they can pass through selective hydration in advance.

From the product materials flow of the optional purification of production of propylene technology can be from cracking technology (steam cracking or catalytic pyrolysis), from dehydrogenating propane, from based on the petroleum chemicals production technique of methyl alcohol (MeOH)/dme or the materials flow of conversion of olefines (transposition or olefin cracking).

These methods are well known in the prior art.The raw material that is used for cracking technology is petroleum naphtha or LPG (liquefied petroleum gas (LPG)).LPG mainly contains propane and butane.

Other raw material can be LNG (natural gas liquids), and it is made up of ethane, LPG and light naphtha basically.

At last, petroleum naphtha itself also is the raw material that can be used to produce propylene.The petroleum naphtha of about 15 weight % is converted to propylene.

Petroleum naphtha is the raw material that is used for steam cracking.Required target product in naphtha cracking generally is an acetylene.In addition, also form relatively large C ₃Hydrocarbon.The variation of the temperature and the residence time (" cracking severity ") makes can regulate production spectra, promptly at C ₂Alkene, C ₃Alkene, C ₄The distribution of alkene aspect.Typical temperature is 800-1000 ℃.Water vapor dilution (so being " steam cracking ") can reach favourable heat distribution in pipe, and because dividing potential drop reduces, can promote the formation of split product.Be used for C ₃The typical case of isolating product materials flow forms the propane of propylene, the 3-7% that will be for example 90-96%, maximum 3% propadiene and propine and possible a spot of other higher hydrocarbon and lower hydrocarbon, for example methane, ethane, ethene, cyclopropane, butane, butylene, C in each case ₅Hydrocarbon and C ₆Hydrocarbon.

Second the largest source of propylene is catalytic pyrolysis, wherein uses fluidized catalytic cracking (FCC) at present usually, and be used to produce fuel by alkylation or condensation reaction in conventional refining.Fluidized catalytic cracking uses sand-like thin catalyzer to carry out (for example pure aluminium silicate), and it has big surface-area.Cracking forms 500-600 ℃ the temperature of being reflected at of alkene and carries out, and the residence time is the several seconds.In the cracking technology process, the catalyzer carbonization that becomes.For regenerated catalyst, catalyzer is discharged from the real reaction device continuously, and regenerate by burn off outside.The energy that discharges between burn period turns back in the technology.

Instead the another kind of cracking technology is selected, and olefin metathesis reactions also can be used to produce propylene.Here, ethene and 2-butylene can react the formation propylene.

At last, the conversion of methyl alcohol or dme also is a kind of method that is used to produce propylene to a certain extent.These reactions are also referred to as " methyl alcohol is to the reaction of alkene ".The purpose of these reactions on zeolite (ZSM-5 or SAPO) is C of preparation propylene/ethylene and trace ₅ ⁺Hydrocarbon, or preparation propylene/gasoline.In both cases, propylene must be from particularly separating more or less a large amount of LPG.

The particularly preferred embodiment that is used to produce the production of propylene technology of optional product materials flow of purifying is the dehydrogenation of propane.

So in a preferred embodiment of the invention, optional product materials flow of purifying is from the cracking technology that is used to produce propylene, dehydrogenating propane, olefin metathesis or methanol conversion, particularly from dehydrogenating propane.

Also can use the suitable mixture of these different product materials flows.

Preferred dehydrogenating propane method may further comprise the steps:

A) provide a kind of feed stream a that comprises propane;

B) will comprise that the feed stream a of propane, optional water vapour and optional oxygen flow send into the dehydrogenation zone and make dehydrogenating propane is propylene, obtains to comprise the product gas flow b of propane, propylene, methane, ethane, ethene, hydrogen, possible carbon monoxide, carbonic acid gas, water vapour and oxygen;

C) product gas flow b cools off, and randomly compresses, and removes water vapour by condensation, obtains the product gas flow c of depleted water steam.

First step A in this method) in, provides the feed stream that comprises propane a.This air-flow comprises the propane of at least 80 volume % usually, the propane of preferred 90 volume %.In addition, the feed stream a that contains propane generally also comprises butane (normal butane, Trimethylmethane).The essentially consist that contains the feed stream of propane is described among DE-A 102 46 119 and the DE-A102 45 585.Usually, the feed stream a that contains propane is obtained by liquefied petroleum gas (LPG) (LPG).

At processing step B) in, the gas feed air-flow that comprises propane is admitted in the dehydrogenation zone and carries out conventional catalytic dehydrogenation.In this processing step, propane in dehydrogenation reactor in the top dehydrogenation of dehydrogenation activity catalyzer so that propylene to be provided.In addition, obtain hydrogen and a spot of methane, ethane, ethene and C ₄ ⁺Hydrocarbon (normal butane, Trimethylmethane, butylene, divinyl).In the gaseous product mixture of propane catalytic dehydrogenation, generally also there are oxycarbide (CO, CO ₂), CO especially ₂, water vapour and possible small amounts of inert gas.Product gas flow from dehydrogenation comprises water vapour usually, these water vapour be originally be added into the dehydrogenation gaseous mixture and/or under the situation of dehydrogenation in the presence of the oxygen (oxidation or non-oxidizing), in certain embodiments, form.When dehydrogenation is carried out in the presence of oxygen, rare gas element (nitrogen) is introduced dehydrogenation zone sending under the oxygen flow, precondition is not send into pure oxygen.Sending under the situation of oxygen-containing gas, its oxygen level is generally at least 40 volume %, preferably at least 80 volume %, more preferably at least 90 volume %.Particularly send into oxygen level〉99% industrial pure oxygen, too high to prevent the rare gas element ratio in the product gas mixture.In addition, only there is unreacted propane in the product gas mixture.

Dehydrogenating propane can carry out in the known all types of reactors of prior art in principle.The summary that is fit to type of reactor of the present invention is found in " Catalytica

Studies Division, Oxidative Dehydrogenation and Alternative Dehydrogenation Process (catalyticing research branch, oxydehydrogenation and other dehydrogenating technology) " (research numbering 4192 OD 1993; 430ferguson Drive; Mountain View; California, 94043-5272, USA).

Dehydrogenation can be carried out with oxidation or non-oxidizable dehydrogenation mode.Dehydrogenation can isothermal or adiabatic carrying out.Dehydrogenation can also be carried out with catalytic way in fixed bed, moving-bed or fluidized-bed reactor.

The oxidation catalysis dehydrogenating propane is preferably to carry out from hot mode.For this reason, in at least one reaction zone, oxygen is mixed with the reaction gas mixtures of dehydrogenating propane in addition, and contained hydrogen and/or hydrocarbon burns at least in part in this reaction mixture, and this causes directly producing the needed part at least of hydrogenation heat at least one reaction zone inner reaction gas mixture.

Compare with the oxidation operation pattern, characteristics of non-oxide operator scheme are intermediate formation hydrogen at least, and this shows in the product gas from dehydrogenation and has hydrogen.In oxydehydrogenation, do not find free hydrogen in the product gas of dehydrogenation.

Suitable type of reactor is fixed-bed tube reactor or shell and tube-type reactor.In these reactors, catalyzer (if dehydrogenation catalyst and suitable special oxide catalyst) as fixed beds in the tube bank of reaction tubes or reaction tubes.Conventional tube inner diameter is about 10-15cm.Typical shell-and-tube dehydrogenation reactor comprises about 300-1000 reaction tubes.The internal temperature of reaction tubes is generally in 300-1200 ℃, preferred 500-1000 ℃.For the propane or butane dehydrogenation of Phillips Petroleum Co. company, operating pressure is generally the 0.5-8 crust, usually being the 1-2 crust when using low steam to dilute, is 3-8 crust (corresponding with steam activation reforming method (STAR method) or Linde method) when using high steam to dilute perhaps.Typical catalyzer air speed (GHSV) is the 500-2000h based on used hydrocarbon meter ^-1The geometrical shape of catalyzer can be for example spherical or cylindrical (hollow or solid).

The catalytic dehydrogenation of propane can also be carried out in the presence of heterogeneous catalyst in fluidized-bed according to the Snamprogetti/Yarsintez-FBD method.Advantageously, two fluidized-bed parallel runnings, one of them is in reproduced state usually.

Operating pressure is generally the 1-2 crust, and desorption temperature is generally 550-600 ℃.The heat that dehydrogenation needs can be introduced in the reaction system by dehydrogenation catalyst is preheating to temperature of reaction.Sneak into the oxygen containing auxiliary charging of bag and can partly save preheater, and by hydrogen and/or hydrocarbon in the presence of oxygen burning and directly produce needed heat in the reaction gas internal system.If suitable, can also sneak into the auxiliary charging that comprises hydrogen in addition.

