CN101506127A - Propylene production process and propylene production apparatus - Google Patents
Propylene production process and propylene production apparatus Download PDFInfo
- Publication number
- CN101506127A CN101506127A CNA2007800303888A CN200780030388A CN101506127A CN 101506127 A CN101506127 A CN 101506127A CN A2007800303888 A CNA2007800303888 A CN A2007800303888A CN 200780030388 A CN200780030388 A CN 200780030388A CN 101506127 A CN101506127 A CN 101506127A
- Authority
- CN
- China
- Prior art keywords
- carbonatoms
- hydrocarbon
- alkene
- propylene
- reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 117
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 228
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 132
- 150000001336 alkenes Chemical class 0.000 claims abstract description 122
- 239000003054 catalyst Substances 0.000 claims abstract description 74
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 48
- 150000001993 dienes Chemical class 0.000 claims abstract description 29
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 22
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 265
- 229930195733 hydrocarbon Natural products 0.000 claims description 227
- 150000002430 hydrocarbons Chemical class 0.000 claims description 227
- 238000002360 preparation method Methods 0.000 claims description 71
- 239000007789 gas Substances 0.000 claims description 65
- 239000000047 product Substances 0.000 claims description 43
- 239000002994 raw material Substances 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 31
- 229910021536 Zeolite Inorganic materials 0.000 claims description 27
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 27
- 239000010457 zeolite Substances 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 12
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 238000005336 cracking Methods 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 5
- 238000007233 catalytic pyrolysis Methods 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 25
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 abstract description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 64
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 50
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 48
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 30
- 239000001294 propane Substances 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 238000004088 simulation Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 230000006866 deterioration Effects 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- -1 propylene, butylene Chemical group 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 239000011981 lindlar catalyst Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000012261 overproduction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
Images
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Disclosed is a process for producing propylene, which comprises supplying a feed gas containing dimethyl ether and/or methanol and a C4-olefin and/or a C5-olefin to a reactor to allow these ingredients to react with each other in the presence of a catalyst, wherein the feed gas is introduced into the reactor at a (the C4-olefin and the C5-olefin)/(dimethyl ether and methanol) ratio of 0.25 to 7.5 inclusive by mole in terms of the number of carbons, and the feed gas is contacted with the catalyst at a temperature ranging from 350 to 600 DEG C inclusive. Also disclosed is a propylene production apparatus, which comprises a hydrogenation reactor for partially hydrogenating an alkyne and/or a diene contained in a C4-hydrocarbon and/or a C5-hydrocarbon to convert the alkyne and/or the diene into an olefin having one double bond; a reactor for reacting a feed gas containing the C4-hydrocarbon and/or the C5-hydrocarbon and dimethyl ether and/or methanol in the presence of a catalyst; and a separator for separating propylene from the resulting reaction product.
Description
Technical field
The present invention relates to prepare the preparation method of propylene of propylene and the preparation facilities of propylene through dehydration condensation by dme and/or methyl alcohol.
The application is willing to 2006-234007 number based on the spy who filed an application in Japan on August 30th, 2006 and the spy that filed an application in Japan on September 28th, 2006 is willing to require right of priority 2006-264513 number, and with its content quotation in this application.
Background technology
At present, along with different to the expansion field of ethene and propylene demand and, the more and more necessary to the selectivity yield-increasing technique of propylene is increased because of set up ethene supply rate rising that the ethane cracking device causes etc. in the Middle East.
Most propylene is to use the raw material that comes from crude oil, and (Fluid Catalytic Cracking, FCC) device waits as the by product preparation of reaction by naphtha cracking, fluid catalystic cracking.Because existing in above-mentioned preparation technology and containing carbonatoms in a large number is that 4 alkene and carbonatoms are the cut of 5 alkene, thereby expects a kind of technology that above-mentioned cut can be converted into effectively propylene.
In the past, known have by being that raw material carries out adding in the device of FCC ZSM-5 type zeolite catalyst, and supplies with methyl alcohol and hydrocarbon simultaneously with hydrocarbon (paraffinic), thereby the thermal equilibrium of heat release of the dehydration condensation of the heat absorption of decomposition reaction of hydrocarbon and methyl alcohol is improved, generate the method (for example, with reference to patent documentation 1) of paraffinic hydrocarbons, the fragrant same clan simultaneously.
In addition, the method (for example, with reference to patent documentation 2) of using zeolite catalyst to generate ethene, the fragrant same clan by the catalysis variation of the mixture of methyl alcohol and/or dme and hydrocarbon is also disclosed.
Patent documentation 1: Japanese kokai publication sho 62-179592 communique
Patent documentation 2: Japanese kokai publication sho 60-120790 communique
Summary of the invention
The problem that invention will solve
Prepare the method for lower hydrocarbon and utilize the thermolysis of petroleum naphtha to prepare in the method for lower hydrocarbon in traditional use FCC apparatus, because propylene is a by product, therefore when only expecting propylene enhancing, above-mentioned preparation method is inapplicable.
And, all generate carbonatoms as by product among above-mentioned arbitrary preparation method and be 4 alkene and carbonatoms and be 5 alkene, be in a kind of situation of overproduction.Wherein, carbonatoms is the volume increase that raw material that the 2-butylene in 4 the alkene can be used as replacement(metathesis)reaction is used for propylene, is that 5 alkene is all used by cheapness as the raw material of chemical products but carbonatoms in addition is 4 alkene and carbonatoms.
In addition, contain alkynes class and alkadiene etc. in the above-mentioned by product, and described alkynes class and alkadiene etc. are the reasons that causes colloid and carbonaceous to be separated out.Thereby, if above-mentioned by product directly as raw material, then have the danger that produces and adhere to solid-state precipitate on the pipe arrangement of reaction unit and the catalysts, may cause the obstruction of reaction unit pipe arrangement, the deterioration of catalysts.
The present invention makes in view of the above problems, its purpose is to provide a kind of preparation method of propylene, this method is by being that 4 alkene and/or carbonatoms are that the cut of 5 alkene is a raw material to contain a large amount of carbonatomss, and supply with dme and/or methyl alcohol simultaneously, can be translated into propylene in high selectivity, wherein, described carbonatoms is that 4 alkene and/or carbonatoms are that 5 alkene is to pass through naphtha cracking at the raw material that use comes from crude oil, obtain among the preparation technology of FCC apparatus etc., and described carbonatoms is that 4 alkene and/or carbonatoms are no matter whether 5 alkene have isomer to have the raw material that all can be used as preparation method of the present invention.
In addition, the present invention also aims to provide on a kind of pipe arrangement that is suppressed at reaction unit and the catalysts produce precipitate, thereby prevent that pipe arrangement from stopping up and the preparation method of the propylene of catalysts deterioration and the preparation facilities of propylene.
The method of dealing with problems
The invention provides a kind of preparation method of propylene, it is that 4 alkene or carbonatoms are that at least a unstripped gas in 5 the alkene is delivered in the reactor that this preparation method will contain at least a and carbonatoms in dme or the methyl alcohol, it is reacted in the presence of catalyzer prepare propylene, wherein, in importing to the above-mentioned raw materials gas of above-mentioned reactor, to make carbonatoms be 4 alkene feed rate and carbonatoms is that the total amount of 5 alkene feed rate is more than 0.25 and below 7.5 with respect to the ratio of dme feed rate and the total amount of methyl alcohol feed rate, this ratio is based on the mol ratio of carbonatoms, and above-mentioned raw materials gas is being contacted with above-mentioned catalyzer more than 350 ℃ and under the temperature below 600 ℃.
Above-mentioned carbonatoms is that to be the product that preferably the alkene generating apparatus generated of 5 alkene separate the carbonatoms that obtains through separator is that 4 alkene or carbonatoms are 5 alkene for 4 alkene or carbonatoms.
The present invention more preferably provides a kind of preparation method of propylene, it is that 4 alkene or carbonatoms are that the unstripped gas of 5 alkene is delivered in the reactor that this preparation method will contain at least a and carbonatoms in dme or the methyl alcohol, it is reacted in the presence of catalyzer prepare propylene, wherein, described unstripped gas comprises at least a in dme or the methyl alcohol, and the product that is obtained by the alkene generating apparatus separates the back and at least a in the carbonatoms of generation to be 4 alkene or carbonatoms be 5 the alkene through separator, described unstripped gas is imported in the above-mentioned reactor, to make carbonatoms be 4 alkene feed rate and carbonatoms is that the total amount of 5 alkene feed rate is more than 0.25 and below 7.5 with respect to the ratio of dme feed rate and the total amount of methyl alcohol feed rate, this ratio is based on the mol ratio of carbonatoms, and above-mentioned raw materials gas is being contacted more than 350 ℃ and under the temperature below 600 ℃ with above-mentioned catalyzer, what will be generated by above-mentioned reactor is that the product of principal constituent turns back in the above-mentioned separator with the propylene again, make it be separated into propylene and other composition (below, sometimes above-mentioned preparation method is called " preparation method's of propylene of the present invention the 1st mode ").
