CN102320912A - Method for maximizing total ethylene and propylene yield in process of preparing low-carbon olefin by oxygen compound conversion - Google Patents
Method for maximizing total ethylene and propylene yield in process of preparing low-carbon olefin by oxygen compound conversion Download PDFInfo
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- CN102320912A CN102320912A CN201110149981A CN201110149981A CN102320912A CN 102320912 A CN102320912 A CN 102320912A CN 201110149981 A CN201110149981 A CN 201110149981A CN 201110149981 A CN201110149981 A CN 201110149981A CN 102320912 A CN102320912 A CN 102320912A
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a method for maximizing the total ethylene and propylene yield in the process of preparing low-carbon olefin by oxygen compound conversion. The process of preparing low-carbon olefin from oxygen compounds is coupled with a hydrocarbon recycling process of hydrocarbon with more than 4 carbon atoms as a by-product and a low-carbon alkane dehydrogenation process, so that the total yield of the target product ethylene and propylene in the process of preparing low-carbon olefin by converting oxygen compounds, such as alcohol or ether, and the like can be maximized, and therefore the economy and benefits of the process of preparing olefin from oxygen compounds, such as methanol or dimethyl ether, and the like.
Description
Technical field
Present invention relates in general to prepare low-carbon alkene, more specifically, relate to preparing low carbon olefin hydrocarbon with oxygen-containing compounds conversion technology is carried out improved method.
Background technology
Ethene and propylene are the important foundation raw materials of modern chemistry industry.Existing low-carbon alkene production technology seriously relies on petroleum resources, and the traditional method of preparation ethene and propylene is light oil (petroleum naphtha, solar oil) cracking technique and refinery's by-product.Along with the shortage of petroleum resources and the imbalance between supply and demand of low-carbon alkenes such as price increase, ethene and propylene become increasingly conspicuous; Countries in the world begin to be devoted to the technological development of low-carbon alkenes such as non-petroleum path system ethene and propylene, are raw material becomes research and development gradually through the preparing low carbon olefinic hydrocarbon with methanol technology focus with Sweet natural gas or coal wherein.Coal system alkene is Coal Chemical Industry and the tie that petrochemical complex is connected mutually, has not only realized the petrochemical material diversification, and has widened the Coal Chemical Industry development field, realized the part of petroleum resources is substituted, and be the most promising development field of novel Coal Chemical Industry.
The key of methanol-to-olefins technology is the exploitation of catalyzer and reaction process.U.S. Mobil company has at first reported the research of methyl alcohol system hydrocarbon in 1976, its catalyzer mainly is to be the basis with the ZSM-5 zeolite molecular sieve.The ZSM-5 duct is big, and product distributes wide, generates more carbon four above high-carbon hydrocarbons, and the selectivity of small molecules low-carbon alkenes such as ethene+propylene is not high, but is difficult for carbon deposit, and inactivation is slow, can use fixed-bed reactor.Mobil company, BASF AG, south chemistry (Sud-Chemie) have been obtained the catalyst based coking of modified ZSM-5 zeolite of certain progress Sud-Chemie company exploitation in the research of ZSM-5 catalysis methanol producing light olefins slow; Can reduce the catalyst regeneration cycle index; One way reaches 500～600h working time; Methanol conversion is greater than 99%, and ethylene selectivity is 5%, and the selectivity of propylene is 35%.Lurgi company based on improved ZMS-5 catalyst development fixed bed preparing propylene from methanol technology (MTP is referring to US 2003.0139635A1).Work as C
2And C
4When cut partly circulated Returning reacting system, the final propene yield of MTP technology can meet or exceed 67%.
The SAPO-34 non-zeolite molecular sieve is a kind of crystalline silicoaluminophosphate salt (referring to U.S.4440871) of U.S. UCC company development in 1984; Has the three dimensional intersection duct; Mean pore size is about
and compares with ZSM-5; SAPO-34 has littler aperture; Be fit to generate micromolecular ethene, propylene and normal paraffin, isomeric hydrocarbon and aromatic hydrocarbons will be severely limited.Because SAPO-34 has the acid and pore passage structure of suitable proton, bigger specific surface area, absorption property and thermostability and hydrothermal stability preferably; SAPO-34 demonstrates catalytic activity and selectivity preferably to methanol to olefins reaction; Selectivity to low-carbon alkene reaches more than 90%, and the SAPO-34 sieve catalyst is the basis (referring to CN 1962573A) of the MTO of Uop Inc. technology (referring to US 006166282A), the DMTO of Dalian Chemistry and Physics Institute technology (referring to CN 1166478A) and the fluidized-bed system propylene FMTP of Tsing-Hua University technology.
