CN101541719A - Process for making dibutyl ethers from dry ethanol - Google Patents
Process for making dibutyl ethers from dry ethanol Download PDFInfo
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- CN101541719A CN101541719A CNA2007800438353A CN200780043835A CN101541719A CN 101541719 A CN101541719 A CN 101541719A CN A2007800438353 A CNA2007800438353 A CN A2007800438353A CN 200780043835 A CN200780043835 A CN 200780043835A CN 101541719 A CN101541719 A CN 101541719A
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- Prior art keywords
- reaction product
- butanols
- catalyst
- reaction
- alcohol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
- C07C29/34—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups by condensation involving hydroxy groups or the mineral ester groups derived therefrom, e.g. Guerbet reaction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
Abstract
The present invention relates to a process for making dibutyl ethers using dry ethanol optionally obtained from a fermentation broth. The dibutyl ethers made by this process find use as additives for fuels, including transportation fuels such as gasoline and diesel fuels.
Description
Invention field
The present invention relates to use the optional dehydrated alcohol that derives from fermented liquid to prepare the method for dibutyl ether.
Background of invention
Dibutyl ether can be used as diesel oil cetane reinforcing agent (article " Ahead of the Curve " of R.Kotrba in " the Ethanol Producer Magazine " in November, 2005); The example that comprises the diesel formulation of dibutyl ether is disclosed among the WO 2001018154.It is known (referring to Karas preparing dibutyl ether by butanols, L. and Piel, W.J. the article " Ethers " in the 576th page at " Kirk-OthmerEncyclopedia of Chemical Technology " the 5th edition the 10th volume the 5.3rd joint), and generally by making the normal-butyl dehydration of alcohols with sulfuric acid, or by at high temperature on iron(ic) chloride, copper sulfate, silicon-dioxide or siallite catalytic dehydration implement.The butanols dehydration generates the formation that dibutyl ether causes water, and therefore these reactions are in the past carried out under anhydrous situation.
The effort of being devoted to improve Air quality and increase the energy that is prepared by renewable resources has caused the interest that has produced again fuel substitute such as ethanol and butanols, alternative gasoline of described fuel substitute and diesel oil, or as the additive in these and other fuel.
Known ethanol is recyclable from multiple source, comprises synthetic feed and fermentation feed.From synthetic aspect, ethanol can derive from the direct catalytic hydration reaction of ethene, the indirect hydration reaction of ethene, the conversion reaction of synthetic gas, the homologation of methyl alcohol, the carbonylation reaction of methyl alcohol and methyl acetate, and the building-up reactions by homogeneous catalysis and heterogeneous catalysis.The fermentation feed can be fermentable carbohydrate (for example sugarcane, sugar beet and fruit crop) and starch material (such as grain comprises corn, cassava and Chinese sorghum).When using fermentation, can use yeast, described yeast is from the bacterial classification that comprises yeast (Saccharomyces).Can use bacterium equally from strain fermentation Zymomonas mobilis (Zymomonas), especially zymomonas mobilis (Zymomonas mobilis).Ethanol generally is recovered with the form with the azeotrope of water, so its content is about 95 weight % by water and ethanol mixed weight." Ullmann ' s Encyclopedia ofIndustrial Chemistry " sixth version the 12nd volume 398-473 page or leaf (Wiley-VCH VerlagGmbH ﹠amp referring to people such as Kosaric; Co.KGaA, Weinhe im, Germany) and " Adv.Biochem.Eng. " the 23rd volume (1982) 27-84 pages or leaves of people such as P.L.Rogers.Ethanol can be by methods known in the art by further dry (referring to the aforementioned documents of Kosaric), comprises making the ethanol-water azeotropic mixture by molecular sieve and with entrainment agent (normally benzene) component distillation ethanol-water mixture.
Method by ethanol preparation 1-butanols is known.Knownly use so-called " Guerbet reaction ", at high temperature make ethanol condensation on basic catalyst prepare the 1-butanols.Referring to for example article of J.Logsdon in " Kirk-Othmer Encyclopedia of Chemical Technology " (John Wiley and Sons, Inc., New York, 2001).
