CN103269791B - Olefin metathesis method and comprise the catalyst of tungsten fluorine bond - Google Patents
Olefin metathesis method and comprise the catalyst of tungsten fluorine bond Download PDFInfo
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- CN103269791B CN103269791B CN201180061787.7A CN201180061787A CN103269791B CN 103269791 B CN103269791 B CN 103269791B CN 201180061787 A CN201180061787 A CN 201180061787A CN 103269791 B CN103269791 B CN 103269791B
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- catalyst
- compound
- tungsten
- alkene
- carrier
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- 238000000034 method Methods 0.000 title claims abstract description 88
- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000005865 alkene metathesis reaction Methods 0.000 title claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 64
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 41
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 40
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 39
- 239000010937 tungsten Substances 0.000 claims abstract description 39
- 238000001465 metallisation Methods 0.000 claims abstract description 29
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims abstract description 24
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001336 alkenes Chemical class 0.000 claims description 80
- 239000004215 Carbon black (E152) Substances 0.000 claims description 63
- 229930195733 hydrocarbon Natural products 0.000 claims description 62
- 150000002430 hydrocarbons Chemical class 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 31
- -1 2,2-diethylpropyl Chemical group 0.000 claims description 28
- 238000005649 metathesis reaction Methods 0.000 claims description 28
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 150000003657 tungsten Chemical class 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 11
- 125000000962 organic group Chemical group 0.000 claims description 11
- 150000005671 trienes Chemical class 0.000 claims description 11
- 239000005977 Ethylene Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000000859 sublimation Methods 0.000 claims description 3
- 230000008022 sublimation Effects 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 73
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 16
- 238000000354 decomposition reaction Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
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- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- ZKIHCVGCBDREBT-UHFFFAOYSA-N [F].[W] Chemical class [F].[W] ZKIHCVGCBDREBT-UHFFFAOYSA-N 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
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- 238000006555 catalytic reaction Methods 0.000 description 3
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- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
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- UMRUUWFGLGNQLI-QFIPXVFZSA-M (2s)-2-(9h-fluoren-9-ylmethoxycarbonylamino)-6-[(2-methylpropan-2-yl)oxycarbonylamino]hexanoate Chemical compound C1=CC=C2C(COC(=O)N[C@@H](CCCCNC(=O)OC(C)(C)C)C([O-])=O)C3=CC=CC=C3C2=C1 UMRUUWFGLGNQLI-QFIPXVFZSA-M 0.000 description 2
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
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- 229910021607 Silver chloride Inorganic materials 0.000 description 2
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- 230000029936 alkylation Effects 0.000 description 2
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- 150000007522 mineralic acids Chemical class 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N n-alpha-hexadecene Natural products CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
- C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/122—Metal aryl or alkyl compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/54—Metathesis reactions, e.g. olefin metathesis
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/66—Tungsten
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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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 present invention has developed usually and has been particularly useful for producing from ethene and butylene method and the catalyst of the olefin metathesis of propylene.This catalyst contains the tungsten metallization compound comprising at least one tungsten-fluorine bond, and it disperses or grafts on carrier.The instantiation of this catalyst is the compound WOF (CH grafted on silica supports
2cMe
3)
3.
Description
prioity claim
The application advocates the U.S. Provisional Application the 61/427th to applying on December 29th, 2010, No. 884, on December 29th, 2010 application U.S. Provisional Application the 61/427th, No. 893, on June 9th, 2011 application U. S. application the 13/156th, No. 860 and on June 9th, 2011 application U. S. application the 13/156th, the priority of No. 918, its content is incorporated herein in full with way of reference.
Technical field
The present invention relates to usually and be particularly useful for producing from ethene and butylene method and the catalyst of the olefin metathesis (metathesis) of propylene.
Prior art
Mainly due to propylene in the polypropylene for packaging material and other commodity is produced with being precursor, therefore in petro chemical industry, the demand of propylene significantly to be increased.Other downstream application of propylene comprises manufacture acrylonitrile, acrylic acid, methacrylaldehyde, expoxy propane and propane diols, plasticiser oxo alcohol (oxoalcohol), isopropylbenzene, isopropyl alcohol and acetone.At present, most of propylene produces during the steam cracking or pyrolysis of the hydrocarbon feeds such as such as natural gas, petroleum liquid and carbonaceous material (such as, coal, recycled plastic and organic material).But, the primary product of steam cracking normally ethene but not propylene.
Steam cracking relates to the extremely complicated combination of reaction and gas recovery system.In the presence of steam, under condition for validity, raw material is loaded into thermal cracking district, to produce pyrolysis reactor eluting gas mixture.Then make stabilized with mixture and be isolated into purification fractions by a series of low temperature and conventional fractionating step.Usually, product ethylene reclaims from ethylene/ethane separation device tower as low boiler cut (such as overhead streams), this ethylene/ethane separation device tower due to the relative volatility of be separated ethene and ethane similar and need a large amount of theory stage.C can be used
4and the known double decomposition of heavier alkene or the combination of disproportionation process and hydrocracking step in the presence of a zeolite catalyst improve the productive rate of ethene and the propylene produced from steam cracking and other method, as at (such as) US5,026,935 and US5,026, set forth in 936.Alkene in crack hydrocarbon feeds, with the C obtained in comfortable refinery and steam cracking unit
4mixture produces so comparatively light olefin and is set forth in US6,858, and 133, US7,087,155 and US7,375, in 257.
Whether no matter combine with conventional double decomposition and/or cracking of olefins step, steam cracking all cannot produce enough propylene to meet worldwide demand.Therefore, other important propylene source is needed.It is the fluid catalytic cracking (FCC) of target and the accessory substance of residual oil fluid catalytic cracking (RFCC) with gasoline production that such source comprises usual.FCC is set forth in (such as) US4,288,688 and other document in.By separation of C
4hydrocarbon, propane, ethane and other compound are by the mixing alkene class C of FCC
3/ C
4propylene purification in byproduct stream is to grade polymer specification.
Therefore, current many production of propylene not ' specially ', but as the accessory substance of ethene and gasoline production.This causes being difficult to production of propylene ability to combine with its market demand.In addition, many new steam cracking abilities will based on use ethane as raw material, and it only produces ethene usually as end product.Although there is the hydrocarbon that some are heavier than ethene, its output is usually not enough, therefore does not allow to reclaim it with economized form.In view of the current demand to propylene grows at top speed, from the reduction of the amount of the raw propylene of steam cracking common property only can promote the effect of the increase of propylene demand and value in market.