UOP/Hydro process using fluidized-bed reaction-revivifier is 400～500 ℃ in temperature of reaction, and pressure is under 0.1～0.3MPa, and ethene, propylene ratio can be regulated between 0.75-1.5, and ethene, propylene selectivity sum reach 80%.In the technology of preparing low carbon olefin hydrocarbon with oxygen-containing compounds conversion such as alcohol or ether, produce low-carbon alkanes and C such as methane, ethane, propane inevitably
4(4 carbon atoms) above hydro carbons.In order further to improve ethene and propene yield; UOP LLC company disclosed methanol-to-olefins fluidized-bed reactor and carbon four, the reaction of carbon pentaene hydrocarbon catalytic pyrolysis riser tube or fluidized-bed reactor has been coupled to improve the technology (referring to US 005914433A) of ethene and propene yield in 1999; Technology after the improvement makes the ratio of propylene and ethene in the product can reach 1.75, and ethene and propylene total recovery reach 85%～90%.But this method has only been considered the recycle of by product carbon four, carbon pentaene hydrocarbon, does not consider the recycle of by product alkane such as ethane, propane.
The dehydrogenating technology of low-carbon alkanes is divided into oxydehydrogenation and catalytic dehydrogenation; Oxidative dehydrogenation process is prone to deep oxidation takes place, and is wayward; The product complicacy is not easily separated, olefin yields is low.Low-carbon alkanes catalytic dehydrogenation system alkene comprises the Oleflex technology of Uop Inc., the Catofin technology of Lummus-Sud-Chemie company, the STAR technology of Krupp Uhde company, the PDH technology of the common exploitation of Linde-BASF-Statoil, and preceding two have full scale plant; But these process energy consumptions are high, and the catalyzer life cycle is short, need constantly regeneration.
The catalyzer of low-carbon alkanes catalytic dehydrogenation comprises catalyzer such as vanadium base, chromium base, molybdate, phosphoric acid salt and platinum base, and the carrier that adopts usually comprises SiO
2, γ-Al
2O
3, MAl
2O
4Deng.Wherein Pt is carried on γ-Al
2O
3Supported catalyst has than highly selective and yield alkene.The catalyzer that is used for dehydrogenating propane in the industry is like Cr
2O
3/ Al
2O
3And Pt/Al
2O
3, because side reactions such as oligomeric and cracking seriously cause a large amount of carbon deposits and rapid deactivation.Because the ZSM-5 molecular sieve has unique pore passage structure and higher shape selectivity and anti-carbon deposit performance, is widely used in aromizing, catalytic cracking, isomerizing and the other field of lower carbon number hydrocarbons; In recent years, the ZSM-5 molecular sieve begins to be applied in the dehydrogenating low-carbon alkane field.
Prepare alkene purpose product ethene and propylene selectivity for improving alcohol or ether, Tsing-Hua University discloses the coupling process method that alcohol or ether is prepared alkene and dehydrating alkanes.This method is that the hybrid technique gas in ether or the alcohol preparation olefin process is got into gas separation system; Alkane by-product is carried out the dehydrating alkanes reaction in the reactor drum with getting into after the alkene principal product separates independently; Hybrid technique gas after the dehydrogenation returns gas separation system and further isolates olefin product; Improved the yield of purpose product alkene, although the improved compared with techniques of this method and UOP, the dehydrogenation that has increased propane, butane transforms link; But this method and not mentioned by product ethane dehydrogenation, and the scission reaction of higher hydrocarbons still is confined to the scission reaction of butylene, amylene and hexene.Because butane dehydrogenation is carried out in different reactor drums respectively with the butylene scission reaction; Require very high to separation system; Need to adopt the C4 rectifying tower that alkene is separated with alkane, and this technology indication scission reaction, comprise the cracking of butylene, amylene and hexene; Amylene and hexene rectifying tower need be set separately, increase separating technology facility investment and energy consumption.
In order to improve the selectivity that oxygenatedchemicalss such as alcohol or ether prepare purpose product ethene and propylene to greatest extent, this patent has proposed a kind of with itself and ethane, the dehydrating alkanes reaction of propane, the above hydrocarbon cracking reaction of C4 coupled process method.Because ether or pure low carbon olefin preparation by using oxygenated chemical purpose product ethene, purified propylene reach respectively and just meet polymerization-grade more than 99.9% and 99.5%; The tower base stream of ethene and propylene knockout tower is respectively ethane and propane, this part alkane is directly got into carry out dehydrogenation reaction in the dehydrating alkanes reactor drum.The above component of C4 is not separated, directly get into and carry out catalytic cracking reaction in the cracking reactor, reduced separating device investment, running cost, cut down the consumption of energy, and farthest improved purpose product ethene and propylene selectivity.
Summary of the invention
The objective of the invention is to maximize low-carbon alkene ethene and propylene total recovery in the preparing low carbon olefin hydrocarbon with oxygen-containing compounds conversion technology.
In order to achieve this end, the invention provides a kind of ethene and method of propylene total recovery that maximizes in the preparing low carbon olefin hydrocarbon with oxygen-containing compounds conversion technology, said method comprises:
(1) go out ethene and propylene through gas separation system from hybrid technique gas delivery as the purpose product from said preparation low-carbon alkene technology, and as the C of by product
4Above hydro carbons, low-carbon alkanes and contain H
2Dry gas with methane;
(2) make said C
4Above hydrocarbon cracking reaction, preparation ethene and propylene;
(3) make said low-carbon alkanes that dehydrogenation reaction take place under the dehydrogenation catalyst effect, preparation ethene and propylene.