The catalytic dehydrogenation of propane can be carried out in the tower tray reactor.When dehydrogenation is autothermally carried out by supplying with oxygen flow, preferably in the tower tray reactor, carry out.This reactor comprises one or more successive catalyst beds.The quantity of catalyst bed can be 1-20, advantageously is 1-6, preferred 1-4, and especially 1-3.Reactant gases preferably radially or axially flows through catalyst bed.Usually, this type of tower tray reactor uses the stationary catalyst bed operation.Under the simplest situation, stationary catalyst bed axially is distributed in the shaft furnace reactor or is distributed in the circular clearance of concentric cylindrical grid.The shaft furnace reactor is equivalent to a tower tray.In single shaft furnace reactor, carry out dehydrogenation and be equivalent to a kind of embodiment.In another kind of preferred implementation, dehydrogenation reaction is carried out in having the tower tray reactor of 3 catalyst beds.

Usually, select to add the amount of the oxygen-containing gas in the reaction gas mixture, if make the needed heat of dehydrogenating propane by the hydrogen that exists in the reaction gas mixtures and suitable be present in the hydrocarbon in the reaction gas mixtures and/or burn with the carbon that the carbon deposits form exists produce.Usually, based on the total amount of propane, the oxygen total amount that provides is 0.001-0.8mol/mol, preferred 0.001-0.6mol/mol, more preferably 0.02-0.5mol/mol.Oxygen can provide with the form of pure oxygen or the form that comprises the oxygen-containing gas of rare gas element.But, the propane and the high loss of propylene of (stating as follows) in handle, importantly the oxygen level of used oxygen-containing gas is high and be at least 40 volume %, preferably at least 80 volume %, more preferably at least 90 volume %.Particularly preferred oxygen-containing gas is that oxygen level is the industrial pure oxygen of about 99 volume %.

If incendiary hydrogen is the hydrogen that produces in the propane catalytic dehydrogenation and suitablely adds hydrogen in the reaction gas mixtures as hydrogen-containing gas in addition in order to produce heat.The amount of hydrogen should preferably make after sending into oxygen, the H in the reaction gas mixtures ₂/ O ₂Mol ratio is 1-10mol/mol immediately, preferred 2-5mol/mol.In staged reactor, if this requirement is adapted to each middle supply of oxygen-containing gas and suitable hydrogen-containing gas.

Hydrogen carries out catalyticcombustion.Used dehydrogenation catalyst usually can also catalytic hydrocarbon burning and the burning of hydrogen and oxygen, therefore, do not need other special oxide catalyst in principle.In one embodiment, use the hydrogen catalyzed and oxygen incendiary oxide catalyst in the presence of hydrocarbon of one or more energy selectivity.Therefore the burning of these hydrocarbon and oxygen generates CO, CO ₂Only proceed to minimum degree with the operation of water.Dehydrogenation catalyst preferably is present in the different reaction zones with oxide catalyst.

Under the situation of reaction of high order pattern, oxide catalyst can only exist only in a reaction zone, a plurality of reaction zone or all reaction zones.

Preferably the catalyzer with the hydrogen catalyzed oxidation of energy selectivity is placed on oxygen partial pressure than the high position of other point in the reactor, particularly supplies with the place of position near oxygen-containing gas.Oxygen-containing gas and/or hydrogen-containing gas can be sent into from one or more positions of reactor.

In a kind of embodiment of the inventive method, the upstream of each tower tray of tower tray reactor carry out oxygen-containing gas and hydrogen-containing gas in the middle of supply with.In the another kind of embodiment of the inventive method, oxygen-containing gas and hydrogen-containing gas are sent in the upstream of each tower tray except that first tower tray.In one embodiment, having the special layer of oxidation catalyst of one deck in the downstream of each feed point, then is dehydrogenation catalyst layer.In another embodiment, there is not special oxide catalyst.Desorption temperature is generally 400-1100 ℃, and the pressure of last catalyst bed of tower tray reactor is generally the 0.2-15 crust, preferred 1-10 crust, more preferably 1-5 crust.Air speed (GHSV) is generally 500-2000h ^-1, and under heavy-duty service, even up to 100000h ^-1, preferred 4000-16000h ^-1

Can comprise oxide compound and/or phosphoric acid salt by the hydrogen catalyzed incendiary preferred catalyst of selectivity, be selected from the oxide compound and/or the phosphoric acid salt of germanium, tin, lead, arsenic, antimony and bismuth.Other preferred catalyst of the hydrogen catalyzed incendiary of energy comprises the precious metal of periodic table of elements transition group VIII family and/or I family.

Used dehydrogenation catalyst comprises carrier and active composition usually.Carrier comprises heat-resistant oxide or mixed oxide usually.Dehydrogenation catalyst preferably comprises and is selected from following metal oxide as carrier: zirconium dioxide, zinc oxide, aluminum oxide, silicon-dioxide, titanium dioxide, magnesium oxide, lanthanum trioxide, cerium oxide and their mixture.Described mixture can be a physical mixture, can be the chemical mixing phase also, as mixed oxide, and for example oxidation magnalium or zinc oxide aluminum.Preferred carrier is zirconium dioxide and/or silicon-dioxide, the mixture of preferred especially zirconium dioxide and silicon-dioxide.

Appropriate catalyst formed body geometrical shape is extrudate, star, annular, saddle, sphere, foams and the material all in one piece with characteristic dimension 1-100mm.

The active composition of dehydrogenation catalyst comprises one or more period of element Table VIII transition elements usually, preferred platinum and/or palladium, more preferably platinum.In addition, dehydrogenation catalyst can comprise one or more period of element Table I and/or II main group element, preferred potassium and/or caesium.Dehydrogenation catalyst can further comprise one or more period of element Table III transition elements, comprises group of the lanthanides and actinium series, preferred lanthanum and/or cerium.At last, dehydrogenation catalyst can comprise one or more period of element Table III and/or IV main group element, and preferably one or more are selected from boron, gallium, silicon, germanium, tin and plumbous element, more preferably tin.

In a preferred embodiment, dehydrogenation catalyst comprises at least a transition group VIII element, at least a I and/or II main group element, at least a III and/or IV main group element and at least a III transition element that comprises group of the lanthanides and actinium series.

For example, by WO99/46039, US4,788,371, EP-A705 136, WO99/29420, US5,220,091, US5,430,220, US 5,877, and 369, all dehydrogenation catalysts of disclosing of EP0 117 146, DE-A199 37 106, DE-A199 37 105 and DE-A199 37 107 can use according to the present invention.For above-mentioned propane self-heating dehydrogenation scheme, particularly preferred catalyzer is according to DE-A199 37107

embodiment

1,2,3 and 4 described catalyzer.

Preferably in the presence of water vapour, carry out the dehydrogenation of propane self-heating.The water vapour that adds plays the vaporization of organic sediments on the effect of thermal barrier and the cocatalyst, the duration of service that this has resisted the carbonization of catalyzer and has prolonged catalyzer.Like this organic sediments is converted into carbon monoxide, carbonic acid gas and possible water.The water vapor dilution has increased equilibrium conversion.

Dehydrogenation catalyst can be regenerated in known mode itself.For example, water vapour can be added in the reaction gas mixtures or can make every now and then oxygen-containing gas under elevated temperature by catalyst bed and burn sedimentary carbon.After the regeneration, if suitable, catalyzer reduces with hydrogen-containing gas.

Product gas flow b can be divided into two tributaries, and one of them tributary enters the self-heating dehydrogenation according to the recycle gas pattern recirculation that DE-A102 11275 and DE-A100 28 582 describe.

Dehydrogenating propane can carry out in the oxydehydrogenation mode.Oxidative dehydrogenation of propane can carry out in the mode of homogeneous oxidizing dehydrogenation or heterogeneous catalytic oxidation dehydrogenation.

When the dehydrogenating propane in the inventive method is feature with the homogeneous oxidizing dehydrogenation, can carry out according to the description of following file in principle: US-A 3,798, and 28, CN-A 1,105,352, AppliedCatalysis, 70 (2), 1991, the 175-187 page or leaf, Catalysis Today 13,1992,673-678 page or leaf and patent application DE-A 1 96 22 331 more early.

The temperature of homogeneous oxidizing dehydrogenation is generally 300-700 ℃, and preferred 400-600 ℃, more preferably 400-500 ℃.Pressure can be 0.5-100 crust or 1-50 crust.Pressure usually is 1-20 crust, especially 1-10 crust.

