CN1771214A - Autothermal cracking process - Google Patents
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- CN1771214A CN1771214A CN 200480009405 CN200480009405A CN1771214A CN 1771214 A CN1771214 A CN 1771214A CN 200480009405 CN200480009405 CN 200480009405 CN 200480009405 A CN200480009405 A CN 200480009405A CN 1771214 A CN1771214 A CN 1771214A
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Abstract
The present invention provides a process for the production of olefins which process comprises co-feeding at least one unsaturated hydrocarbon with a paraffinic hydrocarbon-containing feedstock and a molecular oxygen-containing gas to an autothermal cracker, wherein they are reacted in the presence of a catalyst capable of supporting combustion beyond the normal fuel rich limit of flammability to provide a hydrocarbon product stream comprising olefins.
Description
The present invention relates to the preparation of monoolefine, it is that the autothermal cracking of the autothermal cracking by the paraffinic hydrocarbons with two or more carbon atoms, especially ethane, propane and butane carries out.
Can comprise that the steam cracking of hydrocarbon or the dehydrogenation by paraffinic feedstock prepare alkene for example ethene and propylene by many methods.Recently, found and can prepare alkene by a kind of method that is called autothermal cracking.In this method, paraffinic feedstock and oxygen-containing gas mixed and with catalyzer (its can in the flammable limit support burning of the rich fuel that surpasses conventional fuel) thus contact the hydrocarbon product stream that comprises alkene be provided.Burning of hydrocarbon feeding part and the heat that is produced are used to drive dehydrogenation reaction.This method is recorded in for example EP-B1-0332289.
The hydrocarbon steam cracking that produces monoolefine has produced other unsaturated hydrocarbons, for example diolefine and alkynes usually jointly.
Diolefine is separated from the product stream of steam cracker usually, and it comprises for example second cyanogen of a large amount of toxicity combustible solvents of use.In case after separating, diolefine then is considered as high-value product and is used for the derivative preparation example such as synthetic rubber prepares.Yet diolefine is difficult to transmission, because it is easy to degrade by oligomerization, and the derivative factory that therefore uses the diolefine charging usually and the source of supply colocated.In the place of the throughput of the derivative that does not use diolefine, then the preparation of diolefine just is a problem.This is because contain carbon fouling in the equipment because it is easy to cause, it is undesirable that diolefine is recycled to steam cracker, and therefore diolefine must be hydrogenated before being recycled to steam cracker, perhaps must stand of short duration stove working time (furnace run-time), economical and operational defective have taken place thereupon.
Produce other unsaturated hydrocarbons (for example alkynes) by steam cracking and also produce similar problem.If be recycled to steam cracker, then they also are easy to cause carbon fouling, and therefore must be hydrogenated before reclaiming, and perhaps stand of short duration stove working time.
Therefore now found that autothermal cracking process can allow the common charging of unsaturated hydrocarbons, and can not cause carbon fouling, and can the feeding unsaturated hydrocarbons and can not cause that shorten working time.More specifically, found that now autothermal cracking process can be by improving at least a unsaturated hydrocarbons (especially diolefine or alkynes) and paraffinic feedstock and the common feeding autothermal cracking of molecular oxygen-containing gas device.Having found can provide growth based on the olefins yield of the paraffinic feedstock amount that is transformed with the common feeding of at least a unsaturated hydrocarbons.Though do not expect to be limited by theoretical, we think that this is because the unsaturated hydrocarbons of common feeding is easier to burning than the paraffinic hydrocarbons in the charging.And found that most of unsaturated hydrocarbons can be transformed, and surprisingly there is not significant incarbonization to come across on the catalyzer, and be on catalyzer, to produce the unexpectedly added compound of low levels (relevant), for example benzene or toluene with incarbonization.
Therefore the invention provides a kind of method that is used to prepare alkene, this method comprises a kind of charging that contains paraffinic hydrocarbons of feeding (i); (ii) at least a unsaturated hydrocarbons and (iii) a kind of gas of molecule-containing keto to the autothermal cracking device, wherein they can react under the situation of supporting the incendiary catalyzer to exist outside the flammable limit of the rich fuel that surpasses conventional fuel, thereby the hydrocarbon product stream that comprises alkene is provided.
As used in this, " unsaturated hydrocarbons " comprises alkene.
Therefore, unsaturated hydrocarbons can be an alkene, for example ethene, propylene, butylene, amylene, hexene, heptene, more high-grade alkene and cycloolefin such as cyclopropylene, cyclobutene, cyclopentenes, tetrahydrobenzene, suberene and high-grade cycloolefin more.
Unsaturated hydrocarbons can be an aromatic substance.Suitable aromatic substance comprises benzene,toluene,xylene, ethylbenzene, vinylbenzene and substituted vinylbenzene, indenes and substituted indenes.The autothermal cracking device is operated under low relatively pressure herein, is generally normal atmosphere to 5 crust, and preferred aromatic substance is dimethylbenzene, indenes and vinylbenzene.Under high pressure more in (in common 5 Palestine and Israels) operation, preferred aromatic substance is benzene and/or toluene at the autothermal cracking device.