In a preferred implementation, preparing low carbon olefin hydrocarbon with oxygen-containing compounds conversion technology is in fluidized-bed reactor, carry out in the presence of the catalyzer that with the SAPO-34 molecular sieve is active ingredient.
In a preferred implementation, C
4The catalytic cracking reaction of above hydro carbons is to carry out in the presence of the catalyzer of active ingredient in fluidized-bed reactor, at ZSM-5, SAPO-34, SAPO-5 molecular sieve or their metal modified molecular screen.
In a preferred implementation, the dehydrogenation reaction of low-carbon alkanes is carried out at fixed bed dehydrogenation reactor.
In a preferred implementation, the used catalyzer of the dehydrogenation reaction of low-carbon alkanes is with the ZSM-5 of Fe, Pt, Cr, Sn or Zn modification or SAPO-34 molecular sieve.
In a preferred implementation, the used catalyzer of the dehydrogenation reaction of low-carbon alkanes is the SiO that load has Mo, V, Cr, Sn, Fe or Pt
2, γ-Al
2O
3, MAl
2O
4
In a preferred implementation, also be included in the revivifier and regenerate because of the catalyzer of carbon deposit inactivation.
In a preferred implementation, the catalyzer of preparing low carbon olefin hydrocarbon with oxygen-containing compounds conversion technology and said C
4The catalyzer of the catalytic cracking reaction of above hydro carbons adopts continuous mode to regenerate in identical reactor-regenerator system, and the catalyzer of the dehydrogenation reaction of low-carbon alkanes adopts intermittent mode to regenerate.
In a preferred implementation, oxygenatedchemicals is to be selected from methyl alcohol, dme, ethanol, propyl alcohol, butanols and their any mixture one or more.
In a preferred implementation, C
4Above hydro carbons is to be selected from normal butane, Trimethylmethane, one or more in butylene, pentane, amylene, hexene and their any mixture.
In a preferred implementation, C
4The catalytic cracking reaction of above hydro carbons transforms in the same reactor for preparing low-carbon alkene at said oxygen compound and carries out.
In a preferred implementation, C
4The catalytic cracking reaction of above hydro carbons carries out in riser reactor or fluidized-bed reactor.
In a preferred implementation, low-carbon alkanes comprises ethane and propane.
In a preferred implementation, from said C
4The hybrid technique gas of the catalytic cracking reaction of above hydro carbons and separate through shared said gas separation system from the hybrid technique gas of the dehydrogenation reaction of said low-carbon alkanes.
In a preferred implementation, the temperature of reaction of the technology of preparing low carbon olefin hydrocarbon with oxygen-containing compounds conversion is that 450～500 ℃, pressure are 0.1～0.3MPa, and the mass space velocity of said oxygenatedchemicals is 1～9h
-1
In a preferred implementation, C
4The temperature of the catalytic cracking reaction of above hydro carbons is that 580～650 ℃, pressure are 0.1～0.3MPa, and said C
4The mass space velocity of above hydro carbons is 1～9h
-1
In a preferred implementation, the temperature of the dehydrogenation reaction of low-carbon alkanes is 400～700 ℃, and pressure is 0.12～0.5MPa, and the mass space velocity of said low-carbon alkanes is 1～5h
-1
In a preferred implementation, the dehydrogenation reaction of low-carbon alkanes is carried out under hydro condition (hydrogen environment), and the mol ratio of hydrogen and said low-carbon alkanes is 0.05～0.35: 1 in the said dehydrogenation reaction.
In a preferred implementation, the regeneration temperature of the catalyzer of inactivation is 580～680 ℃ in the preparing low carbon olefin hydrocarbon with oxygen-containing compounds conversion technology, and pressure is 0.12～0.3MPa.
In a preferred implementation, C
4The regeneration temperature of decaying catalyst is 600～750 ℃ in the catalytic cracking reaction of above hydro carbons, and pressure is 0.1～0.3MPa.
In a preferred implementation, the regeneration temperature of the catalyzer of inactivation is 400～650 ℃ in the dehydrogenation reaction of low-carbon alkanes, and pressure is 0.1～0.3MPa.
In a preferred implementation, contain H
2With the dry gas of the methane gas that acts as a fuel be that the dehydrogenation reaction of said low-carbon alkanes provides heat.
Through the present invention, at coupling C
4Behind the cracking technology of above hydro carbons and the dehydrogenating technology of low-carbon alkanes, can maximize such as ethene in the preparing low carbon olefin hydrocarbon with oxygen-containing compounds conversion technologies such as ether or alcohol and propylene total recovery and for example bring up to more than 92% from existing about 85%.
Description of drawings
Fig. 1 has schematically shown according to the coupling of one embodiment of the present invention C
4The process flow sheet of the preparing low carbon olefin hydrocarbon with oxygen-containing compounds conversion of the cracking technology of above hydro carbons and the dehydrogenating technology of low-carbon alkanes.
Fig. 2 schematically shown another embodiment according to the present invention coupling C
4The process flow sheet of the preparing low carbon olefin hydrocarbon with oxygen-containing compounds conversion of the cracking technology of above hydro carbons and the dehydrogenating technology of low-carbon alkanes.
