CN101115697A - Method for the production of propene from propane - Google Patents
Method for the production of propene from propane Download PDFInfo
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- CN101115697A CN101115697A CNA2006800040110A CN200680004011A CN101115697A CN 101115697 A CN101115697 A CN 101115697A CN A2006800040110 A CNA2006800040110 A CN A2006800040110A CN 200680004011 A CN200680004011 A CN 200680004011A CN 101115697 A CN101115697 A CN 101115697A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
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- C07C5/3337—Catalytic processes with metals of the platinum group
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Abstract
Preparation of propene from propane comprises preparing a feed stream containing propane; feeding the feed stream to a dehydrogenation zone; cooling the obtained product gas stream; contating the cooled product gas stream with a selective inert absorption agent; optionally depressurizing the obtained propane charged absorption agent stream; and releasing a propene-containing gas stream. Preparation of propene from propane comprises: (i) preparing a feed stream containing propane; (ii) feeding the feed stream containing propane, optionally: steam and an oxygen-containing gas stream to a dehydrogenation zone and propane undergoes a dehydrogenation to give propene (where a product gas stream (b) containing propane, propene, methane, ethane, ethene, carbon monoxide, carbon dioxide, steam, and optionally hydrogen and oxygen, is obtained); (iii) cooling (b) and optionally compressing and steam separating, by condensation, to give a product gas stream (c) stripped of steam; (iv) contacting (c) with a selective inert absorption agent, which selectively absorbs propene in a first absorption zone, to give an essentially propane charged absorption agent stream (d1) and a gas stream (d2) containing propane, methane, ethane, ethene, carbon monoxide, carbon dioxide and hydrogen; (v) optionally depressurizing (d1), in a first desorption zone, to give an essentially propene-charged absorption agent stream (e1) and a gas stream (e2) (which is recycled into the first absorption zone), containing propene; and (vi) releasing a propene-containing gas stream (f1) from (d1) and (e1) in at least one second desorption zone by depressurization, heating and/or stripping of the absorption agent stream (d1) and (e1) with recycling of the selective absorption agent.
Description
The present invention relates to a kind of method for preparing propylene by propane.
On technical scale, propylene obtains by dehydrogenating propane.
In being called as the method for UOP-oleflex, in order to make dehydrogenating propane become propylene, the gaseous feed logistics that will comprise propane is preheating to 600-700 ℃ and comprising hydrogenation on the catalyzer that is stated from the platinum on the aluminum oxide in moving numb dehydrogenation reactor, obtains mainly to comprise the product gas stream of propane, propylene and hydrogen.In addition, low boiling hydrocarbon (methane, ethane, ethene) and a spot of high boiling fraction (C that also exists cracking to form in the product gas stream
4 +Hydrocarbon).Cooled product gaseous mixture and with a plurality of stage compression.Then, by condensation in " ice chest " with C
2And C
3Hydrocarbon and high boiling fraction separate from the hydrogen that forms hydrogenation and methane.Then in first tower, remove C by distillation
2Hydrocarbon and remaining methane, and in second column with C
3Hydrocarbon stream is separated into to have highly purified propylene cut and also comprises C
4 +The propane fraction of hydrocarbon, thus the liquid hydrocarbon condensation product separated.
The shortcoming of this method is that the ice chest condensation has caused C
3The hydrocarbon loss.Owing to a large amount of hydrogen that form in the dehydrogenation and balance each other the C of larger amt
3Hydrocarbon is also followed hydrogen/methane waste product discharging, carries out unless be condensate under the low-down temperature.Thereby, must be in operation under-20 ℃ to-60 ℃ temperature with the C of restriction with hydrogen/methane waste product logistics discharging
3The hydrocarbon loss.
The method that to the purpose of this invention is to provide a kind of improved dehydrogenating propane be propylene.
Described purpose is by a kind of method realization for preparing propylene by propane, and this method may further comprise the steps:
A) provide a kind of feed gas stream a that comprises propane;
B) if if will comprise that the feed gas stream a of suitable oxygen-containing gas logistics of propane and suitable steam sends into dehydrogenation zone and make dehydrogenating propane is propylene, if if obtain to comprise the product gas stream b of propane, propylene, methane, ethane, ethene, carbon monoxide, carbonic acid gas, the suitable hydrogen of steam and suitable oxygen;
C) product gas stream b cools off, if suitable compression, and would remove devaporation to obtain the product gas stream c of dilution steam by condensation;
D) product gas stream c contacts with selectivity, the inertia absorption agent that the energy selectivity absorbs propylene in first absorption region, if if obtain the absorbent stream d1 and the gas stream d2 that comprises propane, propylene, methane, ethane, ethene, carbon monoxide, the suitable hydrogen of carbonic acid gas and suitable oxygen of basic load propylene;
E) if suitable, absorbent stream d1 separates in first desorption zone and is depressed into lower pressure, obtains the absorbent stream e1 and the gas stream e2 that comprises propylene of basic load propylene, and gas stream e2 recirculation is entered first absorption region,
F) from the absorbent stream d1 or e1 of basic load propylene, at least one second desorption zone,, discharge the gas stream f1 that comprises propylene and reclaim selective absorber by decompress(ion), heating and/or stripping absorbent stream d1 or e1.
In the first step A of this method, provide the feed gas stream that comprises propane.This logistics comprises the propane of at least 80 volume % usually, preferred 90 volume % propane.In addition, the feed gas stream a that contains propane generally also comprises butane (normal butane, Trimethylmethane).The essentially consist that contains the feed gas stream of propane is described among DE-A 102 46 119 and the DE-A102 45 585.Usually, the feed gas stream that contains propane is obtained by liquefied petroleum gas (LPG) (LPG).