This unsaturated hydrocarbons is a diolefine in first preferred embodiment.This diolefine can be selected from the diolefine of any appropriate, but is preferably selected from propadiene, 1,2 divinyl, 1,3 divinyl, 1,3 pentadiene, 1,4 pentadiene, cyclopentadiene, 1,3 hexadienes, 1,4 hexadienes, 1,5 hexadiene, 2,4 hexadienes, 1,3 cyclohexadiene and 1, the substitutive derivative of 4 cyclohexadiene and above-mentioned substance, for example alkyl-substituted derivatives such as each molecule are with surpassing a kind of substituent methyl-derivatives, and wherein substituting group can be identical or different.Most preferably this diene is selected from 1,2 divinyl, 1,3 divinyl, 2 methyl, 1,3 divinyl, 1,3 pentadiene, 1,4 pentadiene and cyclopentadiene.Advantageously this diene is 1,3 divinyl.
In second preferred embodiment, unsaturated hydrocarbons can be an alkynes, for example acetylene, propine and/or butine.Especially preferred alkynes is acetylene.
The mixture of single unsaturated hydrocarbons or unsaturated hydrocarbons can be fed into the autothermal cracking device.
The method of alkene produced according to the present invention mainly produces monoolefine (alkene), especially ethene and propylene, although also can produce a certain amount of other alkene.
Although can be with the common feeding of alkene and carbon fouling in can production process, and can expect that its burning is better than the paraffinic hydrocarbons in the charging, the preferred usually common feeding alkene identical with this method desired product.Yet if the identical alkene of feeding and this method expection product jointly is the words that their exist as the part of the logistics that has also comprised other unsaturated hydrocarbons.Perhaps, for example, although usually because produced the ethene and/or the propylene of main amount, and preferably not with ethene and/or the common feeding autothermal cracking of propylene device, but advantageously common other alkene of feeding such as butylene are even described method has also produced described other alkene.
In addition, when alkene as the exhaust flow (it also can comprise alkane) of olefin derivative process in unreacted alkene and when existing, the common feeding of alkene such as ethene and propylene also can be favourable.Therefore ethene can be present in the waste gas of ethene derivatives technology (for example polyethylene process, ethylbenzene process, ethanol and vinyl acetate technology).Propylene can be present in the waste gas of acryloyl derivative technology (for example polymarization method for prodcing polyacrylates, propenal technology, Virahol technology and vinylformic acid technology).
Therefore preferably, the unsaturated hydrocarbons of feeding autothermal cracking device of the present invention technology comprises the unsaturated hydrocarbons beyond at least a alkene, and for example diene and alkynes is at least a.More preferably, at least a unsaturated hydrocarbons feeding autothermal cracking device except alkene, and be less than the 1wt% of independent alkene (for example ethene and propylene), for example be less than 0.5wt%, based on the paraffinic hydrocarbons weight of feeding reactor.Even more preferably, at least a unsaturated hydrocarbons feeding autothermal cracking device except alkene, and be less than the 1wt% of total olefin, for example be less than 0.5wt%, based on the paraffinic hydrocarbons weight of feeding reactor.Most preferably, the charging of autothermal cracking device comprises at least a in diolefine and the alkynes, and does not have alkene substantially.
Replace in the embodiment at one, the unsaturated hydrocarbons of feeding autothermal cracking device of the present invention technology can comprise at least a unsaturated hydrocarbons except that aromatic substance.
Provide unsaturated hydrocarbons as the separate feeds except containing paraffinic feedstock.Yet, should be noted that containing paraffinic feedstock also can comprise unsaturated hydrocarbons, and contain the unsaturated hydrocarbons charging and also can comprise paraffinic hydrocarbons.
Unsaturated hydrocarbons can be from the product stream of conventional steam cracking reaction device.Perhaps, unsaturated hydrocarbons can be from the exhaust flow of fluid catalytic cracking reactor or can be from the unitary exhaust flow of delayed coking unit unit, visbreaker unit or alkanisation.This unsaturated hydrocarbons also can be used as from coker, fluid catalytic cracking (FCC) or the unitary cut of heavy oil fluid catalytic cracking (RCC) and provides.
This unsaturated hydrocarbons can be by plastics recovery technology such as thermopolymer cracking and is provided in addition.
This unsaturated hydrocarbons is as providing from the part of polymer cracking reactor product stream in one embodiment of the invention.Except unsaturated hydrocarbons, also can comprise paraffinic hydrocarbons from the product of polymer cracking reactor stream, and therefore total paraffinic hydrocarbons of at least a portion feeding technology of the present invention is provided.
Auto thermal cracking reactor has produced the product stream that comprises unsaturated hydrocarbons (alkene and other unsaturated hydrocarbons).In a preferred embodiment of the present invention, the unsaturated hydrocarbons of feeding auto thermal cracking reactor is from the autothermal cracking reacting product stream.
Therefore the present invention also provides a kind of method for preparing alkene, and this method comprises the following steps:
(a) will contain the charging of paraffinic hydrocarbons and the gas feeding autothermal cracking device of molecule-containing keto, wherein they can react under the situation that the rich fuel flammable limit that surpasses conventional fuel supports the incendiary catalyzer to exist, thereby the hydrocarbon product stream that comprises alkene is provided
(b) reclaim alkene that at least a portion step (a) produces and
(c) unsaturated hydrocarbons that at least a step (a) is produced is back to the autothermal cracking device.
In a preferred embodiment, the hydrocarbon product stream of step (a) generation is separated into second logistics that has comprised first logistics that contains the hydrocarbon that is less than 4 carbon atoms and comprised the hydrocarbon that contains at least 4 carbon atoms.