The special approach producing light olefin (comprising propylene) is paraffin dehydrogenate, as at US3,978,150 and other document in set forth.But the huge capital cost of dehydrogenating propane equipment is only worthwhile usually in the situation of extensive production of propylene unit (such as, usual 250,000 public ton/year or more).The a large amount of propane feed supplies maintained needed for this ability can obtain from rich propane liquefied petroleum gas (LPG) stream from gazogene source usually.To produce the high severity catalytic cracking that other method that light olefin is target relates to naphtha and other hydrocarbon part.Commercially important Naphtha cracking method is set forth in US6,867, in 341.
Recently, in the industry such as, because expecting, from propylene and other light olefin not based on the substituting charging of oil, to have used oxygenate (oxygenate), alcohol, and more specifically methyl alcohol, ethanol and higher alcohol or derivatives thereof.Specifically, methyl alcohol is used in (such as) US5,914, the methyl alcohol of setting forth in 433 is in alkene (MTO) method for transformation.Cracking of olefins can be used in cracking of olefins reactor to transform the part or all of C of MTO
4 +product improves the productive rate of the light olefin from such method, as at US7, and 268, set forth in 265.Method oxygenate being converted into light olefin is set forth in US7, and 586, in 018, the productive rate wherein by using the double decomposition of two of ethene polymerizations and ethene and butylene (two kinds of products of this method for transformation) to increase propylene.
Use although industrial various special and non-dedicated approach to produce light olefin, the demand of propylene has still been exceeded to the ability of such common method.In addition, expecting can growth further to the demand of propylene.Therefore, need in the industry cost effective method, the method can increase from the productivity of propylene based on both the existing refinery hydrocarbon of crude oil and non-petroleum source feed source.
Summary of the invention
The present invention relates to the method for olefin metathesis and catalyst.Therefore, one embodiment of the invention are the catalyst containing tungsten metallization compound, and the feature of this tungsten metallization compound is that it comprises at least one tungsten-fluorine bond, and this compound is scattered in refractory oxide carrier, and wherein this compound chemistry is bonded to this carrier.
In a specific embodiment, Tungstenic compound is selected from by WR
4f, WOFR
3, W (NR ') FR
3and composition thereof the group of composition, and wherein " R " is the organic group in the β position relative to tungsten without any hydrogen atom.
On the other hand, the present invention relates to the olefin metathesis method using catalyst, this catalyst contains the tungsten compound with at least one tungsten-fluorine bond.Therefore, embodiment contains olefin metathesis method, the method contains makes hydrocarbon feed and catalyst exposure to produce olefin product under metathesis conditions, wherein this hydrocarbon feed contains and comprises the first alkene and the carbon number alkene than second alkene of this first alkene large at least 2, to produce the alkatrienes with middle carbon number, and this catalyst contains tungsten metallization compound, the feature of this tungsten metallization compound is that it comprises at least one tungsten-fluorine bond, this compound is scattered in refractory oxide carrier, and wherein this compound chemistry is bonded to this carrier.
In a specific embodiment, the first alkene is ethene, and the second alkene is butylene, and alkatrienes is propylene.
In a specific embodiment, tungsten compound is selected from by WOF (CH
2cMe
3)
3, W (NR ') F (CH
2cMe
3)
3and composition thereof the group of composition, and wherein R ' is selected from the group be made up of H, phenyl, 2,6-3,5-dimethylphenyls and methyl, and carrier is silica.
In another embodiment, at 75 ° of C (167 °F) to the absolute pressure of the temperature of 400 ° of C (752 °F), 50kPa (7.3psi) to 3,500kPa (508psi) and 1hr
-1to 100hr
-1weight (hourly) space velocity (WHSV) under, make hydrocarbon feed and catalyst exposure.
According to detailed description of the present invention can understand of the present invention like this and other object, embodiment and details.
embodiment
As mentioned above, the present invention relates to the method for olefin metathesis and catalyst.This catalyst contains and has at least one tungsten-fluorine bond and the tungsten metallization compound be scattered in refractory oxide carrier, and this compound chemistry is bonded to this carrier.Therefore, a necessary component of the present invention is the tungsten metallization compound with at least one tungsten-fluorine bond.This tungsten metallization compound has following empirical formula: WR
4f, WOFR
3or W (NR ') FR
3, wherein R is the organic group in the β position relative to tungsten without any hydrogen atom, and its limiting examples is neopentyl (-CH
2cMe
3); Methyl, 2,2-diethylpropyl (-CH
2c (CH
2cH
3)
2and 2,2-diethyl butyl (-CH Me)
2c (CH
2cH
3)
2cH
2cH
3).R ' is organic group, such as (but being not limited to) H, phenyl, 2,6-3,5-dimethylphenyls and methyl.Oxygenatedchemicals is by synthesizing with under type: first make O=WCl
4with alkylation reactions such as such as RMgCl, RLi, RNa or RK to obtain O=WR
3cl, then makes O=WR
3the fluorization agents such as Cl and such as AgBF4, HF or NaF react to form O=WR
3f compound.By alkali treatment product to remove BF
3impurity, this alkali is such as (but being not limited to) NR ' '
3, wherein the limiting examples of R ' ' comprises H, methyl, ethyl and phenyl.Total process may be summarized as follows, and wherein R is neopentyl and R ' ' is ethyl.
The alternative of synthesizing oxygen-containing tungsten fluorine compounds makes (O=W-O-W=O) R
6react to produce O=WR with fluorization agent (same as above)
3f.(O=W-O-W=O) R
6synthesis be set forth in J.AMER.CHEM.SOC., 1983, the 105th volume, in 7176-7, it is incorporated in full with way of reference.
For synthesizing imine based compound, usually make initial O=WCl
4compound and R ' isocyanate reaction, to produce CO
2and R ' N=WCl
4, then carry out as alkylation above and fluoridize.The example of this synthesis is shown in hereafter in diagrammatic form.
Another selection to use NH
3replace R ' isocyanates, to produce HN=WCl
4and H
2o.As above shown by text response formula, if do not remove all boron, then it is by removing by silica-treated.
Obtain after comprising the compound of tungsten-fluorine bond, disperseed now or graft on inorganic refractory support.Spendable suitable inorganic refractory support includes, but is not limited to silica, aluminium oxide, silica-alumina, zirconia, titanium oxide etc., wherein preferred silica.Also the mixture of refractory oxide can be used and it is within the scope of the present invention.Carrier has 50m usually
2/ g to 1000m
2/ g and preferred 80m
2/ g to 500m
2the surface area of/g.Should point out, silica-alumina is not the physical mixture of silica and aluminium oxide, but means acid amorphous materials that is cogelled or co-precipitation.This term for known by the industry, see (such as) US3,909,450, US3,274,124 and US4,988,659, it is all incorporated in full with way of reference.In addition, native silicon dioxide-aluminium oxide (such as attapulgite clay (attapulgite clay), imvite (montmorillonite clay) or diatomite (kieselguhr)) is in the definition of silica-alumina.