In processing step B, the gas feed logistics 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 obtain a spot of oxycarbide (CO, CO
2), CO especially
2If, steam and suitable rare gas element.The product gas stream of dehydrogenation comprises steam usually, these steam be added into the dehydrogenation gaseous mixture and/or under the situation of carrying out dehydrogenation (oxidation or non-oxidizing) in the presence of the oxygen, 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-containing gas logistics, 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 the industrial pure oxygen of oxygen level＞99%, too high to prevent the rare gas element ratio in the product gas mixture.In addition, there is unconverted propane in the product gas mixture.
Dehydrogenating propane can carry out in the reactor of the known any kind 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 " (Study Number 4192 OD 1993,430 ferguson Drive, Mountain View, California, 94043-5272, USA).
Dehydrogenation can also be carried out with oxidation or non-oxidizable dehydrogenation mode.Dehydrogenation can isothermal or adiabatic carrying out.Dehydrogenation can also catalytically be carried out in fixed bed, moving-bed or fluidized-bed reactor.
Non-oxide catalysis dehydrogenating propane preferably autothermally carries out.For this reason, in at least one reaction zone, oxygen is mixed with the reaction gas mixtures of dehydrogenating propane in addition, and the hydrogen and/or the hydrocarbon that are present in this reaction mixture burn at least in part, produces the needed part at least of hydrogenation heat like this at least one reaction zone inner reaction gas mixture.
Compare with method for oxidation, characteristics of non-oxide method are intermediate formation hydrogen at least, and this shows in the product gas of 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 tube bundle reactor.In these reactors, catalyzer (if dehydrogenation catalyst and suitable special oxide catalyst) as fixed beds in the tube bank of reaction tubes and reaction tubes.Conventional tube inner diameter is about 10-15cm.Typical dehydrogenation tube bundle reactor comprises about 300-1000 reaction tubes.The internal temperature of reaction tubes generally changes in 300-1200 ℃, preferred 500-1000 ℃.The propane of Phillips Petroleum Co. company or the operating pressure of butane dehydrogenation are 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 gas hourly space velocity (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 under heterogeneous catalyst in fluidized-bed according to the Snamprogetti/Yarsintez-FBD method.Suitably, 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.Add the oxygen containing auxiliary charging of bag and can 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 also be carried out in the tower tray reactor.When dehydrogenation is autothermally carried out by supplying with the oxygen-containing gas logistics, 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, the amount that adds the oxygen-containing gas in the reaction gas mixture is selected in the following manner: if 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 coke 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 %.
For if to produce heat incendiary hydrogen be the hydrogen that produces in the propane catalytic dehydrogenation and suitablely add hydrogen in the reaction gas mixtures as hydrogen-containing gas in addition.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, can selectivity hydrogen catalyzedly operating in the presence of the incendiary oxide catalyst in the presence of the hydrocarbon at one or more with oxygen.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.
When reaction was carried out with the multistage that surpasses one, oxide catalyst can only exist only in a reaction zone, surpass in one the reaction zone or all reaction zones.
Preferably selectivity catalytic hydrocarbon incendiary catalyzer is placed on oxygen partial pressure than the high point of other point, the particularly place of close oxygen-containing gas feed point in the reactor.Oxygen-containing gas and/or hydrogen-containing gas can be sent into from one or more points of reactor.
In a kind of preferred implementation of the inventive method, the upstream of each tower tray of tower tray reactor exists the middle feed point of oxygen-containing gas and hydrogen-containing gas.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.GHSV is generally 500-2000h
-1, and under heavy-duty service, even up to 100 000h
-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 selectivity comprises the precious metal of periodic table of elements transition group VIII family and/or I family.
Used dehydrogenation catalyst has carrier and active composition usually.Carrier is made up of 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, also can be that chemical mixing is mutually as oxidation magnalium or zinc oxide aluminum mixed oxide.Preferred carrier is zirconium dioxide and/or silicon-dioxide, the mixture of preferred especially zirconium dioxide and silicon-dioxide.
The appropriate catalyst geometrical shape is squeeze-up, star, annular, saddle, sphere, foams and the material all in one piece with reference 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 territory II main group element, at least a III and/or IV main group element and at least a transition III family 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, US5,877,369, 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 steam, carry out the dehydrogenation of propane self-heating.The steam that adds plays the vaporization of organic sediments on the effect of thermal barrier and the support catalyst, the duration of service that this has resisted the carbonization of catalyzer and has prolonged catalyzer.If like this organic sediments is converted into carbon monoxide, carbonic acid gas and suitable water.With the steam dilution balance is moved to dehydrogenation product.
Dehydrogenation catalyst can be regenerated in known mode itself.For example, steam can be added in the reaction gas mixtures or can make every now and then comprise oxygen gas under elevated temperature by catalyst bed and burn sedimentary carbon.After the regeneration, if suitable, catalyzer reduces with hydrogen-containing gas.
Product gas stream 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-A10211275 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 existing application DE-A 1 96 22 331.
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 tube bundle reactor, for example with the adverse current tube furnace of waste gas as thermal barrier, or with the tube bundle reactor of salt-melting as thermal barrier.
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 answers 〉=1: 1, for example 〉=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 the condition of reaction compartment surface-area and the ratio minimum 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, silica glass, borosilicate, stainless steel and aluminium.
