CN1298427C - Molecular sieve compositions, catalyst thereof, their making and use in conversion processes - Google Patents
Molecular sieve compositions, catalyst thereof, their making and use in conversion processes Download PDFInfo
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- CN1298427C CN1298427C CNB038047616A CN03804761A CN1298427C CN 1298427 C CN1298427 C CN 1298427C CN B038047616 A CNB038047616 A CN B038047616A CN 03804761 A CN03804761 A CN 03804761A CN 1298427 C CN1298427 C CN 1298427C
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- Prior art keywords
- carbon monoxide
- olefin polymeric
- molecular sieve
- metal oxides
- oxide
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 99
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims description 61
- 239000000203 mixture Substances 0.000 title abstract description 61
- 239000003054 catalyst Substances 0.000 title abstract description 50
- 230000008569 process Effects 0.000 title description 8
- 150000001336 alkenes Chemical class 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 230000000737 periodic effect Effects 0.000 claims abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 108
- 229910052799 carbon Inorganic materials 0.000 claims description 104
- 150000004706 metal oxides Chemical class 0.000 claims description 100
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 72
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 50
- 239000000463 material Substances 0.000 claims description 38
- 239000011230 binding agent Substances 0.000 claims description 29
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 25
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
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Classifications
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
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- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
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- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
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- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/83—Aluminophosphates (APO compounds)
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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Abstract
The invention relates to a catalyst composition, a method of making the same and its use in the conversion of a feedstock, preferably an oxygenated feedstock, into one or more olefin(s), preferably ethylene and/or propylene The catalyst composition comprises a molecular sieve and at least one oxide of a metal from Group 4, optionally in combination with at least one metal from Groups 2 and 3, of the Periodic Table of Elements.
Description
And their preparation method and the application in method for transformation
The present invention relates to combination of molecular sieve and the catalyst that contains said composition, the synthetic method of these compositions and catalyst and these compositions and the catalyst purposes in production conversion of olefines method.
Alkene is produced by petroleum by catalysis or process for steam cracking traditionally.These cracking methods, especially steam cracking has obtained light olefin by various types of hydrocarbon feeds, as ethene and/or propylene.Ethene and propylene are the important petroleum chemicals that can be used to prepare the whole bag of tricks of plastics and other compounds.
In petro chemical industry, known oxygenatedchemicals, especially alcohol can be converted into light olefin for some time.The alcohol that is preferred for light-olefin production is that methyl alcohol is light olefin with the feedstock conversion that is preferred for containing methyl alcohol, and the method for main ethene and/or propylene comprises allows this raw material contact with molecular sieve catalyst composition.
Known have many dissimilar molecular sieves the feedstock conversion that contains oxygenatedchemicals can be one or more alkene.For example, U.S. patent No.5,367,100 to have described that zeolite ZSM-5 is used for methanol conversion be the purposes of alkene; U.S. patent No.4,062,905 has discussed the use crystal silicon-aluminate zeolite, and for example zeolite T, ZK5, erionite and chabasie are the method for ethene and propylene with methyl alcohol and other oxygenate; U.S. patent No.4,079,095 to have described that ZSM-34 is used for methanol conversion be the purposes of hydrocarbon products such as ethene and propylene; With U.S. patent No.4,310,440 have described use crystalline aluminium phosphate (usually is expressed as AlPO
4) method of producing light olefin by alcohol.
Being used for methanol conversion is that some the most useful molecular sieves of alkene are silicoaluminophosphate (SAPO) molecular sieves.Silicoaluminophosphamolecular molecular sieve contains [SiO
2], [AlO
2] and [PO
4] the three-dimensional micropore crystallization skeleton structure of angle tetrahedron element altogether.SAPO molecular sieve synthetic, it is formulated as the method for catalyst and is that the application (being under the situation of methyl alcohol at raw material especially) of alkene is disclosed in U.S. patent Nos.4,499,327 with feedstock conversion, 4,677,242,4,677,243,4,873,390,5,095,163,5,714,662 and 6, in 166,282, all these introduce for reference at this paper comprehensively.
When using in methanol-to-olefins transforms, most of molecular sieves (comprising the SAPO molecular sieve) have suffered coking fast and have therefore needed frequent regeneration, typically comprise allowing catalyst contact high temperature and steam ambient.As a result, present methanol conversion catalyst often has limited useful life, and therefore the molecular sieve catalyst composition that has especially shown the life-span of improving in methanol-to-olefins transforms when using need be provided.
U.S. patent No.4,465,889 have described to be used for methyl alcohol, dimethyl ether or their mixture be converted into and have been rich in different-C
4The carbon monoxide-olefin polymeric that comprises the silicate molecular sieve that floods with thorium, zirconium or titanium oxide of the hydrocarbon products of component.
U.S. patent No.6,180,828 have discussed modified molecular screen is used for the purposes of producing methylamine by methyl alcohol and ammonia, wherein for example with silicoaluminophosphamolecular molecular sieve and one or more modifier, as zirconia, titanium dioxide, yittrium oxide, montmorillonite or kaolinite merging.
U.S. patent No.5,417,949 relate to and use molecular sieve and metal oxide binding agent will contain the method that harmful nitrogen oxide type in the oxygen emission is converted into nitrogen and water, and wherein preferred binding agent is that titanium dioxide and molecular sieve are alumino-silicates.
EP-A-312981 discloses to use and has comprised supporting be embedded in the zeolite in the inorganic fire-resistant host material and at least a oxide of beryllium, magnesium, calcium, strontium, barium or lanthanum that on silica containing carrier material the carbon monoxide-olefin polymeric cracking of preferred magnesian physical mixture contains the method for the hydrocarbon feed stream of vanadium.
Kang and Ihui, " by the effect that the sour number of loci on the Ni-SAPO-34 crystalline catalysts outer surface reduces that is positioned at of methylene chemistry method " (Effects of decrease innumber of acid sites located on the external surface of Ni-SAPO-34crystalline catalyst by the methanochemical method), CatalysisLetters 53, pages 171-176 (1998) discloses, in using methyl alcohol-conversion of ethylene of Ni-SAPO-34, by using the MgO that supports on microspheroidal atresia silica, CaO, BaO or Cs
2The O abrasive catalyst can improve shape selective and reduce coke formation, and wherein BaO is most preferred.
Oxygenatedchemicals-alkene that international open No.WO 98/29370 discloses on containing the aperture non-zeolite molecular sieve that is selected from the metal in lanthanide series, actinides, scandium, yttrium, 4 family's metals, 5 family's metals or their mixture transforms.
In one aspect, the invention belongs to the carbon monoxide-olefin polymeric of the oxide that comprises the metal in molecular sieve and at least a 4 families that are selected from the periodic table of elements, wherein said metal oxide has at least 0.03 under 100 ℃, generally 0.035mg/m at least
2The carbon dioxide absorption rate of metal oxide.
Preferably, this carbon monoxide-olefin polymeric also comprises at least a of binding agent different with described metal oxide and host material.
This carbon monoxide-olefin polymeric can also comprise 2 families that are selected from the periodic table of elements and the oxide of the metal in 3 families.In one embodiment, 4 family metal oxides comprise that zirconia and 2 families and/or 3 family metal oxides comprise one or more oxides that are selected from calcium oxide, barium monoxide, lanthana, yittrium oxide and the scandium oxide.
Preferably, the suitable silicoaluminophosphate that comprises of molecular sieve.
In yet another aspect, the invention belongs to and comprise active 4 family metal oxides and 2 families and/or 3 family metal oxides, binding agent, the molecular sieve catalyst composition of host material and silicoaluminophosphamolecular molecular sieve.
In yet another aspect, the invention belongs to the method for preparing carbon monoxide-olefin polymeric, this method comprises first kind of particle that physical mixed contains molecular sieve and contains 4 family metal oxides and have 0.03mg/m at least
2Second kind of particle of carbon dioxide absorption rate (100 ℃) of metal oxide particle.
Preferably, described second kind of particle precipitates from contain described metal ion solution by the hydration precursor that makes described 4 family metal oxides, and hydrothermal treatment consists hydration precursor reaches at the most 10 days and produces at this hydration precursor of temperature lower calcination of 400-900 ℃ then under at least 80 ℃ temperature.