Above-mentioned alkene generating apparatus comprises the device that makes the hydrocarbon thermo-cracking and/or makes the device of hydrocarbon catalytic pyrolysis, in addition, also can consider to use dimerization device that ethene is carried out dimerization etc.
Above-mentioned catalyzer is preferably MFI structural zeolite catalyzer.
Above-mentioned catalyzer is preferably the MFI structural zeolite catalyzer that contains alkaline-earth metal, and wherein, the Si/Al mol ratio of preferred described MFI structural zeolite is more than 10 and 300 following, alkaline-earth metal/Al mol ratio is more than 0.75 and below 15.
In addition, the invention provides a kind of preparation method of propylene, it is that 4 hydrocarbon and/or carbonatoms are that the unstripped gas of 5 hydrocarbon is delivered in the reactor that this preparation method will contain at least a and carbonatoms in dme or the methyl alcohol, it is reacted in the presence of catalysts prepare propylene, wherein
Described carbonatoms is that 4 hydrocarbon and/or carbonatoms are to contain at least a in alkynes class or the alkadiene in 5 the hydrocarbon, to described carbonatoms is that 4 hydrocarbon and/or carbonatoms are hydrogen supply in 5 the hydrocarbon, after by partial hydrogenation described olefines or alkadiene being converted into the alkene with two keys, at least a in itself and above-mentioned dme or the methyl alcohol supplied in the above-mentioned reactor simultaneously (below, sometimes above-mentioned preparation method is called " preparation method's of propylene of the present invention the 2nd mode ").
Above-mentioned carbonatoms is that 4 hydrocarbon and/or carbonatoms are that can to contain carbonatoms that the product that generated by the alkene generating apparatus obtains through separation in 5 the hydrocarbon be that 4 hydrocarbon and/or carbonatoms are 5 hydrocarbon.And, carbonatoms be 4 hydrocarbon and/or carbonatoms be hydrocarbon preferably based on the hydrocarbon of alkene.
Above-mentioned alkene generating apparatus can be selected to hydrocarbon carry out thermo-cracking device, hydrocarbon is carried out the device of catalytic pyrolysis and makes more than one device in the device of oxygen-containing hydrocarbon generation dehydration condensation.
At least a portion that supplies to above-mentioned carbonatoms and be 4 hydrocarbon and/or carbonatoms and be the hydrogen in 5 the hydrocarbon can be generated by above-mentioned reaction maker.
Above-mentioned catalysts can be a MFI structural zeolite catalyzer.
Above-mentioned catalysts can be the MFI structural zeolite catalyzer that contains alkaline-earth metal, and wherein, the Si/Al mol ratio of described MFI structural zeolite is more than 10 and 300 following, alkaline-earth metal/Al mol ratio is more than 0.75 and below 15.
In addition, the invention provides a kind of preparation facilities of propylene, this device has: hydrogenation reactor, in described hydrogenation reactor, one of at least carbonatoms is that 4 hydrocarbon and/or carbonatoms are hydrogen supply and utilize partial hydrogenation that described olefines or alkadiene are converted into to have the alkene of two keys in 5 the hydrocarbon in containing alkynes class or alkadiene; Reactor makes in described reactor that to contain the above-mentioned carbonatoms that obtains in hydrogenation reactor be that 4 hydrocarbon and/or carbonatoms are that 5 hydrocarbon and at least a unstripped gas in dme or the methyl alcohol react in the presence of catalyzer; Separator in described separator, is isolated propylene in the reaction product that obtains from above-mentioned reactor.
By containing the hydrogenation catalyst of palladium, above-mentioned hydrogenation reactor can be reached purpose better.
Simultaneously, at least a portion that supplies to the hydrogen in the above-mentioned hydrogenation reactor can be generated by above-mentioned reactor.
The effect of invention
The preparation method's of propylene of the present invention the 1st mode is to be that 4 alkene or carbonatoms are that at least a unstripped gas in 5 the alkene is delivered in the reactor with containing at least a and carbonatoms in dme or the methyl alcohol, make it in the presence of catalyzer, react the method for preparing propylene, wherein, in importing to the above-mentioned raw materials gas of above-mentioned reactor, because to make carbonatoms be 4 alkene feed rate and carbonatoms is that the total amount of 5 alkene feed rate is more than 0.25 and below 7.5 with respect to the ratio of dme feed rate and the total amount of methyl alcohol feed rate, this ratio is based on the mol ratio of carbonatoms, and above-mentioned raw materials gas is being contacted more than 350 ℃ and under the temperature below 600 ℃ with above-mentioned catalyzer, thereby with carbonatoms is that 4 alkene or carbonatoms are that 5 alkene is sent in the reactor, therefore, selectivity can be improved, and the ultimate yield of target product can be improved target products such as propylene.
The preparation method's of preferred propylene of the present invention the 1st mode is to be that 4 alkene or carbonatoms are that at least a unstripped gas in 5 the alkene is delivered in the reactor with containing at least a and carbonatoms in dme or the methyl alcohol, make it in the presence of catalyzer, react the method for preparing propylene, wherein, described unstripped gas comprises at least a in dme or the methyl alcohol, and the product that is obtained by the alkene generating apparatus separates the back and at least a in the carbonatoms of generation to be 4 alkene or carbonatoms be 5 the alkene through separator, and described unstripped gas imported in the above-mentioned reactor, to make carbonatoms be 4 alkene feed rate and carbonatoms is that the total amount of 5 alkene feed rate is more than 0.25 and below 7.5 with respect to the ratio of dme feed rate and the total amount of methyl alcohol feed rate, this ratio is based on the mol ratio of carbonatoms, and above-mentioned raw materials gas is being contacted more than 350 ℃ and under the temperature below 600 ℃ with above-mentioned catalyzer, what will be generated by above-mentioned reactor is that the product of principal constituent turns back in the above-mentioned separator with the propylene again, makes it be separated into propylene, carbonatoms is that 4 alkene or carbonatoms are alkene and other composition of 5; By being that 4 alkene or carbonatoms are that 5 alkene is sent in the above-mentioned reactor with isolated carbonatoms, can improving in whole technology selectivity, thereby can improve the ultimate yield of target product target products such as propylene.
In addition, according to the preparation method's of propylene of the present invention the 2nd mode, can will supply to the alkynes class/alkadiene that is contained in the unstripped gas in the reactor of preparation propylene by partial hydrogenation and be converted into alkene with two keys.By utilizing hydrogenation reactor that alkynes class/alkadiene is converted into the alkene with two keys, can make the content of the alkynes class/alkadiene in the unstripped gas that supplies in the reactor few.
In addition, described hydrogenation can be any in liquid phase reaction, the gas-phase reaction.
By utilizing hydrogenation reactor that alkynes class/alkadiene is converted into alkene with two keys, makes the content of alkynes class/alkadiene contained in the unstripped gas that supplies in the reactor few, can be suppressed in the pipe arrangement that is connected on the reactor and on the catalysts and separate out carbonaceous solid-state precipitate.Thus, can positively prevent to be attached with the fault that precipitate causes deterioration etc. because of the pipe arrangement on being connected to reactor stops up or is filled to because of precipitate on the catalysts in the reactor.
Description of drawings
Fig. 1 is the synoptic diagram of an embodiment of the 1st mode that the preparation method of propylene of the present invention is shown.
Fig. 2 be illustrate temperature of reaction (℃) and the productive rate (quality %) of methane between the graphic representation of relation.
Fig. 3 is the explanatory view of an example that the preparation facilities of propylene of the present invention is shown and utilizes preparation method's (the 2nd mode of the preparation method of propylene of the present invention) of this preparation facilities.
Nomenclature
2 reactors
4 separators
6 alkene generating apparatus
The preparation facilities of 10 propylene
11 alkene generating apparatus
12 hydrogenation reactors
13 reactors
14 separators
Embodiment
At first, the embodiment at the preparation method's of propylene of the present invention the 1st mode describes.
Need to prove that this embodiment is specify of carrying out in order to understand main contents of the present invention better, during short of specifying, the present invention is not subjected to the qualification of following embodiment.