Although carrier can use in powder form, preferably make powder forming shaped object.The example of molded article includes, but is not limited to spheroid, pill, extrudate, irregularly shaped particles and tablet.The method forming so different goods is for known by the industry.Carrier also can in the form of inert core layer in the heart, such as, as at US6, and 177, setting forth in 381, it is incorporated to way of reference full text.
Spheric granules is by being formed from (such as) preferential oxidation aluminium with under type: alumina powder is converted into alumina sol by reacting with the acid of suitable peptization and water by (1), and thereafter the mixture of gained colloidal sol and gelling agent being instilled to form alumina gel spheric granules in oil bath, such alumina gel spheric granules is converted into gamma-aluminium oxide carrier easily through known method; (2) method by accepting extensively forms extrudate from powder, and makes thereafter extrudate particle roll on the rotating pan, till formation spheric granules, and then can be dry and calcine such spheric granules to form the spherical carrier particle of expectation; And (3) use suitable peptizing agent wetting powder, and thereafter powder particle is rolled into the spherical block of expectation size.
Can as US2,620, prepare spheroid described in 314 but not make alumina powder peptization, it is incorporated in full with way of reference.The first step of the method relates to arbitrary technology by institute's teaching in the industry and preferably by making aluminum metal and hydrochloric acid reaction form the aluminium hydrosol.The gelling agent that the gained hydrosol and such as hexa (HMT) etc. are suitable for combines.The instillation of gained mixture is maintained in the oil bath at the temperature of 90 ° of C to 100 ° of C.The droplet of mixture is remained in oil bath, till it solidifies and forms hydrogel spheroid.Afterwards, spheroid is taken out continuously from oil bath, and with the ammonia solution process 2 little time up to 2.5 hours at the temperature of 80 ° of C to 95 ° of C.After with ammonia solution process, dry spheroid at the temperature of 80 ° of C to 150 ° of C, and at the temperature of 400 ° of C to 700 ° of C, then calcined for the 1 little time up to 24 hours.
Prepare extrudate in the following manner: inorganic hydroxide or oxide are mixed with water and suitable peptizing agent (such as nitric acid, acetic acid etc.), till formation can extrude cream group.Then the mouth mould of gained cream group through suitable size is extruded, to form extrudate particle.Dry extrudate particle at the temperature of 150 ° of C to 200 ° of C, and then calcined 0.5 little of 10 hours at the temperature of 450 ° of C to 800 ° of C, to realize the preferred form of refractory inorganic oxide.
Preferred vector is silica, and amorphous silica is a type of silica.Example comprises
(W.R.Grace & Co., Columbia, MD) and other is through precipitated silica.No matter which kind of source, the surface area after the optional acid pickling step of silica when receiving or in Catalyst Preparation Procedures will be at least 50m
2/ g, and preferred 80m
2/ g to 500m
2/ g, and most preferably 400m
2/ g to 500m
2/ g.Another silica form spendable is the arbitrary crystalline mesoporous silica being defined as in fact pure silicon dioxide.Such silica comprises the materials such as such as MCM-41 and SBA-15.Other silica form is the zeolite being defined as in fact pure silicon dioxide.Zeolite is crystalline alumino salt composite, and it is micropore and it is from corner-sharing AlO
2and SiO
2tetrahedron is formed.In fact pure silicon dioxide zeolite refer in fact all aluminium all since then skeleton remove.As everyone knows, in fact all aluminium can not be removed.Numerically, when Si/Al ratio has at least 3,000, preferably 10,000 and most preferably 20,000 value time, zeolite is in fact pure silicon dioxide.
Above-mentioned silica optionally through pickling (see U.S. Patent application the 12/701st, No. 508, it is incorporated in full with way of reference), to improve the character of gained catalyst further.Pickling relates to makes silica contact with acid (comprising organic acid or inorganic acid).Concrete inorganic acid comprises nitric acid, sulfuric acid and hydrochloric acid, wherein preferred nitric acid and hydrochloric acid.Aqueous solution acid concentration for pickling is generally at 0.05 mole (M) in the scope of 3M, and is often 0.1M to 1M.Pickling is implemented under static conditions (such as, batch) or flox condition (such as, one way (once through), recirculation or use supplements and the mix flow of recirculation solution).
The representative contact conditions of pickling silica supports comprise general 20 ° of C (68 °F) to 120 ° of C (248 °F), usual 30 ° of C (86 °F) to 100 ° of C (212 °F) and often 50 ° of C (122 °F) to the temperature of 90 ° of C (194 °F).Time of contact is generally 10 minutes to 5 hours, and is often 30 minutes to 3 hours.Determine, pickling makes the BET surface area increase at least 5% (such as, 5% to 20%) of silica supports, and frequent at least 10% (such as, 10% to 15%).For the silica of forms of zeolite, pickling reduces the amount of aluminium in skeleton, namely increases Si/Al ratio.The third effect of pickling reduces the average pore diameter of silica supports.Generally speaking, bore dia reduces at least 5%, and often at least 10%.
By the one in some technology, tungsten-fluorine compounds are grafted on the carrier of expectation now, such technology comprises makes carrier contact with the solution comprising tungsten-carrier, make tungsten compound sublime up on carrier and tungsten compound is directly contacted with expectation carrier.When using solution to make tungsten compound and carrier contact, first this compound is dissolved in appropriate solvent.The solvent that can be used for dissolving this compound includes, but is not limited to Anaesthetie Ether, pentane, benzene and toluene, depends on R group and compound reactivity.At the temperature of-75 ° of C to 35 ° of C, the contact time of 5 minutes to 24 hours is implemented and preferred contact time of 15 minutes to 4 hours at the temperature of-100 ° of C to 80 ° of C, preferably.The amount being scattered in the tungsten-fluorine compounds on carrier can change in wide region, but usually in metal is catalyst (carrier adds compound) 0.5 % by weight to 10 % by weight.Preferably, the amount of compound is 1.5 % by weight to 7 % by weight.
