CN105683172B - The preparation method of terephthalic acid (TPA) - Google Patents

The preparation method of terephthalic acid (TPA) Download PDF

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CN105683172B
CN105683172B CN201480059762.7A CN201480059762A CN105683172B CN 105683172 B CN105683172 B CN 105683172B CN 201480059762 A CN201480059762 A CN 201480059762A CN 105683172 B CN105683172 B CN 105683172B
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furans
cycloaddition
substituted
solvent
cyclic ethers
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CN105683172A (en
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曹光
J·R·莱特纳
J·古兹曼
S·L·罗
G·D·默尔
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ExxonMobil Chemical Patents Inc
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    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
    • C07C45/66—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups by dehydration
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    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
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    • C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
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Abstract

The present invention relates to prepare terephthalic acid (TPA) 1 as follows) cycloaddition of the furans of 2,5 substitutions (such as 2,5 pairs of hydroxymethylfurans or 5 hydroxymethylfurfurals) and ethene, and the cycloaddition product of the dehydration then 2) is oxidized to terephthalic acid (TPA).The present invention more particularly relates to be prepared the overall biological base path of terephthalic acid (TPA) by carbohydrate such as hexose (for example, glucose or fructose).

Description

The preparation method of terephthalic acid (TPA)
Inventor：Guang Cao、James R.Lattner、Javier Guzman、Shifang L.Luo、Gary D.Mohr
Priority
This application claims the USSN 61/898,521 submitted on November 1st, 2013 priority, the disclosure of the document Content is incorporated herein by reference.The application also require on January 29th, 2014 EP14153048.5 submitted it is preferential Power.
Technical field
The present invention relates to the furans by substituting and ethene to prepare terephthalic acid (TPA).The present invention is more particularly related to by carbon hydrate Thing such as hexose (for example, glucose or fructose) prepares the overall biological base path of terephthalic acid (TPA).
Background technology
Terephthalic acid (TPA) can be used for preparing various polymer for example poly- (ethylene glycol terephthalate), poly- (terephthaldehyde Acid propylene glycol ester) and it is poly- (mutual-phenenyl two acid bromide two alcohol ester).Terephthalate polymer, such as poly- (terephthalic acid (TPA) second two Alcohol ester) (PET) has many applications, for example, being used to manufacture synthetic fibers and food-grade container (for example, beverage bottle).To benzene two The main source of formic acid includes the paraxylene stream that oxidation derives from crude oil refining.Produced with preparing hydrocarbon fuel components and petrochemistry The related growing concern of the high cost of product such as paraxylene causes the attention to substituting source such as renewable raw materials. Renewable biomass resources can be used for the substitute of product derived from synthetic petroleum, and be constantly needed to synthesize from organism-based raw material It is traditionally the method for the additional compound of oil and/or petrochemical products.However, the carbohydrate structure by natural 6- carbon Build section such as glucose or the fructose converting difficulty into desirable final products has been hindered in some key areas Progress.Newest research is had shown that the carbohydrate-modifying feasibility into 2,5- dimethyl furans (DMF) of hexose.Example Such as, Leshkov, Y.R. etc. are reported prepares 5 hydroxymethyl furfural (HMF) with high yield as follows：By fructose acid-catalyzed dehydration, connect Using based on the catalyst of copper by HMF selective hydrations into DMF (NATURE, in June, 2007, (447):pp.982-5).This Outside, Zhao, H. etc. are described since glucose in l- alkyl -3- methylimidazolium chloridesIn metal halide (for example, Chromium chloride (II)) in the presence of synthesize HMF (Science, in June, 2007, (Vol.316, No.5831)；pp.1597-1600).
US 7,385,081 describes synthesizes terephthalic acid (TPA) by carbohydrate derivates.HMF is oxidized to furan first Mutter dicarboxylic acids (FDCA), then can be esterified into 2,5- furan dicarboxylic acid esters.Ethene is set to be reacted with the FDCA or dicarboxylic ester To form two cyclic ethers, two cyclic ethers is then set to be dehydrated into terephthalic acid (TPA) or terephthalate.This is referred to as route I.
Route I
WO 2010/151346 is disclosed by making DMF with ethene under the conditions of cycloaddition reaction and existing in catalyst Lower reaction prepares paraxylene.Then can by by p xylene oxidation prepared by this route into terephthalic acid (TPA).This is referred to as Route II.
Route II
American Chemical Society Catalysis 2012,2, pp.935-939, which is disclosed, converts HMF Into dimethyl furan, the dimethyl furan is then changed into by paraxylene by cycloaddition.
Other bibliography of concern include：US 6,245,920, WO2012/125218, WO2013/040514 and WO2013/048248。
The method of terephthalic acid (TPA) and terephthalate is prepared in WO by the parent material of some biomass deriveds Referred in 2010/148081 and WO 2010/151346.
Via route I by it is carbohydrate-modifying into terephthalic acid (TPA) or ester in ethene cycloaddition step (formed FDCA Or FDCA dimethyl ester) in lock into low-yield (according to US 7,385,081, less than 1%).Via route II by carbon hydrate Thing changes into paraxylene and locked into be needed to add the hydrogen of 3 molecules to prepare DMF to each molecule HMF.This addition Hydrogen removes eventually as the water in the step of being finally oxidized to terephthalic acid (TPA).It is desirable that from carbohydrate to benzene two The route of formic acid does not lock into low-yield (route I) or adds more mol of hydrogen (route II) for each carbohydrate molecule Needs.What is also needed is the improvement to route II, wherein by producing compared with paraxylene for being oxidized to terephthaldehyde The more active intermediate molecule of acid promotes last oxidation step.
The content of the invention
Summary of the invention
The present invention relates to use diels-Alder (Diels Adler) cycloaddition reaction ethene by substituted furans (SF) compound changes into terephthalic acid (TPA), especially by 5 hydroxymethyl furfural (HMF) or the double hydroxymethylfurans (BHMF) of 2,5- Two cyclic ethers are changed into, then two cyclic ethers is dehydrated into the phenyl of 2,5 substitutions, then the phenyl by described 2,5 substitutions aoxidizes Into terephthalic acid (TPA).Advantageously, this path does not require to hydrogenate the SF before ethene cycloaddition step.
In the first embodiment, the present invention relates to by ethene cycloaddition to the substituted furans by being represented with following formula on：
To prepare the bicyclic compound by being represented with following formula：
Then the bicyclic compound is dehydrated to form substituted phenyl, by being represented with following formula：
Wherein R is=O, OH, OC (O) CH3 and R*It is=O, OH, OC (O) CH3 or H, then can be oxidized paired benzene Dioctyl phthalate.In a preferred embodiment in accordance with this invention, the SF is not hydrogenated to two before the cycloaddition step Alkyl is (for example, R and R*Not all it is alkyl).However, in some embodiments of the present invention, SF can walk in the cycloaddition Rapid forward part hydrogenation.For example, HMF can be hydrogenated to BHMF in the forward part of the cycloaddition step, but endless perhydrogenating Into 2,5- dimethyl furans.Or for hydrogen of every SF molecules addition less than two molecules before ethene cycloaddition step.
As follows, the cycloaddition of ethene obtains the cyclic ether compounds of intermediate two, then by the cyclic ethers of intermediate two Compound is dehydrated into the dibasic benzyl rings of 1,4-.Then the dibasic phenyl of 1,4- can be oxidized to terephthalic acid (TPA)：
In one embodiment of the invention, ethene is made to be reacted with HMF in the case where not adding hydrogenation gas first.Second Alkene cycloaddition and subsequent HMF dehydrations produce 4- (methylol) benzaldehyde (HMBA), as follows, referred to as route III：
Route III
In another embodiment of the present invention, HMF molecules are hydrogenated with a molecule hydrogen first and obtains BHMF. BHMF ethene cycloaddition and dehydration obtains Isosorbide-5-Nitrae-phenylene dimethanol (PDM), as follows, referred to as route IV：
Route IV
Then the 1,4- phenylenes dimethanol (PDM) can be oxidized to terephthalic acid (TPA).Or PDM can be used for Other application, for example, forming diester by adding organic acid, or polyester is prepared by polymerizeing with diacid.