Fig. 1 is the synoptic diagram of an embodiment of the 1st mode that the preparation method of propylene of the present invention is shown.
In the preparation method of the propylene of this embodiment, at least a unstripped gas that will contain at least a and carbonatoms in dme or the methyl alcohol and be 4 alkene or carbonatoms and be in 5 the alkene is sent in the reactor 2.
Here, wait via managing 1 from gas supply device (diagram slightly) and send in the reactor 2 with gaseous phase with any dme or the methyl alcohol or with dme and methyl alcohol.Meanwhile, use, utilize alkene generating apparatus 6 to generate the product that contains light alkene through managing 3 raw materials that are fed in the alkene generating apparatus 6.Then, this product delivered to separator 4, utilize separator 4 to separate these products, and the carbonatoms that will obtain thus is that 4 alkene and/or carbonatoms are that 5 alkene is sent in the reactor 2 via pipe 7 via pipe 5.
In addition, in dme or methyl alcohol at least a, at least a in dme or methyl alcohol, can also contain gases such as water vapour, nitrogen, argon gas, carbonic acid gas.
And, in the preparation method of the propylene of this embodiment, in the unstripped gas that imports to reactor 2, to make carbonatoms be 4 alkene feed rate and carbonatoms is that the total amount of 5 alkene feed rate is more than 0.25 and below 7.5 with respect to the ratio of dme feed rate and the total amount of methyl alcohol feed rate, preferably be more than 1.0 and below 6.0, this ratio is the mol ratio based on carbonatoms.
Wherein, described " based on the mol ratio of carbonatoms " is to utilize following formula to calculate the value of gained.
(C4 molar flow (Mol Flow Rate) * 4+C5 molar flow * 5)/(DME molar flow * 2+MeOH molar flow * 1)
When the carbonatoms of representing based on the mol ratio of carbonatoms be 4 alkene feed rate with carbonatoms be the total amount of 5 alkene feed rate with respect to the ratio of dme feed rate and the total amount of methyl alcohol feed rate less than 0.25 the time, reactor internal cause thermopositive reaction and cause that temperature significantly rises, temperature out becomes high temperature, the deterioration of accelerator activator not only, and will cause the generation of by product to increase.On the other hand, when the carbonatoms of representing based on the mol ratio of carbonatoms be 4 alkene feed rate with carbonatoms be the total amount of 5 alkene feed rate with respect to the ratio of dme feed rate and the total amount of methyl alcohol feed rate greater than 7.5 the time, reactor internal cause thermo-negative reaction and cause that temperature declines to a great extent, therefore must be on reactor additional heating device or improve the unstripped gas temperature, and this complicates the initiating device structure or separate out problem such as carbonaceous on the unstripped gas pipeline.
In reactor 2, be filled with catalyzer, and reaction such as the dehydration condensation that takes place by the effect that utilizes this catalyzer generates the lower hydrocarbon of carbonatoms below 6 such as ethene as primary product, propylene, butylene, amylene, hexene.
As above-mentioned catalyzer, MFI structural zeolite catalyzer be can use, MFI structural zeolite catalyzer, aluminium silicophosphate class catalyzer of alkaline-earth metal etc. contained, can adopt modes such as fluidized-bed, fixed bed, moving-bed.In above-mentioned catalyzer, preferred MFI structural zeolite catalyzer more preferably contains the MFI structural zeolite catalyzer of alkaline-earth metal, because they can obtain lower hydrocarbon with high yield.
As the reaction conditions in the reactor 2, can more than 350 ℃ and under the temperature below 600 ℃ above-mentioned raw materials gas be contacted with catalyzer.Simultaneously, the relative mass of the dme of supplying with in the unit catalyst quality, unit time (being designated hereinafter simply as " DME ") is that weight hourly space velocity (being designated hereinafter simply as " WHSV ") is preferably below the above and 50g-DME/ of 0.025g-DME/ (g-catalyzer hour) (g-catalyzer hour), and pressure is preferably selected in the scope more than normal pressure and below the 1MPa.
When unstripped gas and catalyzer contact temperature less than 350 ℃ the time, the formation speed of target product is low, and is uneconomical.On the other hand, when unstripped gas and catalyzer contact temperature greater than 600 ℃ the time, the deterioration of catalyzer is fast, the generation of by products such as methane increases.
In addition, as WHSV during less than 0.025g-DME/ (g-catalyzer hour), the productivity step-down of the unit volume of fixed-bed reactor, uneconomical.On the other hand, as WHSV during greater than 50g-DME/ (g-catalyzer hour), catalyst life and catalyst activity become insufficient.
By the reaction conditions in the conditioned reaction device 2, can change the containing ratio of the target product lower hydrocarbon in the product, for example, in order to improve the shared ratio of propylene, preferably making reaction pressure is low pressure.
By reactor 2 obtain with the propylene be the product of principal constituent being sent in the heat exchanger and cooling off via pipe 8, be sent to then in the separator 4, wherein, described heat exchanger does not provide diagram.In separator 4, above-mentioned product is separated into each composition, and for example light composition such as methane, ethane, ethene, propylene, carbonatoms are that 4 alkene or carbonatoms are 5 alkene, the heavy hydrocarbon of carbonatoms more than 6.
In separated each composition of separator 4, carbonatoms is that 4 alkene or carbonatoms are that 5 alkene is directed in the reactor 2 via pipe 7.In addition other composition is reclaimed respectively.
Preparation method according to the propylene of this embodiment, can in separator 4, isolate carbonatoms and be 4 alkene or carbonatoms and be 5 alkene, and these alkene are sent in the reactor 2, selectivity can be improved in whole technology, thereby the ultimate yield of target product can be improved target products such as propylene.
In addition, be that 4 alkene or carbonatoms are that at least a unstripped gas in 5 the alkene supplies in the reactor 2 by containing carbonatoms, can improve by being sent to the life of catalyst that dme in the reactor 2 and/or methyl alcohol prepare propylene.This be because, carbonatoms is that 4 alkene or carbonatoms are that 5 the reaction of alkene in reactor 2 is thermo-negative reaction in general, its can relax by dme and/or methyl alcohol in reactor 2 thermopositive reaction and the intensification that causes, the result can reduce the deterioration of catalyzer.
Thereby, the reduction of catalyzer loading level, catalyst regeneration cycle stretch-out etc. can be made, and then cost of equipment, running expense can be cut down.
Below describe at the embodiment of the preparation facilities of the preparation method's of propylene of the present invention the 2nd mode and propylene.Need to prove that this embodiment is specify of carrying out in order to understand main contents of the present invention better, short of specifying, the present invention just is not subjected to the qualification of following embodiment.
Fig. 3 is the explanatory view of flow process of the 2nd mode that the summary of propylene production device of the present invention is shown and utilizes the propylene production method of the present invention of this preparation facilities.
The preparation facilities 10 of the propylene of this embodiment has alkene generating apparatus 11, hydrogenation reactor 12, reactor 13 and separator 14.In maker 11, generate the product that contains lower hydrocarbon by the raw material of supplying with.In hydrogenation reactor 12, be that 4 hydrocarbon and/or carbonatoms are that carbonatoms that 5 hydrocarbon and refluxed by separator 14 described later comes is that 4 hydrocarbon and/or carbonatoms are adding hydrogen and make its reaction in 5 the hydrocarbon to the carbonatoms that in maker 11, generates.And making above-mentioned carbonatoms is that 4 hydrocarbon and/or carbonatoms are that the alkynes class/alkadiene that contains in 5 the hydrocarbon is converted into the alkene with 1 two key by partial hydrogenation.
In reactor 13, be that 4 hydrocarbon and/or carbonatoms are to supply with dimethyl ether and make its reaction generate the hydrocarbon that contains propylene in 5 the hydrocarbon by the carbonatoms that in hydrogenation reactor 12, obtains.In separator 14, to the hydrocarbon that contains propylene that in reactor 13, obtains separate, purifying, tell propylene, oil, water, hydrogen, and carbonatoms be that 4 hydrocarbon and/or carbonatoms are each compositions such as hydrocarbon of 5.In the mentioned component, carbonatoms is that 4 hydrocarbon and/or carbonatoms are that 5 hydrocarbon and hydrogen are back in the hydrogenation reactor 12 once more.