Embodiment
In technology, produce low-carbon alkanes and C such as methane, ethane, propane inevitably such as preparing low carbon olefin hydrocarbon with oxygen-containing compounds conversion such as alcohol or ethers
4(4 carbon atoms) above hydro carbons.The present invention is with by product ethane, dehydrogenating propane technology, C
4The coupling of low carbon olefin preparation by using oxygenated chemical technologies such as the Deep Catalytic Cracking process of above hydro carbons and alcohol or ether, maximizing ground improves ethene and propylene total recovery.This technology with the tower of ethylene separation tower and propylene knockout tower at the bottom of by product ethane and propane cycles utilization, get into carry out dehydrogenation system ethene in the dehydrogenation reactor, propylene reacts.The above component of C4 is directly carried out scission reaction without separation.After will the above component of C4 not being separated into alkane, alkene, alkane and alkene carry out dehydrogenation reaction and scission reaction respectively again.Improve ethene and propylene selectivity to the full extent, reduced separating technology facility investment and running cost.
The catalyzer that methanol conversion prepares low-carbon alkene contains active ingredient SAPO-34 molecular sieve, inorganic oxide cakingagent and inert host material.Fluidized reaction-regeneration system rapidly requires catalyzer to have enough intensity and the size-grade distribution that is fit to.The too high or too low abrasive wear resistance that all will reduce preformed catalyst of slurry solid content; Slurries total solid content (massfraction) is preferably 40%～45%; Wherein molecular sieve accounts for 38%～42% in total solid content; Cakingagent accounts for 15%～20% in total solid content, carrier accounts for 40%～45% in total solid content.In the scheme of material proportion, the best proportioning of cakingagent and molecular sieve is 0.15～0.25 in optimizing slurries, and the abrasion index of preformed catalyst (in massfraction) optimum is (0.2%～2.0%)/h.
C
4The reaction of above hydrocarbon cracking can with the shared identical catalyzer of methanol conversion system olefine reaction.C
4The reaction of above hydrocarbon catalytic cracking can with the shared fluidized-bed reactor of preparing light olefins from methanol.Also can adopt fluidized-bed reactor or riser reactor separately.
It is the catalyzer of active ingredient that ethane or dehydrogenating propane reaction are adopted with ZSM-5.In order to improve activity of such catalysts and selectivity, can like load Fe, Pt, Cr metal, improve the dehydrating alkanes catalytic performance of catalyzer in the enterprising row metal modification of ZSM-5 catalyzer.
Dehydrogenating low-carbon alkane such as ethane or propane is reflected in the independent dehydrogenation reactor and carries out, the catalyzer super regeneration.Adopt O
2, air, water vapor, CO
2Deng coke burning regeneration.The dehydrogenating low-carbon alkane reaction need be carried out under higher temperature for thermo-negative reaction, contains H
2With the dry gas of the methane gas that acts as a fuel be that the dehydrating alkanes reaction provides heat.Methanol conversion system alkene catalyst regeneration burning process is an exothermic process, and the mode of the low-carbon alkanes that separation system is come out through interior heat-obtaining is to raw material preheating.The oxygenatedchemicals catalytic cracking reaction prepares the hybrid technique gas and the C of low-carbon alkene
4 +The hybrid technique gas of product gas, ethane or the dehydrogenating propane of scission reaction can the common gas separation system.Alcohol or ether prepare and contain the water byproduct that responds and produce, C in the mixture process gas of alkene
4 +Not moisture in the product gas of scission reaction and the hybrid technique gas of ethane or dehydrogenating propane.For cutting down the consumption of energy, get into quench tower cooling, dehydration after reactor product gas and the virgin gas heat exchange.
In an embodiment of the invention; Provide to the invention provides a kind of ethene and method of propylene total recovery that maximizes in the preparing low carbon olefin hydrocarbon with oxygen-containing compounds conversion technology, this method comprises: oxygenatedchemicals such as alcohol or ether etc. is got into carry out catalytic cracking reaction in the fluidized-bed reactor to prepare low-carbon alkene.Wherein, the hybrid technique gas that will transform the preparation low-carbon alkene from alcohol or ether is isolated purpose product ethene, propylene, by product C through separation system
4Above hydro carbons, low-carbon alkanes (ethane and propane) and contain H
2Dry gas with methane.
In the present invention, make above isolating C
4Above hydro carbons gets into and carries out catalytic cracking reaction in the cracking reactor with the preparation low-carbon alkene.This C
4The scission reaction of above hydro carbons can be carried out in the fluidized-bed reactor of preparing low carbon olefin hydrocarbon with oxygen-containing compounds conversion such as methyl alcohol or dme, also can in fluidized-bed reactor independently, carry out.
And, in the present invention, make low-carbon alkanes such as above isolating ethane and/or propane get into dehydrogenation reactor, dehydrogenation reaction takes place under the dehydrogenation catalyst effect prepare low-carbon alkenes such as ethene, propylene.
After catalytic pyrolysis, make from C
4The product gas of above hydrocarbon cracking reaction gets into gas separation system; To isolate purpose product alkene (ethene, propylene), low-carbon alkanes and higher hydrocarbons by product; Higher hydrocarbons product wherein gets into once more in the catalytic cracking reaction device and generates ethene and propylene so that scission reaction to take place, and low-carbon alkanes wherein such as ethane and propane get in the dehydrogenation reactor to carry out dehydrogenation reaction once more.