When first step of reaction of the inventive method was feature with the heterogeneous catalytic oxidation dehydrogenation, 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; 21 (1992) 592, WO97/36849, DE-A 1 97 53 817; 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; 284; Applied Catalysis A:General, 100 (1993) 111-130, J.of Catalysis 148; 56-67 (1994); V.Cort é s Corber á nand S.vic Bell ó n (editor), New development in Selective Oxidation II, 1994; Elsevier Science B.V.; the 305-313 page or leaf, 3rd World Congress onOxidation Catalysis 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:
A) Otsuka, K; Uragami, Y; Komatsu, T.; Hatano, M., Natural GasConversion, Stud.Surf.Sci.Caral.; Holmen A.; Jens, K.J.; Kolboe, S., editor; Elsevier Science:Amsterdam, 1991; The 61st volume, the 15th page;
B) Seshan, K.; Swaan, H.M.; Smits, RH.H.; Van Ommen, J.G.; Ross, J.R.H., New Developments in Selective Oxidation; Stud.Surf. Sci.Catal.; Centi.G.; Trifir ò, F., editor; EIsevier Science:Amsterdam 1990; The 55th volume, the 505th page;
C) Smits, R.H.H.; Seshan, K.; Ross, J.R.H., New Developments inSelective Oxidation by Heterogeneous Catalysis; Stud.Surf. Sci.Catal; Ruiz, P.; Delmon, B., editor; EIsevier Science:Amsterdam, 1992a; The 72nd volume, the 221st page;
d)Smits，R.H.H.；Seshan，K.；Ross，J.R.H.Proceedings，Symposiumon Catalytic Selective Oxidation，Washington DC；American ChemicalSociety：Washington.DC，1992b；1121；
e)Mazzocchia.，C.；Aboumrad，C.；Daigne，C.；Tempesti，E.；Herrmann，JM.；Thomas，G.CataL Lett.1991，10，181；
f)Bellusi，G.；Conti，G.；Perathonar，S.；Trifiro，F.Proceedings，Symposium on Catalytic Selective Oxidation，Washington，DC；AmericanChemical Society：Washington，DC，1991；P 1242；
G) Ind.Eng.Chem.Res.1996,35,2137-2143 and
h)Symposinm on Heterogeneous Hydrocarbon Oxidation Presentedbefore the Division of Petroleum Chemistry，Inc.211th National Meeting，American Chemical Society 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.In other words, 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-A100 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, and air (mixture of rare gas element and oxygen) for example can also be 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 compound 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, oxalate, Citrate trianion, acetate, carbonate, complexing amine salt, ammonium salt and/or oxyhydroxide particularly.
Multimetal oxide compositions can be used for the inventive method with powder type or to be shaped to certain catalyzer geometrical shape, and moulding can form before or after final calcining.Suitable do not carry attached catalyzer geometrical shape and be for example solid cylinder 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).Do not carry attached catalyzer and can certainly have spherical geometries, the diameter of ball can be 2-10mm in this case.
Also there are not the powdered activated composition of incinerating or its powder precursor composition can certainly be by being applied to moulding on the preformed inert catalyst carrier.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 pure aluminium silicate.Carrier 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 tube bundle reactor, and for example the citing document in EP-A 700893 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 of propane in the described initial gaseous mixture and molecular oxygen≤6: 1, 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 spot of C
1, C
2And C
4Hydrocarbon.
When leaving dehydrogenation zone, product gas stream 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, 0-30 volume % oxycarbide, 0-70 volume % steam and 0-25 volume % hydrogen, 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, 0.1-30 volume % oxycarbide, 1-70 volume % steam and 0.1-25 volume % hydrogen, and the rare gas element of 0-30 volume %.
In processing step C, at first from product gas stream b, remove and anhydrate.Water remove by condensation, cooling and, if suitable, compressed product gas stream b carries out, and if can carry out with one or more coolings and suitable compression stage.For this purpose, product gas stream b is cooled to 20-80 ℃ usually, preferred 40-65 ℃.In addition, product gas stream 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 stream b passes through from one group of heat exchanger, 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 steam of most of quantity, but also condensation goes out to be present in the portion C among the product gas stream 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 stream c of dilution steam.This product generally still comprises the steam of 0-10 volume %.For water is all removed from product gas stream c basically, when at step D) in when using special solvent, the drying of utilizing molecular sieve or film can be provided.
At processing step D) in, product gas stream c contacts with the inert solvent that selected energy selectivity absorbs propylene in first uptake zone, obtains load C
3Hydrocarbon, be essentially the absorbent stream d1 of propylene and comprise the gas stream d2 of propane, methane, ethane, ethene, carbon monoxide, carbonic acid gas and hydrogen.Propylene can also be present among the gas stream d2 slightly.
At implementing process step D) before, can from product gas stream c, remove carbonic acid gas by gas sweetening, obtain the product gas stream c of dilution carbonic acid gas.Carbon dioxide purifies and can be undertaken by combustion step independently, and wherein carbon monoxide optionally is oxidized to carbonic acid gas.
In order to remove CO
2, the decontaminating liquid of use is generally sodium hydroxide solution, potassium hydroxide solution or chain triacontanol amine solution; The preferred activatory N methyldiethanol amine solution that uses.Usually, before carrying out gas sweetening, product gas stream c is compressed to the pressure of 5-25 crust by compression in one or more steps.
The CO that the product gas stream d of the dilution carbonic acid gas that is obtained has
2Content usually＜100ppm, preferred＜10ppm.
Described absorption can make logistics c be undertaken by absorption agent simply.But, also can in tower, carry out.Can carry out in the mode of following current, adverse current or cross-flow.Suitable absorption tower is the column plate tower that for example has bubble cap plate, valve column plate and/or filter column plate, has the tower of structure weighting material, and for example fibrefill or specific surface area are 100-1000m
2/ m
3The sheet metal weighting material, Mellapak 250Y and have the tower of random weighting material for example, the ball, ring or the saddle that for example have metal, plastics or pottery are as random weighting material.But, can also use drip and spray tower, graphite block absorption agent, surface absorber such as thick film and film absorber and have and do not have the bubble-plate column of internals.