Therefore another embodiment of the present invention provides a kind of method for preparing ethene and/or propylene, and this method comprises the following steps:
(a) will contain the charging of paraffinic hydrocarbons and the gas feeding autothermal cracking device of molecule-containing keto, wherein they can react under the situation that the rich fuel flammable limit that surpasses conventional fuel supports the incendiary catalyzer to exist, thereby the hydrocarbon product stream that comprises ethene and/or propylene is provided
(b) hydrocarbon product stream that step (a) is produced is separated into second logistics that has comprised first logistics that contains the hydrocarbon that is less than 4 carbon atoms and comprised the hydrocarbon that contains at least 4 carbon atoms, comprises at least a unsaturated hydrocarbons that contains at least 4 carbon atoms
(c) retrieve from the ethene of first logistics and/or propylene and
(d) at least a portion second logistics is back to the autothermal cracking device.
In this embodiment, the unsaturated hydrocarbons that preferably contains at least 4 carbon atoms is recovered and recycled to the autothermal cracking device from second logistics.
At this unsaturated hydrocarbons that contains at least 4 carbon atoms can be the above-mentioned unsaturated compound that contains at least 4 carbon atoms arbitrarily.Preferably, this unsaturated hydrocarbons that contains at least 4 carbon atoms is selected from 1,2 divinyl, 1,3 divinyl, 2 methyl, 1,3 divinyl, 1,3 pentadiene, 1,4 pentadiene and cyclopentadiene and 1,3 divinyl advantageously.
As mentioned above, unsaturated hydrocarbons can be an alkynes in second preferred embodiment, for example acetylene, propine and/or butine.
Therefore, the present invention also provides a kind of method for preparing ethene and/or propylene, and this method comprises the following steps:
(a) will contain the charging of paraffinic hydrocarbons and the gas feeding autothermal cracking device of molecule-containing keto, wherein they can react under the situation that the rich fuel flammable limit that surpasses conventional fuel supports the incendiary catalyzer to exist, thereby the hydrocarbon product stream that comprises ethene and/or propylene and at least a alkynes is provided
(b) reclaim ethene that at least a portion step (a) produces and/or propylene and
(c) alkynes that at least a step (a) is produced is back to the autothermal cracking device.
In this preferred embodiment, found that at least a alkynes of common feeding can provide remarkable improvement aspect ethylene yield, common in addition feeding alkynes can suppress methane production.
Can be with the mixture input autothermal cracking device of single alkynes or alkynes.Perhaps, can be with mixture and one or more other unsaturated compounds (as one or more alkenes and/or diolefine) input autothermal cracking device of one or more alkynes.
As mentioned above, at least a portion unsaturated hydrocarbons is from autothermal cracking product stream itself, promptly from hydrocarbon product stream.If the words that need, from the unsaturated hydrocarbons of hydrocarbon product stream can by from one or more other source (as product stream from the steam cracking reaction device of routine, the exhaust flow of fluid catalytic cracking reactor, the exhaust flow of delayed coking unit unit, visbreaker unit or alkylation or from for example thermopolymer cracking of plastics recovery technology) extra unsaturated hydrocarbons replenish.
When unsaturated hydrocarbons was the alkynes mixture of at least a alkynes (or comprise), if need, especially preferred additional alkynes source was the acetylene that is obtained by the acetylene preparation process from methane.This acetylene preparation process is well-known, and comprises for example oxidation and non-oxide pyrolysis and oxidative coupling method.Most preferably, the methane that is used to prepare acetylene himself can flow from the autothermal cracking product, as long as at least some any methane that form in the autothermal cracking process are converted into acetylene in main-process stream, improve olefin yield and suppress further methane formation thereby then its common feeding is got back to autothermal cracking technology.Therefore, when unsaturated hydrocarbons was alkynes, present method can provide significant benefits (being reductive action) aspect the overall selectivity of methane.
The suitable charging that contains paraffinic hydrocarbons can be ethane, propane or butane or its mixture.Hydrocarbonaceous feed can comprise other hydrocarbon and randomly other material, for example nitrogen, carbon monoxide, carbonic acid gas, steam or hydrogen.Particularly, except at least a unsaturated hydrocarbons charging, the charging that contains paraffinic hydrocarbons also can comprise unsaturated hydrocarbons, for example alkene and aromatic hydrocarbon.The charging that contains paraffinic hydrocarbons can comprise part for example petroleum naphtha, diesel oil, vacuum diesel oil or its mixture.Usually the charging that contains paraffinic hydrocarbons comprises the gaseous paraffin hydrocarbons mixture that is produced by the methane separation from Sweet natural gas, mainly comprises ethane.
This gas that contains the charging of alkane, at least a unsaturated hydrocarbons and molecule-containing keto all can be used as independent fluid input autothermal cracking device.
Usually this at least a unsaturated hydrocarbons with contain the merging of paraffinic feedstock premix and import the autothermal cracking device subsequently.Usually gained fluidic unsaturated hydrocarbons weight percent is for 0.01wt% at least, preferably 0.1wt%, most preferably 1wt% and advantageously 2wt% at least at least at least, based on paraffinic hydrocarbons weight meter.
Usually the unsaturated hydrocarbons weight percent is 0.01-50wt%, preferred 0.1-30wt%, most preferably 1-20wt% and 2-15wt% advantageously, based on paraffinic hydrocarbons weight meter.
When unsaturated hydrocarbons was the diene mixture of at least a diene (or comprise), the diene of the preferred 1-20wt% of diene weight percent of this unsaturated hydrocarbons, preferred 2-15wt% was based on paraffinic hydrocarbons weight meter.
When unsaturated hydrocarbons was the alkynes mixture of at least a alkynes (or comprise), the alkynes weight percent of this unsaturated hydrocarbons was preferably the alkynes of 0.1-5wt%, preferred 1-5wt%, based on paraffinic hydrocarbons weight meter.