Under the oxydehydrogenation condition, the residence time of reaction gas mixtures was generally from 0.1 or 0.5 second to 20 seconds, preferably from 0.1 or 0.5 second to 5 seconds.Reactor used can be for example tube furnace or shell and tube-type reactor, for example with the adverse current tube furnace of waste gas as heat-transfer medium, or with the shell and tube-type reactor of salt-melting as heat-transfer medium.

Propane/oxygen proportion in the used starting mixt can be 0.5:1-40:1.In the described starting mixt mol ratio of propane and molecular oxygen preferred≤6:1, more preferably≤5:1.Usually, above-mentioned mol ratio is answered 〉=1:1, for example 〉=and 2:1.Described starting mixt can also comprise other essence inert component, for example H ₂O, CO ₂, CO, N ₂, rare gas and/or propylene.Propylene can be included in from purified C ₃In the cut.Under reaction compartment surface-area and the as far as possible little condition of the ratio of reaction compartment volume, be propylene advantageously, because the homogeneous oxidizing dehydrogenation of propane can be undertaken and the effect of free-radical scavengers is played on the reaction compartment surface usually by free radical mechanism with the dehydrogenation of propane homogeneous oxidizing.Particularly advantageous surfacing is aluminum oxide, pyrogenic silica, borosilicate, stainless steel and aluminium.

If first step of reaction of the inventive method is carried out in heterogeneous catalytic oxidation dehydrogenation mode, this can be undertaken by following document is described in principle: US-A4,788; 371, CN-A1,073; 893, CatalysisLetters 23 (1994) 103-106, W.Zhang; Gaodeng Xuexiao Huaxue Xuebao (SCI); 14 (1993) 566, Z.Huang, Shiyou Huangong (petrochemical complex); 21 (1992) 592; WO97/36849, DE-A 1 97 53 817, and US-A 3; 862; 256, US-A 3,887; 631; DE-A 1 95 30 454, and US-A 4,341; 664; J.of Catalysis 167,560-569 (1997), J.of Catalysis 167; 560-569 (1997); Topics in Catalysis 3 (1996) 265-275, US-A 5,086; 032; Catalysis Letters 10 (1991) 181-192, Ind.Eng.Chem.Res.1996,35; 14-18; US-A 4,255, and 284; Applied Catalysis A:General; 100 (1993) 111-130, J.of Catalysis 148,56-67 (1994); V.Cort é sCorber á n and S.vic Bell ó n (editor); New development in SelectiveOxidation II (the new development II of selective oxidation), 1994, Elsevier Science B.V.; the 305-313 page or leaf, 3 ^RdWorld Congress on Oxidation Catalysis (oxidation catalysis world conference for the third time) R.K.Grasselli, S.T.Oyama, A.M.Gaffney and J.E.Lyons (editor), 1997, Elseviser Science B.V., the 375th page and following pages.Particularly, all oxy-dehydrogenation catalysts of above-mentioned document specifies can use.The statement of doing about above-mentioned document is equally applicable to:

I) Otsuka, K; Uragami, Y; Komatsu, T.; Hatano, M., Natural GasConversion (conversion of Sweet natural gas), Stud.Surf.Sci.Caral.; Holmen A.; Jens, K.J.; Kolboe, S., editor; Elsevier Science:Amsterdam, 1991; The 61st volume, the 15th page;

Ii) Seshan, K.; Swaan, H.M.; Smits, RH.H.; Van Ommen, J.G.; Ross, J.R.H., New Developments in Selective Oxidation (new development of selective oxidation); Stud.Surf.Sci.Catal.; Centi.G.; Trifir ò, F., editor; EIsevier Science:Amsterdam 1990; The 55th volume, the 505th page;

Iii) Smits, R.H.H.; Seshan, K.; Ross, J.R.H., New Developments inSelective Oxidation by Heterogeneous Catalysis (new development in the heterogeneous catalyst selective oxidation); Stud.Surf.Sci.Catal; Ruiz, P.; Delmon, B., editor; EIsevierScience:Amsterdam, 1992a; The 72nd volume, the 221st page;

Iv) Smits, R.H.H.; Seshan, K.; Ross, J.R.H.Proceedings, Symposiumon Catalytic Selective Oxidation (catalytic selectivity oxidation collection of thesis), Washington DC; American Chemical Society:Washington.DC, 1992b; 1121;

v)Mazzocchia.，C.；Aboumrad，C.；Daigne，C.；Tempesti，E.；Herrmann，JM.；Thomas，G.CataL?Lett.1991，10，181；

Vi) Bellusi, G.; Conti, G.; Perathonar, S.; Trifiro, F.Proceedings, Symposium on Catalytic Selective Oxidation (catalytic selectivity oxidation collection of thesis), Washington, DC; American Chemical Society:Washington, DC, 1991; P1242;

Vii) Ind.Eng.Chem.Res.1996,35,2137-2143 and

Viii) Symposium on Heterogeneous Hydrocarbon OxidationPresented before the Division of Petroleum Chemistry (the mixed phase hydrocarbon oxidation collection of thesis in petroleum chemistry field), Inc.211th National Meeting, American ChemicalSociety New Orleans, LA.March 24-29.1996.

Specially suitable oxy-dehydrogenation catalyst is multimetal oxide compositions or the catalyst A of DE-A1 97 53 817, and as preferably the poly-metal deoxide or the catalyst A of regulation are very particularly advantageous.Therefore, the active composition that is suitable for is the poly-metal deoxide of general formula I particularly,

M ¹ _aMo _1-bM ² _bO _x (I)

Wherein,

M ¹=Co, Ni, Mg, Zn, Mn and/or Cu,

M ²=W, V, Te, Nb, P, Cr, Fe, Sb, Ce, Sn and/or La,

a＝0.5-1.5

B=0-0.5 and

X=is by the valency of other element outside the deoxygenation among the formula I and the number of frequency decision.

Other poly-metal deoxide that is suitable as oxy-dehydrogenation catalyst is described in detail as follows:

Suitable Mo-V-Te/Sb-Nb-O multi-metal-oxide catalyst is disclosed in EP-A 0 318295, EP-A 0 529 853, EP-A 0 603 838, EP-A 0 608 836, EP-A 0 608 838, EP-A 0 895 809, EP-A 0 962 253, EP-A 1 192 987, DE-A 198 35 247, DE-A 100 51 419 and DE-A 101 19 933.

Suitable Mo-V-Nb-O multi-metal-oxide catalyst is described in E.M.Thorsteinson, T.P.Wilson, F.G.Young especially, P.H.Kasei, Journal of Catalysis52 (1978), 116-132 page or leaf and US4,250,346 and EP-A 0 294 845 in.

Suitable Ni-X-O multi-metal-oxide catalyst is described among the WO00/48971, wherein X=Ti, Ta, Nb, Co, Hf, W, Y, Zn, Zr, Al.

In principle, suitable active composition can according to plain mode by obtain very uniformly by its suitable component source compound, preferably the segmentation drying composite consistent with stoichiometry and 450-1000 ℃ down calcining obtain.Calcining can be carried out under rare gas element or oxidizing atmosphere, air (mixture of rare gas element and oxygen) for example, or at reducing atmosphere (for example rare gas element, oxygen and NH ₃, CO and/or H ₂Mixture) under carry out.For the component of many metal actives composition and stark suitable source comprises oxide compound and/or can be converted into those compounds of oxide compound by heating (at least in the presence of oxygen).Except that oxide compound, this type of initial compounds that is suitable for is halogenide, nitrate, formate, oxalate, Citrate trianion, acetate, carbonate, complexing amine salt, ammonium salt and/or oxyhydroxide particularly.

For the purposes of the present invention, multimetal oxide compositions can use with powder type or as the formed body with geometry in particular, and wherein moulding can be carried out before or after final calcining.Suitable full active catalyst geometrical shape is solid cylinder for example or hollow cylinder with 2-10mm external diameter and length.Under the situation of hollow cylinder, suitable wall thickness is 1-3mm.The geometrical dimension of suitable hollow cylinder is for example 7mm * 7mm * 4mm or 5mm * 3mm * 2mm or 5mm * 2mm * 2mm (being length * external diameter * internal diameter under the various situations).Full active catalyst can certainly have spherical geometries, and the diameter of ball can be 2-10mm in this case.