For distillation, by heating tungsten compound at the temperature of 30 ° of C to 150 ° of C, tungsten compound is sublimed up on carrier under dynamic vacuum (being usually less than 10-3 holder).Then carrier is heated to the temperature of 30 ° of C to 150 ° of C, continues 1 little of 4 hours, and remove excessive tungsten compound by up reversal China and be condensed in cooled region at the temperature of 30 ° of C to 150 ° of C.
For the direct contact method grafted on by tungsten compound on carrier, under inert atmosphere (such as argon), tungsten compound and carrier were stirred for the 2 little times up to 6 hours at the temperature of-10 ° of C to 100 ° of C.All volatile compounds are condensed in another reactor.Then by distillation, such as pentane equal solvent is introduced in this reactor, and with solvent (such as pentane) via filtration-condensation cycle by solids wash 3 times.After the solvent evaporates, dry catalyst powder under vacuo.Not for being limited to theory, thinking and no matter using which kind of preparation method, the hydroxyl on carrier surface and W-R key react to form W-O-carrier key, discharge RH simultaneously.
Catalyst of the present invention can be used as metathesis catalyst.Olefin metathesis (or disproportionation) method relates to makes hydrocarbon feed and above-mentioned catalyst exposure under metathesis reaction conditions.Hydrocarbon feed refers to total combined feed of the catalyst be fed in double decomposition reactor or reaction zone, it comprises any recirculation hydrocarbon stream, but do not comprise any nonhydrocarbon gaseous diluent (such as, nitrogen), according to some embodiments, such nonhydrocarbon gaseous diluent can add together with charging.Hydrocarbon feed (but nonessential) only can contain hydrocarbon.Hydrocarbon feed is generally main containing (namely at least 50 % by weight) hydrocarbon, usually containing at least 80% (such as, 80% to 100%) hydrocarbon, and often containing at least 90% (such as, 90 % by weight to 100 % by weight) hydrocarbon.
Equally, in olefin metathesis method of the present invention, the hydrocarbon comprised in hydrocarbon feed generally main (namely at least 50 % by weight, such as 60 % by weight to 100 % by weight) be alkene, it usually containing at least 75 % by weight (such as, 75 % by weight to 100 % by weight) alkene, and it is often containing at least 85 % by weight (such as, 85 % by weight to 100 % by weight or 95 % by weight to 100 % by weight) alkene.In other embodiments, such amount of alkene represents the total olefin percentage in hydrocarbon feed self, but not the olefin percentage of hydrocarbon in hydrocarbon feed.In a further embodiment, such amount of alkene represents the percent of total of two kinds of concrete alkene in hydrocarbon feed, these two kinds of concrete alkene have different carbon number, and it can combine to produce the alkatrienes with middle carbon number (namely carbon number is middle than second alkene (or second olefin reactant) of this first alkene large at least 2 with (ii) carbon number between (i) first alkene (or first olefin reactant)) in double decomposition reactor or reaction zone.Generally speaking, with 0.2:1 to 10:1, usually 0.5:1 to 3:1 and often first alkene of 1:1 to 2:1 and the mol ratio of the second alkene are present in and are fed in the hydrocarbon feed of double decomposition reactor these two kinds of alkene.
In exemplary embodiment, two kinds of alkene (first and second alkene) of paying close attention to are ethene (having 2 carbon) and butylene (having 4 carbon), and it combines the propylene (having 3 carbon) producing expectation in double decomposition reactor or reaction zone.Term ' butylene ' is intended to contain C
4the various isomers of alkene butylene, i.e. butene-1, cis-butene-2, trans-butene-2 and isobutene.In the situation of metathesis reaction relating to butylene, butylene is preferably mainly containing (being namely greater than 50 % by weight) butene-2 (cis and transisomer both), and usually containing at least 85% (such as, 85% to 100%) butene-2, because in double decomposition reactor or reaction zone, relative to butene-1 and isobutene, butene-2 is converted into expects the selective usually stronger of product (such as, propylene).In some cases, such as can expecting that by making butylene experience isomerization with the butene-1 will comprised in butylene and isobutene conversion be extra butene-2, increase the butene-2 content of butylene, thus (such as) reaching such scope.Isomerization can be implemented in the reactor be separated with the reactor for olefin metathesis.Another selection is, by (such as) to implement isomerization in the isomerization reaction zone of under type in the same reactor comprising olefin metathesis reaction district: upstream isomerization catalyst being included in olefin metathesis catalyst, or even two kinds of catalyst are combined in single catalyst bed.Implement to expect that isomerization is to increase the catalyst be suitable for of the content of butene-2 in butylene for known by the industry, and comprise (such as) and comprise magnesian isomerization catalyst, as at US4,217, set forth in 244.
As discussed above, alkene can come from oil or non-petroleum sources.Produce alkene and specifically butylene crude oil refining operation be included in the cracking processes do not deposited in fact and implement in the context of hydrogen, such as fluid catalytic cracking (FCC) and RFCC (RCC).The such as alkene such as ethene and butylene is reclaimed from the known separation (comprising fractionation) from the total reactor effluent of such method with enriched concentration.Another important sources of ethene is steam cracking, as discussed above.The stream being rich in ethene reclaims as the low boiler cut relative to the charging being fed to this separator from ethylene/ethane separation device usually, and this separator fractionation comprises the stream of ethene at least partly from total effluent of steam cracker and/or other.In the situation of alkene coming from non-petroleum sources, both ethene and butylene (such as) can be as method oxygenate being converted into alkene and be specifically that the product of the method for light olefin obtains by methanol conversion.Such method for known by the industry, as discussed above, and the selective saturated additional conversion step increasing butylene productive rate of two polymerizations optionally comprised by (such as) ethene and/or butadiene, as at US7,568, set forth in 018.Therefore, according to various embodiments of the present invention, in hydrocarbon feed, ethene obtains from the low boiler cut acquisition of ethylene/ethane separation device and/or the method certainly oxygenate being converted into alkene at least partially of butylene at least partially.
For experience first and second alkene metathetic (such as, ethene and butylene), expect product and accessory substance (such as, propylene and heavier C based on being converted into
5 +hydrocarbon) such reactant in carbon amounts, transforming degree is generally 40 % by weight to 80 % by weight, and normally 50 % by weight to 75 % by weight.Based on ' one way (per pass) ' is through double decomposition reactor or reaction zone, due to balance restriction, usually be difficult to reach significantly higher transforming degree, wherein maximum conversion rate depends on concrete olefin reactant and concentration thereof and method condition (such as, temperature).