Suitable molecular oxygen-containing gas is oxygen or air.Preferably this molecular oxygen-containing gas is an oxygen, randomly by rare gas element such as nitrogen dilution.
The suitable alkane charging that contains is to be used for perfect combustion to become the hydrocarbon of carbonic acid gas and water and 5-13.5 times of oxygen-containing gas stoichiometric ratio with the ratio of molecular oxygen-containing gas mixture.The 5-9 that preferred ratio is hydrocarbon and oxygen-containing gas stoichiometric ratio doubly.
Comprise that at least a additional feed stream from carbon monoxide, carbonic acid gas, steam and hydrogen also can import the autothermal cracking device.Preferably, the additional feed stream input autothermal cracking device that comprises hydrogen.Preferably this comprises the additional feed stream of hydrogen and contains the paraffinic feedstock pre-mixing and import the autothermal cracking device subsequently.
The autothermal cracking device can suitably be operated under greater than 500 ℃ temperature, for example greater than 650 ℃, usually greater than 750 ℃, and be preferably more than 800 ℃.Upper temperature limit can suitably reach 1200 ℃, for example reaches 1100 ℃, preferably reaches 1000 ℃.
Usually, this autothermal cracking device can be operated under normal atmosphere or high pressure.The pressure of 1-40 crust is suitable, is preferably the 1-5 bar pressure, for example can use 1.8 crust.Yet can use the total pressure greater than 5 crust, total pressure is greater than 15 crust usually.Advantageously the autothermal cracking device is operated between 15-40 bar pressure scope, for example between the 20-30 crust, for example 25 clings to.
When unsaturated hydrocarbons is the mixture of alkene, aromatic substance or alkene and/or aromatic substance, this autothermal cracking device is preferably operated under the total pressure greater than 5 crust, usually greater than 15 total pressures of clinging to, and advantageously is 15-40 bar pressure scope, for example between the 20-30 crust, for example 25 cling to.
Preferably, the gas that contains paraffinic feedstock, the gas that comprises at least a unsaturated hydrocarbons and molecule-containing keto is greater than 80000hr
-1Gas hourly space velocity (GHSV) mix down input autothermal cracking device.Preferably, this GHSV surpasses 200000hr
-1, especially surpass 1000000hr
-1Be purpose of the present invention, GHSV is defined as: (combined feed total feed volume under the NTP/hour)/(catalytic bed volume).
Rightly, catalyzer is to support the platinum metals.Preferably, metal is platinum or palladium or its mixture.When unsaturated hydrocarbons was the alkynes mixture of at least a alkynes (or comprise), this metal preferably included the mixture of platinum and palladium.
Although can obtain solid support material widely, preferably use aluminum oxide as carrier.Solid support material can spherical, granular or ceramic foam form.Preferably, this foam is continuous hyperchannel ceramic structure, often is the material all in one piece of honeycomb outward appearance.The carrier that preferably is used for catalytically active material is a gamma-alumina.By well known to a person skilled in the art that ordinary method is with carrier loaded platinum and/or palladium.Advantageously, also catalyst aid can be carried on the carrier.Proper auxiliary agent comprises copper and tin.Usually when making its quenching when the autothermal cracking device comes out temperature be less than in 150 milliseconds the forming process, product is reduced to below 650 ℃.
When autothermal cracking device pressure maintains the pressure of 1.5-2.0 crust, usually product quenching and temperature are reduced to below 650 ℃ in the forming process of 100-150 millisecond.
When autothermal cracking device pressure maintains the pressure of 2.0-5.0 crust, usually product quenching and temperature are reduced to below 650 ℃ in the forming process of 50-100 millisecond.
When autothermal cracking device pressure maintains the pressure of 5.0-10.0 crust, usually product quenching and temperature are reduced to below 650 ℃ in 50 milliseconds forming process.
When autothermal cracking device pressure maintains the pressure of 10.0-20.0 crust, usually product quenching and temperature are reduced to below 650 ℃ in 20 milliseconds forming process.
At last when autothermal cracking device pressure maintains pressure in 20.0 Palestine and Israels, usually product is quenched and temperature is reduced to below 650 ℃ in 10 milliseconds forming process.
This is just avoided taking place further to react and kept the high olefin selectivity.
Can adopt with steam cracking technology in the rapid heat exchangers of similar type product is quenched.In addition or replacedly, can use direct quenching.Suitable quenching liquid comprises water.
The present invention provides greater than 40% usually, be preferably more than 50% and most preferably greater than 60% gaseous paraffin hydrocarbons percent conversion.
Further, the present invention provides greater than 50% usually, has been preferably more than 60% and most preferably greater than 70% monoolefine selectivity.
The present invention further aspect, a kind of method that is used to prepare alkene is provided, this method comprises that the gas of feeding paraffinic hydrocarbons, at least a unsaturated hydrocarbons and molecule-containing keto is to the autothermal cracking device, wherein they can react under the situation that the rich fuel flammable limit that surpasses conventional fuel supports the incendiary catalyzer to exist, thereby the hydrocarbon product stream that comprises alkene is provided, and described method feature is that the total hydrocarbon of feeding autothermal cracking device comprises 20wt% unsaturated hydrocarbons at least.