Some reference that further describe by ethanol preparation 1-butanols comprise: Chinese patent No.CN12168383C; C.Yang and the Z.Meng article in " J.of Catalysis " (1993) the 142nd volumes (1) 37-44 page or leaf; A.S.Ndou, N.Plint and the N.J.Coville article in " Applied Catalysis, A:General " (2003) the 251st volumes (2) 337-345 pages or leaves; The article of T.Takahashi in " Kogyo Kagaku Zasshi " (1946) the 49th volume 113-114 pages or leaves; The article of T.Takahashi in " Kogyo Kagaku Zasshi " (1946) the 49th volume 114-115 pages or leaves; V.Nagarajan, the N.R.Kuloor article in " IndianJournal of Technology " (1966) the 4th volumes (2) 46-54 pages or leaves; V.Nagarajan is at " Chemical Processing ﹠amp; Engineering " (Bombay) (1970) the 4th volumes (11) 29-31 pages or leaves, the article in the 38th page; The article of V.Nagarajan in " Indian Journal of Technology " (1971) the 9th volumes (10) 380-386 pages or leaves; V.Nagarajan is at " Chemical Processing ﹠amp; Engineering " (Bombay) articles of (1971) the 5th volumes in (10) the 23-27 pages or leaves; K.W.Yang, X.Z.Jiang and the W.C.Zhang article in " Chinese Chemical Letters " (2004) the 15th volumes (112) 1497-1500 pages or leaves; The Chinese patent No.1528727 of K.Yang, W.Zhang and X.Jiang (transferring Zhejiang Univ.); The United States Patent (USP) 5,095,156 (transferring Amoco Corp.) of C.A.Radlowski and G.P.Hagen; C.Y.Tsu and the K.L.Yang article in the 39-47 page or leaf of " Huaxue " (1958) (the 1st phase); B.N.Dolgov and the Yu.N.Volnov article in " Zhurnal Obshchei Khimii " (1993) the 3rd volume 313-318 pages or leaves; M.J.L.Gines and the E.Iglesia article in " J.ofCatalysis " (1998) the 176th volumes (1) 155-172 page or leaf; The U.S. Patent No. 6,323,383 of T.Tsuchida, AK.Atsumi, S.Sakuma and T.Inui (transferring Kabushiki Kaisha Sangi); And English Patent No.381,185 (transfer British Industrial Solvents, Ltd.).
Summary of the invention
The present invention relates to be used to prepare the method for butyl ether, described method comprises:
A) make dehydrated alcohol contact alkaline catalysts, comprise first reaction product of 1-butanols with preparation;
B) first reaction product of recovery part purifying from described first reaction product, described partially purified first reaction product are formed by the 1-butanols and by the water that 1-fourth alcohol and water combination weight is no more than 5 weight % basically; With
C) about 50 ℃ to about 450 ℃ temperature and about 0.1MPa extremely under the pressure of about 20.7MPa, choose wantonly in the presence of solvent, make that partially purified first reaction product contacts at least a acid catalyst in the step (b), to prepare second reaction product, described second reaction product comprises at least a butyl ether, and from described second reaction product, reclaim described at least a butyl ether, to obtain the butyl ether of at least a recovery.
Above the dehydrated alcohol in the step a) can choose wantonly self-contained alcoholic acid fermented liquid.
The dibutyl ether that discovery is prepared by method described in the invention can be used as the additive of fuel, and described fuel comprises transport fuel such as gasoline, diesel oil and aviation fuel.
Detailed Description Of The Invention
The present invention relates to prepare by dry butanols the method for dibutyl ether by dehydrated alcohol.As used herein, " dry butanols " is meant basically by the 1-butanols and by 1-fourth alcohol and water combination weight and is no more than the product that the water of 5 weight % is formed.Herein, express " basically by ... form " be meant that the 1-butanols can comprise a small amount of other component, as long as they can obviously not influence the performance of 1-fourth alcohol and water combination in the subsequent handling.
Described dehydrated alcohol can derive from any convenient source, comprises using microbial process fermentation well known by persons skilled in the art.Fermentable microorganism and matrix source are not critical for the object of the invention.The achievement of fermentation is a fermented liquid, then its refining is flowed with the preparation aqueous ethanol.Refining process can comprise at least one distillation tower, comprises first overhead streams of second alcohol and water with preparation.After the ethanol-water azeotropic thing is boiled off, can implement one or more drying meanss, to form " dehydrated alcohol ".Though known multiple drying means, generally make reaction product (being ethanol in the case) by siccative such as molecular sieve, until the water of removing desired amount.