In yet another aspect, the present invention relates to by containing molecular sieve and having 0.03mg/m at least
2The existence of carbon monoxide-olefin polymeric of activity 4 family metal oxides of carbon dioxide absorption rate (100 ℃) of metal oxide under with raw material, as oxygenatedchemicals, be alcohol aptly, for example methanol conversion is the method for one or more alkene.
In yet another aspect, the present invention relates to comprise molecular sieve, binding agent, host material and be different from binding agent and the molecular sieve catalyst composition of the mixture of the metal oxide of host material in the presence of feedstock conversion is the method for one or more alkene.
In one embodiment, this carbon monoxide-olefin polymeric has greater than 1, as greater than increasing index (LEI) in service life of 1.5.LEI is defined as the ratio in service life with the service life of the same catalyst composition that does not have reactive metal oxides of carbon monoxide-olefin polymeric in this article.
The present invention relates to molecular sieve catalyst composition and at hydrocarbon feed, especially the purposes in oxidation raw material-conversion of olefines.Have been found that molecular sieve and the merging of one or more reactive metal oxides have been obtained to have the more carbon monoxide-olefin polymeric of long life when more specifically methanol conversion is for alkene when being used for raw material such as oxygenatedchemicals.In addition, the gained carbon monoxide-olefin polymeric has often obtained more substantial required light alkene, and the especially undesired ethane of propylene and less amount and propane and other undesirable compounds are as aldehydes and ketone, particularly acetaldehyde.
Preferred reactive metal oxides is to have use at " chemistry and physics CRC handbook (CRC Handbook of Chemistry and Physics) ", the 78th edition, CRC Press, Boca Raton, those of 4 family's metals of the periodic table of elements of the IUPAC form described in the Florida (1997) (for example zirconium and hafnium).In some cases, find, when this carbon monoxide-olefin polymeric also contains the oxide of at least a 2 families that are selected from the periodic table of elements and/or the metal in 3 families, obtained improved result.
Molecular sieve
Molecular sieve is classified according to the regulation of the zeolite name IUPAC committee (IUPAC Commission on Zeolite Nomenclature) by international zeolite structure joint committee (Structure Commission ofthe International Zeolite Association).According to this classification, matrix type zeolite and determined that the zeolite-type molecular sieve of structure is given three alphanumeric codes, and be described in " Altas zeolitic frameworks type " (Atlas of ZeoliteFramework Types), the 5th edition, Elsevier, London, among the England (2001), the document is introduced for reference in this article comprehensively.
Preferred molecular sieve, the feedstock conversion that is particularly useful for containing oxygenatedchemicals are that the non-limitative example of the molecular sieve of alkene comprises AEL, AFY, AEI, BEA, CHA, EDI, FAU, FER, GIS, LTA, LTL, MER, MFI, MOR, MTT, MWW, TAM and TON.In a preferred embodiment, the molecular sieve that uses in carbon monoxide-olefin polymeric of the present invention has AEI topological structure or CHA topological structure, or their combination, most preferably the CHA topological structure.
The crystalline molecular sieve material has common angle [TO
4] tetrahedral three-dimensional, the four sides connect skeleton structure, wherein T is any tetrahedral coordination cation, as [SiO
4], [AlO
4], and/or [PO
4] tetrahedron element.Can be used for the molecular sieve here is fit to comprise and contains [AlO
4] and [PO
4] tetrahedron element (being aluminate or phosphate (AlPO) molecular sieve), or [SiO
4], [AlO
4] and [PO
4] skeleton structure of tetrahedron element (being silicoaluminophosphate (SAPO) molecular sieve).Most preferably, the molecular sieve that can be used for here is silicoaluminophosphate (SAPO) molecular sieve or replacement, and preferable alloy replaces the SAPO molecular sieve.The substituent example of metal that is fit to is the alkali metal of 1 family of the periodic table of elements, the alkaline-earth metal of 2 families of the periodic table of elements, and the rare earth metal of 3 families of the periodic table of elements comprises lanthanide series: lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, erbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium; With scandium or yttrium, the transition metal of the 4-12 family of the periodic table of elements, or the mixture of any of these metallics.
Preferably, molecular sieve used herein has by [TO
4] the fixed pore system of tetrahedral 8 yuan of ring gauges and having less than 5 , to 5 , for example 3 are to 4.5 such as 3 , and especially 3.5 are to the average pore size of 4.2 .
The limiting examples of SAPO that can here use and AlPO molecular sieve comprises SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44 (U.S. patent No.6,162,415), SAPO-47, SAPO-56, AlPO-5, AlPO-11, AlPO-18, AlPO-31, AlPO-34, AlPO-36, AlPO-37, AlPO-46, and a kind of or mixture in their the metallic molecular sieve.In the middle of these, useful especially molecular sieve is SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56, a kind of or mixture in AlPO-18 and AlPO-34 and their the metallic derivative, such as SAPO-18, SAPO-34, AlPO-34 and AlPO-18, and a kind of or mixture in their the metallic derivative, especially SAPO-34 and AlPO-18, and a kind of or mixture in their the metallic derivative.
In one embodiment, molecular sieve is the coexisting material that has two or more different crystalline phases in a kind of combination of molecular sieve.Especially, coexisting molecular sieve is described among open No.2002-0165089 of U.S. patent application and on April 16th, the 1998 disclosed international publication number WO98/15496, and the two introduces for reference here comprehensively.For example, SAPO-18, AlPO-18 and RUW-18 have the AEI framework types, and SAPO-34 has the CHA framework types.Therefore, molecular sieve used herein can comprise the coexisting phase of at least a AEI and CHA framework types, and especially wherein the ratio of CHA framework types and AEI framework types (measuring by the DIFFaX method that discloses in the open No.2002-0165089 of U.S. patent application) was greater than 1: 1.
Preferably, be under the situation of silicoaluminophosphate at molecular sieve, this molecular sieve has and is less than or equal to 0.65, such as 0.65-0.10, preferred 0.40-0.10, more preferably 0.32-0.10 and most preferably the Si/Al ratio of 0.32-0.15.
Reactive metal oxides
Useful here reactive metal oxides is those metal oxides that are different from typical binding agent and/or host material, when being used in combination with molecular sieve, provides benefit in catalysis conversion method.Preferred reactive metal oxides is to have 4 family's metals, those metal oxides such as zirconium and/or hafnium, they can be separately or are used in combination with 2 families (for example magnesium, calcium, strontium and barium) and/or 3 family's metals (comprising group of the lanthanides and actinides) oxide (for example yttrium, scandium and lanthanum).Most preferred active 4 family metal oxides are zirconium metal oxides, and it can be used in combination separately or with calcium oxide, barium monoxide, lanthana and/or yittrium oxide.Generally, the oxide of silicon, aluminium, and their mixture is not preferred.
Especially, reactive metal oxides is those metal oxides that are different from typical binding agent and/or host material, when it uses in carbon monoxide-olefin polymeric with molecular sieve, can effectively prolong the service life of carbon monoxide-olefin polymeric, especially at the raw material that comprises methyl alcohol to one or more conversion of olefines methods.The quantification that catalyst life prolongs is by measuring as increasing index (LEI) service life of equation definition in order to down:
Wherein in same procedure under the same conditions the service life of catalyst or carbon monoxide-olefin polymeric be to drop to certain prescribed level up to the conversion of raw material of bringing by carbon monoxide-olefin polymeric, the cumulant of the raw material that the every g carbon monoxide-olefin polymeric till for example below 10% is handled.The non-activity metal oxide perhaps can shorten the service life of carbon monoxide-olefin polymeric to having the very little not effect that affacts the service life of carbon monoxide-olefin polymeric, therefore has to be less than or equal to 1 LEI.Therefore, reactive metal oxides of the present invention is those metal oxides that are different from typical binding agent and/or host material, when it is used in combination with molecular sieve, provides the molecular sieve catalyst composition that has greater than 1 LEI.According to definition, the molecular sieve catalyst composition that combines with reactive metal oxides does not have and equals 1.0 LEI.
Have been found that by introducing reactive metal oxides and molecular sieve simultaneously, can obtain to have, such as the carbon monoxide-olefin polymeric of the LEI of 1.5-10 greater than 1 to 20.Typically, the catalyst according to the invention compositions display greater than 1.1,1.2-15 for example is more specifically greater than 1.3, such as greater than 1.5, such as greater than 1.7, such as greater than 2 LEI value.