The absorption tower preferably has absorber portion and rectifying section.Absorption agent is generally introduced from cat head, and logistics c introduces from centre or upper part of tower usually.In order to utilize rectificating method to improve the enrichment degree of propylene in solvent, can at the bottom of tower, introduce heat.As selection, can at the bottom of tower, send into the stripping air-flow, for example form by nitrogen, air, steam or propylene, preferably form by propylene.Part overhead product can condensation and is introduced with the restriction solvent loss from cat head with reflux type again.
The selective solvent that suitable energy selectivity absorbs propylene is a N-Methyl pyrrolidone (NMP) for example, comprise the NMP/ water mixture of 20 weight % water at the most, meta-cresol, acetate, methylpyrazine, methylene bromide, dimethyl formamide (DMF), Texacar PC, N-methylmorpholine, ethylene carbonate, methane amide, propane dinitrile, gamma-butyrolactone, oil of mirbane, dimethyl sulfoxide (DMSO) (DMSO), tetramethylene sulfone, the pyrroles, lactic acid, vinylformic acid, the 2-chloropropionic acid, the trimellitic acid triallyl, tri trimellitate (2-ethylhexyl) ester, dimethyl terephthalate (DMT), Succinic acid dimethylester, the 3-chloropropionic acid, morpholine, acetonitrile, octyl group sulfuric acid 1-butyl-3-Methylimidazole quinoline, toluenesulphonic acids ethyl-methyl tetrahydroglyoxaline, xylidine, adiponitrile and formic acid.
Preferred selective absorber is NMP, contains the NMP/ water mixture of the highest 20 weight % water, acetonitrile, and the mixture of acetonitrile, organic solvent and/or the water of ethane nitrile content 〉=50 weight %, and xylidine.
Absorption step D) clings to, more preferably carries out under the 10-20 bar pressure at 2-40 crust, preferred 5-20 usually.Except that propylene, propane is also absorbed to a certain degree by the selectivity absorption agent.In addition, a spot of ethene and butylene also are absorbed.
In optional step e) in, absorbent stream d1 be extracted in first uptake zone to lower pressure with the absorbent stream e1 that obtains the basic load propylene with mainly comprise propylene and still comprise the gas stream e2 of small amounts of propane, and gas stream e2 is recycled and enters first uptake zone, preferably enters the rectifying section on absorption tower as Purge gas.
For this reason, absorbent stream d1 from absorption stage D) corresponding pressure unzips to the pressure of common 1-20 crust, preferred 1-10 crust.Decompress(ion) can be undertaken by a plurality of stages, general maximum 5 stages, for example 2 stages.The absorbent stream of load is heating in addition.
Acquisition comprises the gas stream e2 of propylene, wherein comprises the propane of 0-5 volume %, propylene and other gaseous fraction of 0-15 volume % such as the solvent of steam, ethene and oxycarbide and 0-50 volume % of 50-99 volume % usually.This logistics recirculation enters the uptake zone.Preferably the lower part on the absorption tower adds recycle gas logistics e2, and for example the height at the 1st to the 10th theoretical tray adds.As the result of recirculation propylene stream, the propane that is dissolved in absorption agent is gone out by stripping, and therefore the enrichment degree of propylene in absorption agent be improved.
In step F) in, from the absorbent stream d1 or e1 of basic load propylene,,, discharge the gas stream f1 that comprises propylene and reclaim selective absorber by decompress(ion), heating and/or stripping absorbent stream d1 or e1 at least one (second) desorption zone.If suitable, may comprise C
4 +This absorbent stream of the part of hydrocarbon is discharged, handles and reclaims, and is perhaps discarded.
For desorb is dissolved in gas in the absorption agent, is heated and/or separates and be depressed into lower pressure.As selection, desorb can also be undertaken by stripping, generally uses steam stripped, and perhaps decompress(ion), heating and stripping are carried out in combination in one or more processing steps.
Based on hydrocarbon content, comprise propylene and the gas stream f1 that discharged by desorb comprises the propylene of at least 98 volume %, preferably at least 99 volume % propylene, more preferably at least 99.5 volume % propylene usually.In addition, can also comprise propane and a spot of low boiling hydrocarbon such as methane and the ethene of 0-2 volume %, but be no more than 0.5 volume % usually, preferably be no more than 0.2 volume %.When carrying out desorb by steam stripped, gas stream f1 also comprises steam, and content is generally the maximum 50 volume % based on this gas stream total amount meter.
When propylene by in step F, during desorb, then again steam being removed from gas stream f1 usually with steam stripped.If this remove can by condensation, by the cooling and suitable compressed gas stream f1 carry out.If describedly remove operation and can in one or more coolings and suitable compression step, carry out.
For this purpose, usually gas stream f1 is cooled to 0-80 ℃, preferred 10-65 ℃.In addition, product gas stream can be compressed to for example pressure of 2-50 crust.To anhydrate in order removing fully basically, the drying of utilizing molecular sieve can be provided from gas stream f1.Described drying can also be undertaken by known other drying means of absorption, membrane sepn, rectifying or prior art.
In order to make gas stream f1 reach extra high propylene content, preferably will comprise propylene and in step F) the portion gas logistics f1 that obtains is recycled to the uptake zone.The ratio of recycle gas logistics is generally the 0-25% of gas stream f1, and preferred 0.10%.Usually, be present in and be recycled to dehydrogenation zone to small part propane among the gas stream d2.
In a kind of embodiment of the inventive method, the gas stream d2 that comprises propane directly is recycled to dehydrogenation zone to small part, and tributary (purge gas stream) shifts out with discharging rare gas element, hydrogen and oxycarbide from gas stream d2 usually.Purge gas stream can be burned.But the tributary of gas stream d2 can directly be recycled to dehydrogenation zone, and propane can shift out and be recycled to dehydrogenation zone from other tributary by absorption and desorption.