Certainly, incinerating powder precursor composition can be by not being applied to moulding on the preformed inert catalyst carrier yet as yet for powdered activated composition or its.The layer thickness that is applied to the powder composition on the carrier is suitably selected in 50-500mm, preferred 150-250mm scope.The solid support material that is suitable for comprises traditional porous or non-porous aluminas, silicon-dioxide, thorium dioxide, zirconium dioxide, silicon carbide or silicate such as Magnesium Silicate q-agent or silico-aluminate.Formed body can have rule or irregular shape, the regular shape carrier that preferably has remarkable surfaceness, and for example sphere, hollow cylinder or size are at the saddle of 1-100mm scope.Be fit to use basic atresia, shaggy spherical talcum carrier, its diameter is 1-8mm, preferred 4-5mm.

The temperature of reaction of propane heterogeneous catalytic oxidation dehydrogenation is generally 300-600 ℃, and representative temperature is 350-500 ℃.Pressure is the 0.2-15 crust, preferred 1-10 crust, for example 1-5 crust.Have been found that the pressure that is higher than 1 crust, for example the 1.5-10 crust is particularly advantageous.Usually, the heterogeneous catalytic oxidation dehydrogenation of propane is carried out on stationary catalyst bed.The latter suitably is positioned at the pipe of shell and tube-type reactor, and for example the citing document in EP-A700 893 and EP-A 700 714 and these files is described.The mean residence time of reaction gas mixtures in catalyst bed is generally 0.5-20 second.According to the present invention, at the initial action gaseous mixture of preparing to be used for the dehydrogenation of propane heterogeneous catalytic oxidation, the ratio of propane and oxygen can be 0.5:1-40:1.Advantageously, the mol ratio≤6:1 of propane in the described initial gaseous mixture and molecular oxygen, preferred≤5:1.Usually, aforementioned proportion can 〉=1:1, for example 2:1.Described initial gaseous mixture can further comprise basic inert component such as H ₂O, CO ₂, CO, N ₂, rare gas and/or propylene.In addition, can also comprise a certain amount of C ₁Hydrocarbon, C ₂Hydrocarbon and C ₄Hydrocarbon.

When leaving dehydrogenation zone, product gas flow b is in 0.2-15 crust, preferred 1-10 crust, the more preferably pressure of 1-5 crust usually, and has 300-700 ℃ temperature.

In the dehydrogenating propane process, obtain to have usually the gaseous mixture of following composition: 10-80 volume % propane, 5-50 volume % propylene, methane, ethane, ethene and the C of 0-20 volume % ₄ ⁺Hydrocarbon, the oxycarbide of 0-30 volume %, the hydrogen of the water vapour of 0-70 volume % and 0-25 volume %, and the rare gas element of 0-50 volume %.

In preferred self-heating dehydrogenating propane, obtain to have usually the gaseous mixture of following composition: 10-80 volume % propane, 5-50 volume % propylene, methane, ethane, ethene and the C of 0-20 volume % ₄ ⁺Hydrocarbon, the oxycarbide of 0.1-30 volume %, the hydrogen of the water vapour of 1-70 volume % and 0.1-25 volume %, and the rare gas element of 0-30 volume %.

At processing step C) in, at first from product gas flow b, separate water outlet.The separation of water by condensation, cooling and randomly compressed product air-flow b carry out, and can carry out with one or more coolings and optional compression stage.For this purpose, product gas flow b is cooled to 20-80 ℃ usually, preferred 40-65 ℃.In addition, product gas flow can be compressed to the pressure of common 2-40 crust, the pressure of preferred 5-20 crust, the more preferably pressure of 10-20 crust.

In a kind of embodiment of the inventive method, product gas flow b is from one group of heat exchanger stage UNICOM mistake, thereby at first is cooled to 50-200 ℃ temperature, and then water further is cooled to 40-80 ℃ temperature in quench tower, for example 55 ℃.So not only condensation goes out the water vapour of most of quantity, but also condensation goes out to be present in the portion C among the product gas flow b ₄ ⁺Hydrocarbon, particularly C ₅ ⁺Hydrocarbon.Suitable heat exchanger is for example direct heat exchanger and counterflow heat exchanger, for example gas-circulation of vital energy in the wrong direction regenerative heat exchanger, and air-cooler.

Obtained the product gas flow c of depleted water steam.This product generally still comprises the water vapour of 0-10 volume %.For water is all removed from product gas flow c basically, when at step D) in when using special adsorbent, the drying of utilizing molecular sieve (particularly molecular sieve 3a, 4A, 13X) or preferred aluminum oxide or film can be provided.

At the processing step (a) of implementing industrial separation cyclopropene method of the present invention before, can from product gas flow c, remove carbonic acid gas by gas sweetening or by absorption on solid adsorbent.Carbon dioxide purifies and can be undertaken by combustion step independently, and wherein carbon monoxide optionally is oxidized to carbonic acid gas.

CO ₂Remove common use sodium hydroxide solution, potassium hydroxide solution or chain triacontanol amine solution carry out as washings; The preferred activatory N methyldiethanol amine solution that uses.Usually, before carrying out gas sweetening, product gas flow c is compressed to the pressure of 5-25 crust by compression in one or more steps.Can obtain the materials flow c of dilution carbonic acid gas, its CO ₂Content usually＜1000ppm, preferred＜100ppm, preferred＜20ppm especially.

But, preferably isolate CO by absorption on suitable solid adsorbent ₂, for example molecular sieve 13X, calcium oxide, barium oxide, magnesium oxide or hydrotalcite.

In particularly preferred embodiments, the product materials flow representative of the purification that obtains from production of propylene technology contains the air-flow of propane and propylene at least in this way, and this air-flow is used for the method for industrial separation propylene of the present invention.

Porous metal organic frameworks contains at least a organic compound of bidentate at least with at least a metallic ion coordination.The example of this metal-organic framework materials (MOF) is for example described in following document: US 5,648, and 508; EP-A-0 709 253; People such as M.O ' Keeffe, J.Sol.StateChem., 152(2000), 3-20 page or leaf; People such as H.Li, Nature 402(1999), below the 276th page; People such as M.Eddaoudi, Topics in Catalysis 9 (1999) is p.105-111; People such as B.Chen, Science 291(2001), 1021-23 page or leaf; DE-A 101 11 230; WO-A 2005/049892; A.C.Sudik etc., J.Am.Chem.Soc., 127 (2005), 7110-7118 page or leaf.

The used metal-organic framework materials of the present invention contains porose, particularly micropore and/or mesopore.Micropore is defined as those holes that diameter is equal to or less than 2nm, and mesopore is defined as the hole of diameter in the 2-50nm scope, in each case according at Pure Applied Chem.57 (1985), and 603-619, the particularly definition that provides in 606 pages.The existence of micropore and/or mesopore can detect research by absorption, and these detect according to DIN 66131 and/or DIN 66134 determines that MOF absorbs the loading capacity of nitrogen under 77K.

Preferably, for the framework material of powder type, be greater than 5m according to the specific surface area that DIN 66135 (DIN66131,66134) calculates according to Langmuir's model ²/ g is more preferably greater than 10m ²/ g is also more preferably greater than 50m ²/ g.Also more preferably greater than 500m ²/ g especially is preferably greater than 1000m ²/ g is preferably greater than 1500m especially ²/ g.

The MOF formed body can have lower active surface area; But, be preferably greater than 10m ²/ g is more preferably greater than 50m ²/ g.Also more preferably greater than 500m ²/ g is particularly greater than 1000m ²/ g.

For the object of the invention, the maximum value of pore diameter distribution should be at least

This maximum value preferably exists In the scope.Preferred especially

Metal component in the used framework material of the present invention is preferably selected from Ia, IIa, IIIa, IVa-VIIIa and the Ib-VIb family element of the periodic table of elements.The more preferably IIa of the periodic table of elements, IIIb, IIIa to VIa and lanthanon, V, Mn, Fe, Ni, Co.Preferred especially Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ro, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb and Bi.More preferably Mg, Al, In, Cu, Zn, Fe, Ni, Co, Mn, Zr, Ti, Sc, Y, La, Ce.Preferred especially Mg, Al, In, Cu, Zn, Fe, Zr, Y.Under the situation of copper, preferably do not have the MOF of free Cu hapto.