Especially, the metal oxide that can here use has under 100 ℃ 0.03mg/m at least
2Metal oxide particle, such as 0.035mg/m at least
2The carbon dioxide absorption rate of metal oxide.Though the upper limit of the carbon dioxide absorption rate of metal oxide is not important, metal oxide used herein has the 10mg/m of being lower than usually under 100 ℃
2Metal oxide, such as being lower than 5mg/m
2The carbon dioxide absorption rate of metal oxide.Typically, metal oxide used herein has 0.04-0.2mg/m
2The carbon dioxide absorption rate of metal oxide.
In order to measure the carbon dioxide absorption rate of metal oxide, adopt following operation.By in moving air, sample being heated to 200-500 ℃, up to obtaining constant weight, promptly till " dry weight " with the sample dehydration of metal oxide.Sample temperature is reduced to 100 ℃ then, allows carbon dioxide on sample, pass through continuously or with pulse mode, once more till obtaining constant weight.It by the increase of the weight of the sample of the sample (dry weight in sample is a benchmark) of mg/mg the amount of the carbon dioxide that absorbs.
In the embodiment of following report, under environmental pressure, use Metteler TGA/SDTA851 Thermogravimetric System to measure the carbon dioxide absorption rate.The dehydration 1 hour in reaching 500 ℃ moving air of burning matter sample.In the helium that flows, the temperature of sample is reduced to 100 ℃ then.After the balance, the 10wt% carbon dioxide that contains that 20 independent veins of sample contact dash (about 12 seconds/pulse) is the admixture of gas of helium with its excess in sample is flowing helium under required absorption temperature.After each subpulse that absorbs gas, the burning matter sample is used mobile helium purge 3 minutes.Increase by the weight of the sample of mg/mg absorbent (is benchmark with the absorbent weight after 500 ℃ are handled down) is the amount of the carbon dioxide of absorption.The surface area of sample is according to as ASTM D 3663 disclosed Brunauer, and the method for Emmett and Teller (BET) is measured, so that carbon dioxide/m by mg to be provided
2The carbon dioxide absorption rate of metal oxide meter.
Suitable is that this reactive metal oxides has greater than 10m
2/ g is such as greater than 10m
2/ g is to 300m
2The BET surface area of/g.Preferably, this reactive metal oxides has 20m at least
2/ g is such as 20m
2/ g is to 250m
2The BET surface area of/g.More preferably, this reactive metal oxides has 25m at least
2/ g is such as 25-200m
2The BET surface area of/g.In a preferred embodiment, this reactive metal oxides comprises having greater than 20m
2/ g is such as greater than 25m
2/ g and especially greater than 30m
2The BET surface area of/g.
This reactive metal oxides can make in all sorts of ways and prepare.Preferably, by the reactive metal oxides precursor, such as slaine, as halide, nitrate, sulfate or acetate prepare reactive metal oxides.Other metal oxide that is fit to sources are included in the compound that forms metal oxide in the calcination process, such as oxychloride and nitrate.Alkoxide also is the source of 4 family metal oxides that are fit to, for example zirconium-n-propylate.Preferred 4 family metal oxides source is a hydrous zirconium oxide(HZO).The term hydrous zirconium oxide(HZO) is used for representing to comprise via the bridging oxygen atom and is connected in the zirconium atom of other zirconium atoms with covalent bond, and further comprises the material of available hydroxyl.
In one embodiment, hydrous zirconium oxide(HZO) is comprising at least 80 ℃, carries out hydrothermal treatment consists under the condition of preferred at least 100 ℃ temperature.Hydrothermal treatment consists is typically carried out in being higher than atmospheric airtight container.Yet preferred processing mode comprises use open-top receptacle under refluxad.The stirring of hydration 4 family metal oxides in the liquid medium effect of withdrawing fluid and/or stirring (for example by) promoted the effective interaction of hydrous oxide and liquid medium.Hydrous oxide was suitably at least 1 hour with the duration that contacts of liquid medium, such as at least 8 hours.The liquid medium that is used for this processing generally has about 6 or higher, such as 8 or higher pH.The limiting examples of the liquid medium that is fit to comprises water, and hydroxide solution (comprises NH
4 +, Na
+, K
+, Mg
2+And Ca
2+Hydroxide), carbonate and bicarbonate solution (comprise NH
4 +, Na
+, K
+, Mg
2+And Ca
2+Carbonate and bicarbonate), pyridine and derivative thereof, and alkyl/hydroxylamine.
In another embodiment, this reactive metal oxides is for example by allowing the liquid solution that comprises 4 family's metal ion sources, for example the aqueous solution stands to be enough to cause the condition of the hydration precursor precipitation of solid oxide material, for example prepares by precipitating reagent is joined in this solution.Suitable is that precipitation is by carrying out under the pH more than 7.For example, precipitating reagent can be that alkali is such as NaOH or ammonium hydroxide.
In the time will preparing the mixture of 4 family metal oxides and 2 families and/or 3 family metal oxides, first liquid solution that contains 4 family's metal ion sources can be merged with second liquid solution that contains 2 families and/or 3 family's metal ion sources.The merging of these two kinds of solution can be enough to cause that the hydration precursor of mixed oxide material carries out under the condition under the co-precipitation from this solution as solid.In addition, the ion gun of the ion gun of 4 family's metals and 2 families and/or 3 family's metals can be merged into single solution.This solution can stand to be enough to cause that the co-precipitation of hydration precursor is the condition of solid mixed oxide material then, such as by precipitating reagent is joined in this solution.
The temperature that solution keeps in precipitation process generally is lower than 200 ℃, and for example 0 ℃ to being lower than 200 ℃.A specific range of temperatures of precipitation usefulness is 20 ℃ to 100 ℃.The gained gel is then preferably at least 80 ℃, hydrothermal treatment consists under preferred at least 100 ℃ the temperature.Hydrothermal treatment consists is generally under atmospheric pressure carried out.In one embodiment, gel carries out hydrothermal treatment consists and reaches 10 days, such as reaching 5 days, for example reaches 3 days.
For example by the hydration precursor of filtration or centrifugal recovery metal oxide, wash again and drying then.The gained material then can be such as in oxidizing atmosphere, at least 400 ℃, and such as at least 500 ℃, for example 600-900 ℃, 650-800 ℃ temperature lower calcination especially, thus form reactive metal oxides or active mixed-metal oxides.Calcination time at the most 48 hours typically, such as 0.5-24 hour, for example 1.0-10 hour.In one embodiment, calcining was carried out 1-3 hour under about 700 ℃.
In another embodiment, 4 family metal oxides and 2 families and/or 3 family metal oxides prepare separately, and contact together forms mixed-metal oxides then, contacts with molecular sieve then.For example, 4 family metal oxides can contact with molecular sieve before introducing 2 families and/or 3 family metal oxides, and perhaps, 2 families and/or 3 family metal oxides can contact with molecular sieve before introducing 4 family metal oxides.
Comprise at carbon monoxide-olefin polymeric under the situation of 4 family metal oxides and 3 family metal oxides, the mol ratio of 4 family metal oxides and 3 family metal oxides can be 1000: 1 to 1: 1, such as 500: 1 to 2: 1, preferred 100: 1 to 3: 1, more preferably 75: 1 to 5: 1, based on the total mole number of 4 families and 3 family metal oxides.In addition, this carbon monoxide-olefin polymeric can contain 1-25wt%, preferred 1-20wt%, more preferably 3 family's metals of 1-15wt%, based on the gross weight of mixed-metal oxides, be that lanthanum or yttrium metal oxide and 4 family metal oxides are under the situation of zirconium metal oxide especially at 3 family metal oxides.
Comprise at this carbon monoxide-olefin polymeric under the situation of 4 family metal oxides and 2 family metal oxides, the mol ratio of 4 family metal oxides and 2 family metal oxides can be 1000: 1 to 1: 2, such as 500: 1 to 2: 3, preferred 100: 1 to 1: 1, more preferably 50: 1 to 2: 1, based on the total mole number of 4 families and 2 family metal oxides.In addition, this carbon monoxide-olefin polymeric can contain 1-25wt%, preferred 1-20wt%, more preferably 2 family's metals of 1-15wt%, based on the gross weight of mixed-metal oxides, be that calcium oxide and 4 family metal oxides are under the situation of zirconium metal oxide especially at 2 family metal oxides.