In any one in route III or IV, the product and pair of pass course II preparations of cycloaddition and dehydration Dimethylbenzene intermediate is compared more active to being oxidized to terephthalic acid (TPA).Because when being prepared respectively by route III or IV, Substituent (such as methyl) on phenyl ring in HMBA or PDM intermediates is already partially oxidised.
Brief description
Fig. 1 shows preferred embodiment of the present invention according to route III.
Fig. 2 shows preferred embodiment of the present invention according to route IV.
Fig. 3 shows route III preferred embodiment, wherein identical solvent be used for HMF extract and cycloaddition/ Dehydration.
Fig. 4 shows route III preferred embodiment, and wherein HMBA is used as HMF extractions and ethene cycloaddition/dehydration Solvent in both reactions.
Fig. 5 shows route IV preferred embodiment, wherein identical solvent be used for HMF extractions, HMF hydrogenations and Cycloaddition/dehydration.
Fig. 6 shows route IV preferred embodiment, and wherein PDM is used as HMF extractions, HMF hydrogenations and ethene ring and added Solvent into/dehydration.
Fig. 7 shows the preferred embodiment of any route III or IV cycloaddition/dehydration.
Detailed description of the invention
The new numbering plan of each race of the periodic table of elements used herein is according to Chemical and Engineering News, 63 (5), p.27, described in (1985) like that.
Term " substituted " refers to that hydrogen-based is replaced with alkyl, hetero atom or containing heteroatomic group.For example, 2,5- bis- Methylfuran is to substitute the furyl for having methyl at 2 and 5.
Term " alkyl (hydrocarbyl radical) ", " alkyl (hydrocarbyl) " and " alkyl (hydrocarbyl group) " is used interchangeably in whole file.For present disclosure, " alkyl " is defined as C1-C20Group, they can be linear, branched or ring-type (aromatics is non-aromatic), such as methyl, ethyl, vinyl；With third Base, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, the isomers of undecyl and/or dodecyl." alpha-olefin " Be the alkene and alpha-olefin that there is double bond in α (or 1-) position example include ethene, propylene, 1- butylene, 1- amylenes, 1- oneself Alkene, 1- heptene, 1- octenes, 1- nonenes, 1- decene, 1- endecatylenes and 1- dodecylenes.
5 hydroxymethyl furfural (HMF) with following formula by being represented：
The double hydroxymethylfurans (BHMF) of 2,5- with following formula by being represented：
BHMF can be obtained by the way that 5 hydroxymethyl furfural is hydrogenated, such as " Catalytic Hydrogenation over Platinum Metals ", P.N.Rylander, Academic Press, New York, disclosed in 1967, pp.246-249 that Sample.
It can hereinafter referred to as use throughout the specification：Me is methyl, and Ph is phenyl, and RT is room temperature, unless otherwise rule Determine, it is specified that for 25 DEG C, tol is toluene.
The present invention is relevant with substituted furans (SF) to be changed into the method for two cyclic ethers, and two cyclic ethers then is dehydrated into shape Into substituted phenyl, the substituted phenyl is then oxidized to terephthalic acid (TPA).Preferably, the pin before two cyclic ethers are changed into (1.5 molecules are preferably less than, preferably less than 1 molecule, preferably SF is not by hydrogen to hydrogen of every SF molecules addition less than two molecules Change).Or for each mole of hydrogen of the SF additions less than two moles before two cyclic ethers are changed into, preferably less than 1.5 rub You, preferably less than 1 mole, preferably SF is not hydrogenated.More specifically, ethene connects to SF, such as BHMF or HMF cycloaddition The dehydration of two formed cyclic ethers, is then aoxidized, can be used for saving preparation to benzene two with good yield and production cost Formic acid, because reduce or eliminating the step of hydrogenation (one or more) of costliness.In an optional embodiment, by BHMF Combined with acid, such as acetic acid, to prepare diester before cycloaddition.
In a preferred embodiment, the present invention relates to the preparation method of terephthalic acid (TPA), including substituted furan is made Mutter with ethene under the conditions of cycloaddition reaction and in catalyst (such as activated carbon, the activated carbon of pickling, silica, oxidation Aluminium, zeolite molecular sieve or non-zeolite molecular sieve) in the presence of reaction to prepare two cyclic ethers, then two cyclic ethers is dehydrated to be formed and taken The phenyl in generation, and afterwards, the substituted phenyl is oxidized to terephthalic acid (TPA), wherein the substituted furans is by with following formula table Show：
Two cyclic ethers with following formula by being represented：
The substituted phenyl with following formula by being represented：
Wherein R is=O, OH or OC (O) CH3, R*It is=O, OH, OC (O) CH3 or H, but condition is the R on the SF And R*Corresponding alkyl is not hydrogenated to before the cycloaddition step.Therefore, in the preferable implementation of the present invention In scheme, for hydrogen of every SF molecules addition less than two moles before ethene cycloaddition step, preferably less than 1.5 rub You, does not preferably hydrogenate SF before the cycloaddition step by preferably less than 1 mole.
In a preferred embodiment in accordance with this invention, the substituted furans with following formula by being represented：
And/or
Two cyclic ethers with following formula by being represented：
And/or
The substituted phenyl with following formula by being represented：
Wherein R*It is=O, H or OH, preferably=O or OH.
In a preferred embodiment in accordance with this invention, R and R*It is identical.In another embodiment of the present invention, R And R*It is different.In a preferred embodiment in accordance with this invention, R is OH and R*It is=O.In another embodiment party of the present invention In case, R and R*It is OH or R and R*All it is=O.
Advantageously, SF (such as BHMF or HMF) parent material of methods described can be synthesized by carbohydrate, carried accordingly It is supplied to the Production of Terephthalic Acid route that small part relies on renewable raw materials.For example, using glucose or fructose as SF, such as BHMF or HMF source obtains the method that 6 (75%) derives from carbohydrate in wherein 8 terephthalic acid (TPA) carbon atoms. In addition, obtained used as the ethene of the reactant in the method according to the invention by wood-based composites, then prepare to benzene two Formic acid is completely derived from (that is, all 8 in its 8 carbon atoms) renewable raw materials.
The use of solvent can be used for forming HMF from sugar, and available for ethene cycloaddition reaction.For example, Leshkov, Etc. Y.R. report and 5 hydroxymethyl furfural is prepared with high yield using biphasic reaction flow by the acid-catalyzed dehydration of fructose (HMF), wherein from water-containing reacting medium solvent extraction HMF products, for example, by the use of butanol as solvent (NATURE, in June, 2007, (447):pp.982-5).In ethene cycloaddition reaction, Chang etc. reports molten using hexane in ethene and DMF reaction Agent is to prepare paraxylene (GREEN CHEMISTRY (2013) DOI:10.1039/c3gc40740c).In additional embodiment party In case, use and identical solvent in ethene cycloaddition step in HMF production stages.When hydrogenation HMF (is used and is less than two moles of hydrogen Gas/mole HMF) when, identical solvent is used for all three steps.In another embodiment, used solvent is second The identical material that is prepared in alkene cycloaddition and dehydration is for example, PDM in HMBA and route IV in route III.
It is probably unfavorable for water in cycloaddition/dehydration, in reactant mixture being present, because it can make furan nucleus water Solve and/or slow down or limit dehydration.In another embodiment, continuously water is removed from reactant mixture as follows：Allow Excess ethylene circulates through reacting fluid, water is condensed and is separated from gaseous ethene effluent, and unreacted ethene is steamed Pneumatic transmission returns to reactant mixture.