In the another kind of preferred implementation of the inventive method, comprise propane and at step D) in the logistics of the portion gas at least d2 that obtains at further step G) in contact with high-boiling absorbent, then make the desorption of gases that is dissolved in the absorption agent, obtain mainly by propane recirculation stream g1 that forms and the exhaust gas stream g2 that comprises methane, ethane, ethene, carbon monoxide, carbonic acid gas and hydrogen.The main recirculation stream of being made up of propane is recycled to first dehydrogenation zone.
For this reason, in the absorption stage, gas stream d2 contacts with the inertia absorption agent with propane and a spot of C
2Hydrocarbon is absorbed in the inertia absorption agent, and obtains the absorption agent and the waste gas that comprises the residual gas component of load propane.In fact, these remaining ingredients are oxycarbide, hydrogen, rare gas element, C
2Hydrocarbon and methane.In desorption phase, propane discharges from absorption agent again.
The inertia absorption agent that uses in absorption stage generally is the high boiling point non-polar solvent, and the solubleness of the propane that remove in this absorption agent is significantly higher than the remaining gas component.Absorption can be carried out through absorption agent by making logistics d2 simply.But, can also in Ta Nei or rotation resorber, carry out.Can operate with following current, adverse current or cross-flow mode.Suitable absorption tower is the column plate tower that for example has bubble cap plate, centrifugal column plate and/or filter column plate, has the tower of structure weighting material, and for example fibrefill or specific surface area are 100-1000m
2/ m
3The sheet metal weighting material, Mellapak for example
250Y and have the tower of random weighting material.Can also use drip and spray tower, graphite block absorption agent, surface absorber such as thick film and film absorber, and rotary column, tray scrubber, cross spray washer, rotary scrubber and have and do not have the bubble-plate column of internals.
Suitable absorption agent is nonpolar relatively organic solvent, for example aliphatic C
4-C
18Alkene, petroleum naphtha or aromatic hydrocarbon be as from oil distillate in the middle of the paraffin distillatory, or have the ether of bulky group or the mixture of these solvents, can add polar solvent in these solvents as 1, the 2-rutgers.Suitable absorption agent also has phenylformic acid and phthalic acid and straight chain C
1-C
18The ester of alkanol, for example positive butyl ester of phenylformic acid, methyl benzoate, ethyl benzoate, dimethyl phthalate, diethyl phthalate, and heat medium oil such as xenyl and diphenyl ether, their chlorine derivative and triaryl alkene.Suitable absorption agent is the mixture of xenyl and diphenyl ether, and the mixture that preferred azeotropic is formed for example can the commercial Diphenyl that obtains.Frequently, this solvent mixture comprises the dimethyl phthalate of 0.1-25 weight %.Suitable absorption agent also has butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, the tetradecane, pentadecane, n-Hexadecane, heptadecane and octadecane, or is obtained and comprised the cut of linear alpha-olefin as main ingredient by refinery steams.
For desorb propane, the absorption agent of load is heated and/or unzips to lower pressure.As selection, desorb can also be undertaken by stripping, generally with steam or oxygen-containing gas stripping, perhaps carries out decompress(ion), heating and stripping with one or more combination of process steps.For example, desorb can be carried out with two stages, and second desorption phase is carried out under the pressure lower than the fs, and the desorption gas of fs is recycled to the absorption stage.The regenerated absorption agent is recycled to the absorption stage in desorption phase.
In one embodiment, desorption procedure is undertaken by the absorption agent of decompress(ion) and/or heating load.In other method scheme, carry out stripping with steam in addition.In other embodiment, carry out stripping with oxygen-containing gas in addition.The consumption of stripping gas can be corresponding with the needed amount of oxygen of self-heating dehydrogenation.
As selection, at processing step G) in, can from gas stream d2 or its tributary, remove carbonic acid gas by gas sweetening, obtain the recirculation stream g1 of dilution carbonic acid gas.Carbon dioxide purifies and can be undertaken by independent burning phase, and wherein carbon monoxide optionally is oxidized to carbonic acid gas.
In order to remove CO
2, use sodium hydroxide solution, potassium hydroxide solution or chain triacontanol amine solution usually as decontaminating liquid; The preferred activatory N methyldiethanol amine solution that uses.Usually, before carrying out gas sweetening, product gas stream c is compressed to the pressure of 5-25 crust by a stage or multistage compression.Can obtain CO
2Content is general＜the recirculation stream g1 of the dilution carbonic acid gas of 100ppm, preferred＜10ppm.
If suitable, can absorb by membrane sepn or transformation and from gas stream d2, remove hydrogen.
In order to remove the hydrogen that exists in the exhaust gas stream, exhaust gas stream can (if suitable) after the cooling for example in direct heat exchanger by film, described film is generally in a tubular form and only can permeable molecule hydrogen.The molecular hydrogen of removing like this is passable, if necessary, is used for dehydrogenation or sends into other application facility to small part, for example produces electric energy in fuel cell.As selection, off-gas flows can burn.
The present invention will further set forth by following embodiment.
Embodiment
The embodiment of the present invention that shows among the figure is by calculating mimic.The processing parameter supposition is as follows.
Suppose the ability of 320kt/a propylene plant under 8000 hour working time.
Except that 98 weight % propane, fresh propane generally comprises 2 weight % butane.Can be with the dilution of butane content to 0.01 weight % in having the C3/C4 knockout tower of 40 theoretical trays with the reflux ratio of 10 working pressures that cling to and 0.41.Below, for fresh propane logistics 1, its propane content is assumed to 100%.