The 2nd mode at the preparation method of the propylene of the present invention of the propylene production device that adopts this spline structure describes.At first, raw material sent in the alkene generating apparatus 11, generate the product that contains light alkene via pipe 21.Then, utilizing tripping device (not shown) that described product is separated, is that 4 hydrocarbon and/or carbonatoms are 5 hydrocarbon thereby obtain carbonatoms.The separation of above-mentioned product also can be carried out in separator 14.At this moment, carbonatoms is that 4 hydrocarbon and/or carbonatoms are that 5 hydrocarbon is admitted in the hydrogenation reactor 12 via pipe 24, makes and has only used a separator to get final product in whole propylene production device, thereby can seek the simplification of device and technology.
Then, via pipe 22 will separate the product of maker 11 and the carbonatoms that obtains to be 4 hydrocarbon and/or carbonatoms be that 5 hydrocarbon is sent in the hydrogenation reactor 12, simultaneously, hydrogen is sent in the hydrogenation reactor 12 via pipe 23.At least a portion in the above-mentioned hydrogen can be the hydrogen that is generated by reactor 13 is refluxed via pipe 24 and to be supplied to hydrogen in the hydrogenation reactor 12.In addition, can will be that 4 hydrocarbon and/or carbonatoms are that 5 hydrocarbon is sent in the hydrogenation reactor 12 via pipe 24 by separator 14 isolated carbonatomss also.
Making the above-mentioned carbonatoms that is fed in the hydrogenation reactor 12 is that 4 hydrocarbon and/or carbonatoms are 5 hydrocarbon and hydrogen reaction, and making carbonatoms is that 4 hydrocarbon and/or carbonatoms are that the alkynes class/alkadiene generation partial hydrogenation that contains in 5 the hydrocarbon is converted into the alkene with 1 two key.In hydrogenation reactor 12, be filled with hydrogenation catalyst, utilize the effect of this hydrogenation catalyst, generate alkene with 1 two key as primary product.As described hydrogenation catalyst, can preferably use the catalyzer that for example contains palladium.
Then, be that 4 hydrocarbon and/or carbonatoms are at least a being sent in the reactor 13 in 5 hydrocarbon (the alkynes class/alkadiene that is contained is converted into the material that alkene with 1 pair of keys obtains by partial hydrogenation) and dme or the methyl alcohol via pipe 25 carbonatomss that will in hydrogenation reactor 12, obtain.In addition, at least a in described dme or methyl alcohol, at least a in dme or methyl alcohol, can also contain gases such as water vapour, methane, ethane, nitrogen, argon gas, carbonic acid gas.
Be filled with catalysts in reactor 13, the dehydration condensation that takes place by the effect that utilizes this catalysts or catalytic cracking reaction etc. obtain propylene.Simultaneously,, will generate the lower hydrocarbon of carbonatoms below 6 such as ethene, butylene, amylene, hexene as the primary product of above-mentioned reaction, and water, small quantity of hydrogen.
As the catalysts in the reactor 13, MFI structural zeolite catalyzer be can use, MFI structural zeolite catalyzer, aluminium silicophosphate class catalyzer of alkaline-earth metal etc. contained, can adopt modes such as fluidized-bed, fixed bed, moving-bed.In above-mentioned catalyzer, preferred MFI structural zeolite catalyzer more preferably contains the MFI structural zeolite catalyzer of alkaline-earth metal, because they can obtain lower hydrocarbon with high yield.
As an example of the reaction conditions in the reactor 13, can more than 350 ℃ and under the temperature below 600 ℃ above-mentioned raw materials gas be contacted with catalysts.Simultaneously, the relative mass of the dme of supplying with in the unit catalyst quality, unit time (being designated hereinafter simply as " DME ") is that weight hourly space velocity (being designated hereinafter simply as " WHSV ") is preferably below the above and 50g-DME/ of 0.025g-DME/ (g-catalysts hour) (g-catalysts hour), and pressure is preferably selected in the scope more than normal pressure and below the 1MPa.
When unstripped gas and catalysts contact temperature less than 350 ℃ the time, the formation speed of target product is low, and is uneconomical.On the other hand, when unstripped gas and catalysts contact temperature greater than 600 ℃ the time, the deterioration of catalyzer is fast, the generation of by products such as methane increases.
In addition, as WHSV during less than 0.025g-DME/ (g-catalysts hour), the productivity of the unit volume of fixed-bed reactor descends, and is uneconomical.On the other hand, as WHSV during greater than 50g-DME/ (g-catalyzer hour), catalyst life and catalyst activity become insufficient.
By the reaction conditions in the conditioned reaction device 13, can change the containing ratio of the target product lower hydrocarbon in the product, for example, in order to improve the shared ratio of propylene, preferably making reaction pressure is low pressure.
What obtained by reactor 13 is that the product of principal constituent is sent in the heat exchanger and cools off via pipe 26 with the propylene, is sent to then in the separator 14, and wherein, described heat exchanger does not provide diagram.In separator 14, above-mentioned product is separated into each composition, and for example light composition such as methane, ethane, ethene, propylene, carbonatoms are that 4 hydrocarbon and/or carbonatoms are 5 hydrocarbon, carbonatoms heavy hydrocarbon more than 6 etc.
In separator 14 in separated each composition, carbonatoms is that 4 hydrocarbon and/or carbonatoms are that 5 hydrocarbon is back in the hydrogenation reactor 12 via pipe 24.In addition other composition is reclaimed respectively.
According to the preparation facilities of the propylene of above-mentioned formation, and the preparation method of propylene, can be that 4 hydrocarbon and/or carbonatoms are that the alkynes class/alkadiene that contains in 5 the hydrocarbon is converted into the alkene with 1 two key by partial hydrogenation with supplying to carbonatoms in the reactor 13 of preparation propylene.By utilizing hydrogenation reactor 12 that alkynes class/alkadiene is converted into the alkene with 1 two key, can reduce to the content of alkynes class/alkadiene in the unstripped gas that supplies in the reactor 13 extremely low.
If contain a large amount of alkynes class/alkadienes in the unstripped gas, then exist in the pipe arrangement that is connected on the reactor 13 and the danger that produces and be attached with carbonaceous solid-state precipitate on the catalysts.Especially when carbonatoms be that 4 hydrocarbon and/or carbonatoms are that the total amount of the feed rate of 5 hydrocarbon is when increasing with respect to the ratio of dme feed rate and the total amount of methyl alcohol feed rate, the temperature that will cause causing because of thermo-negative reaction in the reactor 13 reduces change greatly, thereby the temperature of unstripped gas is improved, if but improved the temperature of unstripped gas, the solid-state precipitate of this hydrocarbonaceous would then very easily be produced.
; as described herein; by utilizing hydrogenation reactor 12 alkynes class/alkadiene to be converted into alkene with 1 two key; it is extremely low that thereby the content that makes the alkynes class/alkadiene that contains in the unstripped gas that supplies to reactor 13 is reduced to, and can be suppressed at thus in the pipe arrangement that is connected on the reactor 13 and on the catalysts and separate out carbonaceous solid-state precipitate.Thus, can positively prevent to adhere to the fault that precipitate causes deterioration etc. because of having the obstruction that precipitate causes in the pipe arrangement on being connected to reactor 13 or being filled on the catalysts in the reactor 13.
In addition, owing to realized in separator 14, isolating carbonatoms and be 4 hydrocarbon and/or carbonatoms and be 5 hydrocarbon and these hydrocarbon are refluxed and these hydrocarbon are sent in the reactor 13 by hydrogenation reactor 12, selectivity can be improved in whole technology, thereby the ultimate yield of target product can be improved target products such as propylene.
In addition, by containing carbonatoms is that 4 hydrocarbon and/or carbonatoms are that at least a unstripped gas in 5 the hydrocarbon supplies in the reactor 13, can improve by the life-span that is fed to the catalysts that dme in the reactor 13 and/or methyl alcohol prepares propylene.In addition, carbonatoms is that 4 hydrocarbon and/or carbonatoms are that 5 hydrocarbon is preferably the hydrocarbon based on alkene.
Carbonatoms is that 4 alkene or carbonatoms are that 5 alkene is that the reaction of hydrocarbon in reactor 13 of main body is thermo-negative reaction in general, its can relax by dme and/or methyl alcohol in reactor 13 thermopositive reaction and the intensification that causes, the result can reduce the deterioration of catalysts.Therefore, can make the reduction of catalyzer loading level, catalyst regeneration cycle stretch-out etc., and then can cut down cost of equipment, running expense.
Embodiment
Below, by embodiment the present invention is carried out more specific description, but the present invention is not subjected to the restriction of following embodiment.