Carbon monoxide-olefin polymeric
Carbon monoxide-olefin polymeric of the present invention comprises foregoing any molecular sieve and one or more above-mentioned reactive metal oxides, optional binding agent that is different from reactive metal oxides and/or host material.Typically, the molecular sieve in carbon monoxide-olefin polymeric and the weight ratio of reactive metal oxides are 5-800wt%, preferred 10-600wt%, more preferably 20-500wt%, most preferably 30-400wt%.
Have many different can be used for and form the binding agent of carbon monoxide-olefin polymeric of the present invention.Can be separately or the limiting examples of the binding agent that is used in combination comprise various types of hydrated aluminas, silica, and/or other inorganic oxide sols.A kind of preferred salic colloidal sol is aluminium chlorohydrate (aluminum chlorhydrol).Inorganic oxide sol works as glue, synthesis of molecular sieve and other material such as matrix is bonded together, especially after heat treatment.When heating, inorganic oxide sol (preferably having low viscosity) is converted into the inorganic oxide binder component.For example, alumina sol is converted into alumina binder after heat treatment.
Aluminium chlorohydrate, the aluminium base colloidal sol of hydroxylating that contains the chlorine counter ion counterionsl gegenions has Al
mO
n(OH)
oCl
pX (H
2O) general formula, wherein m is 1-20, and n is 1-8, and o is 5-40, and p is that 2-15 and x are 0-30.In one embodiment, binding agent is Al
13O
4(OH)
24Cl
712 (H
2O), as people such as G.M.Wolterman, Stud.Surf.Sci.and Catal., 76, described in the 105-144 page or leaf (1993).In another embodiment, one or more binding agents and one or more other alumina material such as aluminum oxyhydroxide, gama-alumina, boehmite, diaspore and conventional aluminium oxide such as Alpha-alumina, beta-alumina, gama-alumina, δ-aluminium oxide, ε-aluminium oxide, κ-aluminium oxide, ρ-aluminium oxide, aluminium hydroxide, as gibbsite, bayerite, nordstrandite, doyelite and their mixture are used in combination.
The limiting examples that is purchased colloidal alumina colloidal sol comprises can be from Nalco ChemicalCo., the Nalco 8676 that Naperville, Illinois obtain and can be from Nyacol NanoTechnologies, Inc., Ashland, the Nyacol AL20DW that Massachussetts obtains.
Contain at this carbon monoxide-olefin polymeric under the situation of host material, it preferably is different from reactive metal oxides and any binding agent.Host material generally can effectively reduce the total catalyst cost, and the hot cave as in regenerative process makes carbon monoxide-olefin polymeric closely knit, improves catalyst physical property such as crushing strength and wear resistence.
The limiting examples of the host material that can here use comprises one or more inactive metal oxides, comprise beryllium oxide, quartzy, silica or colloidal sol, and their mixture, silica-magnesia for example, silica-zirconia, silica-titania, silica-alumina and silica-alumina-thorium oxide.In one embodiment, host material is a natural clay as from those of montmorillonite and kaolin families.These natural claies comprise sabbentonites and for example are called as Dixie, McNamee, those kaolin of Georgia and Florida clay.The limiting examples of other host material comprises: galapectite (haloysite), kaolinite, dickite, nacrite, or anauxite.Host material can carry out known method of modifying such as calcining and/or acid treatment and/or chemical treatment such as clay.
In a preferred embodiment, host material is clay or clay based composition, preferably has the clay or the clay based composition of low iron or content of titanium dioxide, most preferably is kaolin.Find that kaolin has formed pumpable highly filled slurry, it is long-pending that it has low fresh surface, and compress together easily owing to its platelet structure.Host material, most preferably kaolinic preferred average particle size are about 0.1 to about 0.6 μ m, and the D90 size distribution is less than about 1 μ m.
Contain at this carbon monoxide-olefin polymeric under the situation of binding agent or host material, this carbon monoxide-olefin polymeric typically contains 1-80wt%, 5-60wt% preferably approximately, and the more preferably molecular sieve of 5-50wt% is based on the gross weight of carbon monoxide-olefin polymeric.
Contain at this carbon monoxide-olefin polymeric under the situation of binding agent and host material, the weight ratio of binding agent and host material is 1: 15 to 1: 5, such as 1: 10 to 1: 4, and especially 1: 6 to 1: 5.The amount of binding agent about typically 2 to about 30wt%, such as about 5 to about 20wt%, especially about 7 to about 15wt%, based on binding agent, the gross weight of molecular sieve and host material.
This carbon monoxide-olefin polymeric typically has 0.5g/cc-5g/cc, such as 0.6g/cc-5g/cc, and for example 0.7g/cc-4g/cc, the especially density of 0.8g/cc-3g/cc.
The carbon monoxide-olefin polymeric formulation
In the preparation of carbon monoxide-olefin polymeric, synthesis of molecular sieve is at first preferably crossed or the state physical mixed of calcining with dried substantially, dry with reactive metal oxides then.Most preferably, molecular sieve and reactive metal oxides are with its calcined state physical mixed.Can enough any methods known in the art, such as using mixing and grinding machine, trommel mixer, ribbon/oar formula blender, kneader or analog mix and obtain sufficient physical mixed.Chemical reaction between molecular sieve and metal oxide is unnecessary, and generally is not preferred.
Contain at this carbon monoxide-olefin polymeric under the situation of matrix and/or binding agent, suit at first this molecular sieve to be mixed with catalyst precarsor with matrix and/or binding agent, the precursor with this reactive metal oxides and this preparation merges then.Reactive metal oxides can add as the non-particle that supports, or can with carrier, add together such as binding agent or host material.The gained carbon monoxide-olefin polymeric can be shaped to the particle of useful shape and granularity then by known technology such as spray-drying, granulation, extrude etc.
In one embodiment, this combination of molecular sieve and host material, optional binding agent and liquid merge, and form slurry, mix then, obtain to contain the basic mixture uniformly of this combination of molecular sieve.The limiting examples that is fit to liquid comprises water, alcohol, ketone, aldehydes, and/or ester class.Most preferred liquid is water.Slurry with combination of molecular sieve, binding agent and host material adds shaped device then, such as spray dryer, this carbon monoxide-olefin polymeric is shaped to required form, for example microsphere.
In case molecular sieve catalyst composition with basic do or drying regime moulding, for the carbon monoxide-olefin polymeric of further sclerosis and/or activation moulding, is heat-treated such as calcining usually.The typical calcined temperature is 400-1,000 ℃, and preferred 500-800 ℃ and more preferably 550-700 ℃.The typical calcined environment is air (can comprise a spot of steam), nitrogen, helium, flue gas (combustion product of anoxic), or their any mixture.
In a preferred embodiment, this carbon monoxide-olefin polymeric temperature at 600-700 ℃ in nitrogen heated common 30 minutes to 15 hours, preferred 1 hour to about 10 hours, more preferably about 1 hour to about 5 hours, most preferably about 2 hours to about 4 hours time.
The application of carbon monoxide-olefin polymeric
Above-mentioned carbon monoxide-olefin polymeric can be used for diversified method, comprising: cracking, and for example the feed naphtha cracking is that light olefin (U.S. patent No.6,300,537) or HMW (MW) cracking hydrocarbon are low MW hydro carbons; Hydrocracking, for example, the hydrocracking of heavy oil and/or ring-type raw material; Isomerization, for example aromatic compounds is such as the isomerization of dimethylbenzene; Polymerization, the polymerization of for example producing one or more alkene of polymer product; Reform; Hydrogenation; Dehydrogenation; Dewaxing, the dewaxing of for example removing the hydro carbons of linear paraffin; Absorption for example is used to separate the absorption of the Alkylaromatics of its isomers; Alkylation, for example alkylation of aromatic hydrocarbons such as benzene and alkylbenzene; Transalkylation, for example transalkylation of the mixture of aromatics and many alkyl aromatics hydro carbons; Dealkylation; Hydrogenated ring-opened; Disproportionation for example prepares the disproportionation of the toluene of benzene and xylene; Oligomeric, for example straight chain and branched-chain alkene is oligomeric; And dehydrocyclization.