In this one side of the present invention, paraffinic hydrocarbons and at least a unsaturated hydrocarbons all can be used as and have comprised the independent hydrocarbonaceous feed of 20wt% unsaturated hydrocarbons at least.For example this independent hydrocarbonaceous feed can be the fluid boiling point of middle runnings scope (common 150 ℃-400 ℃) or naphtha range (common 30 ℃-220 ℃), but has the higher unsaturated hydrocarbons content of charging than those feeding steam crackers routinely (not carried out Macrodilution by the saturated charging from other source).Suitable charging comprises from coker, fluid catalytic cracking (FCC) or the unitary cut of heavy oil fluid catalytic cracking (RCC).
Owing to allowing the unsaturated hydrocarbons of significant quantity, the autothermal cracking device do not have the ability of carbon fouling, at the logistics that is regarded as to be used for steam crackers (not carried out Macrodilution) traditionally feeding autothermal cracking device easily by saturated charging from other source.Removed restriction, also can make and more advantageously operate in the method that produces cracking material (preparing virgin naphtha) traditionally as crude distillation to the unsaturated hydrocarbons content of hydrocarbonaceous feed.
Preferably, the total hydrocarbon of feeding autothermal cracking device comprises 20-70wt%, as 25-50wt%, unsaturated hydrocarbons.Usually, unsaturated hydrocarbons can comprise alkene (for example 10wt% alkene) at least and aromatic hydrocarbons (as 10wt% aromatic hydrocarbons at least).As used at this aspect, weight percent (wt%) is based on the gross weight meter of the hydrocarbon in the autothermal cracking device co-feeding.
The present invention will set forth in following examples and accompanying drawing 1.
The synoptic diagram of accompanying drawing 1 expression autothermal cracking equipment.
Accompanying drawing 1 has been described autothermal cracking equipment, and it comprises quartz reactor 1, is centered on by electrothermal oven 2.Reactor 1 is coupled to oxygen-containing gas supply equipment 3 and hydrocarbon charging supply equipment 4 (alkane and unsaturated hydrocarbons).The preheating in electrothermal oven 5 of hydrocarbon charging supply equipment 4.Randomly, the hydrocarbon charging can comprise further common charging, for example hydrogen and thinner such as nitrogen.During use, reactor 1 has catalytic domain 6, and it can be supported to surpass the burning of fuel rich fuel ultimate and comprise catalytic bed 7.Catalytic bed 7 is between hot baffle 8,9.
In use, stove 2 is set and makes further minimum heat losses.When reactant contact catalysis bed 7, some hydrocarbon charging burnings are to produce water and oxycarbide.The optional common charging of the hydrogen generation water that also burns.These combustion reactionss all are heat releases, and the heat that from then on produces is used to drive the cracking of hydrogen and produces alkene.
Embodiment
Catalyst A
Flood repeatedly and prepare the autothermal cracking catalyzer by in deionized water, closing platinum (II) and cupric chloride (II) solution by the chlorination tetramine, it comprises and is deposited on the aluminum oxide foam (15mm diameter * 30mm degree of depth, 30 hole/inches, by Vesuvius Hi-Tech Ceramics, Alfred, NY USA supply) 3wt% platinum and 1wt% copper on.If all metal-salts all sneak into the final catalyst prescription, this metal salt solution has that sufficient concentration obtains required Pt and Cu supports.After each dipping, remove excess solution, and the aluminum oxide foam before dipping next time at 120 ℃ of-140 ℃ of air dryings and in 450 ℃ of air, calcine.It is after in case all solution all is absorbed, then that foam is dry and reduced one hour in 650-700 ℃ of hydrogen/nitrogen atmosphere.
Catalyst B
By in deionized water, closing the solution that platinum (II) and 0.495g chlorination tetramine close palladium (II), utilize initial humidity dipping 100g alumina balls (by Condea supply, 1.8mm diameter alumina balls, specific surface area 210m by comprising 4.415g chlorination tetramine
2/ g) prepare and comprise the platinum that is deposited on the alumina balls and the autothermal cracking catalyzer of palladium.This spheroid was calcined 6 hours at 1200 ℃ in 120 ℃ of dryings in air in 1 hour then.
Comprised that the platinum that is deposited on the aluminum oxide foam (two catalyst A produce 60mm dark bed) and the autothermal cracking catalyzer of copper place the autothermal cracking device, and this cracker is heated to 850 ℃.
The incoming flow that comprises ethane, nitrogen and hydrogen is input to the autothermal cracking device.Thereby then oxygen is imported the autothermal cracking device and started reaction.Hydrogen and oxygen volume ratio maintain 1.9: 1 (v/v).This reaction is under atmospheric pressure carried out.
Analytic sample under the oxygen of 0.35,0.44,0.53 and 0.61 (v/v) and ethane feed ratio.
Replace nitrogen and replicate analysis with the incoming flow that is included in 1,3 divinyl of 9.65 volume % in the nitrogen then.
Measure the ethane conversion percentage and to selectivity of ethylene and be displayed in Table 1 the result.
Embodiment 2
Use the hydrogen and the multiple embodiment 1 of oxygen bulk specific gravity of 1: 1 (v/v).Measure the ethane conversion percentage and to selectivity of ethylene and be displayed in Table 2 the result.
Use the hydrogen and the multiple embodiment 1 of oxygen bulk specific gravity of 0.5: 1 (v/v).
Analytic sample under the oxygen of 0.35,0.44 and 0.53 (v/v) and ethane feed ratio.Measure the ethane conversion percentage and to selectivity of ethylene and be displayed in Table 3 the result.