Embodiment A
[Preparation of catalysts]
＜catalyst preparation example 1 〉
Utilize TOHKEMY 2005-138000 number preparation method to prepare calcareous MFI structural zeolite.
Then, use hydrochloric acid to make it become proton type, and after carrying out 5 hours dryings under 120 ℃, in air, under 520 ℃, carry out 10 hours sintering, obtain the calcic MFI structural zeolite catalyzer of proton type by routine operation.
When reality is used this catalyzer, it is prepared into following state: do not use tackiness agent that it is carried out the even-grained catalyzer (hereinafter referred to as " HCaMFI-A catalyzer ") that obtains after the compression molding and as tackiness agent it is shaped with aluminum oxide after the catalyzer (hereinafter referred to as " HCaMFI-B catalyzer ") that obtains.
＜catalyst preparation example 2 〉
Under 530 ℃, be that 80 ammonium type MFI structural zeolite (manufacturing of Zeolyst company) carries out 6 hours sintering, obtain the HMFI catalyzer the Si/Al mol ratio.
When reality is used this catalyzer, it is prepared into following state: the even-grained catalyzer that obtains after not using tackiness agent to its compression molding.
[synthesizing of lower hydrocarbon]
Use above-mentioned HCaMFI-A catalyzer, HCaMFI-B catalyzer, HMFI catalyzer as catalyzer, only by dme or by dme and the synthetic lower hydrocarbon of iso-butylene.
In addition, when with dme and iso-butylene being the synthetic lower hydrocarbon of raw material, the productive rate of each lower hydrocarbon (quality %) defines with following formula (1).In addition, conversion for isobutene (quality %) defines with following formula (2).
Yi=(Ri-RDMEi)/FC4 * 100 formulas (1)
(in formula (1), Yi: the productive rate for preparing lower hydrocarbon (component i) by iso-butylene; Ri: component i is in the mass rate of reactor exit when being raw material with dme and iso-butylene; RDMEi: component i is in the mass rate of reactor exit when only being raw material with the dme; FC4: iso-butylene is in the mass rate at reactor inlet place).
Conv.=100-YC4 formula (2)
(in formula (2), Conv.: conversion for isobutene; YC4: the carbonatoms that is obtained by iso-butylene is the productive rate of 4 hydrocarbon).
＜experimental example 1A 〉
Use the HCaMFI-A catalyzer, utilize isothermal reactor by the synthetic lower hydrocarbon of dme.
(flow is 1291Ncm to mix dme
3/ hour) and nitrogen (flow is 1291Ncm
3/ hour), and this gas mixture delivered in the isothermal reactor, make its under 530 ℃ of temperature, normal pressure with catalyst reaction.With the feed rate ratio of raw material dme (DME) and catalyzer is that weight hourly space velocity (WHSV) is set at 9.6g-DME/ (g-catalyzer hour).
Methane, carbonatoms are that 2 hydrocarbon, propylene, propane, carbonatoms are that 4 hydrocarbon and the carbonatoms productive rate (quality %) that is the hydrocarbon more than 5 is as shown in table 1.
＜experimental example 2A 〉
Except use the HCaMFI-B catalyzer, (flow is 448Ncm to mix dme
3/ hour) and nitrogen (flow is 448Ncm
3/ hour) and this gas mixture delivered in the isothermal reactor and weight hourly space velocity (WHSV) is set at 3.3g-DME/ (g-catalyzer hour) and in addition, adopts the method identical with experimental example 1A to synthesize lower hydrocarbon by dme.
Methane, carbonatoms are that 2 hydrocarbon, propylene, propane, carbonatoms are that 4 hydrocarbon and the carbonatoms productive rate (quality %) that is the hydrocarbon more than 5 is as shown in table 1.
＜embodiment 1A 〉
Use the HCaMFI-A catalyzer, utilize isothermal reactor by dme and the synthetic lower hydrocarbon of iso-butylene.
(flow is 1279Ncm to mix dme
3/ hour), (flow is 732Ncm to iso-butylene
3/ hour) and nitrogen (flow is 1279Ncm
3/ hour), and this gas mixture delivered in the isothermal reactor, make its under 530 ℃ of temperature, normal pressure with catalyst reaction.With the feed rate ratio of raw material dme (DME) and catalyzer is that weight hourly space velocity (WHSV) is set at 9.5g-DME/ (g-catalyzer hour).
Methane, carbonatoms are that 2 hydrocarbon, propylene, propane, carbonatoms are that 4 hydrocarbon and the carbonatoms productive rate (quality %) and the conversion for isobutene (quality %) that are the hydrocarbon more than 5 is as shown in table 1.＜embodiment 2A 〉
Use the HCaMFI-B catalyzer, utilize isothermal reactor by dme and the synthetic lower hydrocarbon of iso-butylene.
(flow is 448Ncm to mix dme
3/ hour), (flow is 441Ncm to iso-butylene
3/ hour) and nitrogen (flow is 448Ncm
3/ hour), and this gas mixture delivered in the isothermal reactor, make its under 530 ℃ of temperature, normal pressure with catalyst reaction.With the feed rate ratio of raw material dme (DME) and catalyzer is that weight hourly space velocity (WHSV) is set at 4.0g-DME/ (g-catalyzer hour).
Methane, carbonatoms are that 2 hydrocarbon, propylene, propane, carbonatoms are that 4 hydrocarbon and the carbonatoms productive rate (quality %) and the conversion for isobutene (quality %) that are the hydrocarbon more than 5 is as shown in table 1.
＜embodiment 3A 〉
(flow is 448Ncm except having mixed dme
3/ hour), (flow is 1348Ncm to iso-butylene
3/ hour) and nitrogen (flow is 448Ncm
3/ hour) and deliver to this gas mixture in the isothermal reactor beyond, adopts the method identical to synthesize lower hydrocarbon by dme with embodiment 2A.
Methane, carbonatoms are that 2 hydrocarbon, propylene, propane, carbonatoms are that 4 hydrocarbon and the carbonatoms productive rate (quality %) and the conversion for isobutene (quality %) that are the hydrocarbon more than 5 is as shown in table 1.
＜embodiment 4A 〉
Except use the HMFI catalyzer, (flow is 448Ncm to mix dme
3/ hour), (flow is 441Ncm to iso-butylene
3/ hour) and nitrogen (flow is 448Ncm
3/ hour) and this gas mixture delivered in the isothermal reactor and down beyond the reaction, adopts the method identical with embodiment 2A to synthesize lower hydrocarbon by dme 470 ℃ of temperature.
Methane, carbonatoms are that 2 hydrocarbon, propylene, propane, carbonatoms are that 4 hydrocarbon and the carbonatoms productive rate (quality %) and the conversion for isobutene (quality %) that are the hydrocarbon more than 5 is as shown in table 1.＜embodiment 5A 〉
(flow is 1475Ncm except mixing dme
3/ hour), (flow is 672Ncm to iso-butylene
3/ hour), (flow is 448Ncm to nitrogen
3/ hour) and water (flow is 1480Ncm
3/ hour) and deliver to this gas mixture in the isothermal reactor beyond, adopts the method identical to synthesize lower hydrocarbon by dme with embodiment 2A.
Methane, carbonatoms are that 2 hydrocarbon, propylene, propane, carbonatoms are that 4 hydrocarbon and the carbonatoms productive rate (quality %) and the conversion for isobutene (quality %) that are the hydrocarbon more than 5 is as shown in table 1.
＜comparative example 1A 〉
Except do not supply with dme, (flow is 672Ncm to mix iso-butylene
3/ hour), (flow is 448Ncm to nitrogen
3/ hour) and water (flow is 1480Ncm
3/ hour) and deliver to this gas mixture in the isothermal reactor beyond, adopts the method identical to synthesize lower hydrocarbon by dme with embodiment 2A.
Methane, carbonatoms are that 2 hydrocarbon, propylene, propane, carbonatoms are that 4 hydrocarbon and carbonatoms are as shown in table 1 in the productive rate (quality %) and the conversion for isobutene (quality %) of the hydrocarbon more than 5.
[table, 1]
In table 1, the distribution of reaction products that is obtained by iso-butylene among embodiment 1A～5A is from the resulting afterwards data of experimental result (products distribution) of (shown in experimental example 1A or experimental example 2A) when synthetic by dme only of deduction the reactor exit products distribution.The distribution of reaction products representative is by the productive rate (quality %) of each target component of iso-butylene acquisition.
As shown in Table 1, in embodiment 1A～5A,, conversion for isobutene is reached about 63～67 quality % by dme and iso-butylene are sent in the reactor simultaneously.