Preferable methods comprises the method that naphtha is converted into many aromatic mixtures; Light olefin is converted into the method for gasoline, distillate and lubricant; With oxygenate is the method for alkene; Light paraffins is converted into the method for alkene and/or aromatic compounds; With unsaturated hydro carbons (ethene and/or acetylene) is converted into aldehydes so that be converted into the method for alcohols, acids and ester class.
Most preferred method of the present invention is with the method for feedstock conversion for one or more alkene.Typically, this raw material contains one or more compound that contains the aliphatic structure part, preferably one or more oxygenatedchemicals, make aliphatic structure partly contain 1 to about 50 carbon atoms, preferred 1-20 carbon atom, more preferably 1-10 carbon atom, most preferably 1-4 carbon atom.
The limiting examples of the compound that contains the aliphatic structure part that is fit to comprises that alcohols is such as methyl alcohol and ethanol, alkyl hydrosulfide is such as methyl mercaptan and ethanethio, alkyl thioether such as dimethyl sulphide, alkylamine is such as methylamine, and alkyl ether is such as dimethyl ether, diethyl ether and methyl ethyl ether, alkyl halide is such as methyl chloride and ethyl chloride, alkyl ketone is such as dimethyl ketone, and aldehydes and various acids are such as acetate.Preferably, this raw material comprises methyl alcohol, ethanol, dimethyl ether, diethyl ether or their mixture, more preferably methyl alcohol and/or dimethyl ether, most preferably methyl alcohol.
Use above-mentioned various raw material, especially contain the raw material of oxygenatedchemicals, such as alcohol, carbon monoxide-olefin polymeric of the present invention can mainly be converted into one or more alkene with this raw material effectively.The alkene of being produced typically has 2-30 carbon atom, preferred 2-8 carbon atom, more preferably 2-6 carbon atom, also more preferably 2-4 carbon atom, most preferably ethene and/or propylene.
Typically, carbon monoxide-olefin polymeric of the present invention can be effectively with the feedstock conversion that contains one or more oxygenatedchemicals for containing above 50wt%, typically surpass 60wt%, such as surpassing 70wt%, the product that preferably surpasses the alkene of 80wt% is based on the gross weight of the hydrocarbon in this product.And based on the gross weight of the hydrocarbon in the product, the ethene of being produced and/or the amount of propylene typically are higher than 40wt%, for example are higher than 50wt%, preferably are higher than 65wt%, more preferably are higher than 78wt%.Typically,, be higher than 20wt%,, for example be higher than 40wt% such as being higher than 30wt% by the amount of the ethene of being produced of wt% based on the gross weight of the hydrocarbon products of being produced.In addition,, be higher than 20wt%,, for example be higher than 30wt%, preferably be higher than 35wt% such as being higher than 25wt% by the amount of the propylene of being produced of wt% based on the gross weight of the hydrocarbon products of being produced.
When using feedstock conversion that carbon monoxide-olefin polymeric of the present invention is used for comprising methyl alcohol and dimethyl ether as ethene and propylene, find, with under the same conversion condition, but the similar carbon monoxide-olefin polymeric without the activated metal oxide component is compared, the generation of ethane and propane can reduce above 10%, such as surpassing 20%, for example surpass 30%, especially 30-40%.
Except oxygenatedchemicals ratio of component such as methyl alcohol, this raw material can contain one or more diluents, and they generally do not react with raw material or molecular sieve catalyst composition, typically are used for reducing the concentration of raw material.The limiting examples of diluent comprises helium, argon gas, nitrogen, carbon monoxide, carbon dioxide, water, non-reacted substantially paraffinic (especially alkane such as methane, ethane, and propane), non-reacted substantially aromatic compounds and their mixture.Most preferred diluent is water and nitrogen, and wherein water is particularly preferred.
The inventive method can be at wide temperature range, such as 200 ℃ to 1000 ℃, and for example 250 ℃ to 800 ℃, comprise 250 ℃ to 750 ℃, suitable 300 ℃ to 650 ℃, preferred 350 ℃ to 600 ℃ and more preferably carry out in 350 ℃ to 550 ℃ the scope.
Similarly, this method can be carried out in comprising the wide pressure limit of self-generated pressure.Typically, in the method the dividing potential drop of the raw material except any diluent wherein of Shi Yonging be 0.1kPaa to 5MPaa, preferred 5kPaa to 1MPaa and more preferably 20kPaa to 500kPaa.
Weight hourly space velocity (WHSV) be defined as the gross weight of the raw material except any diluent/hour/weight of molecular sieve in the carbon monoxide-olefin polymeric, can be 1 to 5000hr
-1, preferred 2 to 3000hr
-1, more preferably 5 arrive 1500hr
-1, and most preferably 10 arrive 1000hr
-1In one embodiment, WHSV is 20hr at least
-1Contain at raw material under the situation of methyl alcohol and dimethyl ether, WHSV is 20 to 300hr
-1
Method of the present invention is suitable carries out as fixed-bed approach, or more generally as bed process (comprising the turbulent bed method), such as the continuous fluid bed process, the high flow rate bed process carries out especially continuously.
In one embodiment, this method is carried out as the bed process that uses reactor assembly, regenerative system and recovery system.In this method, fresh feed, one or more optional diluents add one or more riser reactors of reactor assembly with molecular sieve catalyst composition.This raw material is converted into gaseous effluent in riser reactor, in the coking catalyst composition enters separation container in the reactor assembly.The coking catalyst composition separates in separation container with gaseous effluent, generally by cyclone separator, adds stripping zone then, common bottom at separation container.At stripping zone, coking catalyst composition and gas, such as argon gas, preferred steam contacts as steam, methane, carbon dioxide, carbon monoxide, hydrogen and/or inert gas, so that from the coking catalyst composition, reclaim the hydro carbons of absorption, be incorporated in the regenerative system then.
In regenerative system, coking catalyst composition and regenerating medium, preferred oxygen-containing gas is at the coke of coking catalyst composition that can burn, and preferably reaches the regeneration condition contact down based on the level below the 0.5wt% of the gross weight of the coked molecular sieve catalyst composition that enters regenerative system.For example, regeneration condition can comprise 450-750 ℃, preferred 550-700 ℃ temperature.
Regenerated catalyst composition and fresh molecular sieve carbon monoxide-olefin polymeric and/or egr molecule sieve catalyst composition and/or raw material and/or live gas or liquid merging from regenerative system is discharged turn back in the riser reactor again.
Gaseous effluent is discharged from piece-rate system, enters recovery system again, is used for separating the light olefin with the purified gases emission, especially ethene and propylene.
In one embodiment, method of the present invention has formed by hydrocarbon feed, and especially methane and/or ethane are produced the part of the integrated approach of light olefin.The first step of this method is with gas raw material, preferably adds the synthesis gas production area with current, thereby produces synthetic air, generally comprises carbon dioxide, carbon monoxide and hydrogen.Then by with heterogeneous catalyst, general copper-based catalysts contacts under the pressure of 150-450 ℃ temperature and 5MPa-10MPa, synthetic air is converted into the materials flow that contains oxygenatedchemicals.After purifying, the materials flow that contains oxygenatedchemicals can be used as the above-mentioned light olefin that is used to produce, such as the raw material in the method for ethene and/or propylene.The limiting examples of this integrated approach is described among the EP-B-0933345, and the latter introduces for reference at this paper comprehensively.
In the integrated approach, the alkene of being produced enters and is used for producing various polyolefinic one or more polymerizations another that combines with above-mentioned integrated approach optional more completely.
In order to understand the present invention better, comprise its representative advantages, following examples are provided.
In an embodiment, LEI is defined as containing the ratio in service life of service life and the same molecular sieve that does not have metal oxide (be defined as have 1 LEI) of the molecular sieve catalyst composition of reactive metal oxides.In order to measure LEI, be defined as service life up to conversion ratio drop to its initial value about 10% till the cumulant of the oxygenatedchemicals (preferably being converted into one or more alkene) that transformed of every g molecular sieve.If conversion ratio does not drop to 10% of its initial value during to off-test, estimate service life by linear extrapolation according to the conversion ratio decrease speed between last two data points in test.