Embodiment of the present invention is related to the preparation method of terephthalic acid (TPA), including makes substituted furans, for example, BHMF or HMF under the conditions of cycloaddition reaction, preferably reacts to prepare two cyclic ethers, then by two ring in the presence of a catalyst with ethene Ether is dehydrated to prepare substituted phenyl, and the substituted phenyl then is oxidized into terephthalic acid (TPA).Representational cycloaddition is anti- Answering condition includes the temperature of about 100 DEG C of (212 ℉)-about 300 DEG C (572 ℉), and about 1000kPa (145psig)-about 10,000kPa (14500psig) ethylene partial pressure, and the reactor residence time of about 1 hour-about 48 hours.The side Method can interval or in a continuous manner, such as allow SF, such as BHMF or HMF and ethylene reaction thing continuously to consolidate in catalyst Pass through on fixed bed.Representational catalyst is activated carbon (such as in solidapowder form), especially by using acid for example H3PO4The carbon for washing and being activated.Other solid materials, especially with high surface area (for example, zeolite or non-zeolite molecular sieve) And/or for aromatics and olefinic feed component there are those of adsorption capacity to be also used as catalyst.These any catalyst Optionally it can be promoted with alkali metal or alkaline earth promoters.
Cycloaddition reaction condition and catalyst can provide SF, such as BHMF or HMF at least about 50% conversion, wherein Terephthalic acid (TPA) accounts at least about the 60% of the furans of conversion, (that is, is selected based on mole for terephthalic acid (TPA) at least about 60% Selecting property, or prepare at least about 0.6 moles terephthalic acid for the SF of each mole of conversion).
Therefore, according to an embodiment of the present invention, hexose such as glucose or fructose connects to SF, such as HMF or BHMF conversions Cycloaddition, terephthalic acid (TPA) is then oxidized to and provides using at least one renewable carbohydrate raw material preparation terephthaldehyde The basis of acid.The embodiment that the present invention is particularly useful is related to the method based on carbohydrate for preparing terephthalic acid (TPA), bag Include hexose such as glucose or fructose converting into HMF or BHMF, the phenyl of substitution is then prepared with ethene cycloaddition, then will The substituted phenyl is oxidized to terephthalic acid (TPA).
It is not intended to be fettered by theory, it is believed that diels-Alder of the reaction via ethene to HMF or BHMF furan nucleus Cycloaddition and carry out, then open loop and the dibasic phenyl of water removal (dehydration) generation.Suitable catalyst and reaction condition can be with Productivity ratio or yield are improved, particularly compared with heat or uncatalyzed reaction.Term " catalyst " and " catalysis " are intended to reduce The reagent of activation energy required for desired reaction, and improve the accelerator of the validity of such reagent.
Suitable catalyst includes the carbon with high surface area, especially activated carbon, such as with according to BET method (ASTM 6556-09) at least about 700 meters squared per gram (m of measurement2/ gram) surface area.In general, surface area is big in about 700- About 3000m2/ gram, generally about 700- about 1500m2/ gram in the range of.Catalyst with special advantage is included with acid, example Such as, phosphoric acid washing and the carbon that is activated, to provide high surface area in these representational scopes and possibly many other Desirable performance.These performances include at least about 1wt% (for example, about 1wt%- about 20wt%, generally about 1wt%- about 10wt%) total oxygen content.
Hot-working or activation may also be used for obtaining the porous carbon particle with big internal surface area.No matter activate whether with Chemical mode is carried out with hot mode, and activated carbon granule can be supplied with granular, spherical, pellet or powder by many commercial manufacturers Should, including Norit Americas, Inc. (Marshall, TX USA), Japan Enviro Chemicals (Tokyo, ), Japan Jacobi Carbons AB (Kalmar, Sweden) and Calgon Carbon Corporation (Pittsburg, PA).Representational particle mean size for the Powdered Activated Carbon of method described herein is less than about 300 microns (50 mesh) and led to Often in the range of about 50 microns of (300 mesh)-about 300 micron (50 mesh).Can in some cases using screening with up to To desired particle mean size.
In general, activated carbon is derived from organic origin, such as timber, grind cocoanut shell etc..Various forms of activated carbons Activated carbon, graphite, graphite oxide or carbon nanomaterial including surface oxidation.Carbon nanomaterial includes, but are not limited to carbon and received Mitron, carbon nanohorn, carbon nano-fiber, buckyball (buckyball) etc..Absorbent charcoal material also includes having one or more tables Those of face modification, for example, being carried out as follows surface modification：Covalently bonded acid or basic matterial is with Controlled acidity and/or introducing The conversion of one or more organic compounds for absorption is in the metal of catalytic activity.Therefore these surfaces, which are modified, can supplement Catalytic activity of (promotion) activated carbon for expectation conversion.
In addition to activated carbon, there is higher BET surface area { for example, at least about 200m2/ gram, generally about 200m2/ Gram-about 500m2/ gram), and it is also used as solid with many other materials of enough absorbed organic reactant abilities Catalyst.These materials include inorganic oxide such as silica (for example, being in silica gel form), aluminum oxide, zirconium oxide, with And zeolite molecular sieve and non-zeolite molecular sieve.The zeolite molecular sieve for being suitable as catalyst is crystal aluminosilicate, and it is in calcination Form, can be with expressed by the following formula：
M2/n O:Al2O3:xSiO2:yH2O
Wherein M is cation, such as H, alkali metal (Na, K etc.), alkaline-earth metal (Mg, Ca etc.), rare earth metal (La, Y etc.) And transition metal, and NH4, n is the chemical valence of cation, and x has about 5-100 value, and y has about 2-10 value.Zeolite By D.W.Breck Zeolite Molecular Sieves, John Wiley and Sons, New York (1974) and Other places are described in detail.In useful embodiment, catalyst includes large pore zeolite, such as Y, zeolite beta, mercerising Zeolite, ZSM-12, ZSM-18, MCM-22 and/or MCM-49 and/or mesopore zeolite, for example, ZSM-5, ZSM-11, ZSM-23, ZSM-48 and ZSM-57.
In useful embodiment, catalyst includes zeolite, such as ZSM-5, zeolite beta, ITQ-13, MCM-22, MCM- 49th, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-48, ZSM-57, it is preferably modified by decatize so that There is about 0.1-15Sec when being measured at a temperature of 120 DEG C and under the 2,2- dimethylbutane pressures of 60 supports (8kPa)-1's To the diffusion parameter of 2,2- dimethylbutanes.Or catalyst can include ZSM-5, MCM-22, PSH-3, SSZ-25, ERB- 1st, ITQ-1, ITQ-2, ITQ-13, ITQ-39, MCM-36, MCM-49, MCM-56, X zeolite, zeolite Y, zeolite beta etc..Diffusion parameter It is defined in WO 2013/009399 [0033] section.
Non-zeolite molecular sieve includes the molecular sieve for having the chemical composition represented by following empirical formula based on anhydrous basis：
(ELxAlyPz)q2
Wherein EL be selected from silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium and its mixture element, x be EL molar fraction simultaneously And it is that at least 0.005, y is Al molar fraction and is that at least 0.01, z is P molar fraction and is at least 0.01, x+y+ Z=l, q are oxygen.When el is a mixture of metals, the total amount of element mixture existing for x representatives.Preferably element (EL) is Silicon, magnesium and cobalt, wherein silicon are particularly preferred.These non-zeolite molecular sieves are also referred to as " ELAPO ".Various ELAPO preparation is It is as known in the art and describe for example, US 7,317,133, US 5,191,141, US 4,554,143, US 4,440, 871st, in US4,853,197, US 4,793,984, US 4,752,651 and US 4,310,440.