After dehydrogenation reaction, from the hybrid technique gas entering gas separation system of dehydrogenation reactor, isolate purpose product ethene and propylene, and if the C that exists
4Above hydro carbons, low-carbon alkanes such as ethane and propane, wherein C
4Above hydro carbons carries out above-mentioned catalytic cracking reaction once more, and low-carbon alkanes such as ethane and propane carry out dehydrogenation reaction once more.
Methyl alcohol or dme system olefin hydrocarbon reactor and C
4The catalyzer of inactivation can get into catalyst regenerator continuously and carries out for example coke burning regeneration in the above hydrocarbon cracking reactor drum, and the catalyzer in the dehydrogenation reactor can carry out super regeneration.
Fig. 1 has schematically shown according to the coupling of one embodiment of the present invention C
4The process flow sheet of the preparing low carbon olefin hydrocarbon with oxygen-containing compounds conversion of the cracking technology of above hydro carbons and the dehydrogenating technology of low-carbon alkanes, wherein C
4The scission reaction of above hydro carbons is carried out in independent fluidized-bed reactor, and the dehydrogenation reaction of low-carbon alkanes is carried out in fixed-bed reactor.
Fig. 2 schematically shown another embodiment according to the present invention coupling C
4The process flow sheet of the preparing low carbon olefin hydrocarbon with oxygen-containing compounds conversion of the cracking technology of above hydro carbons and the dehydrogenating technology of low-carbon alkanes, wherein C
4The scission reaction of above hydro carbons is carried out in riser reactor; Hybrid technique gas and catalyzer from this scission reaction get into the fluidized-bed reactor that oxygenatedchemicals (like alcohol or ether) transforms the preparation low-carbon alkene through riser reactor, and the dehydrogenation reaction of low-carbon alkanes is carried out in fixed-bed reactor.
Like what indicate among Fig. 1 and Fig. 2, label declaration wherein is following:
100-oxygenatedchemicals (like alcohol or ether) transforms the reactor drum of preparation low-carbon alkene; The 101-gas separation system; 102-C
4The cracking reactor of above hydro carbons; The dehydrogenation reactor of 103-low-carbon alkanes; The 104-catalyst regenerator;
10-oxygenatedchemicals (like alcohol or ether) raw material; 11-transforms the hybrid technique gas of preparation low-carbon alkene from oxygenatedchemicals (like alcohol or ether); 12-C
4Above hydro carbons; 13-is from C
4The hybrid technique gas of above hydrocarbon cracking reaction; 14,15-low-carbon alkanes ethane and/or propane; 16-is from the hybrid technique gas of dehydrogenating low-carbon alkane reaction; 17,18-low-carbon alkene ethene and/or propylene; 19-contains H
2Dry gas with methane;
The catalyzer of inactivation in the 24-reactor drum 100; Catalyzer after the 26-regeneration; The catalyzer of inactivation in the 32-reactor drum 102; Catalyzer after the 32-regeneration.
As use in the present invention, low-carbon alkene mainly is ethene and propylene.
As use in the present invention, oxygenatedchemicals mainly is alcohol or ether compound, preferably is selected from methyl alcohol, dme, ethanol, propyl alcohol, butanols and their any mixture one or more.
As use in the present invention, C
4Above hydro carbons mainly is to be selected from normal butane, Trimethylmethane, one or more in butylene, pentane, amylene, hexene and their any mixture.
In the present invention, preferably, from C
4The hybrid technique gas of the catalytic cracking reaction of above hydro carbons and from the hybrid technique gas of the dehydrogenation reaction of low-carbon alkanes through separating with shared gas separation systems of converting oxygen-containing compound to low-carbon olefins reaction process gas such as alcohol or ethers.
In the present invention, preferably, the temperature of reaction of preparing low carbon olefin hydrocarbon with oxygen-containing compounds conversion can be 450～500 ℃, and pressure is 0.1～0.3MPa, and the mass space velocity of oxygenatedchemicals is 1～9h
-1
In the present invention, preferably, C
4The temperature of the catalytic cracking reaction of above hydro carbons is 580～650 ℃, and pressure is 0.1～0.3MPa, and C
4The mass space velocity of above hydro carbons is 1～9h
-1Preferably, C
4The catalytic cracking reaction of above hydro carbons is to carry out under the catalyzer of active ingredient in fluidized-bed reactor, at ZSM-5, SAPO-34, SAPO-5 molecular sieve or their metal modified molecular screen.
In the present invention, preferably, the temperature of the dehydrogenation reaction of low-carbon alkanes is 400～700 ℃, and pressure is 0.12～0.5MPa, and the mass space velocity of low-carbon alkanes is 1～5h
-1
In the present invention, preferably, the dehydrogenation reaction of low-carbon alkanes is at hydro condition, carry out under promptly in the hydrogen environment, and the mol ratio of hydrogen and low-carbon alkanes is 0.05～0.35: 1 in the dehydrogenation reaction.Preferably, the dehydrogenation reaction of low-carbon alkanes is carried out at fixed bed dehydrogenation reactor.And the used catalyzer of the dehydrogenation reaction of low-carbon alkanes can be the metal modified molecular screen catalyzer, as with Fe, Pt, Cr, Sn or Zn modified ZSM-5 or SAPO-34 molecular sieve.Also can be that oxygenatedchemicals is (like SiO
2, γ-Al
2O
3, MAl
2O
4) go up the catalyzer of loaded metal (Mo, V, Cr, Sn, Fe or Pt).