Result when only iso-butylene being sent to reactor has been shown among the comparative example 1A, and its conversion for isobutene is lower as can be known, is about 46 quality %.
By the result of the foregoing description 1A～5A and comparative example 1A as can be known, by supplying with dme and alkene simultaneously, has the effect that improves olefin conversion.
＜embodiment 6A 〉
Use the HCaMFI-B catalyzer, utilize the simulation insulating reactor by dme and the synthetic lower hydrocarbon of iso-butylene.
Mix dme (flow is 13g/ hour), carbonatoms and be 4 hydrocarbon and carbonatoms and be 5 hydrocarbon (flow is 37.9g/ hour), and with this gas mixture deliver to the simulation insulating reactor in, make its under 530 ℃ of reactor inlet place temperature, normal pressure with catalyst reaction.
Measured the temperature that is arranged on the catalyst layer ingress of simulation in the insulating reactor (℃) with the temperature in catalyst layer exit (℃) poor.Its result is as shown in table 2.
In addition, carbonatoms is that 1 hydrocarbon, carbonatoms are that 2 hydrocarbon, propylene, propane and carbonatoms are that the productive rate (quality %) of the hydrocarbon more than 6 is as shown in table 2.
Need to prove that in table 2, it is 1 that C1 represents carbonatoms; It is 2 that C2 represents carbonatoms; It is 4 that C4 represents carbonatoms; It is 5 that C5 represents carbonatoms; It is more than 6 that C6+ represents carbonatoms.
In addition, also showing carbonatoms in the table 2 is that 4 alkene, carbonatoms are that 4 paraffinic hydrocarbons, carbonatoms are that 5 alkene and carbonatoms are the ratio of the feed rate of 5 paraffinic hydrocarbons.
＜embodiment 7A 〉
Except mixing dme (flow is 18g/ hour), carbonatoms is that 4 hydrocarbon and/or carbonatoms are 5 hydrocarbon (flow is 38.7g/ hour) and this gas mixture delivered in the simulation insulating reactor, and to make reactor inlet place temperature be beyond 501 ℃, adopts the method identical with embodiment 6A by dme and the synthetic lower hydrocarbon of iso-butylene.
Be arranged on the catalyst layer ingress of simulation in the insulating reactor temperature (℃) with the temperature in catalyst layer exit (℃) difference measurement result, be that 1 hydrocarbon, carbonatoms are that 2 hydrocarbon, propylene, propane and carbonatoms are that the productive rate (quality %) of the hydrocarbon more than 6 is shown in Table 2 with carbonatoms.
＜embodiment 8A 〉
Except having mixed dme (flow is 34g/ hour), carbonatoms is that 4 hydrocarbon and/or carbonatoms are 5 hydrocarbon (flow is 41.1g/ hour) and this gas mixture delivered in the simulation insulating reactor, and to make reactor inlet place temperature be beyond 435 ℃, adopts the method identical with embodiment 6A by dme and the synthetic lower hydrocarbon of iso-butylene.
Be arranged on the catalyst layer ingress of simulation in the insulating reactor temperature (℃) with the temperature in catalyst layer exit (℃) the measurement result of difference and carbonatoms be that 1 hydrocarbon, carbonatoms are that 2 hydrocarbon, propylene, propane and carbonatoms are that the productive rate (quality %) of the hydrocarbon more than 6 is shown in Table 2.
＜embodiment 9A 〉
Except mixing dme (flow is 55g/ hour), carbonatoms is that 4 hydrocarbon and/or carbonatoms are 5 hydrocarbon (flow is 44.7g/ hour) and this gas mixture delivered in the simulation insulating reactor, and to make reactor inlet place temperature be beyond 382 ℃, adopts the method identical with embodiment 6A by dme and the synthetic lower hydrocarbon of iso-butylene.
Be arranged on the catalyst layer ingress of simulation in the adiabatic reactor temperature (℃) with the temperature in catalyst layer exit (℃) the measurement result of difference and carbonatoms be that 1 hydrocarbon, carbonatoms are that 2 hydrocarbon, propylene, propane and carbonatoms are that the productive rate (quality %) of the hydrocarbon more than 6 is shown in Table 2.
＜embodiment 10A 〉
Except mixing dme (flow is 98g/ hour), carbonatoms is that 4 hydrocarbon and/or carbonatoms are 5 hydrocarbon (flow is 51.2g/ hour) and this gas mixture delivered in the simulation insulating reactor, and to make reactor inlet place temperature be beyond 379 ℃, adopts the method identical with embodiment 6A by dme and the synthetic lower hydrocarbon of iso-butylene.
Be arranged on the catalyst layer ingress of simulation in the adiabatic reactor temperature (℃) with the temperature in catalyst layer exit (℃) the measurement result of difference and carbonatoms be that 1 hydrocarbon, carbonatoms are that 2 hydrocarbon, propylene, propane and carbonatoms are that the productive rate (quality %) of the hydrocarbon more than 6 is shown in Table 2.
[table 2]
As shown in Table 2, in embodiment 6A～10A, along with carbonatoms is that 4 hydrocarbon and/or carbonatoms are that the feed rate of 5 hydrocarbon reduces with respect to the ratio of the feed rate of dme, the temperature of catalyst layer ingress (℃) with the temperature in catalyst layer exit (℃) difference become big.That is, can confirm: along with above-mentioned ratio reduces, the integrated heat release amount that reaction produces increases.
＜experimental example 3A 〉
Use the HCaMFI-A catalyzer, utilize isothermal reactor by dme and the synthetic lower hydrocarbon of iso-butylene.
(flow is 1279Ncm to mix dme
3/ hour), (flow is 732Ncm to iso-butylene
3/ hour) and nitrogen (flow is 1279Ncm
3/ hour), and this gas mixture delivered in the isothermal reactor, make its under 380 ℃ of temperature, normal pressure with catalyst reaction.With the feed rate ratio of raw material dme (DME) and catalyzer is that weight hourly space velocity (WHSV) is set at 4.1g-DME/ (g-catalyzer hour).
Methane, carbonatoms are that 2 hydrocarbon, propylene, propane, carbonatoms are that 4 hydrocarbon and the carbonatoms productive rate (quality %) that is the hydrocarbon more than 5 is as shown in table 3.
＜experimental example 4A 〉
Except making temperature of reaction is 430 ℃, adopt the method identical by dme and the synthetic lower hydrocarbon of iso-butylene with experimental example 3A.
Methane, carbonatoms are that 2 hydrocarbon, propylene, propane, carbonatoms are that 4 hydrocarbon and the carbonatoms productive rate (quality %) that is the hydrocarbon more than 5 is as shown in table 3.
＜experimental example 5A 〉
Except making temperature of reaction is 480 ℃, adopt the method identical by dme and the synthetic lower hydrocarbon of iso-butylene with experimental example 3A.
Methane, carbonatoms are that 2 hydrocarbon, propylene, propane, carbonatoms are that 4 hydrocarbon and the carbonatoms productive rate (quality %) that is the hydrocarbon more than 5 is as shown in table 3.
＜experimental example 6A 〉
Except making temperature of reaction is 530 ℃, adopt the method identical by dme and the synthetic lower hydrocarbon of iso-butylene with experimental example 3A.
Methane, carbonatoms are that 2 hydrocarbon, propylene, propane, carbonatoms are that 4 hydrocarbon and the carbonatoms productive rate (quality %) that is the hydrocarbon more than 5 is as shown in table 3.
＜experimental example 7A 〉
Except making temperature of reaction is 580 ℃, adopt the method identical by dme and the synthetic lower hydrocarbon of iso-butylene with experimental example 3A.
Methane, carbonatoms are that 2 hydrocarbon, propylene, propane, carbonatoms are that 4 hydrocarbon and the carbonatoms productive rate (quality %) that is the hydrocarbon more than 5 is as shown in table 3.
＜experimental example 8A 〉
Except making temperature of reaction is 620 ℃, adopt the method identical by dme and the synthetic lower hydrocarbon of iso-butylene with experimental example 3A.
Methane, carbonatoms are that 2 hydrocarbon, propylene, propane, carbonatoms are that 4 hydrocarbon and the carbonatoms productive rate (quality %) that is the hydrocarbon more than 5 is as shown in table 3.
[table 3]
The enforcement of experimental example 3A～8A is in order to observe the state of alkene decomposition reaction under the differential responses temperature.As shown in Table 3, along with temperature of reaction raises, carbonatoms is that the ratio of the hydrocarbon more than 5 reduces, and the ratio of lower hydrocarbon increases.