In one or the separating for several times (such as, fractionation) in double decomposition reactor or reaction zone downstream, by removing and reclaim unconverted olefin (such as, ethene and butylene) and byproduct of reaction (such as, C
5 +hydrocarbon, comprises olefin oligomerisation thing and alkylbenzene), reclaim with pure in fact form and expect product (such as, propylene).The recirculation of unconverted olefin reactant is back to double decomposition reactor or reaction zone can desirably be reached completely usually or overall conversion in fact completely, or at least than the above-mentioned overall conversion (such as, 80 % by weight to 100 % by weight or 95 % by weight to 100 % by weight) significantly higher by the conversion per pass degree of balance restriction.Special in propylene situation, usually implement downstream separation to reach the high-purity expecting product.Such as, propylene product has at least 99 volume % and the purity of frequent at least 99.5 volume % usually, to meet grade polymer specification.According to other embodiment, purified propylene can be lower, and this depends on the final use of this product.Such as, for non-polymer technology (such as acrylonitrile process) or for the polypropylene manufacturing process that can adapt to compared with low-purity propylene, the purity of at least 95 volume % (such as, in the scope of 95 volume % to 99 volume %) is acceptable.
Under above-mentioned conversion per pass degree, based on the carbon amounts in converted product, through conversion feedstock alkene component (such as, ethene and propylene) be converted into there is middle carbon number expectation alkene (such as, propylene) selective be generally at least 75 % by weight (such as, in the scope of 75 % by weight to 100 % by weight), usually at least 80 % by weight (such as, in the scope of 80 % by weight to 99 % by weight), and frequent at least 90 % by weight (such as, in scopes of 90 % by weight to 97 % by weight).Expect that the one-pass yield of alkene is converted into this/product of the selective and conversion per pass of such product, it can be in above-mentioned scope.Use as discussed above the overall production rate of the separation of unconverted olefin reactant and recirculation can close to should/such selectivity of product, because acquisition transforms substantially completely (deduct some purges and the solution loss of raw material and product, and the loss caused because downstream separation efficiency is low).
Above-mentioned conversion ratio and selective value are reached by making above-mentioned hydrocarbon feed and catalyst described herein contact continuously or in batches.Usually, contact implemented by the fixed bed by making hydrocarbon feed continue to pass through catalyst in olefin metathesis reaction device or reaction zone.Such as, oscillating bed (swing bed) system can be utilized, wherein periodically make the hydrocarbon feed of flowing change route with (i) get around exhaust or inactivation catalyst bed and (ii) contacts fresh catalyst bed subsequently.For other suitable systems some of implementing hydrocarbon/contact raw for known by the industry, wherein concrete raw material, catalyst deactivation rate and other factors are depended in optimal selection.Such system comprises moving bed system (such as, countercurrent flow system, radial flow system etc.) and fluidized bed system, and wherein any one all can be integrated with continuous catalyst regenerating, known by the industry.
The representative of conditions (that is, making the condition that hydrocarbon feed contacts in olefin metathesis reaction device or reaction zone with catalyst) that can obtain the olefin metathesis of above conversion and selective degree comprises: 75 ° of C (167 °F) to 600 ° of C (1112 °F) and usual 100 ° of C (212 °F) to the temperature of 500 ° of C (932 °F); 50kPa (7.3psi) to 8,000kPa (1160psi) and the absolute pressure of usual 1,500kPa (218psi) to 4,500KPa (653psi); And 1hr
-1to 100hr
-1weight (hourly) space velocity (WHSV) (WHSV).As in the industry understand, WHSV be hydrocarbon feed weight flow divided by catalyst bed weight and represent the equivalent catalyst bed weight of the charging of process per hour.WHSV is relevant to the inverse of reactor holdup time.Under above-mentioned olefin metathesis condition, hydrocarbon feed is gas phase usually in olefin metathesis reaction device or reaction zone, but it also can be liquid phase in the situation of (such as) heavier (higher plate number) olefin feedstock.
Illustrate following examples so that the present invention to be described.Should be understood that such embodiment only for illustration of and and to be not intended to excessively limit in appended claims illustrated wide region of the present invention.
All experiments all use standard Schlenk and glove box techniques (glove-box technique) to implement.According to standardization program purifying and dry solvent.SiO
2-(700)in the following manner from the Aerosil from Degussa
tMsilica (200m
2the specific area of/g) prepare: in 700 ° of C and high vacuum (10
-5holder) lower part dehydroxylation 15h to be to obtain having 190m
2the specific area of/g and comprise 0.7OH nm
-2white solid.
Embodiment 1, W=OF (CH
2cMe
3)
3synthesis
[W=O (CH is implemented according to following reaction
2cMe
3)
3f] synthesis.
W=O (CH
2cMe
3)
3cl is by literature procedure people such as (, J.AMER.CHEM.SOC.1984,106,6305-10) Schrock synthesis.At room temperature, in 20mL toluene by [W=O (CH
2cMe
3)
3cl] (1.5g) and AgBF4 (0.65g) stir 1 hour.Filter reactant mixture to remove insoluble AgCl, and add NEt
3(1.1mL) to pass through with BF
3n (C
2h
5)
3precipitation removes BF
3part.At room temperature by gained solution stirring 16h and then through diatomite filtration.Then solvent is removed under vacuo to provide white solid, in 60 ° of C and decompression (3.10
-5holder) under make this white solid distil to produce 1.13g product.Analyze this product and find that it comprises 41.47%C, 7.89%H and 4.72%F, this and C
15h
33oFW to calculate percentage 41.69%C, 7.69%H and 4.42%F extremely consistent.
Embodiment 2, W (NPh) F (CH
2cMe
3)
3synthesis
By making WOCl
4with C
6h
5nCO reacts, and synthesizes W (NPh) F (CH afterwards with the alkylation of neopentyl magnesium chloride
2cMe
3)
3, as shown below.
The phenylisocyanate just distilled (3.214g) is added into [W=OCl
4] in (9.000g) suspension in 200mL heptane.At a reflux temperature this mixture is heated 4 days, to provide dark-brown precipitate.Remove solvent under vacuo and add Et
2o (20mL), thus produce green solution mixture, filter this mixture to remove insoluble impurities, and then remove Et under vacuo
2o, thus produce [W=N (C
6h
5) Cl
4] (Et
2o) green crystals powder.Preparation 10.6g [W=N (C
6h
5) Cl
4] (Et
2o) solution in toluene also stirs rapidly.This solution is cooled to the 2.17M ethereal solution that-78 ° of C also add (dropwise) 30mL neopentyl magnesium chloride wherein.Make mixture slowly be warming up to room temperature to stir continuously simultaneously, now remove solvent under vacuo.Extract products therefrom with pentane, and use activated carbon treatment extract, stirred 30 minutes, filter through bed of diatomaceous earth, and then remove solvent under vacuo.Collect yellowish-brown residue on the frit, also dry with freezing pentane washing, thus obtain [W=N (the C that 3.8g is brown ceramic powder form
6h
5) (CH
2cMe
3)
3cl].