About 150 ℃ to about 500 ℃ temperature and about 0.1MPa extremely under the pressure of about 20.7MPa, in vapor phase or liquid phase, make dehydrated alcohol (its available rare gas element such as nitrogen and carbonic acid gas dilution) contact at least a alkali (or alkalescence) catalyzer, comprise first reaction product of water and butanols with preparation.First reaction product also comprises unreacted ethanol, multiple organic product and water usually.Described organic product comprises butanols, mainly is the 1-butanols.
Described at least a alkaline catalysts can be homogeneous phase or heterogeneous catalyst.Homogeneous catalyst is that wherein all reactants and catalyzer all are scattered in a catalyzer in mutually with molecular form.The homogeneous phase alkaline catalysts includes but not limited to alkali metal hydroxide.
Heterogeneous catalyst is meant that wherein catalyzer has constituted and reactant and the isolating catalyzer mutually of product.To solid catalyst and how to determine that whether concrete catalyzer is the description of alkalescence, referring to for example Hattori, H. article (Chem.Rev. (1995) 95:537-550) and " Solid Acidand Base Catalysts " (Tanabe, K. the article in " Catalysis:Science andTechnology ", Anderson, J. and Boudart, M (editor), 1981, Springer-Verlag, New York).
Be applicable to alkaline catalysts in the inventive method be as
The material that can accept proton of definition, or as the material with unshared electron pair of Lewis definition, described unshared electron pair can with atom, molecule or ion formation covalent linkage.
The example of suitable alkaline catalysts includes but not limited to metal oxide, oxyhydroxide, carbonate, silicate, phosphoric acid salt, aluminate and their combination.Preferred alkaline catalysts is metal oxide, carbonate, silicate and phosphoric acid salt.Preferred metal can be selected from the 1st family, the 2nd family and the rare earth element of the periodic table of elements in the above-claimed cpd.Especially preferred metal is caesium, rubidium, calcium, magnesium, lithium, barium, potassium and lanthanum.
Alkaline catalysts can load on the common support of the catalyst of catalytic field.Suitable support of the catalyst includes but not limited to aluminum oxide, titanium dioxide, silicon-dioxide, zirconium white, zeolite, carbon, clay, double-deck oxyhydroxide, hydrotalcite and their combination.Can use any method of preparation loaded catalyst known in the art.A kind of method that is used to prepare loaded catalyst is that metal carboxylate is dissolved in the water.With described solution that carrier is wetting such as silicon-dioxide, calcination then.This method changes into metal oxide, carbonate, oxyhydroxide or their combination with the metal carboxylate of load.Carrier can be neutral, acid or alkaline, as long as the surface of described catalyst/support combination is an alkalescence.The common technology that processing has a carrier of metal catalyst sees that (B.L.Shapiro edits, Texas A ﹠amp in " HeterogeneousCatalysis " the 2nd volume 1-29 page or leaf of B.C.Gates; MUniversity Press, College Station, TX, 1984).
Alkaline catalysts of the present invention also can comprise and will strengthen the catalyst additive and the promotor of catalyst efficiency.The relative percentage of catalyst promoting agent can change on demand.Promotor can be selected from the 8th family's metal of the periodic table of elements, and copper and chromium.
The commercially available acquisition of alkaline catalysts of the present invention maybe can use methods known in the art by suitable feedstock production.Being used for catalyzer of the present invention can powder, particle or other particle form are used.The selection of catalyzer optimal average particle size will be depended on this type of processing parameter such as reactor retention time and desired reactor flow velocity.
Use alkaline catalysts to become the example of the method for butanols to be discussed in ethanol conversion below with reference in the document.
" J.of Organic Chemistfy " (1957) the 11st volume 540-542 pages or leaves of M.N.Dvornikoff and M.W.Farrar disclose use MgO-K
2CO
3-CuCrO
2Catalyst system promotes more high-grade alcohol of ethanol condensed one-tenth, comprises the 1-butanols.The liquid phase reaction of this catalyzer of use that is disclosed shows that ethanol conversion is 13%, and the selectivity of generation 1-butanols is 47%.