As noted before, any of above solid catalyst can include promoting desired metal of the conversion with catalytic activity Enter agent.Representational metal includes alkali and alkaline earth metal ions, and rare earth and transition metal.The group of two or more metals Conjunction can be applied in combination (for example, as carrier material) with any of the above described solid catalyst.
Or ACS Catalysis, any catalyst disclosed in 2012,2, pp.935-939 can use herein.
The reaction of HMF and/or BHMF and ethene is entered in the presence of above-mentioned catalyst under the conditions of suitable cycloaddition reaction OK.It can be advantageous to the use for the solvent (for example, dimethyl sulfoxide (DMSO)) for making to be not involved in desired response path minimizes or even Exclude.According to some embodiments, therefore, cycloaddition reaction condition includes solvent-free or substantially solvent-free reactant mixture (that is, containing less than about 10%, less than about 5%, or the solvent even less than about 1%).Wherein arrange catalyst Reactor or reaction zone (for example, the fixation for being arranged in batch reactor or being arranged as in continuous reaction system or moving bed) In exemplary temperature in about 100 DEG C of (212 ℉)-about 300 DEG C (572 ℉), generally about 150 DEG C (302 ℉)-about In the range of 225 DEG C (437 ℉).Favourable cycloalkylation reaction condition also includes at least about 1000kPa (145psig), and one As about 1000kPa (145psig)-about 10,000kPa (1450psig), generally about 2000kPa- about 5000kPa's Ethylene partial pressure.Gross pressure is generally higher by about 2%- about 50% than ethylene partial pressure, this be attributed to (i) SF (i.e. HMF and/or BHMF) vapour pressure at the reaction temperatures, and/or (ii) possible diluent and/or impurity (for example, ethane) to reactor or The contribution of gross pressure in reaction zone.
No matter whether reaction is intermittently or continuously carried out, cycloaddition reaction condition be also commonly included in about 1 hour-it is big Reactor residence time in the range of about 48 hours, generally about 3 hours-about 30 hours.However, wherein will be unconverted SF and/or ethylene recycle to provide the continuation method of higher overall conversion in the case of, reactor residence time can show Write ground to reduce, even if one way (per-pass) conversion ratio is significantly less and such.Reactant SF can be continuously fed ring Addition reaction area, for example, the liquid hourly space velocity (LHSV) (LHSV) by about 0.05hr- about 5hr.As is understood in the art, liquid When air speed (LHSV, being represented with unit hr) be volume of liquid flow velocity above catalyst bed divided by bed volume and represent per hour plus The equivalents of the catalyst bed volume of the liquid of work.LHSV is therefore reciprocal closely related with reactor residence time.
All it is electron-donating group if instead of base, then ethene adds to diels-Alder ring of the dibasic furans of 2,5- Into will be promoted.In 5 hydroxymethyl furfural, one of substituent is formaldehyde, and it is electrophilic, and another is supplied for electronic Methylol.Selective addition of one hydrogen molecule to the carboxaldehyde radicals on HMF molecules will make electrophilic carbonyl change into supplied for electronic Methylol.The double hydroxymethylfurans (BHMF) of the 2,5- of gained as dienophile and are using BHMF or HMF conducts using ethene Than 5 hydroxymethyl furfural (HMF) with more reactivity in the diels of diene-Alder cycloaddition reaction.Furans -2- formaldehyde (or Furfural) selective hydration into 2- furancarbinols (or furfuryl alcohol) be known to the technical staff in furfuryl alcohol production field. Kaufmann and Adams early stage works reports on the platinum catalyst of reduction high conversion from furfural to furfuryl alcohol and selectivity (J.Am.Chem.Soc.,Dec 1923,pp.3029-3044).It is also reported that the conversion on nickel and palladium catalyst. In Sharma et al. newer works, it was recently reported that in Cu:Zn:Cr:100% conversion of the furfural to furfuryl alcohol, has on Zr catalyst 96% selectivity (App.Cat A:Gen 454,pp.127-136(2013)DOI:10.1016/ j.apcata.2012.12.010).Similar catalyst and condition can be used to 5 hydroxymethyl furfural changing into the double hydroxyl first of 2,5- Base furans.
In exemplary continuation method, reactant SF and ethene are continuously fed one of the fixed bed containing catalyst Or multiple reactors (for example, in oscillating bed (swing-bed) reactor assembly with multiple fixed bed reactors), and even The product of the dibasic phenyl of 1,4- (such as HMBA or PDM) comprising conversion is taken out continuously together with unconverted reactant and anti- Answer accessory substance.The unconverted material of preferable separate, for example, being separated based on their relative volatility difference using one or more Operation (for example, flash separation or distillation) is separated using single phase or the contact of multistage vapor-liquid equilibrium.
It is unconverted from the separation of cycloaddition reaction area effluent using single phase flash separation according to a particular Ethene, together with lower boiling accessory substance and impurity.Then allow this flash separation liquid bottoms product flow to it is at least one Multistage destilling tower is with the dibasic phenyl of the 1,4- of individually recovery purifying and unconverted SF.Can be by unconverted SF And/or unconverted ethylene recycle is optionally purging the one of any of these streams or both to cycloaddition reaction area After part is to limit the accumulation of the accessory substance with similar boiling points.In a specific embodiment, Excess ethylene is added Into reactor with from reaction zone water stripping；Make this water cooling coalescence and ethylene separation, be then recycled to reactor.According to one Specific continuous operation, ethylene reaction thing is controlled to the flow velocity of cycloaddition reaction device or reaction zone to maintain desired gross pressure. Such a operation based on pressure requirements ensures that ethene (is attributed to dissolving and possibly gas by substantially being consumed with it plus loss Caused by purging (exhaust)) speed that matches supplies.
Whether SF is catalytically converted into substituted phenyl using intermittently or serially method, cycloaddition reaction condition is general At least about 50% is provided, such as (this can be with for about 50%- about 90%, generally about 50%- about 75% SF conversion ratios It is the conversion per pass in cycloaddition reaction area, in the case where being operated with unconverted SF circulation).Unconverted SF Circulation, such as be recycled to disappearance or almost disappear, overall conversion completely or almost completely can be provided.In the SF of conversion, Selectivity to substituted phenyl is usually at least about 60%, refers to produce at least about for the SF of each mole of conversion The phenyl of 0.6 mole of substitution.Typical selectivity to substituted phenyl is about 60%- about 95%.In view of these are represented The conversion ratio and selective value of property, the gross production rate of substituted phenyl is usually at least about the 30% of theoretical yield, generally about 30%- about 90%, generally about 90%- about 75%, the theoretical yield are based on SF and stoichiometry (1:1 mole) ethene Complete conversion and no accessory substance to substituted phenyl are formed.
After SF is combined with ethene and adds catalyst, two cyclic ethers are formed.Then preferably the ether is dehydrated and formed Substituted phenyl.The bicyclic compound can in same reaction step and in the presence of same catalyst, and with ethene Cycloaddition reaction undergoes dehydration under the same conditions.
After SF is combined with ethene and adds catalyst, two cyclic ethers are formed.Then preferably the ether is dehydrated and formed Substituted phenyl, the substituted phenyl is then oxidized to terephthalic acid (TPA).Can use be used for by p xylene oxidation into The substituted phenyl is oxidized to terephthalic acid (TPA) by the same procedure of terephthalic acid (TPA).It is expected that relative in paraxylene Methyl substituents, oxidation reaction, which will occur, for carbonyl or methylol substitution on benzyl ring to be more prone to.It is expected that carbonyl or methylol The reactivity being more prone to of substituent is converted into the higher selectivity to terephthalic acid (TPA).