In the present invention, preferably, be 580～680 ℃ for example in the regeneration preparing low carbon olefin hydrocarbon with oxygen-containing compounds conversion technology because of the temperature of the catalyzer of coking deactivation, pressure is 0.12～0.3MPa.
In the present invention, preferably, regeneration C
4The temperature of the catalyzer of inactivation is 600～750 ℃ in the catalytic cracking reaction of above hydro carbons, and pressure is 0.1～0.3MPa.
In the present invention, preferably, the temperature of the catalyzer of inactivation is 400～650 ℃ in the dehydrogenation reaction of regeneration low-carbon alkanes, and pressure is 0.1～0.3MPa.
Among the present invention, contain H
2Can be used as fuel gas with the dry gas of methane is that the dehydrogenation reaction of low-carbon alkanes provides heat, perhaps reclaims in order to his and uses.
Below utilize embodiment to illustrate according to coupling C of the present invention
4The technology of the oxygenatedchemicals of the cracking technology of above hydro carbons, the dehydrogenating technology of low-carbon alkanes (like ether or alcohol) preparation low-carbon alkene.Embodiment is a preferred examples of the present invention, is not limited to scope of the present invention, and the present invention is as the criterion with claims restricted portion.
Embodiment
Embodiment 1
In fluidized-bed reactor, carry out the process that methanol conversion prepares low-carbon alkene, the fluidized-bed reactor catalyst system therefor adopts the spray-drying process moulding, and wherein the SAPO-34 molecular sieve content is 40%, and kaolin content is 40%, and the Si-Al binder content is 20%.Temperature of reaction is 450 ℃, and reaction pressure is 0.12MPa, and the methanol quality air speed is 3h
-1Methanol conversion system olefine reaction is fluidized-bed successive reaction-regenerative process, separates the C that obtains
4 +By product gets into independent fluidized-bed reactor, carries out the preparing low-carbon olefin by catalytically cracking reaction, and the higher hydrocarbons scission reaction is identical with methanol conversion system olefine reaction catalyst system therefor, and temperature of reaction is 600 ℃.Regeneration gas is air or water vapor, and regenerative process is incomplete regen-eration, and regeneration temperature is 600 ℃, and revivifier pressure is 0.11MPa.Dehydrogenation reaction takes place in by product ethane, propane in dehydrogenation reactor, dehydrogenation catalyst is Fe-ZSM-5, and the dehydrogenation reaction temperature is 450 ℃, and dehydrogenation reaction pressure is 0.3MPa, and the weight space velocity of alkane is 2h
-1Methanol conversion is 100%, and ethene and propene yield are 92%.
In fluidized-bed reactor, carry out the process that methanol conversion prepares low-carbon alkene, catalyst system therefor adopts the spray-drying process moulding in the fluidized-bed reactor, and wherein the SAPO-34 molecular sieve content is 40%, and kaolin content is 40%, and the Si-Al binder content is 20%.Temperature of reaction is 495 ℃, and reaction pressure is 0.12MPa, and the methanol quality air speed is 3h
-1Methanol conversion system olefine reaction is fluidized-bed successive reaction-regenerative process.Separate the C that obtains
4 +By product gets into the reaction of riser reactor generation preparing low-carbon olefin by catalytically cracking, and catalyzer and exit gas get in the MTO fluidized-bed reactor jointly, and the riser reactor temperature is 650 ℃.Regeneration gas is air or water vapor, and regenerative process is incomplete regen-eration, and regeneration temperature is 600 ℃, and revivifier pressure is 0.11MPa.Dehydrogenation reaction takes place in by product ethane, propane in dehydrogenation reactor, dehydrogenation catalyst is Pt-ZSM-5, and the dehydrogenation reaction temperature is 590 ℃, and dehydrogenation reaction pressure is 0.3MPa, and the weight space velocity of alkane is 3h
-1Methanol conversion is 100%, and ethene and propene yield are 94.5%.
Embodiment 3
In fluidized-bed reactor, carry out the process that methanol conversion prepares low-carbon alkene, catalyst system therefor adopts the spray-drying process moulding in the fluidized-bed reactor, and wherein the SAPO-34 molecular sieve content is 40%, and kaolin content is 40%, and the Si-Al binder content is 20%.Temperature of reaction is 450 ℃, and reaction pressure is 0.12MPa, and the methanol quality air speed is 3h
-1Methanol conversion system olefine reaction is fluidized-bed successive reaction-regenerative process.Separate the C that obtains
4 +By product gets into the reaction of riser reactor generation preparing low-carbon olefin by catalytically cracking, and catalyzer and exit gas get in the MTO fluidized-bed reactor jointly, and the riser reactor temperature is 650 ℃.Regeneration gas is air or water vapor, and regenerative process is incomplete regen-eration, and regeneration temperature is 600 ℃, and revivifier pressure is 0.11MPa.Dehydrogenation reaction takes place in by product ethane, propane in dehydrogenation reactor, dehydrogenation catalyst is Pt-ZSM-5, and the dehydrogenation reaction temperature is 590 ℃, and dehydrogenation reaction pressure is 0.3MPa, and the weight space velocity of alkane is 3h
-1Methanol conversion is 100%, and ethene and propene yield are 93.5%.