Table 1
With the hydrogen of 1.9: 1 (v/v) volume ratios and oxygen by the Pt-Cu catalyzer ethane and be mixed with the autothermal cracking of the ethane of divinyl.
| Ethane | The ethane divinyl | Ethane | The ethane divinyl | Ethane | The ethane divinyl | Ethane | The ethane divinyl | |
| Total feed rate nl/min | 9.03 | 9.02 | 9.19 | 9.18 | 9.18 | 9.17 | 9.16 | 9.11 |
| O2: C2H6 (v/v) H2: O2 (v/v) N2: O2 (v/v) 1,3 divinyl: ethane (v/v) | 0.353 1.994 0.543 -- | 0.353 1.986 0.490 0.020 | 0.435 1.958 0.492 -- | 0.435 1.969 0.433 0.022 | 0.527 1.868 0.446 -- | 0.527 1.886 0.387 0.024 | 0.605 1.841 0.426 -- | 0.605 1.826 0.375 0.027 |
| Ethane conversion (%) OTR (%) butadiene conversion (%) | 46.00 98.42 -- | 42.87 98.12 93.05 | 58.74 98.30 -- | 55.88 98.42 96.24 | 74.76 98.48 -- | 72.19 98.75 97.66 | 84.65 98.73 -- | 82.40 98.84 100.00 |
| Ethylene yield (g/100g ethane feed) | 36.50 | 35.59 | 44.93 | 44.87 | 53.16 | 54.13 | 55.87 | 57.93 |
| Aromatics yield (g/100g ethane feed) | 0.03 | 0.08 | 0.03 | 0.04 | 0.14 | 0.02 | 0.22 | 0.02 |
| Ethene selection rate (ethane that g/100g transforms) | 79.35 | 83.03 | 76.49 | 80.29 | 71.11 | 74.98 | 66.00 | 70.30 |
Table 2
With the hydrogen of 1: 1 (v/v) volume ratio and oxygen by the Pt-Cu catalyzer ethane and be mixed with the autothermal cracking of the ethane of divinyl.
| Ethane | The ethane divinyl | Ethane | The ethane divinyl | Ethane | The ethane divinyl | Ethane | The ethane divinyl | |
| Total feed rate nl/min | 7.62 | 7.62 | 7.77 | 7.76 | 7.76 | 7.74 | 7.71 | 7.66 |
| O2: C2H6 (v/v) H2: O2 (v/v) N2: O2 (v/v) 1,3 divinyl: ethane (v/v) | 0.353 0.996 0.538 -- | 0.353 0.994 0.484 0.021 | 0.435 1.069 0.483 -- | 0.435 1.068 0.433 0.023 | 0.527 1.055 0.443 -- | 0.527 1.048 0.400 0.026 | 0.602 1.058 0.431 -- | 0.602 1.046 0.378 0.028 |
| Ethane conversion (%) OTR (%) butadiene conversion (%) | 47.86 98.42 -- | 46.15 98.12 93.05 | 60.97 98.85 -- | 59.14 98.74 92.01 | 77.10 98.82 -- | 75.43 98.79 97.47 | 86.44 98.94 -- | 84.98 98.97 98.37 |
| Ethylene yield (g/100g ethane feed) | 35.59 | 36.14 | 44.10 | 44.98 | 52.13 | 53.58 | 54.35 | 56.33 |
| Aromatics yield (g/100g ethane feed) | 0.03 | 0.03 | 0.02 | 0.05 | 0.03 | 0.13 | 0.10 | 0.13 |
| Ethene selection rate (ethane that g/100g transforms) | 74.36 | 78.31 | 72.33 | 76.06 | 67.61 | 71.03 | 62.87 | 66.29 |
Table 3
With the hydrogen of 0.5: 1 (v/v) volume ratio and oxygen by the Pt-Cu catalyzer ethane and be mixed with the autothermal cracking of the ethane of divinyl.
| Ethane | The ethane divinyl | Ethane | The ethane divinyl | Ethane | The ethane divinyl | |
| Total feed rate nl/min | 6.95 | 6.95 | 6.76 | 6.74 | 6.62 | 6.58 |
| O2: C2H6 (v/v) H2: O2 (v/v) N2: O2 (v/v) 1,3 divinyl: ethane (v/v) | 0.435 0.546 0.488 -- | 0.435 0.542 0.442 0.024 | 0.527 0.474 0.452 -- | 0.527 0.477 0.399 0.025 | 0.605 0.460 0.425 -- | 0.605 0.441 0.378 0.030 |
| Ethane conversion (%) OTR (%) butadiene conversion (%) | 64.01 98.43 -- | 63.17 98.42 98.59 | 78.83 98.63 -- | 79.02 98.64 95.49 | 88.11 98.86 -- | 87.97 98.85 93.80 |
| Ethylene yield (g/100g ethane feed) | 43.84 | 45.62 | 50.63 | 51.80 | 51.68 | 53.03 |
| Aromatics yield (g/100g ethane feed) | 0.01 | 0.05 | 0.08 | 0.08 | 0.23 | 0.34 |
| Ethene selection rate (ethane that g/100g transforms) | 68.49 | 72.21 | 64.23 | 65.56 | 58.66 | 60.29 |
Can find out that ethylene yield increases gradually and added at all that ethylene selectivity all increases under the situation of divinyl from the foregoing description.And can find out that the interpolation of divinyl does not cause any significant carbon on catalyst surface to form owing to only produced the fact of a small amount of aromatic hydrocarbons.
Comprised that the platinum that is deposited on the alumina balls (catalyst B) and the autothermal cracking catalyzer of palladium place the autothermal cracking device, and this cracker is heated to 850 ℃.Catalyst bed size is diameter 15mm, dark 60mm.