Or oxidation of the substituted phenyl to terephthalic acid (TPA) can use and the commercial oxidation reality for paraxylene The different Catalyst And Method trampled.These methods will using compared with the methyl of paraxylene methylol and aldehyde radical to oxygen The advantages of reactivity of change is higher.It is high activity and selectivity for conversion of the primary alconol to carboxylic acid that many catalyst systems are known 's.For example, Gorbanev etc. is described in Ru (OH) x/CeO2Ethanol turns to the quantitative of acetic acid in water-bearing media on catalyst Change.Other effective catalyst include Mo, V, NB, and Pd mixed oxide (ACS Catalysis (2012) 2,604- 612,DOI:10.1021/cs200554h)。
Terephthalic acid (TPA) may be used in method well known in the art and prepare polyester such as poly terephthalic acid second Terephthalate polymer (PET).Once manufacture, it is possible to process PET so that preparing for synthetic fibers, beverage, food and other Liquid container；Thermoforming application；The thermoplastic PET resin of the engineering resin generally combined with glass fibre.
Turning now to accompanying drawing, Fig. 1 shows preferred embodiment of the present invention according to route III.First by raw material (100), preferred renewable raw materials, such as sugar, cellulose or lignocellulose change into the dibasic furan compounds of 2,5- (200) such as 5 hydroxymethyl furfural (HMF) (300), release water (250).Then allow the HMF to undergo ring with ethene (500) to add Two cyclic ethers intermediates are formed into condition (400), the two cyclic ethers intermediate are then dehydrated (600), release water (250) turns into The dibasic phenyl of 1,4- such as 4- (methylol) benzaldehyde (HMBA) (700).Optionally can be in the presence of oxygen (850) This product is aoxidized into (800) into terephthalic acid (TPA) (900).
Fig. 2 shows preferred embodiment of the present invention according to route IV.It is preferably renewable first by raw material (100) Raw material, such as sugar, cellulose or lignocellulose change into the dibasic furan compounds of 2,5- (200) such as 5- methylols Furfural (HMF) (300).Then use in the presence of hydrogen (280) and used for each mole of furans less than two mol of hydrogen by described in HMF hydrogenates (275), and forms partially hydrogenated furan compound such as 2, the double hydroxymethylfurans (BHMF) (290) of 5-.Then allow The partially hydrogenated furans ethene (500) undergoes the condition of cycloaddition 400 and forms two cyclic ethers intermediates, then by described two Cyclic ethers intermediate is dehydrated (600) into the dibasic phenyl of 1,4- such as 1,4- phenylenes dimethanol (PDM) (650).Optionally This product can be aoxidized into (800) into terephthalic acid (TPA) (900) in the presence of oxygen (850).
Fig. 3 shows route III preferred embodiment, wherein identical solvent be used for HMF extract and cycloaddition/ Dehydration.In the first step, two-phase reactor (950) is used as such as being described by Leshkov, Y.R. etc., is had Raw material (100) are preferably derived from biomass, converted usually using acid catalyst (855) by machine phase (950A) and aqueous phase (950B) Organic solvent (955) such as butanol, methyl iso-butyl ketone (MIBK), toluene or their mixture are extracted into HMF (300) and by HMF In (NATURE, in June, 2007, (447) pp.982-5).HMF (300) is set to react the second of (400) with ethene (500) wherein In step, regardless of exsolution agent and as the solvent in ethene cycloaddition step.Then solvent is separated and circulated with product (975) To first step (980).Additional solvent can be added as supplementing solvent (990).Can be from two-phase reactor (950) interval Ground continuously removes dead catalyst (951) and aqueous accessory substance (952).
Fig. 4 shows route III preferred embodiment, and wherein HMBA is used as HMF extractions and ethene cycloaddition/dehydration Solvent in both reactions.Step is identical with Fig. 3, but wherein avoids separating solvent from HMBA products.
Fig. 5 shows route IV preferred embodiment, wherein identical solvent be used for HMF extractions, HMF hydrogenations and Cycloaddition/dehydration.In the first step, two-phase reactor (950) is used as such as being described by Leshkov, Y.R. etc., With organic phase (950A) and aqueous phase (950B) by raw material (100), biomass is preferably derived from, usually using acid catalyst (855) change into HMF (300) and by HMF be extracted into organic solvent (955) for example butanol, methyl iso-butyl ketone (MIBK), toluene or they Mixture in (NATURE, in June, 2007, (447) pp.982-5).Regardless of exsolution agent before second step, wherein in phase With in solvent BHMF (290) and water are formed for each mole of HMF with HMF is hydrogenated into (275) less than two mol of hydrogen (280) (250).HMF is reacted (400) with ethene (500) wherein and be dehydrated in the third step of (600), regardless of exsolution agent and be used as Solvent in ethene cycloaddition step.Solvent (955) is then separated to (975) with product PDM (650) and circulates (980) to One step.Additional solvent can be added as supplementing solvent (990).Can be from two-phase reactor (950) intermittently or continuously Ground removes dead catalyst (951) and aqueous accessory substance (952).
Fig. 6 shows route IV preferred embodiment, and wherein PDM is used as HMF extractions, HMF hydrogenations and ethene ring and added Solvent into/dehydration.Step is identical with Fig. 5, but wherein avoids separating solvent from PDM products.
Fig. 7 shows the preferred embodiment of any route III or IV cycloaddition/dehydration.By raw material HMF (300) or BHMF (290) is plus non-essential solvent (955) supply cycloaddition/dehydration reactor (401), the reaction utensil There are gas phase (401A) and aqueous phase (401B), and contain catalyst (420).Ethene (500) is added in the reactions steps, its In from the gas phase of the reactor remove Excess ethylene.Excess steam is used for from liquid reaction mixture water stripping.By vapor stream Go out material flow (512) cooling (283), wherein also from reactor condensate water stripping and some organic materials.By water (250) and not Ethylene vapor (431A) and any organic phase (256) separation (430) of reaction, and discharged from system.Will via compressor (502) Ethylene vapor (501) sends back to reactor.By any condensation organic phase reclaimed in separator or reactor can be sent back to (257A) or as product (257B) discharge.Liquid product (407) is removed from reactor (401).
In another embodiment of the present invention, as the R and R on substituted phenyl*, can be by described in during containing OH bases Substituted phenyl is hydrogenated to the monomer that cycloalkane is not necessarily used as in production of polyester.
Such as：
There is no the ring filling of the hydrogenolysis of methylol, such as Isosorbide-5-Nitrae-benzene dimethanol is hydrogenated to 1,4-CHDM requirement Catalysts selective (such as base metal catalysts Ni, Cu or noble metal Rh, Pt or more metallized metal catalyst).Typical condition Hydrogen Vapor Pressure and 0 DEG C -200 DEG C of temperature including 100-5000kPag.
Both above glycol molecules can be used as the comonomer for preparing polyester independently or together.Especially, Isosorbide-5-Nitrae-hexamethylene Alkane dimethanol is to be used to prepare one of most important comonomer of polyethylene terephthalate (PET).Currently, Isosorbide-5-Nitrae-ring Hexane dimethanol is prepared via the hydrogenation of terephthalate such as dimethyl terephthalate (DMT) at high temperature and pressure.
In another embodiment, the glycol (aromatics is non-aromatic) prepared here can be esterified and gather as polarity The plasticizer of compound (such as polyvinyl chloride and PET).For example, can be by Isosorbide-5-Nitrae-benzene dimethanol and/or 1,4-CHDM (wherein R is C with 2 moles of RCOOH1-C20Alkyl) and catalyst (such as sulfuric acid) combine to obtain diester (as follows).
Such diester can be used as the plasticizer of plasticizer, especially polyvinyl chloride and pet polymer.
Polar polymer is the polymer by being manufactured containing heteroatomic monomer.