At room temperature, by a part of [W=N (C as obtained above
6h
5) (CH
2cMe
3)
3cl] (2.000g) and 0.74g AgBF
4stir 1 hour in 20mL toluene.Filter reactant mixture to remove insoluble AgCl, and add 1.1mL NEt
3.At room temperature gained solution is stirred 16h, through diatomite filtration, and then remove solvent under vacuo to provide light yellow solid.As passed through
11b NMR observed, and this product still comprises boron.The solution of product in pentane is added into SiO
2-(700)(500mg) 4 hours are reacted in.With pentane, silica is extracted 3 times, merge solution, and then remove solvent under vacuo to provide light yellow solid.In 60 ° of C and decompression (3 × 10
-5holder) under this product is distilled, to produce 580mg pure products.Analyze this product and find that it comprises 48.86%C, 7.38%H, 4.54%F, 2.74%N and 34.90%W, this and C
21h
38fNW to calculate percentage 49.71%C, 7.55%H, 3.74%F, 2.76%N and 36.23%W extremely consistent.
Embodiment 3, WOF (CH
2cMe
3)
3/ SiO
2synthesis
Under 25 ° of C, by the product [WO (CH of the embodiment 1 in pentane (10mL)
2cMe
3)
3f] (500mg) and SiO
2-(700)(2g) mixture stirs and spends the night.After filtration, with pentane by solids wash 5 times, and all volatile compounds are condensed in another reactor (there is known volume), to quantize the neopentane disengaged during grafting.In vacuum (10
-5holder) under dry gained white powder.The analysis implemented by gas chromatography is shown, during grafting, form 290 μm of ol neopentanes (1.0 ± 0.1NpH/W).Elementary analysis shows: W4.43 % by weight, C3.27 % by weight.
Embodiment 4, W (NPh) F (CH
2cMe
3)
3/ SiO
2synthesis
Under 25 ° of C, by product (500mg), the SiO of embodiment 2
2-(700)(2g) stir with the mixture of pentane (10mL) and spend the night.After filtration, with pentane by solids wash 5 times.In vacuum (10
-5holder) under dry gained white powder.Elementary analysis: W4.8 % by weight, C6.5 % by weight, N0.5 % by weight.
The catalysis test of catalyst in propylene double decomposition of embodiment 5, embodiment 3
With the stainless steel half inch cylindrical reactor that the Catalyst packing of 128mg embodiment 3 can be isolated with ambiance in glove box.Being connected to gas line and after purging duct, making the purifying propylene of 20ml/min flow through catalyst bed under 80 ° of C.By GC on-line analysis hydrocarbon products.Putting into production 30 constantly little, catalyst presents total turn over number of 8300.Ethene selective is 50% and is 50% to the selective of 2-butylene.Form 2-butylene E/Z ratio be 1.5.
The catalysis test of catalyst in propylene double decomposition of embodiment 6, embodiment 4
With the stainless steel half inch cylindrical reactor that the Catalyst packing of 135mg embodiment 4 can be isolated with ambiance in glove box.Being connected to gas line and after purging duct, making the purifying propylene of 20ml/min flow through catalyst bed under 80 ° of C.By GC on-line analysis hydrocarbon products.Constantly little in continuous running 30, catalyst presents total turn over number of 1150.Ethene selective is 50% and is 50% to the selective of 2-butylene.Form 2-butylene E/Z ratio be 0.9.
In one embodiment, the present invention is the first catalyst for olefin metathesis and containing tungsten metallization compound, the feature of this tungsten metallization compound is that it comprises at least one tungsten-fluorine bond, and this compound is scattered in refractory oxide carrier, and wherein this compound chemistry is bonded to this carrier.In one embodiment, the present invention is the second catalyst according to the first catalyst, and wherein Tungstenic compound is selected from by WR
4f, WOFR
3, W (NR ') FR
3and composition thereof the group of composition, and wherein " R " is the organic group in the β position relative to tungsten without any hydrogen atom.
In one embodiment, the present invention is the 3rd catalyst according to the second catalyst, and wherein R is selected from by neopentyl (-CH
2cMe
3); Methyl, 2,2-diethylpropyl (-CH
2c (CH
2cH
3)
2and 2,2-diethyl butyl (-CH Me)
2c (CH
2cH
3)
2cH
2cH
3) group that forms.In one embodiment, the present invention is that wherein R ' is the organic group being selected from the group be made up of H, phenyl, 2,6-3,5-dimethylphenyls and methyl according to second or the 3rd the 4th catalyst of catalyst.
In one embodiment, the present invention is according to first, second, third or the 4th any one the 5th catalyst in catalyst, and wherein the amount of tungsten using account for catalyst as metal 0.5 % by weight to 10 % by weight exists.In one embodiment, the present invention is that wherein refractory oxide carrier is selected from the group be made up of silica, aluminium oxide, silica-alumina, titanium oxide, zirconia and composition thereof according to first, second, third, fourth or the 5th any one the 6th catalyst in catalyst.In one embodiment, the present invention is the 7th catalyst according to the 6th catalyst, and wherein refractory oxide is silica.In one embodiment, the present invention is the 8th catalyst according to the 7th catalyst, and wherein silica is the silica through pickling.
In one embodiment, the present invention is the 9th catalyst according to any one in the first, second, third, fourth, the 5th, the 6th, the 7th or the 8th catalyst, and wherein refractory oxide carrier has at least 50m
2the surface area of/g.In one embodiment, the present invention is that wherein refractory oxide carrier has 80m according to any one the tenth catalyst in the first, second, third, fourth, the 5th, the 6th, the 7th or the 8th catalyst
2/ g to 500m
2the surface area of/g.
In one embodiment, the present invention is the first method of the catalyst for the preparation of olefin metathesis and containing tungsten metallization compound, the feature of this tungsten metallization compound is that it comprises at least one tungsten-fluorine bond, this compound is scattered in refractory oxide carrier, and wherein this compound chemistry is bonded to this carrier; This first method contains makes this tungsten metallization compound and this carrier contact by being selected from by the method for the following group formed: under solution contact conditions, 1) make this carrier contact with the solution of this compound; 2) under sublimation condition, this tungsten metallization compound is made to sublime up on this carrier; And 3) under direct contact conditions, make this tungsten metallization compound directly contact with this carrier.