Embodiment 4
In fluidized-bed reactor, carry out the process that methanol conversion prepares low-carbon alkene, catalyst system therefor adopts the spray-drying process moulding in the fluidized-bed reactor, and wherein the SAPO-34 molecular sieve content is 40%, and kaolin content is 40%, and the Si-Al binder content is 20%.Temperature of reaction is 450 ℃, and reaction pressure is 0.12MPa, and the methanol quality air speed is 3h
-1Methanol conversion system olefine reaction is fluidized-bed successive reaction-regenerative process, separates the C that obtains
4 +By product gets into the preparing low-carbon olefin by catalytically cracking reaction takes place in the riser reactor, and catalyzer and exit gas get in the MTO fluidized-bed reactor jointly, and the riser reactor temperature is 650 ℃.Regeneration gas is air or water vapor, and regenerative process is incomplete regen-eration, and regeneration temperature is 600 ℃, and revivifier pressure is 0.11MPa.Dehydrogenation reaction takes place in by product ethane, propane in dehydrogenation reactor, dehydrogenation catalyst is Pt-Sn-ZSM-5, and the dehydrogenation reaction temperature is 650 ℃, and dehydrogenation reaction pressure is 0.2MPa, and the weight space velocity of alkane is 2.2h
-1Methanol conversion is 100%, and ethene and propene yield are 91%.
Embodiment 5
In fluidized-bed reactor, carry out the process that methanol conversion prepares low-carbon alkene, catalyst system therefor adopts the spray-drying process moulding in the fluidized-bed reactor, and wherein the SAPO-34 molecular sieve content is 40%, and kaolin content is 40%, and the Si-Al binder content is 20%.Temperature of reaction is 450 ℃, and reaction pressure is 0.12MPa, and the methanol quality air speed is 3h
-1Methanol conversion system olefine reaction is fluidized-bed successive reaction-regenerative process.By product C
4And C
5Hydrocarbon component gets into the reaction of riser reactor generation preparing low-carbon olefin by catalytically cracking after separating, catalyzer and exit gas get into fluidized-bed MTO reaction jointly, and the riser reactor temperature is 650 ℃.Regeneration gas is air or water vapor, and regenerative process is incomplete regen-eration, and regeneration temperature is 600 ℃, and revivifier pressure is 0.11MPa.Dehydrogenation reaction takes place in by product ethane, propane in dehydrogenation reactor, dehydrogenation catalyst is Cr-ZSM-5, and the dehydrogenation reaction temperature is 650 ℃, and dehydrogenation reaction pressure is 0.2MPa, and the weight space velocity of alkane is 3.5h
-1Methanol conversion is 100%, and ethene and propene yield are 94%.
Embodiment 6
In fluidized-bed reactor, carry out the process that dimethyl ether conversion prepares low-carbon alkene; Catalyst system therefor adopts the spray-drying process moulding in the fluidized-bed reactor; Wherein the SAPO-34 molecular sieve content is 40%, and kaolin content is 40%, and the Si-Al binder content is 20%.Temperature of reaction is 450 ℃, and reaction pressure is 0.12MPa, and the dme mass space velocity is 3h
-1Dimethyl ether conversion system olefine reaction is fluidized-bed successive reaction-regenerative process.By product C
4And C
5Hydrocarbon component gets into the reaction of riser reactor generation preparing low-carbon olefin by catalytically cracking after separating, catalyzer and exit gas get into fluidized-bed MTO reaction jointly, and the riser reactor temperature is 650 ℃.Regeneration gas is air or water vapor, and regenerative process is incomplete regen-eration, and regeneration temperature is 600 ℃, and revivifier pressure is 0.11MPa.Dehydrogenation reaction takes place in by product ethane, propane in dehydrogenation reactor, dehydrogenation catalyst is Pt-Sn-SAPO-34, and the dehydrogenation reaction temperature is 650 ℃, and dehydrogenation reaction pressure is 0.2MPa, and the weight space velocity of alkane is 3.5h
-1The dimethyl ether conversion rate is 100%, and ethene and propene yield are 93%.
Through the present invention, coupling C
4Behind the cracking technology of above hydro carbons and the dehydrogenating technology of low-carbon alkanes; Can maximize like ethene in the preparing low carbon olefin hydrocarbon with oxygen-containing compounds conversion technologies such as ether or alcohol and propylene total recovery, wherein ethene and propylene total recovery brought up to more than 92% from existing about 85%.
It will be appreciated by those skilled in the art that according to design requirements and other factors, various changes, combination, son combination and distortion can occur, as long as they are equal in the scope of replacement in accompanying claims or its.