Fresh propane logistics 1 and recirculation stream 21 and 22 are merged so that charging propane logistics 2 to be provided.Charging propane logistics 2 is preheating to 400 ℃, enters the dehydrogenation zone 24 of about 3 crust of pressure and carries out the self-heating dehydrogenation.In addition dehydrogenation zone 24 is sent in pure oxygen logistics 3 and steam stream 4.The transformation efficiency of dehydrogenation is based on 35.3% of propane meter; The selection rate that propylene forms is 95.5%.In addition, form the oxycarbide of 0.8% crackate (ethane and ethene) and 3.7% by whole burnings.Water concentration in the exit gas of dehydrogenation zone is 21 weight %; Residual oxygen in the exit gas is 0 weight %; The temperature out of product gas mixture is 595 ℃.
Under 2.5 crust, exit gas is cooled to 55 ℃, and the condensation water outlet is until the vapour pressure that reaches capacity.Then, product gas mixture divides two stage compression in having intercooled two-stage compressor 25.In first compression stage from 2.5 the crust be compressed to 6 the crust, under subordinate phase in from 5.9 the crust be compressed to 15.3 the crust.Behind first compression stage, gaseous mixture is cooled to 55 ℃, and at the second compression stage postcooling to 30 ℃.When described compression is finished, obtain the condensate stream of mainly forming 7 by water.Under the pressure of 15 crust, contact in absorption tower 26 through overdraft and refrigerative gas stream 6 with water/NMP mixture 17 as absorption agent.Absorption agent 17 is introduced from cat head.The load of discharging has the logistics 8 of propylene only to comprise a spot of propane at the bottom of 26 towers of absorption tower, therefore can save propane/propylene in further treating processes and separate.The logistics that contains propane 9 of 26 tower top discharges can partly 21 recirculation enter dehydrogenation zone 24 as logistics from the absorption tower.Remaining tributary 10 contacts with n-tetradecane (TDC) as absorption agent in absorption/desorb unit 13.Remaining residual gas stream 23 mainly comprises hydrogen and oxycarbide.Desorb provides the gas stream 22 that mainly comprises propane, and it is recycled to dehydrogenation zone 24.Effluent streams 8 is separated the pressure that are depressed into 6 crust at the bottom of the tower of being made up of the absorption agent of load propylene in first desorption phase 27.When aforementioned processing was finished, release mainly comprised the gas stream 11 of propylene, and is recycled to absorption tower 26.The absorption agent of load propylene is sent into desorption tower 28 as logistics 12.In desorption tower 28, be depressed into 1.2 crust, heated base and separate the sucking-off propylene by separating with 16 crust highly compressed steam, 14 strippings, obtain the logistics 13 formed by absorbent regeneration and by the logistics 15 of propylene and vapor composition.Absorbent regeneration 13 usefulness fresh absorbent 16 are replenished and are recycled in the absorption tower 26.15 fen multistage of logistics by tower top discharge is compressed to 15 crust and is cooled to 40 ℃ simultaneously.When described finishing dealing with, the condensation water outlet and as waste water streams 18 from the discharging of this technology, and obtain substantially anhydrous pure propylene stream 19.The pure propylene stream 20 of dilution steam is recycled to the absorption tower.
According to following table, be that unit reproduces described logistics composition with the mass parts.
Table
| Logistics | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| Amount [kg/h] | 44137 | 142747 | 15962 | 24619 | 183327 | 144742 | 38585 |
| O2 | 0.0000 | 0.0000 | 1.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0000 |
| H2 | 0.0000 | 0.0082 | 0.0000 | 0.0000 | 0.0098 | 0.0124 | 0.0000 |
| CO2/CO | 0.0000 | 0.0623 | 0.0000 | 0.0000 | 0.0746 | 0.0945 | 0.0000 |
| Ethene | 0.0000 | 0.0013 | 0.0000 | 0.0000 | 0.0016 | 0.0020 | 0.0000 |
| Ethane | 0.0000 | 0.0028 | 0.0000 | 0.0000 | 0.0034 | 0.0043 | 0.0000 |
| Propane | 1.0000 | 0.8675 | 0.0000 | 0.0000 | 0.4371 | 0.5535 | 0.0003 |
| Propylene | 0.0000 | 0.0572 | 0.0000 | 0.0000 | 0.2620 | 0.3318 | 0.0003 |
| Water | 0.0000 | 0.0006 | 0.0000 | 1.0000 | 0.2114 | 0.0015 | 0.9990 |
| NMP | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0000 |
| TDC | 0.0000 | 0.0001 | 0.0000 | 0.0000 | 0.0001 | 0.0000 | 0.0004 |
| Temperature, ℃ | 100.0 | 400.0 | 100.0 | 250.0 | 594.6 | 30.0 | 49.9 |
| Pressure [crust] | 3.0 | 3.0 | 3.0 | 40.0 | 2.5 | 15.3 | 15.3 |
Continuous table
| Logistics | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 |
| Amount [kg/h] | 2955181 | 104657 | 36630 | 222945 | 2732236 | 2689519 | 1922 | 44638 |
| O2 | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0000 |
| H2 | 0.0000 | 0.0172 | 0.0172 | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0000 |
| CO2/CO | 0.0000 | 0.1306 | 0.1306 | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0000 |
| Ethene | 0.0000 | 0.0028 | 0.0028 | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0000 |
| Ethane | 0.0000 | 0.0060 | 0.0060 | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0000 |