In one embodiment, the present invention is the second method according to the first method, wherein this preparation method contains and makes tungsten metallization polymer solution contact the time of 5 minutes to 24 hours with refractory oxide carrier at the temperature of-100 ° of C to 80 ° of C, and reclaims gained catalyst.In one embodiment, the present invention is the third method according to the first or second method, and wherein this solution contains in the W of metal 0.5 % by weight to 25 % by weight.
In one embodiment, the present invention is the 4th method according to the first method, wherein this preparation method contains distillation, and sublimation condition contains and sublimes up on carrier through the 1 little time chien shih tungsten metallization compound up to 4 hours at the temperature of vacuum and 30 ° of C to 150 ° of C.In one embodiment, the present invention is the 5th method according to the 4th method, is wherein removed any excess tungsten metallic compound by the temperature subinverse distillation self-catalysis agent at 30 ° of C to 150 ° of C and is made its condensation.
In one embodiment, the present invention is the 6th method according to the first method, wherein this preparation method is direct contact, and directly contact conditions contains and the mixture of tungsten metallization compound and carrier to be stirred for the 2 little times up to 6 hours at the temperature of inert atmosphere and-10 ° of C to 100 ° of C.
In one embodiment, the present invention is the 7th method according to any one in the first, second, third, fourth, the 5th or the 6th method, and wherein Tungstenic compound is selected from by WR
4f, WOFR
3or W (NR ') FR
3and composition thereof composition group, wherein R is the organic group in the β position relative to tungsten without any hydrogen atom.In one embodiment, the present invention is all directions method according to the 7th method, and wherein R is selected from by neopentyl (-CH
2cMe
3); Methyl, 2,2-diethylpropyl (-CH
2c (CH
2cH
3)
2and 2,2-diethyl butyl (-CH Me)
2c (CH
2cH
3)
2cH
2cH
3) group that forms.In one embodiment, the present invention is the 9th method according to the 7th or all directions method, and wherein R ' is the organic group being selected from the group be made up of H, phenyl, 2,6-3,5-dimethylphenyls and methyl.
In another embodiment, the present invention is the first olefin metathesis method, it contains makes hydrocarbon feed and catalyst exposure to produce olefin product under metathesis conditions, wherein this hydrocarbon feed contains and comprises the first alkene and the carbon number alkene than second alkene of this first alkene large at least 2, to produce the alkatrienes with middle carbon number, and this catalyst contains tungsten metallization compound, the feature of this tungsten metallization compound is that it comprises at least one tungsten-fluorine bond, this compound is scattered in refractory oxide carrier, and wherein this compound chemistry is bonded to this carrier.
In one embodiment, the present invention is the second olefin metathesis method according to the first olefin metathesis method, and wherein this Tungstenic compound is selected from by WR
4f, WOFR
3, W (NR ') FR
3and composition thereof the group of composition, and wherein R is the organic group in the β position relative to tungsten without any hydrogen atom.In one embodiment, the present invention is the alkatrienes metathesis process according to the second olefin metathesis method, and wherein R is selected from by neopentyl (-CH
2cMe
3); Methyl, 2,2-diethylpropyl (-CH
2c (CH
2cH
3)
2and 2,2-diethyl butyl (-CH Me)
2c (CH
2cH
3)
2cH
2cH
3) group that forms.In one embodiment, the present invention is the alkatetraenes metathesis process according to second or alkatrienes metathesis process, and wherein R ' is the organic group being selected from the group be made up of H, phenyl, 2,6-3,5-dimethylphenyls and methyl.
In one embodiment, the present invention is according to any one pentaene hydrocarbon metathesis process in first, second, third or alkatetraenes metathesis process, and wherein the amount of tungsten using account for catalyst as metal 0.5 % by weight to 10 % by weight exists.In one embodiment, the present invention is that wherein refractory oxide carrier is selected from the group be made up of silica, aluminium oxide, silica-alumina, titanium oxide, zirconia and composition thereof according to the 6 olefin metathesis process of any one in first, second, third, fourth or pentaene hydrocarbon metathesis process.In one embodiment, the present invention is the 7th olefin metathesis method according to 6 olefin metathesis process, and wherein refractory oxide is silica.In one embodiment, the present invention is the 8th olefin metathesis method according to the 7th olefin metathesis method, and wherein silica is the silica through pickling.
In one embodiment, the present invention is that wherein refractory oxide carrier has at least 50m according to any one the 9th olefin metathesis method in the first, second, third, fourth, the 5th, the 6th, the 7th or the 8th olefin metathesis method
2the surface area of/g.In one embodiment, the present invention is that wherein refractory oxide carrier has 80m according to any one the tenth olefin metathesis method in the first, second, third, fourth, the 5th, the 6th, the 7th or the 8th olefin metathesis method
2/ g to 500m
2the surface area of/g.
In one embodiment, the present invention is according to any one hendecene hydrocarbon metathesis process in the first, second, third, fourth, the 5th, the 6th, the 7th, the 8th, the 9th or the tenth olefin metathesis method, wherein alkene with at least 80 of hydrocarbon feed % by weight amount exist.In one embodiment, the present invention be according to first, second, third, fourth, the 5th, the 6th, the 7th, the 8th, the 9th, the tenth or hendecene hydrocarbon metathesis process in any one benzene metathesis process, wherein in hydrocarbon feed, the mol ratio of the first alkene and the second alkene is 0.5:1 to 3:1.
In one embodiment, the present invention be according to first, second, third, fourth, the 5th, the 6th, the 7th, the 8th, the 9th, the tenth, the 11 or benzene metathesis process in any one tridecylene hydrocarbon metathesis process, wherein the first alkene is ethene, second alkene is butylene, and alkatrienes is propylene.In one embodiment, the present invention be according to first, second, third, fourth, the 5th, the 6th, the 7th, the 8th, the 9th, the tenth, the 11, the 12 or tridecylene hydrocarbon metathesis process in any one tetradecene hydrocarbon metathesis process, wherein at 75 ° of C (167 °F) to the temperature of 400 ° of C (752 °F), 0.5 bar (bar) (7.3psi) to the absolute pressure of 35 bar (508psi) and 1hr
-1to 100hr
-1weight (hourly) space velocity (WHSV) under, make hydrocarbon feed and catalyst exposure.In one embodiment, the present invention is the tenth pentaene hydrocarbon metathesis process according to tridecylene hydrocarbon metathesis process, wherein before butene feed is fed to catalyst, makes this charging isomerization.