The United States Patent (USP) 5,300,695 that transfers Amoco Corp. discloses the alcohol that wherein has X carbon atom and has reacted to prepare the method for high molecular weight alcohol on L-type zeolite catalyst.In some embodiments, first alcohol with X carbon atom and the second pure condensation with Y carbon atom have the alcohol of X+Y carbon atom with preparation.In a specific embodiment, use L-type saspachite, use ethanol to prepare butanols.
People such as J.I.DiCosimo have described the influence to pure linked reaction of composition and surface property at " Journal of Catalysis " (2000) the 190th volume (2) 261-275 pages or leaves, and Mg is used in described reaction
yAlO
xCatalyzer is used for the alcohol reaction, comprises ethanol.At Mg
yAlO
xCondensation reaction on the sample also relates at Lewis acid-strong
Form the carbanion intermediate on the base pair site, and generate the product that comprises new C-C key, such as just-C
4H
8O (or just-C
4H
9OH) and different-C
4H
8O (or different-C
4H
9OH).In " Journal of Catalysis " (1998) the 178th volume (2) 499-510 pages or leaves, they have also described and have been oxidized to the reaction that acetaldehyde and aldol condensation become propyl carbinol, its all relate to originally Lewis acid-strong-base group on form surperficial ethylate.
PCT announces that No.WO 2006059729 (transferring Kabushiki Kaisha Sangi) has described by ethanol as raw material, effectively prepares the cleaning method of high molecular weight alcohol, and described alcohol has even number of carbon atoms, such as 1-butanols, hexanol etc.By ethanol as raw material, by means of calcium phosphate compound hydroxyapatite Ca for example
10(PO
4)
6(OH)
2, tricalcium phosphate Ca
3(PO
4)
2, calcium monohydrogenphosphate CaHPO
4* (0-2) H
2O, Calcium Pyrophosphate Ca
2P
2O
7, octocalcium phosphate Ca
8H
2(PO
4)
6* 5H
2O, tetracalcium phosphate Ca
4(PO
4)
2O or amorphous calcium phosphate Ca
3(PO
4)
2* nH
2O, preferred hydroxyapatite generates high molecular weight alcohol as catalyzer, and be 0.4 second or longer duration of contact.
Dehydrated alcohol to the catalyzed conversion of first reaction product that comprises 1-fourth alcohol and water can be intermittently or the successive pattern carry out, as for example H.Scott Fogler " Elements of ChemicalReaction Engineering " the 2nd edition (1992, Prentice-Hall Inc, described in CA).Suitable reactor comprises fixed bed, adiabatic fluidized-bed, carries bed and moving-bed.During reaction process, catalyzer can be contaminated, therefore need make catalyst regeneration.Preferred catalyst regeneration process comprises at high temperature makes catalyzer contact gas, such as, but not limited to air, steam, hydrogen, nitrogen or their combination.
Make the suitable refining process of first reaction product experience then, preparing partially purified first reaction product, described partially purified first reaction product is formed by the 1-butanols and by the water that 1-fourth alcohol and water combination weight is no more than 5 weight % basically.The example of suitable refining process comprises the described product of component distillation, with the condensation product that obtains to be made up of the upper strata butanols that is rich in butanols and water and rich aqueous lower floor butanols and water.Until making from first distillation after unitary upper strata experiences another component distillation mutually with withing fixed attention, can be recovered to anhydrous butanols and flow from distilling for the second time the unit.
These conditions such as temperature, catalytic metal, carrier, reactor configuration and time that one skilled in the art will appreciate that can influence reaction kinetics, product yield and product selectivity.Can use the standard test method to optimize yield from the 1-butanols of described reaction.
The present invention relates to prepare the method for at least a dibutyl ether, described method comprise make partially purified basically by the 1-butanols and be no more than first reaction product that the water of 5 weight % forms by 1-fourth alcohol and water combination weight and contact at least a acid catalyst, second reaction product that comprises at least a dibutyl ether with preparation, and from described second reaction product, reclaim described at least a dibutyl ether, to obtain the dibutyl ether of at least a recovery." at least a dibutyl ether " mainly comprises di-n-butyl ether, yet the dibutyl ether reaction product can comprise other dibutyl ether, and one or two butyl substituting group of wherein said ether is selected from the group of being made up of following: 1-butyl, 2-butyl, the tertiary butyl and isobutyl-.