The productive rate (quality %) that utilizes methane in the table 3 to temperature of reaction (℃) mapping, obtain the result of Fig. 2.
By above-mentioned Fig. 2 as can be known, along with the rising of temperature of reaction, the productive rate of methane (quality %) is increase trend, and particularly when temperature of reaction surpassed 600 ℃, methane production sharply increased.That is, in case temperature of reaction surpasses 600 ℃ as can be known, the methane that will cause not having value added increases sharply, and this makes the economy of this technology descend probably.
Embodiment B
[preparation of catalysts]
Prepare calcareous MFI structural zeolite according to TOHKEMY 2005-138000 number preparation method.Then, use hydrochloric acid to make it become proton type, and after carrying out 5 hours dryings under 120 ℃, in air, under 520 ℃, carry out 10 hours sintering, obtain the calcic MFI structural zeolite catalyzer of proton type by routine operation.
[hydrogenation catalyst]
Can use Lin Dela (Lindlar) catalyzer, wherein, described Lin Dela (Lindlar) catalyzer forms by loaded palladium on lime carbonate.In order to suppress side reaction, to be the hydrogenation of olefines, can use the lindlar catalyst (5%Pd-Pb/CaCO that has added Pb
3) as being used for partially hydrogenated catalyzer.
[synthesizing of lower hydrocarbon]
Use above-mentioned HCaMFI as catalysts, by dme and the carbonatoms that contains divinyl be 4 hydrocarbon and/or carbonatoms be 5 hydrocarbon or by dme and the carbonatoms that does not contain divinyl be that 4 hydrocarbon and/or carbonatoms are 5 hydrocarbon or only by the synthetic lower hydrocarbon of dme.
＜embodiment 1B 〉
(flow is 1291Ncm to mix dme
3/ hour), the carbonatoms that do not contain divinyl is that 4 hydrocarbon or carbonatoms are that (flow is 645Ncm for the gas mixture of 5 hydrocarbon
3/ hour) and nitrogen (flow is 646Ncm
3/ little, the time), it is delivered in the isothermal reactor that is filled with the HCaMFI catalyzer, it is reacted under 530 ℃ of temperature, normal pressure.With the feed rate ratio of raw material dme (DME) and catalyzer is that weight hourly space velocity (WHSV) is set at 9.6g-DME/ (g-catalyzer hour).TG measurement result by 24 hours rear catalysts of reaction calculates the carbon formation speed.
＜embodiment 2B 〉
(flow is 1291Ncm to mix dme
3/ hour), the carbonatoms that contains 5% divinyl is that 4 hydrocarbon or carbonatoms are that (flow is 645Ncm for the gas mixture of 5 hydrocarbon
3/ hour) and nitrogen (flow is 646Ncm
3/ hour), it is delivered in the isothermal reactor that is filled with the HCaMFI catalyzer, it is reacted under 530 ℃ of temperature, normal pressure.With the feed rate ratio of raw material dme (DME) and catalyzer is that weight hourly space velocity (WHSV) is set at 9.6g-DME/ (g-catalyzer hour).TG measurement result by 24 hours rear catalysts of reaction calculates the carbon formation speed.
＜comparative example 1B 〉
(flow is 1291Ncm to mix dme
3/ hour), the carbonatoms that contains 40% divinyl is that 4 hydrocarbon or carbonatoms are that (flow is 645Ncm for the gas mixture of 5 hydrocarbon
3/ hour) and nitrogen (flow is 646Ncm
3/ hour), it is delivered in the isothermal reactor that is filled with the HCaMFI catalyzer, it is reacted under 530 ℃ of temperature, normal pressure.With the feed rate ratio of raw material dme (DME) and catalyzer is that weight hourly space velocity (WHSV) is set at 9.6g-DME/ (g-catalyzer hour).TG measurement result by 24 hours rear catalysts of reaction calculates the carbon formation speed.
＜comparative example 2B 〉
(flow is 1291Ncm to mix dme
3/ hour) and nitrogen (flow is 1291Ncm
3/ hour), it is delivered in the isothermal reactor that is filled with the HCaMFI catalyzer, it is reacted under 530 ℃ of temperature, normal pressure.With the feed rate ratio of raw material dme (DME) and catalyzer is that weight hourly space velocity (WHSV) is set at 9.6g-DME/ (g-catalyzer hour).TG measurement result by 24 hours rear catalysts of reaction calculates the carbon formation speed.
The measurement result of the foregoing description 1B, 2B and comparative example 1B, 2B is as shown in table 4.
[table 4]
According to embodiment 1B, the 2B shown in the table 4, and the measurement result of comparative example 1B, 2B as can be known, with respect in the unstripped gas not carbon atom quantity be that 4 hydrocarbon and/or carbonatoms are the comparative example 2B of 5 hydrocarbon, the carbon formation speed that is mixed with the carbonatoms that contains 40% concentration divinyl in the unstripped gas and is 4 hydrocarbon and/or carbonatoms and be among the comparative example 1B of 5 hydrocarbon is very fast.Promptly, can confirm: with do not supply with carbonatoms in reactor is that 4 hydrocarbon and/or carbonatoms are that the situation of 5 hydrocarbon is compared, the carbonatoms that will contain the high density divinyl is that 4 hydrocarbon and/or carbonatoms are at least a in 5 hydrocarbon and divinyl or the methyl alcohol when supplying in the reactor simultaneously, and is bigger for the influence of catalyst degradation.
In addition, by the contrast of comparative example 1B and embodiment 1B, 2B as can be known, with respect to the comparative example 1B that contains 40% high density divinyl, the carbon formation speed that contains among the embodiment 2B of butadiene concentration lower (5%) is slower, does not compare with the carbon formation speed among the comparative example 1B significantly and reduces and do not contain carbon formation speed among the embodiment 1B of divinyl.Promptly, can confirm: even be that 4 hydrocarbon and/or carbonatoms are under the situation of 5 hydrocarbon in reactor, supplying with carbonatoms, by the divinyl partial hydrogenation being made alkadiene concentration reduce, the carbon formation speed is reduced, thereby can reduce load significantly catalyzer.
Confirm in addition: in butadiene concentration lower embodiment 1B, 2B, can successfully implement reaction test, but in containing the higher comparative example 1B of butadiene concentration, caused that owing in preheating pipe arrangement (about 400 ℃), separating out carbonaceous Δ P raises, thereby produced the pipe arrangement blocking problem.
Can confirm by above-mentioned: utilize partial hydrogenation, can be that 4 hydrocarbon or carbonatoms are that described alkadiene in 5 the hydrocarbon is converted into alkene with the carbonatoms that contains alkadienes such as divinyl, thus, the carbon formation speed is reduced, thereby can effectively prevent solids component separating out on pipe arrangement.
And confirm the weather resistance that is filled in the catalysts in the reactor and be improved.
Claims (16)
1. the preparation method of a propylene, it is that 4 alkene or carbonatoms are that at least a unstripped gas in 5 the alkene is delivered in the reactor that this preparation method will contain at least a and carbonatoms in dme or the methyl alcohol, it is reacted in the presence of catalyzer prepare propylene, wherein, in importing to the above-mentioned raw materials gas of above-mentioned reactor, to make carbonatoms be 4 alkene feed rate and carbonatoms is that the total amount of 5 alkene feed rate is more than 0.25 and below 7.5 with respect to the ratio of dme feed rate and the total amount of methyl alcohol feed rate, this ratio is based on the mol ratio of carbonatoms, and above-mentioned raw materials gas is contacted with above-mentioned catalyzer.
2. the preparation method of the described propylene of claim 1, wherein, described carbonatoms is that 4 alkene or carbonatoms are that to comprise carbonatoms that the product that generated by the alkene generating apparatus obtains after separator separates be that 4 alkene or carbonatoms are 5 alkene for 5 alkene.
3. the preparation method of the described propylene of claim 1, wherein, described carbonatoms is that 4 alkene or carbonatoms are that 5 alkene is that carbonatoms that product that is generated by the alkene generating apparatus and the product that is generated by described reactor obtain after separator separates is that 4 alkene or carbonatoms are 5 alkene.
4. the preparation method of the described propylene of claim 2, wherein, what will be generated by above-mentioned reactor is that the product of principal constituent turns back in the above-mentioned separator with the propylene, makes it be separated into propylene and other composition.
5. the preparation method of claim 2 or 3 described propylene, wherein, described alkene generating apparatus is that hydrocarbon is carried out the device of thermo-cracking and/or hydrocarbon carried out the device of catalytic pyrolysis.