In another embodiment the present invention relates to：
1. the preparation method of terephthalic acid (TPA), including make substituted furans with ethene under the conditions of cycloaddition reaction and urging Reacted in the presence of agent and prepare two cyclic ethers, two cyclic ethers is dehydrated and prepares the phenyl of substitution, afterwards will be described substituted Phenyl is oxidized to terephthalic acid (TPA), wherein the substituted furans with following formula by being represented：
Two cyclic ethers with following formula by being represented：
The substituted phenyl with following formula by being represented：
Wherein R is=O, OH, OC (O) CH3, R*It is=O, OH, OC (O) CH3 or H,
But condition is two substituents on the SF is not hydrogenated to corresponding alkane before the cycloaddition step Base.
2. section 1 method, wherein the cycloaddition reaction condition includes about 100 DEG C-about 300 DEG C of temperature.
3. sections 1 or 2 method, wherein the catalyst include activated carbon, silica, aluminum oxide, zeolite molecular sieve or Non-zeolite molecular sieve.
4. sections 3 method, wherein the catalyst includes activated carbon.
5. sections 4 method, wherein the activated carbon is pickling.
6. the method for either segment in section 1-5, wherein at least six in the carbon atom of the terephthalic acid (TPA) is derived from one kind Or a variety of raw materials that can be regenerated every year.
7. the method for either segment in section 1-6, wherein the substituted furans is obtained by the conversion of glucose or fructose.
8. the method for either segment in above-mentioned section of 1-7, wherein the substituted furans includes 5 hydroxymethyl furfural.
9. the method for either segment in above-mentioned section of 1-8, wherein the substituted furans includes the double hydroxymethylfurans of 2,5-.
10. sections 7 method, wherein the substituted furans is by glucose or fructose converting is obtained into 5 hydroxymethyl furfural.
11. sections 10 method, wherein the 5 hydroxymethyl furfural before ethene cycloaddition with being not converted into 2,5- bis- Methylfuran.
12. the method based on carbohydrate of terephthalic acid (TPA) is prepared, including：
(a) hexose is changed into 5 hydroxymethyl furfural；
(b) make the 5 hydroxymethyl furfural with ethene under the conditions of cycloaddition reaction and react and make in the presence of a catalyst Standby two cyclic ethers, then make two cyclic ethers be dehydrated and prepare the compound represented by formula (I)：
With
(c) compound oxidation represented by formula (I) is prepared into terephthalic acid (TPA) with oxygen；Wherein described 5- methylols chaff Aldehyde is not converted into 2,5- dimethyl furans before step (b).
13. the method based on carbohydrate of terephthalic acid (TPA) is prepared, including：
(a) hexose is changed into the double hydroxymethylfurans of 2,5-；
(b) make the double hydroxymethylfurans of the 2,5- with ethene under the conditions of cycloaddition reaction and react in the presence of a catalyst And two cyclic ethers are prepared, two cyclic ethers is dehydrated and prepare the compound represented by formula (II)：
With
(c) compound oxidation represented by formula (II) is prepared into terephthalic acid (TPA) with oxygen；The double hydroxyls of wherein described 2,5- Methylfuran is not converted into 2,5- dimethyl furans before step (b).
14. section 1 method, wherein the substituted furans with following formula by being represented：
With
Two cyclic ethers with following formula by being represented：
With
The substituted phenyl with following formula by being represented：
Wherein R*It is-C=O or-OH.
15. the method for either segment in above-mentioned section of 1-14, wherein the substituted furans includes the double hydroxymethylfurans of 2,5-, and The double hydroxymethylfurans of the 2,5- are combined to prepare diester with acid before the cycloaddition step.
16. sections 15 method, wherein the acid is acetic acid.
17. section 1 method, wherein for the addition of every SF molecules less than 1.5 moles before the cycloaddition step Hydrogen.
18. section 1 method, wherein for hydrogen of every SF molecules addition less than 1 mole before the cycloaddition step Gas.
19. the method for 1,4-CHDM is prepared, including：
(a) hexose is changed into the double hydroxymethylfurans of 2,5-；
(b) make the double hydroxymethylfurans of the 2,5- with ethene under the conditions of cycloaddition reaction and react in the presence of a catalyst And two cyclic ethers are prepared, two cyclic ethers is dehydrated and prepare the compound represented by formula (II)：
With
(c) hydrogen is used in the presence of as Ni, Cu of base metal catalysts or noble metal Rh, Pt or more metallized metal catalyst The hydrogenation of compounds represented by formula (II) is prepared 1,4 cyclohexane dimethanol by gas；The double hydroxymethylfurans of wherein described 2,5- exist 2,5- dimethyl furans are not converted into before step (b).
20. method, including：
(a) hexose is changed into the double hydroxymethylfurans of 2,5-；
(b) make the double hydroxymethylfurans of the 2,5- with ethene under the conditions of cycloaddition reaction and react in the presence of a catalyst And two cyclic ethers are prepared, two cyclic ethers is dehydrated and prepare the compound represented by formula (II)：
With
The double hydroxymethylfurans of wherein described 2,5- are not converted into 2,5- dimethyl furans before step (b).
21. prepare the method for plastification composite, including by polar polymer and the one or more two by being represented with following formula Ester compounds combine：
Wherein R is C1-C20Alkyl.
22. sections 21 method, wherein the polymer includes polyvinyl chloride and/or pet polymer.
23. sections 21 method, wherein the diester compound is derived from Isosorbide-5-Nitrae-benzene dimethanol and/or Isosorbide-5-Nitrae-hexamethylene diformazan Alcohol, and the Isosorbide-5-Nitrae-benzene dimethanol is obtained as below：
(a) hexose is changed into the double hydroxymethylfurans of 2,5-；
(b) make the double hydroxymethylfurans of the 2,5- with ethene under the conditions of cycloaddition reaction and react in the presence of a catalyst And two cyclic ethers are prepared, two cyclic ethers is dehydrated and prepare the compound represented by formula (II)：
Or 1,4 cyclohexane dimethanol is obtained as below：Used in the presence of base metal or noble metal (single or multiple metal) catalyst The compound represented by formula (II) is further hydrogenated and prepares 1,4 cyclohexane dimethanol by hydrogen；The double hydroxyl first of wherein described 2,5- Base furans is not converted into 2,5- dimethyl furans before step (b).
24. the preparation method of terephthalic acid (TPA), including：
1) hexose is changed into substituted furans in two-phase reactor, the reactor has organic phase and aqueous phase；
2) the substituted furans is extracted from the material as caused by the two-phase reactor using organic solvent；
3) by the combination transfer of solvent and the furans of substitution into cycloaddition reaction device, wherein making in the presence of the solvent The substituted furans reacts under the conditions of cycloaddition reaction and in the presence of a catalyst with ethene and prepares two cyclic ethers,
4) after, two cyclic ethers is dehydrated in the presence of the solvent and produces the phenyl of substitution；
5) reclaim the solvent and the solvent is recycled to step 2；With
6) after, the substituted phenyl is oxidized to terephthalic acid (TPA), wherein the substituted furans is by with following formula table Show：
Two cyclic ethers with following formula by being represented：
The substituted phenyl with following formula by being represented：
Wherein R is=O, OH or OC (O) CH3, R*It is=O, OH, OC (O) CH3 or H,
But condition is the R and R on the substituted furans*Substituent inwhole quilts before the cycloaddition step It is hydrogenated to corresponding alkyl.
25. sections 24 method, wherein (methylol) benzaldehyde is used as the substituted furans extraction and ethene cycloaddition/de- Solvent in both water reactions.