About 50 ℃ to about 450 ℃ temperature, implement to form the reaction of at least a dibutyl ether.In a more particular embodiment, described temperature is about 100 ℃ to about 250 ℃.
Can under inert atmosphere, to about 20.7MPa pressure, implement described reaction at about barometric point (about 0.1MPa).In a more particular embodiment, described pressure is that about 0.1MPa is to about 3.45MPa.Suitable rare gas element comprises nitrogen, argon gas and helium.
Described at least a acid catalyst can be homogeneous phase or heterogeneous catalyst.Homogeneous catalyst is that wherein all reactants and catalyzer all are scattered in a catalyzer in mutually with molecular form.Homogeneous acid catalyst includes but not limited to mineral acid, organic sulfonic acid, heteropolyacid, fluoro-alkyl sulfonic acid, metal sulfonate, metal trifluoroacetate acetate, their compound and their combination.The example of homogeneous acid catalyst comprises sulfuric acid, fluosulfonic acid, phosphoric acid, tosic acid, Phenylsulfonic acid, hydrogen fluoride, phospho-wolframic acid, phospho-molybdic acid and trifluoromethanesulfonic acid.
Heterogeneous catalyst is meant that wherein catalyzer has constituted and reactant and the isolating catalyzer mutually of product.The heterogeneous acid catalysts agent includes but not limited to 1) heterogeneous heteropolyacid (HPA), 2) natural clay mineral, such as comprising those of aluminum oxide or silicon-dioxide, 3) Zeo-karb, 4) metal oxide, 5) blended metal oxide, 6) metal-salt such as metallic sulfide, metal sulfate, metal sulfonate, metal nitrate, metal phosphate, metal phosphinate hydrochlorate, metal molybdate, metal tungstates, metal borate, and 7) zeolite, 8) 1 to 7 group combination.The description of solid catalyst referring to, for example, " Solid Acid and Base Catalysts " 231-273 page or leaf (Tanabe, K. the article in " Catalysis:Science and Technology ", Anderson, J. and Boudart, M (editor), 1981, Springer-Verlag, New York).
The heterogeneous acid catalysts agent also can load on the support of the catalyst.Carrier is that acid catalyst disperses material thereon.Support of the catalyst is well known in the art and is described in for example Satterfield, in " Heterogeneous Catalysis in Industrial Practice " the 2nd edition the 4th chapter (1991, McGraw-Hill, New York) of C.N..
These conditions such as temperature, catalytic metal, carrier, reactor configuration and time that one skilled in the art will appreciate that can influence reaction kinetics, product yield and product selectivity.When 1-butanols contact acid catalyzer, such as employed concrete catalyzer, can prepare the product that is different from dibutyl ether according to reaction conditions.Other products comprises butylene and isooctene.Can use according to the standard test of implementing described in this paper embodiment and optimize the yield that comes self-reacting dibutyl ether.
After the reaction, if desired, can by any appropriate technology well known by persons skilled in the art such as decantation, filtration, extraction or divided thin film from, catalyzer is separated from reaction product (referring to Perry, R.H. and Green, " Perry ' s Chemical Engineer ' sHandbook " of D.W. (editor) the 7th edition the 13rd joint, the 18th joint and the 22nd joint, 1997, McGraw-Hill, NewYork).
Can come from reaction product, to reclaim described at least a dibutyl ether by distillation, as Seader, J.D. wait the described (Perry of people, R.H. and Green, D.W. the distillation in the 7th edition the 13rd joint of " Perry ' sChemical Engineer ' s Handbook " of (editor), 1997, McGraw-Hill, New York).Alternatively, as known in the art, can perhaps, reclaim described at least a dibutyl ether by being separated with The suitable solvent such as trimethylpentane or octane extraction.Can after isolating described at least a dibutyl ether, reclaim unreacted 1-butanols, and with since subsequent reactions in.The additive that the dibutyl ether of described at least a recovery can be acted as a fuel joins in the transport fuel.
Embodiment
General method and material
In following examples, " C " is degree centigrade, and " mg " is milligram; " mL " is milliliter; " temp " is temperature; " MPa " is MPa; " GC/MS " is gas chromatography/mass spectrometry.