6. the preparation method of the described propylene of claim 1, wherein, described catalyzer is a MFI structural zeolite catalyzer.
7. the preparation method of the described propylene of claim 1, wherein, described catalyzer is the MFI structural zeolite catalyzer that contains alkaline-earth metal, and the Si/Al mol ratio of described MFI structural zeolite is more than 10 and 300 following, alkaline-earth metal/Al mol ratio is more than 0.75 and below 15.
8. the preparation method of a propylene, it is that 4 hydrocarbon and/or carbonatoms are that the unstripped gas of 5 hydrocarbon is delivered in the reactor that this preparation method will contain at least a and carbonatoms in dme or the methyl alcohol, it is reacted in the presence of catalysts prepare propylene, wherein
Described carbonatoms is that 4 hydrocarbon and/or carbonatoms are to contain at least a in alkynes class or the alkadiene in 5 the hydrocarbon,
To described carbonatoms is that 4 hydrocarbon and/or carbonatoms are hydrogen supply in 5 the hydrocarbon, described olefines or alkadiene are converted into the alkene with two keys after, with at least a the supplying to simultaneously in the above-mentioned reactor in itself and above-mentioned dme or the methyl alcohol.
9. the preparation method of the described propylene of claim 8, wherein, described carbonatoms is that 4 hydrocarbon and/or carbonatoms are that to comprise carbonatoms that the product that generated by the alkene generating apparatus obtains after separator separates be that 4 alkene or carbonatoms are 5 alkene for 5 hydrocarbon.
10. the preparation method of the described propylene of claim 9, wherein, described alkene generating apparatus be selected to hydrocarbon carry out thermo-cracking device, hydrocarbon is carried out the device of catalytic pyrolysis and makes more than one device in the device of oxygen-containing hydrocarbon generation dehydration condensation.
11. the preparation method of the described propylene of claim 8, wherein, at least a portion that supplies to described carbonatoms and be 4 hydrocarbon and/or carbonatoms and be the hydrogen in 5 the hydrocarbon is generated by above-mentioned reactor.
12. the preparation method of the described propylene of claim 8, wherein, described catalysts is a MFI structural zeolite catalyzer.
13. the preparation method of the described propylene of claim 8, wherein, described catalysts is the MFI structural zeolite catalyzer that contains alkaline-earth metal, and the Si/Al mol ratio of described MFI structural zeolite is more than 10 and 300 following, alkaline-earth metal/Al mol ratio is more than 0.75 and below 15.
14. the preparation facilities of a propylene, this device has:
Hydrogenation reactor, in described hydrogenation reactor, at least a carbonatoms is that 4 hydrocarbon and/or carbonatoms are hydrogen supply in 5 the hydrocarbon in containing alkynes class or alkadiene, and utilizes partial hydrogenation that described olefines or alkadiene are converted into to have the alkene of two keys;
Reactor makes in described reactor that to contain the carbonatoms that obtains in described hydrogenation reactor be that 4 hydrocarbon and/or carbonatoms are that 5 hydrocarbon and at least a unstripped gas in dme or the methyl alcohol react in the presence of catalyzer;
Separator in described separator, is isolated propylene in the reaction product that obtains from above-mentioned reactor.
15. the preparation facilities of the described propylene of claim 14, wherein, described hydrogenation reactor has the hydrogenation catalyst that contains palladium.
16. the preparation facilities of claim 14 or 15 described propylene, wherein, at least a portion that supplies to the hydrogen in the above-mentioned hydrogenation reactor is generated by above-mentioned reactor.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP234007/2006 | 2006-08-30 | ||
| JP2006234007A JP2008056593A (en) | 2006-08-30 | 2006-08-30 | Process for producing propylene |
| JP264513/2006 | 2006-09-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101506127A true CN101506127A (en) | 2009-08-12 |
Family
ID=39239768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800303888A Pending CN101506127A (en) | 2006-08-30 | 2007-08-23 | Propylene production process and propylene production apparatus |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2008056593A (en) |
| CN (1) | CN101506127A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875307A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Method for preparing propylene from methanol |
| CN103153918A (en) * | 2010-07-30 | 2013-06-12 | 日本气体合成株式会社 | Process for manufaturing propylene |
| CN103649020A (en) * | 2011-03-23 | 2014-03-19 | 卢尔吉有限公司 | Process and plant for preparation of low molecular weight olefins |
| CN103827059A (en) * | 2011-09-27 | 2014-05-28 | 卢尔吉有限公司 | Method and system for producing olefins from dimethyl ether |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015189720A (en) * | 2014-03-28 | 2015-11-02 | 三菱化学株式会社 | Method for producing propylene |
| CN107963957B (en) * | 2016-10-19 | 2022-01-25 | 中国科学院大连化学物理研究所 | Method and device for preparing propylene and C4 hydrocarbon |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6124526A (en) * | 1984-07-14 | 1986-02-03 | Agency Of Ind Science & Technol | Preraration of lower olefin |
| JPS6270325A (en) * | 1985-09-20 | 1987-03-31 | Agency Of Ind Science & Technol | Production of lower olefin |
| GB9024342D0 (en) * | 1990-11-08 | 1990-12-19 | British Petroleum Co Plc | Process for the preparation of branched olefins |
| US6888038B2 (en) * | 2002-03-18 | 2005-05-03 | Equistar Chemicals, Lp | Enhanced production of light olefins |
| EP1508555A1 (en) * | 2003-08-19 | 2005-02-23 | Total Petrochemicals Research Feluy | Production of olefins |
-
2006
- 2006-08-30 JP JP2006234007A patent/JP2008056593A/en active Pending
-
2007
- 2007-08-23 CN CNA2007800303888A patent/CN101506127A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103153918A (en) * | 2010-07-30 | 2013-06-12 | 日本气体合成株式会社 | Process for manufaturing propylene |
| CN103649020A (en) * | 2011-03-23 | 2014-03-19 | 卢尔吉有限公司 | Process and plant for preparation of low molecular weight olefins |
| CN102875307A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Method for preparing propylene from methanol |
| CN102875307B (en) * | 2011-07-11 | 2016-01-13 | 中国石油化工股份有限公司 | The method of preparing propylene from methanol |
| CN103827059A (en) * | 2011-09-27 | 2014-05-28 | 卢尔吉有限公司 | Method and system for producing olefins from dimethyl ether |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008056593A (en) | 2008-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101300210B (en) | Process for production of lower hydrocarbon and apparatus for the production | |
| CN101177374B (en) | Method for producing propylene by carbinol or dimethyl ether | |
| CN102666807B (en) | For the production of the method for alkene | |
| WO2009065877A1 (en) | Catalyst particles, process for the preparation of an olefinic product, and process for the preparation of an oxygenate conversion catalyst | |
| EP2058290A1 (en) | Propylene production process and propylene production apparatus | |
| CN101583581A (en) | Oxygenate conversion to olefins with dimerization and metathesis | |
| CN103889934A (en) | Process for preparing ethylene and/or propylene and an iso-olefin-depleted C4 olefinic product | |
| CN101351423A (en) | Light olefin production via dimethyl ether | |
| CN101573313A (en) | Oxygenate conversion to olefins with metathesis | |
| CN103221514B (en) | Heavy feed stock is changed into the method for middle runnings | |
| CN102408296B (en) | Producing 1-butene from oxygenate-to-olefin reaction system | |
| CN101506127A (en) | Propylene production process and propylene production apparatus | |
| JP2009179801A (en) | Method for producing liquefied petroleum gas | |
| CN101506126B (en) | Method and apparatus for producing propylene | |
| WO2014154799A1 (en) | Production of middle distillate hydrocarbon composition | |
| CN103796975A (en) | Process for preparing ethylene and propylene | |
| CA2863285A1 (en) | Process for the conversion of synthesis gas to olefins | |
| CN103333040A (en) | Low energy consumption propylene production technology | |
| CN101279881B (en) | Method for preparing ethylene and propylene by benzin naphtha catalytic pyrolysis | |
| CN103153919B (en) | Process to make olefins from isobutanol | |
| CN113620767A (en) | Method and reaction system for producing low-carbon olefin and aromatic hydrocarbon | |
| CN101585747A (en) | Method for transforming oxygenates into propylene | |
| CN101492337A (en) | Method for preparing propylene, ethylene | |
| CN107540502A (en) | The method that oxygen-containing compound material is catalytically conveted to ethene, propylene and aromatic hydrocarbons | |
| CN103153918A (en) | Process for manufaturing propylene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20090812 |