Claims (22)
1. ethene and method of propylene total recovery that maximizes in the preparing low carbon olefin hydrocarbon with oxygen-containing compounds conversion technology, said method comprises:
(1) go out ethene and propylene through gas separation system from hybrid technique gas delivery as the purpose product from said preparation low-carbon alkene technology, and as the C of by product
4Above hydro carbons, low-carbon alkanes and contain H
2Dry gas with methane;
(2) make said C
4Above hydrocarbon cracking reaction, preparation ethene and propylene;
(3) make said low-carbon alkanes that dehydrogenation reaction take place under the dehydrogenation catalyst effect, preparation ethene and propylene.
2. method according to claim 1, wherein, said preparing low carbon olefin hydrocarbon with oxygen-containing compounds conversion technology is in fluidized-bed reactor, carry out in the presence of the catalyzer that with the SAPO-34 molecular sieve is active ingredient.
3. method according to claim 1, wherein, said C
4The catalytic cracking reaction of above hydro carbons is to carry out in the presence of the catalyzer of active ingredient in fluidized-bed reactor, at ZSM-5, SAPO-34, SAPO-5 molecular sieve or their metal modified molecular screen.
4. method according to claim 1, wherein, the dehydrogenation reaction of said low-carbon alkanes is carried out at fixed bed dehydrogenation reactor.
5. method according to claim 1, wherein, the used catalyzer of the dehydrogenation reaction of said low-carbon alkanes is with the ZSM-5 of Fe, Pt, Cr, Sn or Zn modification or SAPO-34 molecular sieve.
6. method according to claim 1, wherein, the used catalyzer of the dehydrogenation reaction of said low-carbon alkanes is the SiO that load has Mo, V, Cr, Sn, Fe or Pt
2, γ-Al
2O
3, MAl
2O
4
7. method according to claim 1 also is included in the revivifier and regenerates because of the catalyzer of carbon deposit inactivation.
8. method according to claim 4, wherein, the catalyzer of said preparing low carbon olefin hydrocarbon with oxygen-containing compounds conversion technology and said C
4The catalyzer of the catalytic cracking reaction of above hydro carbons adopts continuous mode to regenerate in identical reactor-regenerator system, and the catalyzer of the dehydrogenation reaction of said low-carbon alkanes adopts intermittent mode to regenerate.
9. method according to claim 1, wherein, said oxygenatedchemicals is to be selected from methyl alcohol, dme, ethanol, propyl alcohol, butanols and their any mixture one or more.
10. method according to claim 1, wherein, said C
4Above hydro carbons is to be selected from normal butane, Trimethylmethane, one or more in butylene, pentane, amylene, hexene and their any mixture.
11. method according to claim 1, wherein, said C
4The catalytic cracking reaction of above hydro carbons transforms in the same reactor for preparing low-carbon alkene at said oxygen compound and carries out.
12. according to claim 1 or 8 described methods, wherein, said C
4The catalytic cracking reaction of above hydro carbons carries out in riser reactor or fluidized-bed reactor.
13. method according to claim 1, wherein, said low-carbon alkanes comprises ethane and propane.
14. method according to claim 1, wherein, from said C
4The hybrid technique gas of the catalytic cracking reaction of above hydro carbons and separate through shared said gas separation system from the hybrid technique gas of the dehydrogenation reaction of said low-carbon alkanes.
15. method according to claim 1, wherein, the temperature of reaction of the technology of said preparing low carbon olefin hydrocarbon with oxygen-containing compounds conversion is that 450～500 ℃, pressure are 0.1～0.3MPa, and the mass space velocity of said oxygenatedchemicals is 1～9h
-1
16. method according to claim 1, wherein, said C
4The temperature of the catalytic cracking reaction of above hydro carbons is that 580～650 ℃, pressure are 0.1～0.3MPa, and said C
4The mass space velocity of above hydro carbons is 1～9h
-1
17. method according to claim 1, wherein, the temperature of the dehydrogenation reaction of said low-carbon alkanes is 400～700 ℃, and pressure is 0.12～0.5MPa, and the mass space velocity of said low-carbon alkanes is 1～5h
-1
18. method according to claim 1, wherein, the dehydrogenation reaction of said low-carbon alkanes is carried out under hydro condition, and the mol ratio of hydrogen and said low-carbon alkanes is 0.05～0.35: 1 in the said dehydrogenation reaction.
19. method according to claim 4, wherein, the regeneration temperature of the catalyzer of inactivation is 580～680 ℃ in the said preparing low carbon olefin hydrocarbon with oxygen-containing compounds conversion technology, and pressure is 0.12～0.3MPa.
20. method according to claim 4, wherein, said C
4The regeneration temperature of decaying catalyst is 600～750 ℃ in the catalytic cracking reaction of above hydro carbons, and pressure is 0.1～0.3MPa.
21. method according to claim 4, wherein, the regeneration temperature of the catalyzer of inactivation is 400～650 ℃ in the dehydrogenation reaction of said low-carbon alkanes, and pressure is 0.1～0.3MPa.
22. method according to claim 1, wherein, the said H that contains
2With the dry gas of the methane gas that acts as a fuel be that the dehydrogenation reaction of said low-carbon alkanes provides heat.
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