" main alkene " is the optionally summation to ethene and propylene.Ratio " C
2 =/ C
3 =" be ethene and propylene ratio optionally to test weighting (weighted)." C
3Purity " by with the propylene selectivity divided by propylene and propane optionally summation calculate.Methane, ethene, ethane, propylene, propane, C
4And C
5+ selectivity be to the test weighting average selectivity.Note C
5+ only by C
5, C
6And C
7Form.In table, the summation of selective value is not equal to 100%, because well-known, these values do not have STRENGTH ON COKE to calibrate.
Embodiment A
The preparation of molecular sieve
The silicoaluminophosphamolecular molecular sieve SAPO-34 that makes called after MSA crystallization in the presence of as the tetraethyl ammonium hydroxide (R1) of organic structure directing agent or template agent and dipropylamine (R2).Prepare the mixture that following mol ratio is formed by at first a certain amount of Condea Pural SB being mixed with deionized water, thereby form slurry:
0.2SiO
2/Al
2O
3/P
2O
5/0.9R1/1.5R2/50H
2O
Add a certain amount of phosphoric acid (85%) to this slurry.Carry out when these are added on stirring, thereby form uniform mixture.Add Ludox AS40 (40%SiO to this homogeneous mixture
2), when mixing, add R1 subsequently, form homogeneous mixture.Add R2 to this homogeneous mixture, the gained mixture passes through in stainless steel autoclave then 170 ℃ of heating crystallizations under agitation in 40 hours down.The slurry of crystalline molecular sieve is provided like this.Then by filtering isolation of crystalline from mother liquor.Then molecular sieve crystal is mixed with binding agent and host material, being shaped by spray-drying is particle again.
Embodiment B
Method for transformation
The whole conversion data that provided use the microflow reactor that has the stainless steel reactor (1/4 inch (0.64cm) external diameter) of gasified methanol to form by the adding that is positioned at heating furnace to obtain.Reactor remains under the pressure of 475 ℃ temperature and 25psig (172.4kPag).The flow velocity of methyl alcohol should make that the flow velocity/g molecular sieve (also being called weight hourly space velocity (WHSV)) of methyl alcohol by weight is 100h
-1The product gas that collection is discharged from reactor uses gc analysis.The catalyst dosage is that 50mg and catalyst bed dilute with quartzy, so that the heat spot in the reactor is minimized.
Embodiment 1
Under agitation, with 1kg ZrOCl
28H
2O is dissolved in the 3.0L distilled water.Preparation contains the dense NH of 400g
4Another solution of OH and 3.0L distilled water.Two kinds of solution are heated to 60 ℃.Using nozzle to mix merges the speed of these two kinds of heated solutions with 50ml/min.By adding dense ammonium hydroxide the pH of resulting composite is transferred to about 9.Then this slurry is poured in the polypropylene vial, put into steam chest (100 ℃) and reach 72 hours.Reclaim formed product by filtering, with the excessive water washing with 85 ℃ of down dry a whole nights.The part of this product was calcined 3 hours down at 700 ℃ in moving air, obtain the active oxidation zirconia material.
Embodiment 2
Under agitation, with 500g ZrOCl
28H
2O and 84g La (NO
3)
36H
2O is dissolved in the 3.0L distilled water.Preparation contains the dense NH of 260g
4Another solution of OH and 3.0L distilled water.Two kinds of solution are heated to 60 ℃, re-use the speed merging of nozzle mixing, thereby form final mixture, i.e. slurry with 50ml/min.By adding dense ammonium hydroxide the pH of final mixture is transferred to about 9.Then this slurry is poured in the polypropylene vial, put into steam chest (100 ℃) and reach 72 hours.By the formed product of filtered and recycled, with the excessive water washing with 85 ℃ of down dry a whole nights.The part of this product was calcined 3 hours down at 700 ℃ in moving air, and formation contains the active mixed-metal oxides based on the nominal 10wt%La (lanthanum) of the final weight of mixed-metal oxides.
Embodiment 3
Under agitation, with 50g ZrOCl
28H
2O is dissolved in the 300ml distilled water.Preparation contains the dense La (NO of 4.2g
3)
36H
2Another solution of O and 300ml distilled water.Under agitation these two kinds of solution are merged into final mixture.By adding dense ammonium hydroxide (28.9g) with final mixture, promptly the pH of slurry transfers to about 9.Then this slurry is poured in the polypropylene vial, put into steam chest (100 ℃) and reach 72 hours.By the formed product of filtered and recycled, with the excessive water washing with 85 ℃ of down dry a whole nights.The part of this products therefrom was calcined 3 hours down at 700 ℃ in moving air, and formation contains the active mixed-metal oxides based on the nominal 5wt%La of the final weight of mixed-metal oxides.
Embodiment 4
Under agitation, with 500g ZrOCl
28H
2O and 70g Y (NO
3)
35H
2O is dissolved in the 3.0L distilled water.Preparation contains the dense NH of 260g
4Another solution of OH and 3.0L distilled water.Two kinds of solution are heated to 60 ℃, and the speed of using nozzle to mix with 50ml/min then merges, thereby forms final mixture.By adding dense ammonium hydroxide with final mixture, promptly the pH of slurry transfers to about 9.Then this slurry is poured in the polypropylene vial, put into steam chest (100 ℃) and reach 72 hours.By the formed product of filtered and recycled, with the excessive water washing with 85 ℃ of down dry a whole nights.The part of products therefrom was calcined 3 hours down at 700 ℃ in moving air, and formation contains the active mixed-metal oxides based on the nominal 10wt%Y (yttrium) of the final weight of mixed-metal oxides.
Embodiment 5
Under agitation, with 500g ZrOCl
28H
2O and 56g Ca (NO
3)
24H
2O is dissolved in the 3000ml distilled water.Preparation contains the dense NH of 260g
4Another solution of OH and 3000ml distilled water.Under agitation these two kinds of solution are merged.By adding dense ammonium hydroxide (160g) pH of resulting composite is transferred to about 9.Then this slurry is poured in the polypropylene vial, put into steam chest (100 ℃) and reach 72 hours.By the formed product of filtered and recycled, with the excessive water washing with 85 ℃ of down dry a whole nights.The part of this product was calcined 3 hours down at 700 ℃ in moving air, and formation contains the active mixed-metal oxides based on the nominal 5wt%Ca (calcium) of the final weight of mixed-metal oxides.
Embodiment 6
Under agitation with the TiOSO of 70g
4XH
2SO
4XH
2O (x=1) is dissolved in the 400ml distilled water.Preparation contains 12.8g CeSO
4Another solution with 300ml distilled water.Under agitation these two kinds of solution are merged.By adding dense ammonium hydroxide (64.3g) pH of resulting composite is transferred to about 8.Then this slurry is poured in the polypropylene vial, put into steam chest (100 ℃) and reach 72 hours.By the formed product of filtered and recycled, with the excessive water washing with 85 ℃ of down dry a whole nights.The part of this product was calcined 3 hours down at 700 ℃ in moving air, and formation contains the active mixed-metal oxides based on the nominal 5wt%Ce of the final weight of mixed-metal oxides.
Embodiment 7
Under agitation, with 5g HfOCl
2XH
2O is dissolved in the 100ml distilled water.By adding dense ammonium hydroxide (4.5g) pH of resulting composite is transferred to about 9.Then this slurry is poured in the polypropylene vial, put into steam chest (100 ℃) and reach 72 hours.Reclaim formed product by filtering, with the excessive water washing with 85 ℃ of down dry a whole nights.The part of this catalyst was calcined 3 hours down at 700 ℃ in moving air, obtain the active oxidation hafnium.
Embodiment 8
Under agitation, with 5g HfOCl
2XH
2O and 0.62g La (NO
3)
36H
2O is dissolved in the 100ml distilled water.By adding dense ammonium hydroxide (3.5g) pH of resulting composite is transferred to about 9.Then this slurry is poured in the polypropylene vial, put into steam chest (100 ℃) and reach 72 hours.Reclaim formed product by filtering, with the excessive water washing with 85 ℃ of down dry a whole nights.The part of this catalyst was calcined 3 hours down at 700 ℃ in moving air, and acquisition contains the active mixed-metal oxides based on the nominal 5wt%La of the final weight of mixed-metal oxides.