| Propane | 0.0004 | 0.7643 | 0.7643 | 0.0041 | 0.0001 | 0.0000 | 0.0000 | 0.0031 |
| Propylene | 0.0849 | 0.0783 | 0.0783 | 0.9348 | 0.0155 | 0.0000 | 0.0000 | 0.9502 |
| Water | 0.0390 | 0.0008 | 0.0008 | 0.0333 | 0.0394 | 0.0400 | 1.0000 | 0.0467 |
| NMP | 0.8756 | 0.0000 | 0.0000 | 0.0279 | 0.9447 | 0.9597 | 0.0000 | 0.0000 |
| TDC | 0.0002 | 0.0000 | 0.0000 | 0.0000 | 0.0003 | 0.0003 | 0.0000 | 0.0000 |
| Temperature, ℃ | 72.8 | 23.7 | 23.7 | 124.1 | 124.1 | 149.3 | 200.0 | 50.0 |
| Pressure [crust] | 15.3 | 15.3 | 15.3 | 6.0 | 6.0 | 1.2 | 16.0 | 1.2 |
Continuous table
| Logistics | 16 | 17 | 18 | 19 | 20 | 21 | 22 | 23 |
| Amount [kg/h] | 1 | 2689521 | 1968 | 40040 | 2630 | 68027 | 30583 | 6063 |
| O2 | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0000 |
| H2 | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0172 | 0.0000 | 0.1039 |
| CO2/CO | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.1306 | 0.0000 | 0.7892 |
| Ethene | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0028 | 0.0000 | 0.0168 |
| Ethane | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0060 | 0.0000 | 0.0359 |
| Propane | 0.0000 | 0.0000 | 0.0000 | 0.0032 | 0.0032 | 0.7643 | 0.9059 | 0.0479 |
| Propylene | 0.0000 | 0.0000 | 0.0015 | 0.9946 | 0.9831 | 0.0783 | 0.0926 | 0.0060 |
| Water | 0.0000 | 0.0400 | 0.9984 | 0.0021 | 0.0137 | 0.0008 | 0.0009 | 0.0000 |
| NMP | 1.0000 | 0.9597 | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0000 | 0.0000 |
| TDC | 0.0000 | 0.0003 | 0.0001 | 0.0000 | 0.0000 | 0.0000 | 0.0005 | 0.0002 |
| Temperature, ℃ | 50.0 | 45.0 | 55.0 | 40.0 | 102.3 | 150.0 | 60.7 | 50.1 |
| Pressure [crust] | 15.3 | 15.3 | 15.3 | 15.3 | 15.3 | 15.3 | 3.2 | 15.3 |
Claims (17)
1. one kind prepares the method for propylene by propane, may further comprise the steps:
A) provide a kind of feed gas stream a that comprises propane;
B) if send into the dehydrogenation zone if will comprise the feed gas stream a of suitable steam of propane and suitable oxygen-containing gas logistics, if and making dehydrogenating propane is propylene, obtains to comprise the product gas stream b of following component: if propane, propylene, methane, ethane, ethene, carbon monoxide, carbonic acid gas, the suitable hydrogen of steam and suitable oxygen;
C) product gas stream b cools off, if suitable compression, and would remove devaporation to obtain the product gas stream c of dilution steam by condensation;
D) product gas stream c contacts with the selectivity inertia absorption agent that the energy selectivity absorbs propylene in first absorption region, if if obtain the absorbent stream d1 and the gas stream d2 that comprises propane, propylene, methane, ethane, ethene, carbon monoxide, the suitable hydrogen of carbonic acid gas and suitable oxygen of basic load propylene;
E) if suitable, absorbent stream d1 separates in first desorption zone and is depressed into lower pressure, obtains the absorbent stream e1 and the gas stream e2 that comprises propylene of basic load propylene, and gas stream e2 recirculation is entered first absorption region,
F) from the absorbent stream d1 or e1 of basic load propylene, at least one second desorption zone,, discharge the gas stream f1 that comprises propylene, and reclaim selective absorber by decompress(ion), heating and/or stripping absorbent stream d1 or e1.
2. the method for claim 1, wherein step B) in dehydrogenation carry out in the mode of oxidation or non-oxidizable dehydrogenation.
3. the method for claim 1, wherein step B) in dehydrogenation thermal insulation or isothermal ground carry out.
4. the method for claim 1, wherein step B) in dehydrogenation in fixed-bed reactor, moving-burden bed reactor or fluidized-bed reactor, carry out.
5. the method for claim 1, wherein the oxygen-containing gas logistics is at step B) in send into, described oxygen-containing gas logistics comprises the oxygen of at least 90 volume %.
6. method as claimed in claim 5, wherein dehydrogenation is carried out in self-heating dehydrogenation mode.
7. as each described method among the claim 1-6, wherein comprise propylene and in step F) in a part of gas stream f1 of obtaining be recycled to the uptake zone.
8. as each described method, wherein step D among the claim 1-7) in the selective absorber that uses be selected from NMP, the NMP/ water mixture that comprises maximum 20 weight % water, meta-cresol, acetate, methylpyrazine, methylene bromide, DMF, Texacar PC, N-methylmorpholine, ethylene carbonate, methane amide, propane dinitrile, gamma-butyrolactone, oil of mirbane, DMSO, tetramethylene sulfone, the pyrroles, lactic acid, vinylformic acid, the 2-chloropropionic acid, the trimellitic acid triallyl, tri trimellitate (2-ethylhexyl) ester, dimethyl phthalate, Succinic acid dimethylester, the 3-chloropropionic acid, morpholine, acetonitrile, octyl group sulfuric acid 1-butyl-3-Methylimidazole quinoline, toluenesulphonic acids ethyl-methyl tetrahydroglyoxaline, adiponitrile, xylidine and formic acid.
9. as each described method, wherein step D among the claim 1-8) in the uptake zone be absorption tower with absorber portion and rectifying section, and at the bottom of heat and/or stripping gas sent into tower.