The 1-butanols changes into the general method of dibutyl ether
In the 2mL bottle that is equipped with magnetic stirring bar, comprise 1-butanols and mixture of catalysts.Seal described bottle with serum cap, bore a hole to help gaseous interchange with pin.Bottle is placed in the dry type thermostatted that is loaded in the pressurized vessel.With the described container of nitrogen purging, and pressure is located at 6.9MPa.Make the dry type thermostatted reach specified temperature, and with specified for some time of this temperature maintenance.After cooling and the exhaust, use capillary column ((a) CP-Wax 58[Varian; Palo Alto, CA], 25m * 0.25mm, 45C/6min, 10C/min, until 200C, 200C/10min, or (b) DB-1701[J﹠amp; W (derives from Agilent; Palo Alto, CA)], 30m * 0.25mm, 50C/10min, 10C/min, until 250C, 250C/2min), by the content in the GC/MS analysis bottle.
According to this method, under the specified condition of each embodiment, implement hereinafter embodiment.
Embodiment 1-13
Exsiccant 1-butanols (1-BuOH) and acid catalyst prepared in reaction dibutyl ether
At 6.9MPa N
2Reaction was implemented 2 hours down.
Technician as catalyst field is known, when any catalyzer of utilization, all needs to optimize reaction conditions.Embodiment 1 to 13 shows that under specified requirements, specified catalyzer can the preparing product dibutyl ether.When being not (data not shown goes out) when using under the optimal conditions, some catalyzer shown in the embodiment 1 to 13 are invalid.
Claims (2)
1. method that is used to prepare butyl ether, described method comprises:
A) make dehydrated alcohol contact alkaline catalysts, comprise first reaction product of 1-butanols with preparation;
B) first reaction product of recovery part purifying from described first reaction product, described partially purified first reaction product are formed by the 1-butanols and by the water that 1-fourth alcohol and water combination weight is no more than 5 weight % basically; With
C) about 50 ℃ to about 450 ℃ temperature and about 0.1MPa extremely under the pressure of about 20.7MPa, choose wantonly in the presence of solvent, make partially purified first reaction product in the step (b) contact at least a acid catalyst, to prepare second reaction product, described second reaction product comprises at least a butyl ether, and reclaims described at least a butyl ether to obtain the butyl ether of at least a recovery from described second reaction product.
2. the process of claim 1 wherein that the dehydrated alcohol in the step a) gets self-contained alcoholic acid fermented liquid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US87227606P | 2006-12-01 | 2006-12-01 | |
| US60/872,276 | 2006-12-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101541719A true CN101541719A (en) | 2009-09-23 |
Family
ID=39492810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800438353A Pending CN101541719A (en) | 2006-12-01 | 2007-11-30 | Process for making dibutyl ethers from dry ethanol |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP2089346A2 (en) |
| JP (1) | JP2010511618A (en) |
| CN (1) | CN101541719A (en) |
| BR (1) | BRPI0717684A2 (en) |
| CA (1) | CA2668877A1 (en) |
| WO (1) | WO2008069981A2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11217343A (en) * | 1998-01-30 | 1999-08-10 | Sangi Co Ltd | Synthesis of chemical industrial feedstock and high-octane fuel |
-
2007
- 2007-11-30 EP EP07867595A patent/EP2089346A2/en not_active Withdrawn
- 2007-11-30 JP JP2009539345A patent/JP2010511618A/en active Pending
- 2007-11-30 WO PCT/US2007/024665 patent/WO2008069981A2/en active Application Filing
- 2007-11-30 CA CA002668877A patent/CA2668877A1/en not_active Abandoned
- 2007-11-30 BR BRPI0717684-8A2A patent/BRPI0717684A2/en not_active Application Discontinuation
- 2007-11-30 CN CNA2007800438353A patent/CN101541719A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CA2668877A1 (en) | 2008-06-12 |
| WO2008069981A3 (en) | 2008-12-11 |
| BRPI0717684A2 (en) | 2013-10-29 |
| WO2008069981A2 (en) | 2008-06-12 |
| JP2010511618A (en) | 2010-04-15 |
| EP2089346A2 (en) | 2009-08-19 |
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Open date: 20090923 |