In one embodiment, the present invention is according to any one hexadecylene hydrocarbon metathesis process in the first, second, third, fourth, the 5th, the 6th, the 7th, the 8th, the 9th, the tenth, the 11, the 12, the 13, the 14 or the tenth pentaene hydrocarbon metathesis process, is wherein be greater than 75% to the selective of alkatrienes.In one embodiment, the present invention be according to first, second, third, fourth, the 5th, the 6th, the 7th, the 8th, the 9th, the tenth, the 11, the 12, the 13, the 14, the 15 or hexadecylene hydrocarbon metathesis process in any one the 17 olefin metathesis method, be wherein at least 90% to the selective of alkatrienes.
In one embodiment, the present invention is the octadecylene hydrocarbon metathesis process according to tridecylene hydrocarbon metathesis process, wherein unconverted ethene and butylene and alkatrienes propylene separation is recycled to the method as charging.In one embodiment, the present invention is the 19 olefin metathesis method according to tridecylene hydrocarbon metathesis process, wherein the obtaining or the obtaining from method oxygenate being converted into alkene at least partially of butylene from the low boiler cut of ethylene/ethane separation device at least partially of ethene in hydrocarbon feed, or the obtaining and the obtaining from method oxygenate being converted into alkene at least partially of butylene from the low boiler cut of ethylene/ethane separation device at least partially of ethene in hydrocarbon feed.
Claims (10)
1. for a catalyst for olefin metathesis, it contains tungsten metallization compound, and the feature of this tungsten metallization compound is that it comprises at least one tungsten-fluorine bond, and this compound is scattered in refractory oxide carrier, and wherein this compound chemistry is bonded to this carrier.
2. catalyst as claimed in claim 1, wherein this Tungstenic compound is selected from by WR
4f, WOFR
3, W (NR ') FR
3and composition thereof the group of composition, and wherein " R " is the organic group in the β position relative to this tungsten without any hydrogen atom.
3. catalyst as claimed in claim 2, wherein R is selected from by neopentyl (-CH
2cMe
3); Methyl, 2,2-diethylpropyl (-CH
2c (CH
2cH
3)
2and 2,2-diethyl butyl (-CH Me)
2c (CH
2cH
3)
2cH
2cH
3) group that forms.
4., as the catalyst of Claims 2 or 3, wherein R ' is the organic group being selected from the group be made up of H, phenyl, 2,6-3,5-dimethylphenyls and methyl.
5. catalyst as claimed in claim 1, wherein this tungsten exists using the amount accounting for this catalyst 0.5 % by weight to 10 % by weight as metal.
6. the method for the preparation of the catalyst of olefin metathesis, this catalyst contains tungsten metallization compound, the feature of this tungsten metallization compound is that it comprises at least one tungsten-fluorine bond, and this compound is scattered in refractory oxide carrier, and wherein this compound chemistry is bonded to this carrier; The method contains makes this tungsten metallization compound and this carrier contact by being selected from by the method for the following group formed: under solution contact conditions, 1) make this carrier contact with the solution of this compound; 2) under sublimation condition, this tungsten metallization compound is made to sublime up on this carrier; And 3) under direct contact conditions, make this tungsten metallization compound directly contact with this carrier.
7. an olefin metathesis method, it contains makes hydrocarbon feed and catalyst exposure to produce olefin product under metathesis conditions, wherein this hydrocarbon feed contains and comprises the first alkene and the carbon number alkene than second alkene of this first alkene large at least 2, to produce the alkatrienes with middle carbon number, and this catalyst contains tungsten metallization compound, the feature of this tungsten metallization compound is that it comprises at least one tungsten-fluorine bond, this compound is scattered in refractory oxide carrier, and wherein this compound chemistry is bonded to this carrier.
8. method as claimed in claim 7, wherein in this hydrocarbon feed, the mol ratio of this first alkene and this second alkene is 0.5:1 to 3:1.
9. method as claimed in claim 7, wherein this first alkene is ethene, and this second alkene is butylene, and this alkatrienes is propylene.
10. method as claimed in claim 9, wherein the obtaining or the obtaining from method oxygenate being converted into alkene at least partially of this butylene from the low boiler cut of ethylene/ethane separation device at least partially of this ethene in this hydrocarbon feed, or in this hydrocarbon feed this ethene be at least partially from the low boiler cut of ethylene/ethane separation device obtain and this butylene be obtain from method oxygenate being converted into alkene at least partially.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201061427884P | 2010-12-29 | 2010-12-29 | |
| US201061427893P | 2010-12-29 | 2010-12-29 | |
| US61/427,893 | 2010-12-29 | ||
| US61/427,884 | 2010-12-29 | ||
| US13/156,860 | 2011-06-09 | ||
| US13/156,918 US20120316374A1 (en) | 2011-06-09 | 2011-06-09 | Olefin metathesis process using a catalyst containing tungsten fluorine bonds |
| US13/156,918 | 2011-06-09 | ||
| US13/156,860 US8935891B2 (en) | 2011-06-09 | 2011-06-09 | Olefin metathesis catalyst containing tungsten fluorine bonds |
| PCT/US2011/066065 WO2012092014A2 (en) | 2010-12-29 | 2011-12-20 | Olefin metathesis process and catalyst containing tungsten fluorine bonds |
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| Publication Number | Publication Date |
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| MX (1) | MX2013007351A (en) |
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| WO2018127817A1 (en) | 2017-01-05 | 2018-07-12 | Sabic Global Technologies, B.V. | Conversion of waste plastic to propylene and cumene |
| JP6956187B2 (en) * | 2017-01-05 | 2021-11-02 | サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ | Conversion of waste plastics to propylene and cumene |
| KR102296488B1 (en) | 2020-04-06 | 2021-09-01 | 한국생산기술연구원 | Robot gripper module |
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| Publication number | Publication date |
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| WO2012092014A2 (en) | 2012-07-05 |
| EP2658648A4 (en) | 2015-03-25 |
| WO2012092014A3 (en) | 2013-01-17 |
| CA2822796C (en) | 2016-05-31 |
| SG191375A1 (en) | 2013-08-30 |
| CA2822796A1 (en) | 2012-07-05 |
| TWI458551B (en) | 2014-11-01 |
| JP2014511256A (en) | 2014-05-15 |
| JP5662587B2 (en) | 2015-02-04 |
| CN103269791A (en) | 2013-08-28 |
| MX2013007351A (en) | 2013-08-01 |
| EP2658648A2 (en) | 2013-11-06 |
| TW201233441A (en) | 2012-08-16 |
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