10. method as claimed in claim 9 is wherein at desorption procedure E) in the gas stream that comprises propylene that obtains send at the bottom of the tower on absorption tower as stripping gas.
11. as each described method among the claim 1-10, wherein stripping is in step F) in carry out with steam.
12. method as claimed in claim 11, wherein by one or multistage cooling and compression and vapor condensation gone out and as water from comprise propylene and steam and in step F) remove among the gas stream f1 that obtains, or by absorption, rectifying and/or membrane sepn except that devaporation.
13. as each described method among the claim 1-12, wherein comprise propane and at step D) in the exhaust gas stream d2 that obtains be recycled to dehydrogenation zone to small part.
14. as each described method among the claim 1-13, wherein comprise propane and at step D) in the logistics of the portion gas at least d2 that obtains at further step G) in contact with high-boiling absorbent, then make the desorption of gases that is dissolved in the absorption agent, acquisition is mainly by propane recirculation stream g1 that forms and the exhaust gas stream g2 that comprises methane, ethane, ethene, carbon monoxide, carbonic acid gas and hydrogen, and the recirculation stream g1 that mainly is made up of propane is recycled to dehydrogenation zone.
15. method as claimed in claim 14, wherein step G) in the high-boiling absorbent used be selected from C
4-C
18Alkane, petroleum naphtha or from oil distillate in the middle of the paraffin distillatory.
16., wherein be dissolved in gas in the absorption agent by at step G as claim 14 or 15 described methods) in usefulness steam stripped and desorb.
17. as each described method among the claim 1-13, wherein at further step G) in by gas sweetening with carbonic acid gas at least from step D) remove the low and recirculation stream g1 that be recycled to dehydrogenation zone of acquisition carbon dioxide content in the tributary of the gas stream d2 that comprises propane that obtains.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE200510000798 DE102005000798A1 (en) | 2005-01-05 | 2005-01-05 | Preparation of propene comprises preparing a feed stream containing propane; feeding the feed stream to a dehydrogenation zone; followed by cooling, contacting the cooled product gas stream and depressurizing |
| DE102005000798.8 | 2005-01-05 | ||
| DE102005012291.4 | 2005-03-17 | ||
| DE200510012291 DE102005012291A1 (en) | 2005-03-17 | 2005-03-17 | Preparation of propene comprises preparing a feed stream containing propane; feeding the feed stream to a dehydrogenation zone; followed by cooling, contacting the cooled product gas stream and depressurizing |
| PCT/EP2006/000032 WO2006072572A1 (en) | 2005-01-05 | 2006-01-04 | Method for the production of propene from propane |
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| CN101115697B CN101115697B (en) | 2010-09-29 |
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| CN2006800040110A Expired - Fee Related CN101115697B (en) | 2005-01-05 | 2006-01-04 | Method for the production of propene from propane |
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| EP3708558A1 (en) | 2019-03-15 | 2020-09-16 | Linde GmbH | Method and installation for the production of one or more olefins |
| EP3708557A1 (en) | 2019-03-15 | 2020-09-16 | Linde GmbH | Method and installation for the production of one or more olefins |
| US11560344B2 (en) | 2019-03-15 | 2023-01-24 | Linde Gmbh | Method and system for producing one or more olefins |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6293999B1 (en) * | 1999-11-30 | 2001-09-25 | Uop Llc | Process for separating propylene from propane |
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- 2006-01-04 CN CN2006800040110A patent/CN101115697B/en not_active Expired - Fee Related
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| CN108358162A (en) * | 2011-12-30 | 2018-08-03 | 国际壳牌研究有限公司 | The method for preparing paraffin products |
| CN103896708B (en) * | 2012-12-25 | 2015-09-16 | 中国科学院大连化学物理研究所 | A kind of method utilizing lactic acid or lactic acid salt preparing propone |
| CN103896708A (en) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | Method used for preparing propylene from lactic acid or lactate |
| CN104326857A (en) * | 2013-07-18 | 2015-02-04 | 林德股份公司 | Method and device for generating an alkene |
| US10787402B2 (en) | 2016-04-15 | 2020-09-29 | Sabic Global Technologies B.V. | Separation of off gases from C3 hydrocarbons in propane dehydrogenation process |
| CN108713052A (en) * | 2016-04-15 | 2018-10-26 | 沙特基础工业全球技术公司 | Exhaust gas and C in dehydrogenating propane method3The separation of hydrocarbon |
| CN108713052B (en) * | 2016-04-15 | 2021-03-19 | 沙特基础工业全球技术公司 | Off-gas and C in propane dehydrogenation process3Separation of hydrocarbons |
| CN106588548A (en) * | 2016-11-21 | 2017-04-26 | 中石化宁波工程有限公司 | Olefin separation method |
| CN106588548B (en) * | 2016-11-21 | 2019-05-17 | 中石化宁波工程有限公司 | A kind of alkene separation method |
| CN110177770A (en) * | 2017-01-18 | 2019-08-27 | 晓星化学(株) | Make the method for dehydrating alkanes |
| CN110177770B (en) * | 2017-01-18 | 2022-05-13 | 晓星化学(株) | Process for dehydrogenating alkanes |
| CN110312697A (en) * | 2017-02-22 | 2019-10-08 | 国际壳牌研究有限公司 | Gas purification for alkanes oxidative dehydrogenation effluent |
| CN110312697B (en) * | 2017-02-22 | 2022-03-25 | 国际壳牌研究有限公司 | Gas cleanup for alkane oxidative dehydrogenation effluents |
| CN114656317A (en) * | 2020-12-22 | 2022-06-24 | 中国石油化工股份有限公司 | Method and system for preparing olefin through oxidative coupling of methane and application of method and system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101115697B (en) | 2010-09-29 |
| DE102005000798A1 (en) | 2006-07-13 |
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