Embodiment 9
Under environmental pressure, use Mettler TGA/SDTA 851 Thermogravimetric Systems to measure the carbon dioxide absorption rate of the oxide of embodiment 1-8.The at first dehydration 1 hour in reaching about 500 ℃ moving air of burning matter sample is after this 100 ℃ of absorptivities of measuring carbon dioxide down.The surface area of sample is according to Brunauer, and the method for Emmett and Teller (BET) is measured, with obtain in table 1, to provide by mg carbon dioxide/m
2The carbon dioxide absorption rate of metal oxide meter.
Table 1
| Embodiment | Catalyst dry weight (mg) | CO 2(mg) | Surface area (m 2/g) | CO 2Absorptivity (mg CO 2/m 2) |
| 1 | 76 | 0.0980 | 29 | 0.045 |
| 2 | 115 | 0.7781 | 80 | 0.085 |
| 3 | 73 | 0.4243 | 89 | 0.065 |
| 4 | 97 | 0.3808 | 100 | 0.039 |
| 5 | 78 | 0.5399 | 85 | 0.081 |
| 6 | 43 | 0.1035 | 50 | 0.048 |
| 7 | 158 | 0.3704 | 25 | 0.094 |
| 8 | 164 | 0.7359 | 60 | 0.075 |
Embodiment 10 (contrast)
In table 2 and 3, reported in reactor performance at the molecular sieve MSA of the above tester embodiment A of under the condition described in the Embodiment B, using the 50mg dosage.
Embodiment 11
In the present embodiment, carbon monoxide-olefin polymeric is made up of the active zirconia of the embodiment 1 of the MSA of 40mg embodiment A and 10mg.Carbon monoxide-olefin polymeric and active mixed-metal oxides are fully mixed, with quartzy dilution, form reactor beds then.The result who tests this carbon monoxide-olefin polymeric with the method for Embodiment B has been shown in table 2 and 3.The result shows, active zirconia is joined the service life that has significantly increased combination of molecular sieve in the catalyst bed, and the amount that has reduced undesirable ethane and propane.
Embodiment 12
In the present embodiment, carbon monoxide-olefin polymeric by the MSA of 40mg embodiment A and 10mg as forming at the active mixed-metal oxides that contains 10wt%La described in the embodiment 2.Carbon monoxide-olefin polymeric and active mixed-metal oxides are fully mixed, with quartzy dilution, form reactor beds then.The result who tests this carbon monoxide-olefin polymeric with the method for Embodiment B has been shown in table 2 and 3.Data declaration in the table 2 and 3 by use constituting 20% the active mixed-metal oxides that contains 10wt%La of carbon monoxide-olefin polymeric dosage, has increased by one times the service life of molecular sieve, as by shown in its LEI value 2.In addition, by absolute standard, main alkene has a net increase of long by 1.7%, the major part of this growth belongs to the increase of 2.76% propylene, has remedied a small amount of minimizing of 1.07% ethene.Show the remarkable hydrogen transfer reaction that reduced to the selectivity reduction by 39% of ethane with to selectivity of both propane reduction by 37%.
Embodiment 13
In the present embodiment, carbon monoxide-olefin polymeric by the MSA of 30mg embodiment A and 20mg as forming at the active mixed-metal oxides that contains 10wt%La described in the embodiment 2.Carbon monoxide-olefin polymeric and active mixed-metal oxides are fully mixed, with quartzy dilution, form reactor beds then.The result who tests this carbon monoxide-olefin polymeric with the method for Embodiment B has been shown in table 2 and 3.Table 2 and 3 data declaration, by using 40% the active mixed-metal oxides that contains 10wt%La that constitutes the carbon monoxide-olefin polymeric dosage, increased by 440% the service life of SAPO-34 carbon monoxide-olefin polymeric.The reinforced optionally trend of this catalyst in embodiment 8, see those are similar.
Embodiment 14
In the present embodiment, carbon monoxide-olefin polymeric by the MSA of 40mg embodiment A and 10mg as forming at the active mixed-metal oxides that contains 10wt%Y described in the embodiment 4.Carbon monoxide-olefin polymeric and active mixed-metal oxides are fully mixed, with quartzy dilution, form reactor beds then.The result who tests this carbon monoxide-olefin polymeric with the method for Embodiment B has been shown in table 2 and 3.Yttrium replaces the effect that lanthanum has further increase LEI.Yet, optionally improve not resembling with lanthanum obviously, wherein by absolute standard, the recruitment of main alkene is 1.2%.
Embodiment 15
In the present embodiment, carbon monoxide-olefin polymeric by the MSA of 40mg embodiment A and 10mg as forming at the active mixed-metal oxides that contains 5wt%La described in the embodiment 3.Carbon monoxide-olefin polymeric and active mixed-metal oxides are fully mixed, with quartzy dilution, form reactor beds then.The result who tests this carbon monoxide-olefin polymeric with the method for Embodiment B has been shown in table 2 and 3.As can be seen, as if the active mixed-metal oxides that contains 5wt%La has the effect of the increase LEI stronger than the active mixed-metal oxides that contains 10wt%La of embodiment 8.
Embodiment 16
In the present embodiment, carbon monoxide-olefin polymeric by the MSA of 40mg embodiment A and 10mg as forming at the active mixed-metal oxides that contains 5wt%Ca described in the embodiment 5.Carbon monoxide-olefin polymeric and active mixed-metal oxides are fully mixed, with quartzy dilution, form reactor beds then.This result of experiment more than in table 2 and 3, having illustrated under reactor described in the Embodiment B and condition.The active mixed-metal oxides that contains the 5wt% calcium oxide has increased by 223% with the life-span of combination of molecular sieve.
Embodiment 17 (contrast)
In this comparative example, carbon monoxide-olefin polymeric is by the MSA and the 10mg amorphous silica/aluminium oxide of 40mg embodiment A, and promptly the non-activity mixed oxide is formed.Molecular sieve catalyst composition and non-activity mixed metal oxide catalyst are fully mixed, with quartzy dilution, form reactor beds then.In table 2 and 3, also show the result who tests this carbon monoxide-olefin polymeric with the method for Embodiment B.Comparative example 17 confirmed and embodiments of the invention 11 relatively, when using the non-activity mixed-metal oxides, LEI drops to and is lower than 1.0 value.In addition, main olefine selective loss 1.07%, the generation of ethane and propane does not obviously reduce.
Embodiment 18
In the present embodiment, carbon monoxide-olefin polymeric by the MSA of 40mg embodiment A and 10mg as forming at the active mixed-metal oxides that contains Ce and titanium dioxide described in the embodiment 6.Carbon monoxide-olefin polymeric and active mixed-metal oxides are fully mixed, with quartzy dilution, form reactor beds then.The result who tests this carbon monoxide-olefin polymeric with the method for Embodiment B has been shown in table 2 and 3.The existence of active mixed-metal oxides has increased by 134% with the service life of combination of molecular sieve.
Embodiment 19
In the present embodiment, carbon monoxide-olefin polymeric by the MSA of 40mg embodiment A and 10mg as forming at the active hafnium metal oxide described in the embodiment 7.Carbon monoxide-olefin polymeric and reactive metal oxides are fully mixed, with quartzy dilution, form reactor beds then.The result who tests this carbon monoxide-olefin polymeric with the method for Embodiment B has been shown in table 2 and 3.Table 2 and 3 data declaration, by using 20% the active hafnium metal oxide that constitutes the carbon monoxide-olefin polymeric dosage, increased by 126% the service life of molecular sieve.The selectivity of ethane is reduced by 40% and selectivity of both propane is reduced by 46% show and significantly reduced hydrogen transfer reaction.
Embodiment 20
In the present embodiment, carbon monoxide-olefin polymeric by the MSA of 40mg embodiment A and 10mg as forming at the active mixed-metal oxides that contains 5wt%La described in the embodiment 8.Carbon monoxide-olefin polymeric and active mixed-metal oxides are fully mixed, with quartzy dilution, form reactor beds then.The result who tests this carbon monoxide-olefin polymeric with the method for Embodiment B has been shown in table 2 and 3.Data declaration in the table 2 and 3, by use constituting 20% the active mixed-metal oxides that contains 5wt%La of carbon monoxide-olefin polymeric dosage, increased by 150% the service life of molecular sieve.Show the remarkable hydrogen transfer reaction that reduced to the selectivity reduction by 51% of ethane with to selectivity of both propane reduction by 51%.