As for the ion of these elements, especially can mention: Mg ²⁺, Ca ²⁺, Sr ²⁺, Ba ²⁺, Sc ³⁺, Y ³⁺, Ti ⁴⁺, Zr ⁴⁺, Hf ⁴⁺, V ⁴⁺, V ³⁺, V ²⁺, Nb ³⁺, Ta ³⁺, Cr ³⁺, Mo ³⁺, W ³⁺, Mn ³⁺, Mn ²⁺, Re ³⁺, Re ²⁺, Fe ³⁺, Fe ²⁺, Ru ³⁺, Ru ²⁺, Os ³⁺, Os ²⁺, Co ³⁺, Co ²⁺, Rh ²⁺, Rh ⁺, Ir ²⁺, Ir ⁺, Ni ²⁺, Ni ⁺, Pd ²⁺, Pd ⁺, Pt ²⁺, Pt ⁺, Cu ²⁺, Cu ⁺, Ag ⁺, Au ⁺, Zn ²⁺, Cd ²⁺, Hg ²⁺, Al ³⁺, Ga ³⁺, In ³⁺, Tl ³+, Si ⁴⁺, Si ²⁺, Ge ⁴⁺, Ge ²⁺, Sn ⁴⁺, Sn ²⁺, Pb ⁴⁺, Pb ²⁺, As ⁵⁺, As ³⁺, As ⁺, Sb ⁵+, Sb ³⁺, Sb ⁺, Bi ⁵⁺, Bi ³⁺And Bi ⁺

The organic compound that term " bidentate organic compound at least " expression is such, it contains and can form at least two, at least one functional groups of preferred two coordinate bonds with given metal ion, and/or can with two or more, coordinate bond of preferred each self-forming of two atoms metals.

As the functional group that can form described coordinate bond, can mention for example following functional group :-CO especially ₂H ,-CS ₂H ,-NO ₂,-B (OH) ₂,-SO ₃H ,-Si (OH) ₃,-Ge (OH) ₃,-Sn (OH) ₃,-Si (SH) ₄,-Ge (SH) ₄,-Sn (SH) ₃,-PO ₃H ,-AsO ₃H ,-AsO ₄H ,-P (SH) ₃,-As (SH) ₃,-CH (RSH) ₂,-C (RSH) ₃,-CH (RNH ₂) ₂,-C (RNH ₂) ₃,-CH (ROH) ₂,-C (ROH) ₃,-CH (RCN) ₂,-C (RCN) ₃, wherein R for example preferably has the alkylidene group of 1,2,3,4 or 5 carbon atom, for example methylene radical, ethylidene, inferior n-propyl, isopropylidene, inferior normal-butyl, isobutylidene, the inferior tertiary butyl or inferior n-pentyl; Or contain the aryl of 1 or 2 aromatic ring, for example 2 C ₆Ring, these rings can condense when appropriate, and can be replaced by at least one substituting group in each case suitably independently of one another, and/or can contain at least one heteroatoms independently of one another in each case, for example N, O and/or S.According to similar preferred embodiment, can mention such functional group, wherein there is not above-mentioned radicals R.In this respect, especially can mention-CH (SH) ₂,-C (SH) ₃,-CH (NH ₂) ₂,-C (NH ₂) ₃,-CH (OH) ₂,-C (OH) ₃,-CH (CN) ₂Or-C (CN) ₃At least two functional groups can connect with any suitable organic compound key in principle, and prerequisite is to guarantee that the organic compound with these functional groups can form coordinate bond and can prepare framework material.

Preferably, the organic compound that contains at least two functional groups be derived from saturated or undersaturated aliphatic cpd or aromatic substance or be aliphatic series also be the compound of aromatics.

Aliphatic cpd or be aliphatic series also be that aliphatic structure part in the compound of aromatics can be straight chain and/or branching and/or cyclic, a plurality of rings also may reside in a kind of compound.Further preferably, aliphatic cpd or be aliphatic series also be that aliphatic structure in the compound of aromatics partly contains 1-15 carbon atom, more preferably contain 1-14 carbon atom, more preferably contain 1-13 carbon atom, more preferably contain 1-12 carbon atom, more preferably contain 1-11 carbon atom, especially preferably contain 1-10 carbon atom, for example 1,2,3,4,5,6,7,8,9 or 10 carbon atom.Special optimization methane, diamantane, acetylene, ethene or divinyl.

Aromatic substance or be aliphatic series also be that aromatic structure part in the compound of aromatics can have one or more rings, for example have 2,3,4 or 5 rings, these rings can exist independently of one another, and/or at least two rings can exist with the condensed form.Particularly preferably be, aromatic substance or be aliphatic series also be that aromatic structure in the compound of aromatics partly has 1,2 or 3 ring, especially preferably have 1 or 2 ring.In addition, each ring of described compound can contain at least one heteroatoms independently of one another, for example N, O, S, B, P, Si, Al, preferably N, O and/or S.Further preferred, aromatic substance or be aliphatic series also be that aromatic structure in the compound of aromatics partly contains 1 or 2 C ₆Ring, two this rings exist independently of one another or exist with the form of condensing.Particularly, as aromatic substance, can mention benzene, naphthalene and/or biphenyl and/or dipyridyl and/or pyridyl.

For example, can mention anti--muconic acid or fumaric acid or phenylene diacrylate especially.

At least the bidentate organic compound is preferably derived from dicarboxylic acid, tricarboxylic acid or tetracarboxylic acid or its sulfur analogs.Sulfur analogs is the SH of functional group-(C=O) and its isomer, and C (=S) SH, they can replace one or more carboxyls to use.

For the object of the invention, term " is derived " and is represented that the bidentate organic compound can or all take off proton form with the part deprotonation at least and exist in skeleton.In addition, the bidentate organic compound can contain other substituting group at least, for example-OH ,-NH ₂,-OCH ₃,-CH ₃, NH (CH ₃) ,-N (CH ₃) ₂,-CN and halogenide.

For the purposes of the present invention, the example of dicarboxylic acid for example is:

Oxalic acid, succsinic acid, tartrate, 1,4-butane dicarboxylic acid, 4-oxo pyrans-2, the 6-dicarboxylic acid, 1, the 6-hexane dicarboxylic acid, decane dicarboxylic acid, 1, the 8-heptadecane dicarboxylic acid, 1,9-heptadecane dicarboxylic acid, heptadecane dicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridine dicarboxylic acid, pyridine-2, the 3-dicarboxylic acid, 1,3-butadiene-1, the 4-dicarboxylic acid, 1, the 4-benzene dicarboxylic acid, right-benzene dicarboxylic acid, imidazoles-2,4-dicarboxylic acid, 2-toluquinoline-3,4-dicarboxylic acid, quinoline-2, the 4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloro-quinoxaline-2,3-dicarboxylic acid, 4,4 '-tetramethyl triaminotriphenyl methane NH2-3,3 '-dicarboxylic acid, quinoline-3, the 4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, the imide dicarboxylic acid, pyridine-2,6-dicarboxylic acid, glyoxal ethyline-4,5-dicarboxylic acid, thiophene-3, the 4-dicarboxylic acid, 2 isopropyl imidazole-4,5-dicarboxylic acid, tetrahydropyrans-4,4 '-dicarboxylic acid ， perylene-3,9-dicarboxylic acid ， perylene dianhydride carboxylic acid, Pluriol E 200-dicarboxylic acid, 3,6-two oxa-octane dicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octane dicarboxylic acid, pentane-3,3-dicarboxylic acid, 4,4 '-diaminostilbene, 1 '-phenylbenzene-3,3 '-dicarboxylic acid, 4,4 '-diamino-diphenyl-3,3 '-dicarboxylic acid, p-diaminodiphenyl-3,3 '-dicarboxylic acid, 1,4-pair-(phenyl amino)-benzene-2,5-dicarboxylic acid, 1,1 '-dinaphthyl-5,5 '-dicarboxylic acid, 7-chloro-8-toluquinoline-2, the 3-dicarboxylic acid, 1-anilino anthraquinone-2,4 '-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4-pair-(carboxymethyl)-piperazine-2, the 3-dicarboxylic acid, 7-chloroquinoline-3, the 8-dicarboxylic acid, 1-(4-carboxyl)-phenyl-3-(4-chlorine)-phenyl-pyrazole quinoline-4,5-dicarboxylic acid, 1,4,5,6,7,7-chlordene-5-norbornylene-2,3-dicarboxylic acid, phenyl indane dicarboxylic acid, 1,3-dibenzyl-2-oxo-imidazole alkane-4,5-dicarboxylic acid, 1, the 4-cyclohexane dicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-Benzoylbenzene-1, the 3-dicarboxylic acid, 1,3-dibenzyl-2-oxo-imidazole alkane-4,5-cis-dicarboxylic acid, 2,2 '-two quinoline-4,4 '-dicarboxylic acid, pyridine-3, the 4-dicarboxylic acid, 3,6,9-trioxa undecane dicarboxylic acid, O-hydroxy benzophenone keto-dicarboxylic acid, Pluriol E 300 dicarboxylic acid, Pluriol E 400 dicarboxylic acid, Pluriol E 600 dicarboxylic acid, pyrazoles-3, the 4-dicarboxylic acid, 2,3-pyrazine dicarboxylic acid, 5,6-dimethyl-2,3-pyrazine dicarboxylic acid, 4,4 '-diamino-diphenyl ether-imide dicarboxylic acid, 4,4 '-diaminodiphenyl-methane-imide dicarboxylic acid, 4,4 '-diamino-sulfobenzide imide dicarboxylic acid, 2,6-naphthalene dicarboxylic acids, 1,3-diamantane dicarboxylic acid, 1,8-naphthalene dicarboxylic acids, 2, the 3-naphthalene dicarboxylic acids, 8-methoxyl group-2,3-naphthalene dicarboxylic acids, 8-nitro-2, the 3-naphthalene dicarboxylic acids, 8-sulfo group-2,3-naphthalene dicarboxylic acids, anthracene-2, the 3-dicarboxylic acid, 2 ', 3 '-phenylbenzene-p-terphenyl-4,4 "-dicarboxylic acid; diphenyl ether-4; 4 '-dicarboxylic acid, imidazoles-4,5-dicarboxylic acid; 4 (1H)-oxo benzothiopyrans-2; 8-dicarboxylic acid, the 5-tertiary butyl-1,3-benzene dicarboxylic acid; 7, the 8-quinoline dicarboxylic acid, 4, the 5-imidazole-2-carboxylic acid, 4-tetrahydrobenzene-1, the 2-dicarboxylic acid, hexatriacontane dicarboxylic acid, tetradecane dicarboxylic acid, 1,7-heptane dicarboxylic acid, 5-hydroxyl-1,3-benzene dicarboxylic acid, pyrazine-2, the 3-dicarboxylic acid, furans-2,5-dicarboxylic acid, 1-nonene-6, the 9-dicarboxylic acid, icosa alkene dicarboxylic acid, 4,4 '-dihydroxyl ditan-3,3 '-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2, the 3-dicarboxylic acid, 2, the 5-pyridine dicarboxylic acid, tetrahydrobenzene-2, the 3-dicarboxylic acid, 2,9-dichloro fluorubin-4, the 11-dicarboxylic acid, 7-chloro-3-toluquinoline-6,8-dicarboxylic acid, 2,4-dichloro benzophenone-2 ', 5 '-dicarboxylic acid, 1, the 3-benzene dicarboxylic acid, 2, dipicolimic acid 2,1-methylpyrrole-3,4-dicarboxylic acid, 1-benzyl-1H-pyrroles-3, the 4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazoles dicarboxylic acid, 2-oil of mirbane-1,4-dicarboxylic acid, heptane-1, the 7-dicarboxylic acid, tetramethylene-1,1-dicarboxylic acid, 1, the 14-tetradecane dicarboxylic acid, 5,6-dehydrogenation norbornane-2,3-dicarboxylic acid or 5-ethyl-2, the 3-pyridine dicarboxylic acid;