26. the preparation method of terephthalic acid (TPA), including：
1) hexose is changed into substituted furans in two-phase reactor, the reactor has organic phase and aqueous phase；
2) the substituted furans is extracted from the material as caused by the two-phase reactor using organic solvent；
3) the substituted furans and the furans of each mole relatively substitution are less than 2 moles in the presence of the solvent Hydrogen is with reference to so that the substituted furan fragment to be hydrogenated；
4) by the combination transfer of solvent and partially hydrogenated substituted furan into cycloaddition reaction device, wherein in the solvent In the presence of make the substituted furans and ethene under the conditions of cycloaddition reaction and react in the presence of a catalyst and prepare two rings Ether,
5) after, two cyclic ethers is dehydrated in the presence of the solvent and produces the phenyl of substitution；
6) reclaim the solvent and the solvent is recycled to step 2；With
7) after, the substituted phenyl is oxidized to terephthalic acid (TPA), wherein the substituted furans is by with following formula table Show：
Two cyclic ethers with following formula by being represented：
The substituted phenyl with following formula by being represented：
Wherein R is=O, OH or OC (O) CH3, R*It is=O, OH, OC (O) CH3 or H,
But condition is the R and R on the substituted furans*Substituent inwhole quilts before the cycloaddition step It is hydrogenated to corresponding alkyl.
27. sections 26 method, wherein Isosorbide-5-Nitrae-phenylene dimethanol be used as the substituted furans extraction and ethene cycloaddition/ Solvent in both dehydrations.
28. section 1 method, wherein：
1) by the substituted furans plus cycloaddition/dehydration of the non-essential solvent supply with gas phase and aqueous phase Device, the reactor contain catalyst；
2) ethene is added in the reactions steps, and the gas phase from the reactor removes Excess ethylene；
3) vapor effluent stream is cooled down, and by water and unreacted ethylene vapor and any organic phase separation；
4) water is discharged from system, and ethylene vapor is sent back into cycloaddition/dehydration reactor.
Foresight embodiment
Foresight embodiment 1：HMF converts to HMBA on-catalytic
1.0M HMFs of the 100mL in 2- butanol is added gas access, thermocouple, pressure are housed with 160mL volumes The autoclave of force snesor and magnetic stirring bar.The autoclave is sealed, pressurizeed at room temperature with ethene, and is heated to 250 DEG C reaction temperature.Reaction is run the reaction phase of 24 hours, while maintain the ethylene pressure of 6200kPa in autoclave.Then Reactor is cooled down and obtains the analysis of product.
Foresight embodiment 2：BHMF converts to PMB on-catalytic
1.0M BHMFs of the 100mL in 2- butanol is added gas access, thermocouple, pressure are housed with 160mL volumes The autoclave of force snesor and magnetic stirring bar.The autoclave is sealed, pressurizeed at room temperature with ethene, and is heated to 250 DEG C reaction temperature.Reaction is run the reaction phase of 24 hours, while maintain the ethylene pressure of 6200kPa in autoclave.Then Reactor is cooled down and obtains the analysis of product.
Foresight embodiment 3：Catalyzed conversions of the HMF to HMBA
The experimental arrangement described in foresight embodiment 1 is followed, difference is before being pressurizeed with ethene will to be in The 0.5g solid catalysts of particle shape formula (pellet or powder) are added in reactor.Experiment description is in table 1.
Table 1
Embodiment Catalyst Si/Al ratio Reaction temperature (DEG C) Reactant
A H-BEA 12.5 250 HMF
B H-BEA 19 250 HMF
C H-FAU 2.6 250 HMF
D H-ZSM-5 15 250 HMF
E Niobic acid 250 HMF
F γ-Al2O3 250 HMF
Foresight embodiment 4：Catalyzed conversions of the BHMF to PDM
The experimental arrangement described in foresight embodiment 2 is followed, difference is before being pressurizeed with ethene will to be in The 0.5g solid catalysts of particle shape formula (pellet or powder) are added in reactor.Experiment description is in table 2.
Table 2
Embodiment Catalyst Si/Al ratio Reaction temperature (DEG C) Reactant
A H-BEA 12.5 250 BHMF
B H-BEA 19 250 BHMF
C H-FAU 2.6 250 BHMF
D H-ZSM-5 15 250 BHMF
E Niobic acid 250 BHMF
F γ-Al2O3 250 BHMF
Foresight embodiment 5：Catalytic hydrogenations of the HMF to BHMF
1.0M BHMFs of the 100mL in 2- butanol is added gas access, thermocouple, pressure are housed with 160mL volumes The autoclave of force snesor and magnetic stirring bar.By 0.5g in γ-Al2O31%Pt on catalyst is added to the autoclave In.The autoclave is sealed, at room temperature with pressurized with hydrogen, and is heated to 150 DEG C of reaction temperature.Run reaction, together When maintain autoclave in 2000kPa Hydrogen Vapor Pressure.When consuming monovalent hydrogen, by cooling down and decompressing stopping reactor. Then the analysis of product is obtained.
Foresight embodiment 6：Catalyzed conversions of the BHMF to PDM in various solvents
1.0M BHMFs of the 100mL in solvent (referring to table 3) is added gas access, heat are housed with 160mL volumes The autoclave of galvanic couple, pressure sensor and magnetic stirring bar.H-BEA catalyst of the 0.5g with 12.5 Si/Al ratio is added The reactor.The autoclave is sealed, pressurizeed at room temperature with ethene, and is heated to 250 DEG C of reaction temperature.Make reaction The reaction phase of operation 24 hours, while maintain the ethylene pressure of 6200kPa in autoclave.Then reactor is cooled down and produced The analysis of thing.
Table 3
Embodiment Solvent Catalyst Reaction temperature (DEG C) Reactant
A 2- butanol H-BEA(12.5) 250 BHMF
B Toluene H-BEA(12.5) 250 BHMF
C 1:1 toluene:2- butanol H-BEA(12.5) 250 BHMF
D Methyl iso-butyl ketone (MIBK) H-BEA(12.5) 250 BHMF
E HMBA H-BEA(12.5) 250 BHMF
F PDM H-BEA(12.5) 250 BHMF
This is hereby incorporated by reference in all documents (including any priority documents and/or test procedure) described herein Wen Zhong, to their not degree inconsistent with present disclosure, as long as but not having in the application initially submitted or submit in document Any priority documents enumerated are incorporated herein not over reference.It is obvious from above-mentioned general introduction and particular It is, although having illustrated and described the form of the present invention, without departing from the spirit and scope of the present invention can be with Various modification can be adapted.And it is therefore not desirable to the present invention is so limited.Similarly, term " including (comprising) " is with regard to the big profit of Australia Think synonymous with term " including (including) " for sub- law.Equally, whenever composition, element or element group are in transition Property term " including " above when, it should be understood that further contemplate with transitional term " substantially by ... form ", " By ... form ", " be selected from " or " it is " same combination or element before the composition, element or each element enumerated Group, vice versa.Therefore, term " including " cover term " substantially by ... form ", " being " and " by ... form " And using can use from anywhere in " include " " substantially by ... form ", " being " with " by ... form " replacement.

Claims (28)

1. the preparation method of terephthalic acid (TPA), including make substituted furans with ethene under the conditions of cycloaddition reaction and in catalyst In the presence of react and prepare two cyclic ethers, two cyclic ethers is dehydrated and prepares the phenyl of substitution, and afterwards, by the substituted benzene Base is oxidized to terephthalic acid (TPA), wherein the substituted furans with following formula by being represented：
Two cyclic ethers with following formula by being represented：
The substituted phenyl with following formula by being represented：
Wherein R is=O, OH or OC (O) CH3, R*It is=O, OH, OC (O) CH3Or H,
But condition is the R and R on the substituted furans*Substituent is not hydrogenated all before the cycloaddition step Into corresponding alkyl.
2. the method for claim 1 wherein the cycloaddition reaction condition includes 100 DEG C -300 DEG C of temperature.