The incoming flow that comprises ethane, nitrogen and hydrogen is input to the autothermal cracking device.Thereby then oxygen is imported the autothermal cracking device and started reaction.Hydrogen and oxygen volume ratio maintain 0.7: 1 (v/v).This reaction is under atmospheric pressure carried out.
Three kinds of oxygen in the 0.51-0.60wt% scope: analytic sample under the hydrocarbon feed rate ratio.
Add ethane and replicate analysis that acetylene content is 2.5 volume % then.
Measure the ethane conversion percentage and to selectivity of ethylene and be displayed in Table 4 the result.
Ethylene yield and selectivity all increase along with the interpolation of acetylene as seen from Table 4.And can find out that the interpolation of acetylene does not cause any significant carbon on catalyst surface to form owing to only produced the fact of a small amount of aromatic hydrocarbons.
In addition, and surprisingly, observing methane production descends with the interpolation of acetylene.Can calculablely be to prepare the secondary products of ethene because methane is the dehydrogenation/scission reaction of ethane, then methane production should increase.Therefore, the existence of acetylene seems the formation that has suppressed methane.
Table 4
With the hydrogen of 0.7: 1 (v/v) volume ratio and oxygen by the Pt-Pd catalyzer ethane and be mixed with the autothermal cracking of the ethane of acetylene.
| Ethane | Ethane+acetylene | Ethane | Ethane+acetylene | Ethane | Ethane+acetylene | |
| Total feed rate nl/min | 6.02 | 6.00 | 5.98 | 5.96 | 5.91 | 5.94 |
| O2/C2H6 (v/v) H2: O2 (v/v) N2: O2 (v/v) acetylene: ethane (v/v) O2/ hydrocarbon (wt/wt) | 0.488 0.701 0.598 --- 0.520 | 0.502 0.701 0.592 0.026 0.524 | 0.526 0.699 0.582 --- 0.561 | 0.541 0.699 0.574 0.026 0.565 | 0.563 0.697 0.565 --- 0.600 | 0.571 0.697 0.566 0.026 0.595 |
| Ethane conversion (%) OTR (%) | 67.5 99.4 | 73.1 99.3 | 73.8 99.4 | 78.5 99.4 | 79.1 99.3 | 82.2 99.5 |
| Ethylene yield (g/100g ethane feed) | 45.17 | 50.41 | 48.13 | 52.62 | 49.77 | 53.68 |
| Methane production (g/100g ethane feed) | 4.02 | 3.96 | 4.90 | 4.74 | 5.75 | 5.37 |
| Aromatics yield (g/100g ethane feed) | 0.000 | 0.009 | 0.000 | 0.010 | 0.003 | 0.014 |
| Ethene selection rate (ethane that g/100g transforms) | 67.0 | 69.0 | 65.2 | 67.1 | 62.9 | 65.3 |
The autothermal cracking catalyzer of platiniferous (two catalyzer that comprise the platinum of 3wt%) is placed the autothermal cracking device, and this cracker is heated to 800 ℃.
The incoming flow that comprises Skellysolve A, nitrogen and hydrogen is input to the autothermal cracking device.Thereby then oxygen is imported the autothermal cracking device and started reaction.Hydrogen and oxygen volume ratio maintain 0.5: 1 (v/v).This reaction is under atmospheric pressure carried out.
Oxygen at 0.752,0.675 and 0.636 (v/v): analytic sample under the Skellysolve A feed rate ratio.
The aromatic hydrocarbons that will contain the incoming flow that has comprised dimethylbenzene and indenes (dimethylbenzene: the weight ratio of indenes is 4: 1) is then introduced, and produces total aromatic hydrocarbons and the Skellysolve A ratio of 0.078wt/wt.
Measure the Skellysolve A conversion percentage and to selectivity of ethylene and be displayed in Table 5 the result.
Ethylene yield and selectivity all increase with the interpolation of aromatic substance as seen from Table 5.
Table 5
With the hydrogen of 0.5: 1 (v/v) volume ratio and oxygen by Pt catalyzer and Skellysolve A be mixed with the autothermal cracking of the Skellysolve A of aromatic hydrocarbons.
| Pentane | Pentane aromatic hydrocarbons | Pentane | Pentane aromatic hydrocarbons | Pentane | Pentane aromatic hydrocarbons | |
| Total feed rate nl/min | 3.33 | 3.21 | 3.17 | 3.12 | 3.08 | 3.00 |
| O2/C5H12 (v/v) H2: O2 (v/v) N2: O2 (v/v) aromatic hydrocarbons: pentane (v/v) | 0.752 0.504 0.383 --- | 0.898 0.500 0.335 0.078 | 0.675 0.505 0.445 --- | 0.853 0.500 0.346 0.078 | 0.636 0.505 0.472 --- | 0.786 0.505 0.384 0.078 |
| Pentane transformation efficiency (%) OTR (%) aromatics conversion rate (%) | 84.21 98.17 --- | 83.06 97.74 66.97 | 79.60 98.28 --- | 79.60 97.80 62.56 | 76.56 98.37 --- | 77.16 97.90 60.81 |
| Ethylene yield (g/100g ethane feed) | 33.49 | 33.53 | 30.47 | 31.52 | 28.68 | 29.86 |
| Ethylene selectivity (ethane that g/100g transforms) | 39.77 | 40.37 | 38.28 | 39.59 | 37.46 | 38.70 |
Claims (14)
1. method that is used to prepare alkene, this method comprises a kind of charging that contains paraffinic hydrocarbons with (i); (ii) at least a unsaturated hydrocarbons and (iii) a kind of gas feeding autothermal cracking device of molecule-containing keto, wherein they can react under the situation that the rich fuel flammable limit that surpasses conventional fuel supports the incendiary catalyzer to exist, thereby the hydrocarbon product stream that comprises alkene is provided.