Tricarboxylic acid, for example: 2-hydroxyl-1,2,3-tricarballylic acid, 7-chloro-2,3,8-quinoline tricarboxylic acid, 1,2,4-benzene tricarbonic acid, 1,2,4-butane tricarboxylic acid, 2-phosphono-1,2,4-butane tricarboxylic acid, 1,3,5-benzene tricarbonic acid, 1-hydroxyl-1,2,3-tricarballylic acid, 4,5-dihydro-4,5-dioxo-1H-pyrrolo-[2,3-F] quinoline-2,7, the 9-tricarboxylic acid, 5-ethanoyl-3-amino-6-methylbenzene-1,2, the 4-tricarboxylic acid, 3-amino-5-benzoyl-6-methylbenzene-1,2, the 4-tricarboxylic acid, 1,2,3-tricarballylic acid or aurin tricarboxylic acid;

Or tetracarboxylic acid, for example: 1,1-Er Yang perylene is [1,12-BCD] thiophene-3,4 also, and 9,10-tetracarboxylic acid ， perylene tetracarboxylic acid, Li such as perylene-3,4,9,10-tetracarboxylic acid Huo perylene-1,12-sulfone-3,4,9,10-tetracarboxylic acid, BTCA, for example 1,2,3,4-BTCA or-1,2,3,4-BTCA, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-hexaoxacyclooctadecane-6-2,3,11, the 12-tetracarboxylic acid, 1,2,4,5-benzene tertacarbonic acid, 1,2,11,12-dodecane tetracarboxylic acid, 1,2,5,6-hexane tetracarboxylic acid, 1,2,7,8-octane tetracarboxylic acid, 1,4,5, the 8-naphthalene tetracarboxylic acid, 1,2,9,10-decane tetracarboxylic acid, benzophenone tetracarboxylic acid, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid, tetrahydrofuran (THF) tetracarboxylic acid; Or the pentamethylene tetracarboxylic acid, pentamethylene-1,2,3 for example, 4-tetracarboxylic acid.

Very particularly preferably be, randomly use mono-substitutedly at least to have 1,2,3,4 or the aromatics two of more a plurality of rings-, three-or four-carboxylic acid, each ring can contain at least one heteroatoms, two or more rings can contain identical or different heteroatoms.For example, preferred monocycle dicarboxylic acid, monocycle tricarboxylic acid, monocycle tetracarboxylic acid, dicyclo dicarboxylic acid, dicyclo tricarboxylic acid, dicyclo tetracarboxylic acid, three ring dicarboxylic acid, three ring tricarboxylic acid, three ring tetracarboxylic acids, Fourth Ring dicarboxylic acid, Fourth Ring tricarboxylic acid and/or Fourth Ring tetracarboxylic acid.Suitable heteroatoms is for example N, O, S, B, P, Si, Al, and preferred heteroatoms is N, O and/or S.In this respect suitable substituents especially-OH, nitro, amino, alkyl or alkoxyl group.

As bidentate organic compound at least, especially preferably use acetylene dioctyl phthalate (ADC), phthalic acid, naphthalic acid; The phenylbenzene dioctyl phthalate, for example 4,4 '-phenylbenzene dioctyl phthalate (BPDC); Two pyridine dicarboxylic acids, 2,2 '-two pyridine dicarboxylic acids for example, 2,2 '-two pyridines-5 for example, 5 '-dioctyl phthalate; The benzene tricarbonic acid, for example 1,2,3-benzene tricarboxylic acid or 1,3,5-benzene tricarboxylic acid (BTC); Diamantane tetracarboxylic acid (ATC), diamantane dibenzoate (ADB), benzene three benzoic ethers (BTB), methane four benzoic ethers (MTB), diamantane four benzoic ethers, or dihydric para-phthalic acid, for example 2,5-dihydric para-phthalic acid (DHBDC).

Very particularly preferably be especially to use m-phthalic acid, terephthalic acid, 2,5-dihydric para-phthalic acid, 1,2,3-benzene tricarboxylic acid, 1,3,5-benzene tricarboxylic acid, 2,2 '-two pyridines-5,5 '-dioctyl phthalate, amino terephthalic acid or diamino terephthalic acid.

Except these at least the bidentate organic compound, MOF also can contain one or more unidentate ligands.

Be applicable to solvent especially ethanol, dimethyl formamide, toluene, methyl alcohol, chlorobenzene, diethylformamide, dimethyl sulfoxide (DMSO), water, hydrogen peroxide, methylamine, sodium hydroxide solution, N-Methyl pyrrolidone ether, acetonitrile, benzyl chloride, triethylamine, ethylene glycol and their mixture of producing MOF.Other metal ion, bidentate organic compound and the being used to solvent of producing MOF is described in US-A 5,648 especially at least, 508 or DE-A 101 11 230 in.

The aperture of MOF can by select suitable part and/or at least the bidentate organic compound control.Generally speaking, organic compound is big more, and the aperture is just big more.Preferably, the aperture is 0.2-30nm, and preferred especially 0.3-30nm is based on crystalline material.

But, in the MOF formed body, also bigger hole can appear, and its distribution of sizes can change.But, preferred, total pore volume greater than 50%, especially be that hole by the maximum 1000nm of bore dia forms greater than 75%.But preferred most of pore volume is that the hole by two kinds of diameter ranges forms.So, further preferred total pore volume greater than 25%, especially be to be that the hole of 100-800nm forms by bore dia greater than 50%, also further preferably total pore volume greater than 15%, especially be to form by the hole that bore dia mostly is 10nm most greater than 25%.Pore distribution can detect by mercury hole method.