Table 2
| Embodiment | Reactor beds is formed (wt%) | LEI | Main alkene (%) | C 2 ＝/C 3 ＝ | C 3Purity (%) |
| 10 (contrasts) | 100％MSA | 1 | 74.65 | 0.92 | 92.7 |
| 11 | 80％MSA/20％ZrO 2 | 2.64 | 74.79 | 0.82 | 96.1 |
| 12 | The 10%La/ZrO of 80%MSA/20% 2 | 2.03 | 76.34 | 0.84 | 95.6 |
| 13 | The 10%La/ZrO of 60%MSA/40% 2 | 5.41 | 75.50 | 0.85 | 94.6 |
| 14 | The 10%Y/ZrO of 80%MSA/20% 2 | 2.79 | 75.81 | 0.85 | 94.9 |
| 15 | The 5%La/ZrO of 80%MSA/20% 2 | 4.85 | 75.84 | 0.84 | 94.8 |
| 16 | The 5%Ca/ZrO of 80%MSA/20% 2 | 3.23 | 73.85 | 0.79 | 96.7 |
| 1 (contrast) | The SiO of 80%MSA/20% 2/Al 2O 3 | 0.79 | 73.58 | 0.93 | 93.3 |
| 18 | The Ce/TiO of 80%MSA/20% 2 | 2.34 | 65.65 | 0.87 | 95.1 |
| 19 | The HfO of 80%MSA/20% 2 | 2.26 | 72.98 | 0.71 | 96.2 |
| 20 | The 5%La/HfO of 80%MSA/20% 2 | 2.50 | 72.75 | 0.76 | 96.5 |
Table 3
| Selectivity of product (%) | ||||||||
| Embodiment | Reactor beds is formed (wt%) | CH 4 | C 2 ＝ | C 2 o | C 3 ＝ | C 3 o | C 4 | C 5+ |
| 10 (contrasts) | 100％MSA | 1.51 | 35.82 | 0.95 | 38.83 | 3.05 | 14.50 | 2.12 |
| 11 | 80％MSA/20％ZrO 2 | 1.50 | 33.74 | 0.53 | 41.05 | 1.68 | 14.79 | 3.31 |
| 12 | The 10%La/ZrO of 80%MSA/20% 2 | 1.31 | 34.75 | 0.58 | 41.59 | 1.93 | 14.96 | 2.46 |
| 13 | The 10%La/ZrO of 60%MSA/40% 2 | 1.47 | 34.75 | 0.66 | 40.75 | 2.32 | 14.76 | 2.52 |
| 14 | The 10%Y/ZrO of 80%MSA/20% 2 | 1.32 | 34.92 | 0.66 | 40.88 | 2.20 | 14.41 | 3.07 |
| 15 | The 5%La/ZrO of 80%MSA/20% 2 | 1.26 | 34.59 | 0.64 | 41.25 | 2.28 | 14.96 | 2.52 |
| 16 | The 5%Ca/ZrO of 80%MSA/20% 2 | 1.50 | 32.65 | 0.42 | 41.20 | 1.43 | 14.84 | 5.34 |
| 17 (contrasts) | The SiO of 80%MSA/20% 2/Al 2O 3 | 2.17 | 35.46 | 0.89 | 38.12 | 2.72 | 14.21 | 2.65 |
| 18 | The Ce/TiO of 80%MSA/20% 2 | 6.79 | 30.57 | 0.75 | 35.09 | 1.80 | 12.72 | 3.97 |
| 19 | The HfO of 80%MSA/20% 2 | 1.98 | 31.62 | 0.52 | 41.36 | 1.65 | 14.64 | 4.93 |
| 20 | The 5%La/HfO of 80%MSA/20% 2 | 1.98 | 31.58 | 0.47 | 41.18 | 1.49 | 14.53 | 5.52 |
Claims (12)
1, carbon monoxide-olefin polymeric, its first kind of particle by will comprising molecular sieve mixes with the second kind of practical physical of oxide of metal in comprising at least a 4 families that are selected from the periodic table of elements and prepares, and wherein said second kind of particle is the state of drying or calcination and has 0.03mg/m at least
2The carbon dioxide absorption rate under 100 ℃ of metal oxide.
2, the carbon monoxide-olefin polymeric of claim 1, wherein said second kind of particle has 0.035mg/m at least
2The carbon dioxide absorption rate under 100 ℃ of metal oxide.
3, the carbon monoxide-olefin polymeric of claim 1, wherein said second kind of particle has the 10mg/m of being less than
2The carbon dioxide absorption rate under 100 ℃ of metal oxide.
4, the carbon monoxide-olefin polymeric of claim 1, wherein 4 family metal oxides comprise zirconia.
5, the carbon monoxide-olefin polymeric of claim 1, it also comprises 2 families that are selected from the periodic table of elements and the oxide of the metal in 3 families.
6, the carbon monoxide-olefin polymeric of claim 5, wherein 2 families and/or 3 family metal oxides comprise one or more oxides that are selected from calcium oxide, barium monoxide, lanthana, yittrium oxide and the scandium oxide.
7, the carbon monoxide-olefin polymeric of claim 1, it also comprises at least a of the binding agent that is different from described metal oxide and host material.
8, the carbon monoxide-olefin polymeric of claim 1, wherein molecular sieve comprises CRA framework types molecular sieve and/or AEI framework types molecular sieve.
9, the carbon monoxide-olefin polymeric of claim 1, wherein molecular sieve comprises aluminate or phosphate or silicoaluminophosphate.
10, the carbon monoxide-olefin polymeric of claim 1, wherein said second kind of particle precipitates from contain described metal ion solution by the hydration precursor that makes described 4 family metal oxides, and this hydration precursor of hydrothermal treatment consists reaches at the most 10 days and produces at this hydration precursor of temperature lower calcination of 400-900 ℃ then under at least 80 ℃ temperature.
11, the carbon monoxide-olefin polymeric of claim 10, wherein said 4 family metal oxides source is a hydrous zirconium oxide(HZO).
12, the feedstock conversion that will comprise oxygenatedchemicals is the method for one or more alkene, wherein this method claim 1-11 each carbon monoxide-olefin polymeric in the presence of carry out.
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| US60/366,012 | 2002-03-20 | ||
| US37469702P | 2002-04-22 | 2002-04-22 | |
| US60/374,697 | 2002-04-22 | ||
| US10/215,511 US6906232B2 (en) | 2002-08-09 | 2002-08-09 | Molecular sieve compositions, catalysts thereof, their making and use in conversion processes |
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| CN101239866B (en) * | 2007-02-07 | 2010-12-01 | 中国石油化工股份有限公司 | Method for producing ethylene and propylene from oxygen-containing compounds |
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| CA2578494A1 (en) * | 2007-02-14 | 2008-08-14 | Nova Chemicals Corporation | Catalytic cracking of ethers to 1-olefins |
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| CN107661774B (en) * | 2016-07-27 | 2020-11-03 | 中国科学院大连化学物理研究所 | Catalyst and method for preparing low-carbon olefin by directly converting synthesis gas |
| CN107661773B (en) * | 2016-07-29 | 2020-08-04 | 中国科学院大连化学物理研究所 | Method for preparing liquid fuel and co-producing low-carbon olefin by directly converting catalyst and synthesis gas |
| CN108568311B (en) * | 2017-03-07 | 2021-03-23 | 中国科学院大连化学物理研究所 | Catalyst and method for preparing ethylene by directly converting synthesis gas |
| DE112017007489T5 (en) * | 2017-04-27 | 2020-01-09 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | In situ catalyst production process for the production of at least one of tutol, paraxylene and light olefins and reaction processes |
| CN109939722B (en) * | 2018-01-26 | 2021-05-25 | 中国科学院大连化学物理研究所 | Organic base modified composite catalyst and method for preparing ethylene by hydrogenation of carbon monoxide |
| CN109939667B (en) * | 2018-01-26 | 2021-01-05 | 中国科学院大连化学物理研究所 | Catalyst and method for preparing low-carbon olefin by directly converting synthesis gas |
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