3. the method for claim 1 wherein the catalyst includes activated carbon, silica, aluminum oxide, zeolite molecular sieve or non- Zeolite molecular sieve.
4. the method for claim 1 wherein the catalyst includes activated carbon.
5. the method for claim 4, wherein the activated carbon is pickling.
6. the method for claim 1 wherein at least six in the carbon atom of the terephthalic acid (TPA) can derived from one or more Regenerative raw materials.
7. the method for claim 1 wherein the substituted furans by the conversion acquisition of glucose or fructose.
8. the method for claim 1 wherein the substituted furans includes 5 hydroxymethyl furfural.
9. the method for claim 1 wherein the substituted furans includes the double hydroxymethylfurans of 2,5-.
10. the method for claim 7, wherein the substituted furans is by glucose or fructose converting is obtained into 5 hydroxymethyl furfural .
11. the method for claim 10, wherein the 5 hydroxymethyl furfural before ethene cycloaddition with being not converted into 2,5- Dimethyl furan.
12. the method for claim 1 wherein：
1) the substituted furans is had to cycloaddition/dehydration reactor of gas phase and aqueous phase plus the supply of non-essential solvent, The reactor contains catalyst；
2) ethene is added in the reactions steps, and the gas phase from the reactor removes Excess ethylene；
3) vapor effluent stream is cooled down, and by water and unreacted ethylene vapor and any organic phase separation；
4) water is discharged from system, and ethylene vapor is sent back into cycloaddition/dehydration reactor.
13. the method for claim 1 wherein the substituted furans by being represented with following formula：
With
Two cyclic ethers with following formula by being represented：
With
The substituted phenyl with following formula by being represented：
Wherein R*It is=O or-OH.
14. the method for claim 1 or 13, wherein the substituted furans includes the double hydroxymethylfurans of 2,5-, and in the ring The double hydroxymethylfurans of the 2,5- are combined to prepare diester with acid before addition step.
15. the method for claim 14, wherein the acid is acetic acid.
16. the method for claim 1 wherein be directed to the addition per monobasic Furan Molecules before the cycloaddition step to be less than 1.5 moles of hydrogen.
17. the method for claim 1 wherein be directed to the addition per monobasic Furan Molecules before the cycloaddition step to be less than 1 mole of hydrogen.
18. the method based on carbohydrate of terephthalic acid (TPA) is prepared, including：
(a) hexose is changed into 5 hydroxymethyl furfural；
(b) make the 5 hydroxymethyl furfural with ethene under the conditions of cycloaddition reaction and react in the presence of a catalyst and prepare two Cyclic ethers, then two cyclic ethers is dehydrated and prepared the compound represented by formula (I)：
With
(c) compound oxidation represented by formula (I) is prepared into terephthalic acid (TPA) with oxygen；Wherein described 5 hydroxymethyl furfural exists 2,5- dimethyl furans are not converted into before step (b).
19. the method for claim 18, wherein being less than before the cycloaddition step for the addition of each 5 hydroxymethyl furfural 1.5 moles of hydrogen.
20. the method based on carbohydrate of terephthalic acid (TPA) is prepared, including：
(a) hexose is changed into the double hydroxymethylfurans of 2,5-；
(b) make the double hydroxymethylfurans of the 2,5- with ethene under the conditions of cycloaddition reaction and react and make in the presence of a catalyst Standby two cyclic ethers, then two cyclic ethers is dehydrated and prepared the compound represented by formula (II)：
With
(c) compound oxidation represented by formula (II) is prepared into terephthalic acid (TPA) with oxygen；The double methylols of wherein described 2,5- Furans is not converted into 2,5- dimethyl furans before step (b).
21. the method for claim 20, wherein for the double hydroxymethylfurans additions of every one 2,5- before the cycloaddition step Hydrogen less than 1.5 moles.
22. the method for 1,4-CHDM is prepared, including：
(a) hexose is changed into the double hydroxymethylfurans of 2,5-；
(b) make the double hydroxymethylfurans of the 2,5- with ethene under the conditions of cycloaddition reaction and react and make in the presence of a catalyst Standby two cyclic ethers, then make two cyclic ethers be dehydrated and prepare the compound represented by formula (II)：
With
(c) will with hydrogen in the presence of the base metal catalysts including Ni, Cu or noble metal Rh, Pt or more metallized metal catalyst 1,4 cyclohexane dimethanol is prepared by the hydrogenation of compounds that formula (II) represents；The double hydroxymethylfurans of wherein described 2,5- are in step (b) 2,5- dimethyl furans are not converted into before.
23. method, including：
(a) hexose is changed into the double hydroxymethylfurans of 2,5-；
(b) make the double hydroxymethylfurans of the 2,5- with ethene under the conditions of cycloaddition reaction and react and make in the presence of a catalyst Standby two cyclic ethers, then make two cyclic ethers be dehydrated and prepare the compound represented by formula (II)：
The double hydroxymethylfurans of wherein described 2,5- are not converted into 2,5- dimethyl furans before step (b).
24. the preparation method of terephthalic acid (TPA), including：
1) hexose is changed into substituted furans in two-phase reactor, the reactor has organic phase and aqueous phase；
2) the substituted furans is extracted from the material as caused by the two-phase reactor using organic solvent；
3) by the combination transfer of solvent and the furans of substitution into cycloaddition reaction device, wherein making in the presence of the solvent described Substituted furans reacts under the conditions of cycloaddition reaction and in the presence of a catalyst with ethene and prepares two cyclic ethers,
4) after, two cyclic ethers is dehydrated in the presence of the solvent and produces the phenyl of substitution；
5) reclaim the solvent and the solvent is recycled to step 2)；With
6) after, the substituted phenyl is oxidized to terephthalic acid (TPA), wherein the substituted furans with following formula by representing：
Two cyclic ethers with following formula by being represented：
The substituted phenyl with following formula by being represented：
Wherein R is=O, OH or OC (O) CH3, R*It is=O, OH, OC (O) CH3Or H,
But condition is the R and R on the substituted furans*Substituent is not hydrogenated all before the cycloaddition step Into corresponding alkyl.
25. the method for claim 24, wherein being directed to before the cycloaddition step, per monobasic Furan Molecules, addition is few In 1.5 moles of hydrogen.
26. the method for claim 24, wherein hydroxymethylbenzaldehyde are used as the substituted furans extraction and ethene cycloaddition/de- Solvent in both water reactions.
27. the preparation method of terephthalic acid (TPA), including：
1) hexose is changed into substituted furans in two-phase reactor, the reactor has organic phase and aqueous phase；
2) the substituted furans is extracted from the material as caused by the two-phase reactor using organic solvent；
3) furans of the substituted furans and each mole relatively substitution is less than to 2 moles of hydrogen in the presence of the solvent With reference to so that the substituted furan fragment to be hydrogenated；
4) by the combination transfer of solvent and partially hydrogenated substituted furan into cycloaddition reaction device, wherein existing in the solvent Under make the substituted furans and ethene under the conditions of cycloaddition reaction and react in the presence of a catalyst and prepare two cyclic ethers,
5) after, two cyclic ethers is dehydrated in the presence of the solvent and produces the phenyl of substitution；
6) reclaim the solvent and the solvent is recycled to step 2)；With
7) after, the substituted phenyl is oxidized to terephthalic acid (TPA), wherein the substituted furans with following formula by representing：
Two cyclic ethers with following formula by being represented：
The substituted phenyl with following formula by being represented：
Wherein R is=O, OH or OC (O) CH3, R*It is=O, OH, OC (O) CH3Or H,
But condition is the R and R on the substituted furans*Substituent is not hydrogenated all before the cycloaddition step Into corresponding alkyl.
28. the method for claim 27, wherein Isosorbide-5-Nitrae-phenylene dimethanol are used as the substituted furans extraction and ethene ring adds Solvent into/both dehydrations.
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