Useful especially MOF for example is Cu-BTC (BTC=1,3,5-benzene tricarboxylic acid), Al-terephthalic acid, Cu-terephthalic acid, Zn-terephthalic acid (MOF-5), Zn-terephthalic acid-TEDA, MOF-74, the amino terephthalic acid of Zn-naphthalene-DC (IRMOF-8), Al-.

Metal-organic framework materials generally is used as formed body, for example is used as the irregular bed of ball, ring, extrudate or pellet, or is used as well-regulated internals, for example filler, honeycomb and material all in one piece.

The production of formed body for example is described among the WO-A 03/,102 000.The preferred formed body bed of very closely filling that uses.So formed body preferably has the diameter that is no more than 3mm at its narrowest point,, very particularly preferably be no more than 1.5mm more preferably no more than 2mm.The formed body of pellet form very particularly preferably.The another kind of selection is that monolith structures is installed, because air-flow can flow through the major path here usually, the material in wall is also very closely filled simultaneously.

In the step (a) of the method for industrial separation propylene of the present invention, not propylene other composition from gas must be separated fully.On the contrary, target is to make pure propylene be adsorbed the agent load fully.Because the adsorption index of propylene on sorbent material is higher than other composition of gas,, make in the end optionally adsorbs propylene so other composition of gas is discharged from adsorption site gradually.The propane that this is specially adapted to exist in air-flow.

When air-flow during from dehydrogenating propane, the tributary of containing propane can be recycled in the dehydrogenating propane.

Sorbent material is present in the adsorber usually.Except metal-organic framework materials, sorbent material or adsorber can contain other sorbent material, for example molecular sieve etc.

The adsorber reactor is the part of adsorber system preferably, and the adsorber system contains the adsorber of at least three co-operate in compensated stage (offset phase).

This makes can carry out the release of propylene with false continuous operation mode in the step (b) of industrial separation cyclopropene method of the present invention.

In the step (b) of industrial separation cyclopropene method of the present invention, the release of propylene is preferably undertaken by at least one parameter that change is selected from the pressure and temperature.Preferably carry out one time pressure change at least.

Release by pressure change can be carried out to applying vacuum by reducing pressure.But for the object of the invention, the minimizing of partial pressure of propylene is enough to discharge propylene.This can be for example by replacing propylene to carry out with rare gas element, and rare gas element can easily be separated later.

The step of industrial separation cyclopropene method of the present invention (a) is an absorption phase, and the step of industrial separation cyclopropene method of the present invention (b) is a desorption phase.If absorption and desorb are undertaken by the varying cyclically of pressure and/or temperature then, then those skilled in the art will know that many possibilities for industrial implementation.

In all these, at least two, preferred three, especially preferably at least four adsorbers are operated abreast, and at least two but preferably all these adsorbers operation under with respect to the stage compensation of other adsorber separately.Possible distortion is: a) transformation absorption (PSA), b) Vacuum Pressure Swing Adsorption (VPSA), c) alternating temperature absorption (TSA), or the combination of various processes.These technologies are well known to a person skilled in the art, other details can be referring to textbook, W.Kast for example, " Adsorption aus der Gasphase-Ingenieurwissenschaftliche Grundlagenund technische Verfahren (Gas Phase Adsorption) ", VCH Weinheim, 1988; D.M.Ruthven, S.Farooq, K.S.Knaebel, " Pressure Swing Adsorption (transformation absorption) ", Wiley-VCH, New York-Chichester-Weinheim-Brisbane-Singapore-Toronto, 1994; Or D.Bathen, M.Breibach, " Adsorptionstechnik (adsorption technology) ", Springer Verlag Berlin-Heidelberg, 2001; D.Basmadjian, " The Little Adsorption Book (absorption handbook) ", CRC Press Boca Raton, 1996; Or publication, A.Mersmann for example, B.Fill, R.Hartmann, S.Maurer, Chem.Eng.Technol.23/11 (2000) 937.Adsorbent bed is not to comprise single sorbent material of planting, and can be made up of the layer of many differing materials.This can for example be used for making the breakthrough point of adsorbed material more sharp-pointed during absorption phase.

For example, being used for the absorption of the isolating transformation of propane/propylene can followingly carry out: four reactors are according to following compensated stage parallel running: in the stage 1, by introducing live gas, making an adsorber reach working pressure (P with absorption mode from the gas of second adsorber or the waste gas from second adsorber of desorb simultaneously _Maximum).In the stage 2, make the complete load propylene of sorbent material by further introducing charging, preferably up to breaking through whole absorb leading-edge and adsorbs propylene no longer.In this case, second reactor preferably before breaking through the propylene forward position with absorption mode conversion in the downstream.In the stage 3, purge adsorber with pure propylene, thus the remaining propane that is not adsorbed that replacement exists in adsorber.Purging can carry out with following current or reflux type, wherein preferred concurrent.Purging can carry out under adsorptive pressure.But the preferred adsorber pressure that reduces earlier is to save pure propylene; Similar particularly preferably in absorption phase (stage 2) with the partial pressure of propylene in the purge stages (stage 3).Can add another adsorber at the gaseous mixture that will during reduction pressure, discharge during the stage 1, thus pressure boost.In the stage 4, load and the adsorber that purged are extracted, and obtain pure propylene stream.Product is preferably discharged with reflux type.

In addition, can in the stage 4, use superatmospheric pressure.This embodiment is an example of VPSA technology.

In order to compensate because heat of adsorption/temperature effective that desorb cooling produces, the introducing of heat or to remove can be favourable.The introducing of heat can be carried out in every way: transmit via internal exchanger, transmit via external heat exchanger, or transmit by radiation, for example by injection microwave or hertzian wave.Similar, can be used for the propylene desorb of help during the stage 4 in addition above being used to compensate the hot input of desorb refrigerative.This technology is represented the combination of transformation absorption and alternating temperature absorption.

The desorb of required product also can be undertaken by substituting with auxiliary component, for example N ₂, CO ₂Or water vapour.Here, partial pressure of propylene and the while of utilizing auxiliary component can be reduced in the gas phase can keep the absolute pressure constant fact.In addition, for example water vapour or carbonic acid gas also can cause replacing required product from adsorbent surface by the auxiliary component of stronger absorption.But in this case, auxiliary component must be removed from adsorbent surface in another step once more, for example by improving temperature., also can for example set such temperature levels here, it causes for example polymerization of unwanted side reaction in the presence of propylene.Because in this operator scheme, auxiliary agent can enter the gas of desorb, so can carry out separating step subsequently, is for example undertaken by condensation, absorption, membrane sepn, distillation or selective cleaning.

These stages are not to have the identical time length, so can use littler simultaneously or the adsorber of high number more yet.

If the propylene of desorb does not have required purity, then can further purify subsequently, preferably undertaken by absorption, wherein can use different sorbent materials.

Absorption is generally carried out-50 ℃ to 250 ℃ temperature, and preferred-10 ℃ to 90 ℃, preferred 0-80 ℃ especially.In addition, absorption is more preferably carried out 10-70 ℃ temperature, and particularly 20-60 ℃, very particularly preferably 30-50 ℃.

Absorption is generally carried out at the pressure of 1-40 crust, preferred 1.5-20 crust, preferred especially 2-15 crust, especially 2.5-10 crust.Absorption is very particularly preferably carried out at the pressure of 2.5-5 crust.

Desorption phase itself can be by reducing pressure or carrying out by the introducing heat or by the combination of these two kinds of measures.Under the situation that reduces pressure, pressure preferably is reduced to and is lower than 2.5 crust, especially is lower than 2 crust.

The force value here is an absolute value.

Adsorption/desorption can be used as fixed bed, fluidized-bed or moving bed process to carry out.Suitable device for example is a not strainer of fixed-bed reactor, rotation adsorber or Lip river.The summary of possible equipment can be referring to " the Adsorption aus der Gasphase (Gas Phase Adsorption) " of Werner Kast, VCH (Weinheim); H.Brauer " Die Adsorptionstechnik ein Gebiet mitZukunft ", Chem.-Ing.Tech 57 (1985) 8,650-653; Dieter Bathen, MarcBreitbach " Adsorptionstechnik (adsorption technology) ", VDI Book, 2001.

For desorb adsorbed gas on sorbent material, heat and/or unzip to lower pressure.

The preferably feasible propylene that can obtain to have greater than 95 volume % purity of the method for industrial separation propylene of the present invention is based on the volume summation meter of propane and propylene.Purity is more preferably greater than 99 volume %, especially at least 99.5 volume % (polymkeric substance rank).

The present invention further provides the porous metal organic frameworks that contains with at least a organic compound of bidentate at least of at least a metallic ion coordination is used for from containing the purposes of the air-flow industrial separation propylene of propane and propylene at least.