2. according to the process of claim 1 wherein that described unsaturated hydrocarbons is one or more alkenes, aromatic substance, diene and alkynes.
3. according to the method for claim 2, wherein said unsaturated hydrocarbons is 1,2 divinyl, 1,3 divinyl, 2 methyl, 1,3 divinyl, 1,3 pentadiene, 1,4 pentadiene and/or cyclopentadiene, preferred 1,3 divinyl.
4. according to the method for claim 2, wherein said unsaturated hydrocarbons is acetylene, propine and/or butine, preferred acetylene.
5. according to the method for claim 2, wherein said autothermal cracking device operation and described unsaturated hydrocarbons under greater than the stagnation pressures of 5 crust are benzene and/or toluene.
6. according in each method of preceding claim, wherein the unsaturated hydrocarbons of this autothermal cracking device of feeding comprises at least a alkene unsaturated hydrocarbons in addition, for example diene and alkynes is at least a, and the 1wt% that is less than total alkene, for example be less than 0.5wt%, based on the paraffinic hydrocarbons weight meter of feeding reactor.
7. according in each method of preceding claim, wherein said unsaturated hydrocarbons is from the product stream of steam cracking reaction device, the exhaust flow of fluid catalytic cracking reactor, the unitary exhaust flow of delayed coking unit unit, visbreaker unit or alkanisation, or from for example thermopolymer cracking of plastics recovery technology.
8. according in each method of preceding claim, the unsaturated hydrocarbons of wherein said feeding auto thermal cracking reactor flows from the autothermal cracking product.
9. method according to Claim 8, this method comprises the following steps:
(a) will contain the charging of paraffinic hydrocarbons and the gas feeding autothermal cracking device of molecule-containing keto, wherein they can react under the situation that the rich fuel flammable limit that surpasses conventional fuel supports the incendiary catalyzer to exist, thereby the hydrocarbon product stream that comprises alkene is provided
(b) reclaim alkene that at least a portion step (a) produces and
(c) unsaturated hydrocarbons that at least a step (a) is produced is back to the autothermal cracking device.
10. according to the method for claim 9, this method comprises the following steps:
(a) will contain the charging of paraffinic hydrocarbons and the gas feeding autothermal cracking device of molecule-containing keto, wherein they can react under the situation that the rich fuel flammable limit that surpasses conventional fuel supports the incendiary catalyzer to exist, thereby the hydrocarbon product stream that comprises ethene and/or propylene is provided
(b) hydrocarbon product stream that step (a) is produced is separated into second logistics that has comprised first logistics that contains the hydrocarbon that is less than 4 carbon atoms and comprised the hydrocarbon that contains at least 4 carbon atoms, comprises at least a unsaturated hydrocarbons that contains at least 4 carbon atoms
(c) retrieve from the ethene of first logistics and/or propylene and
(d) at least a portion second logistics is back to the autothermal cracking device.
11. according to the method for claim 10, the wherein said unsaturated hydrocarbons that contains at least 4 carbon atoms is selected from 1,2 divinyl, 1,3 divinyl, 2 methyl, 1,3 divinyl, 1,3 pentadiene, 1,4 pentadiene and cyclopentadiene, and preferred 1,3 divinyl.
12. according to the method for claim 9, the method comprising the steps of:
(a) will contain the charging of paraffinic hydrocarbons and the gas feeding autothermal cracking device of molecule-containing keto, wherein they can react under the situation that the rich fuel flammable limit that surpasses conventional fuel supports the incendiary catalyzer to exist, thereby the hydrocarbon product stream that comprises ethene and/or propylene and at least a alkynes is provided
(b) reclaim ethene that at least a portion step (a) produces and/or propylene and
(c) will be back to the autothermal cracking device at least partially at least a alkynes that produces in the step (a).
13. method that is used to prepare alkene, this method comprises the gas feeding autothermal cracking device with paraffinic hydrocarbons, at least a unsaturated hydrocarbons and molecule-containing keto, wherein they can react under the situation that the rich fuel flammable limit that surpasses conventional fuel supports the incendiary catalyzer to exist, thereby the hydrocarbon product stream that comprises alkene is provided, and described method feature is that the total hydrocarbon of feeding autothermal cracking device comprises 20wt% unsaturated hydrocarbons at least.
14. according to the method for claim 13, wherein the total hydrocarbon of feeding autothermal cracking device comprises the alkene of 10wt% at least and the aromatic hydrocarbons of 10wt% at least.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0307759A GB0307759D0 (en) | 2003-04-03 | 2003-04-03 | Autothermal cracking process |
| GB0307759.1 | 2003-04-03 | ||
| GB0329346.1 | 2003-12-18 |
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| CN1771214A true CN1771214A (en) | 2006-05-10 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113939361A (en) * | 2019-05-24 | 2022-01-14 | 伊士曼化工公司 | Composition of pyrolysis oil material suitable for cracking |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113939361A (en) * | 2019-05-24 | 2022-01-14 | 伊士曼化工公司 | Composition of pyrolysis oil material suitable for cracking |
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| GB0307759D0 (en) | 2003-05-07 |
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