Embodiment

Embodiment 1: separate on Cu-BTC

With 1,3 of 193g, 5-Cu-benzene tricarboxylic acid MOF (1.5mm extrudate) tubular reactor of packing into.Use pure propane to set up required adsorptive pressure (the various absolute pressures in 2.5-5 crust scope) subsequently, then charging is switched to the mixture (100 or 200 standard liters/hour) of about 50% propane and 50% propylene.Come the composition of the waste gas of autoreactor to monitor by mass spectrograph.During beginning, propylene is adsorbed, and only detects pure propane.In case propylene is broken through, just stop experiment.Propylene capacity under each experiment condition can be from the Time Calculation (table 1) that at first breaks through.

Sample purged 30 minutes with the pure propane of increasing amount (about 100 standard liters/hour) in room temperature subsequently, and began to set up the required pressure of experiment next time once more.The multiple lock out operation also obtains identical value subsequently.

Embodiment 2: separate on Al-terephthalic acid MOF

Handle the Al-terephthalic acid MOF (3x3mm and 1.5x1.5mm pellet) of 212g according to the mode similar to embodiment 1.

Embodiment 3: Separate on the molecular sieve

Handle 302g's according to the mode similar to embodiment 1

Molecular sieve (4-8 order) (1.5mm extrudate).

Embodiment 4: separate on the 13X molecular sieve

Handle 13X molecular sieve (1.5mm extrudate) according to the mode similar to embodiment 3.

Table 1

Embodiment 5

Volume is filled with the different sorbent materials that are in activated state in all cases for the adsorber of about 0.2L, and they are at the carbonic acid gas that removes residual water-content before the actual detected in addition and adhere in warm nitrogen gas stream.In order to detect separating power, purged adsorber 15 minutes with pure propane in room temperature and normal atmosphere earlier, then the pressure in the system is brought up to 5 crust.Here, by the downstream needle pressure regulating valve.Then charging is switched to propane/propylene mixtures (the GC analytical results: 54.7% propylene, 44% propane, surplus is a nitrogen; Flow be 16 standard liters/hour), and by the IR gas cell along with the concentration of time detecting at the adsorber entrance and exit.Calculate the propylene capacity up to the time of first observed when the propylene signal significantly improves.The results are shown in the table 2.

Table 2

Fig. 1 has shown the IR signal (breakthrough curve) that propylene changed along with the time.Here, IR signal [a.u.] is drawn as the function of time t (unit be minute).

Each curve in Fig. 1 corresponding to the sorbent material of table 2.

Embodiment 6:

In other experiment, by removing propylene from gaseous mixture absorption, described gaseous mixture is probably corresponding to the product stream from dehydrogenating propane.

Cu-BTC-MOF is used as sorbent material with the form of 1.5mm extrudate.

Gaseous mixture is composed of the following components:

-Yue 1.5% ethane,

-Yue 1.5% ethene,

-Yue 2% carbon monoxide,

-Yue 2.5% methane,

-Yue 30.8% propane,

-Yue 30.8% propylene,

The hydrogen of-surplus.

These experiments are carried out in being equipped with the adiabatic tubular reactor (2000mmx35mmID) of 10 times of thermopairs.Reactor feed is the material of regulating from the steel cylinder.Pressure is by the valve regulated in the waste gas.Gas composition detects by the online FTIR analyser in reactor inlet and outlet.

Experiment parameter:

Charging: referring to the experiment A of Fig. 2 and the experiment B of Fig. 3

Reactor pressure: 2.5 crust

Temperature: room temperature (about 20 ℃)

Before experiment, with (about 50 ℃ of warm dried nitrogen of sorbent material; 500 standard liters/hour) purge and to spend the night, thereby remove the water that is adsorbed or the carbonic acid gas of remaining trace.

Experiment A:

In experiment A, reactor is pressurized to 2.5 crust with pure propane.Between the adsorption cycle of propane, observe temperature and be elevated to 50K.After room temperature, allow the absorption feed gas mixtures in reactor cooling.

Propylene and ethane are adsorbed fully during beginning, and the ethene of maximum ratio and the carbon monoxide of small proportion are also adsorbed fully.Methane and propane pass through in the clear.After about 10 minutes, the concentration of ethane in waste gas significantly raises.After 56 minutes, ethylene concentration raises once more.After 134 minutes, the breakthrough of propylene occurs subsequently, making becomes possibility by the desorb separation of propylene.

Between the adsorption cycle of gaseous mixture, observe temperature rising 15K.

In Fig. 2, the concentration of propane and propylene and the progress of charging and pressure have been shown.Here, gas concentration (%) and air-flow (standard liter/hour) c and pressure p (crust) as the time (minute) function show.Curve 1 is corresponding to feed stream, and curve 2 is corresponding to propane concentration, and curve 3 is corresponding to pressure, and curve 4 is corresponding to density of propylene.

Experiment B:

In experiment B, reactor clings to nitrogen pressure to 2.5.After pressurization, allow incoming mixture to enter reactor.

Whole gaseous mixture is adsorbed during beginning, and this causes the slight pressure in the reactor to reduce.So, flow progressively be elevated to 300 standard liters/hour.After about 25 minutes, observe the breakthrough of methane and carbon monoxide at reactor outlet, this reached their starting point concentration after 10 minutes, almost detect to following current ethane, ethene and propane subsequently.Ethane and ethene reached starting point concentration after about 5 minutes.After 50 minutes, the breakthrough of propylene appears, and making becomes possibility by the desorb separation of propylene.

Because a large amount of absorption, it is definitely constant to keep-up pressure at whole experimental session.Between adsorption cycle, observe temperature rising 75K.

In Fig. 3, the concentration of propane and propylene and the progress of charging and pressure have been shown.Here, gas concentration (%) and air-flow (standard liter/hour) c and pressure p (crust) as the time (minute) function show.Curve 1 is corresponding to feed stream, and curve 2 is corresponding to pressure, and curve 3 is corresponding to propane concentration, and curve 4 is corresponding to density of propylene.

Claims

1. the method for an industrial separation propylene from the air-flow that contains propylene and at least a other hydrocarbon, this method may further comprise the steps:

(b) sorbent material from the load propylene discharges propylene.

2. the method for claim 1, wherein said at least a other hydrocarbon is a propane.

3. method as claimed in claim 1 or 2, wherein said air-flow contains the propylene of 5-95 volume %, based on the volume ratio summation meter of the propylene in air-flow and one or more other hydrocarbon.

4. as each described method among the claim 1-3, wherein air-flow is the product materials flow from the optional purification of production of propylene technology.

5. method as claimed in claim 4, wherein optional product materials flow of purifying is from the conversion of the cracking technology that is used to produce propylene, dehydrogenating propane, conversion of olefines, methyl alcohol/dme or the combination of two or more these production of propylene technologies.

6. method as claimed in claim 5, wherein optional product materials flow of purifying is from the dehydrogenating propane that is used to produce propylene.

7. as each described method among the claim 1-6, wherein sorbent material is present in the adsorber.

8. method as claimed in claim 7, wherein adsorber is the part of adsorber system, described adsorber system contains the adsorber of at least three co-operate in compensated stage.

9. method as claimed in claim 8, wherein the release of propylene is carried out with false continuous operation mode.

10. as each described method among the claim 1-9, wherein the release of propylene is to be undertaken by at least one physical parameter that change is selected from the pressure and temperature.

11. as each described method among the claim 1-10, wherein the propylene of Shi Fanging has the purity greater than 95 volume %, based on the volume summation meter of propylene and one or more other hydrocarbon.

12. as each described method among the claim 1-11, wherein contact is to carry out-50 ℃ to 250 ℃ temperature.

13. as each described method among the claim 1-12, wherein contact is to carry out under the absolute pressure of 1-40 crust.

14. as each described method among the claim 1-13, wherein at least a metal ion is selected from Mg, Al, In, Cu, Zn, Fe, Ni, Co, Mn, Zr, Ti, Sc, Y, La and Ce.

15. as each described method among the claim 1-14, the wherein at least a organic compound of bidentate at least is derived from dicarboxylic acid, tricarboxylic acid, tetracarboxylic acid or their sulfur analogs.

16. as each described method among the claim 1-15, wherein metal-organic framework materials is the form of formed body.

17. as each described method among the claim 1-16, wherein the maximum value of pore diameter distribution is 0.4nm at least.

18. the porous metal organic frameworks that comprises with at least a organic compound of bidentate at least of at least a metallic ion coordination is used for from the purposes of the air-flow industrial separation propylene that contains propylene and at least a other hydrocarbon.