CN1179154A - Preparation of 2, 3 -dihydrofurans compounds - Google Patents
Preparation of 2, 3 -dihydrofurans compounds Download PDFInfo
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- CN1179154A CN1179154A CN 96192692 CN96192692A CN1179154A CN 1179154 A CN1179154 A CN 1179154A CN 96192692 CN96192692 CN 96192692 CN 96192692 A CN96192692 A CN 96192692A CN 1179154 A CN1179154 A CN 1179154A
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Abstract
Disclosed is a process for the preparation of 2,3-dihydrofurans from the corresponding isomeric 2,5-dihydrofurans wherein a feed mixture comprising a 2,5-dihydrofuran compound and an aldehyde selected from alkanals containing 2 to 5 carbon atoms and alkenals containing 3 or 4 carbon atoms; an epoxide selected from 1,2-epoxyalkanes containing 2 to 5 carbon atoms and 3,4-epoxy-1-butene; carbon monoxide; or a mixture of 2 or more of such aldehydes, epoxides and carbon monoxide is contacted with a supported, palladium or platinum catalyst to effect the isomerization of 2,5-dihydrofurans to 2,3-dihydrofurans.
Description
The present invention relates to by corresponding isomery 2,5-dihydrofuran compounds prepares improving one's methods of 2,3 dihydro furan compounds.More particularly, the present invention relates at some epoxide, some aldehyde, carbon monoxide or two or more the above mixtures in them exist down, make 2 in the operate out of phase mode, 5-dihydrofuran compounds is with palladium on the carrier or platinum catalyst contact, with 2,5-dihydrofuran compounds catalytic isomerization turns to the 2,3 dihydro furan compounds.The intermediate that can be used as the precursor of making polymkeric substance and medicine with the 2,3 dihydro furan compounds of this law generation.For example, can at an easy rate 2,3 dihydro furan be converted into 1 with known method, 4-butyleneglycol and cyclopanecarboxaldehyde, the former is the precursor monomer that is used to make urethane and polyester, the latter can be used for the synthesising physiological active compound
In the presence of alkali metal alkoxide, 2,5-dihydrofuran compounds can turn to the 2,3 dihydro furan compounds by isomery, this be known (United States Patent (USP) 2,556,325).German Patent 1,248,669 disclose and have used some metal catalyst, and as palladium, platinum, cobalt, ruthenium and nickel, with 2,5-dihydrofuran catalytic isomerization turns to 2,3 dihydro furan.Yet, German Patent 1,248,669 method is with 2, and 5-dihydrofuran compounds is converted into the selectivity of desired 2,3 dihydro furan compounds and has only 75-85%.
At last, United States Patent (USP) 3,651,092 has discussed at the nickel/arsenic catalyzer that uses in the presence of hydrogen and the carbon monoxide mixtures on the carrier, and still, the selectivity that obtains desired 2,3 dihydro furan is still lower.Be noted that and in this patent, always use hydrogen, and when using carbon monoxide, always mix and use with hydrogen.United States Patent (USP) 5,254,701 disclose the homogeneous process of a kind of 2-of production hydroxyl tetrahydrofuran and 4-acetaldol mixture, this method comprises: (1) heats 2, the 5-dihydrofuran in the presence of the catalyst system that contains tertiary phosphine and ruthenium or rhodium, with 2, the 5-dihydrofuran transforms 2,3 dihydro furan, and (2) are in the presence of an an acidic catalyst, make 2, the 3-dihydrofuran contacts with water, 2,3 dihydro furan is converted into the mixture of 2-hydroxyl tetrahydrofuran and 4-acetaldol.
The invention provides a kind of preparation 2,3-dihydrofuran (2,3-DHF) the method for compounds, this method comprises at elevated temperatures and can increase optionally (i) a kind of aldehyde of amount, it is selected from the alkanal that contains 2-5 carbon atom and contains the chain olefine aldehydr of 3 or 4 carbon atoms, (ii) a kind of epoxide, it is selected from and contains 1 of 2-5 carbon atom, 2-epoxyalkane hydrocarbon and 3,4-epoxy-1-butylene, (iii) carbon monoxide, or (iv) two or more these aldehydes, the mixture of epoxide or carbon monoxide exists down, make 2, (2,5-DHF) compounds is with palladium on the carrier or platinum catalyst contact for the 5-dihydrofuran.The selectivity of the isomerization method that this is new generally surpasses 85% mole, and when in the presence of carbon monoxide, and when operating under the preferably combination of method condition, selectivity generally can be above 95% mole.Those skilled in the art can know that transformation efficiency and selectivity normally are mutually related in catalytic process, and next increase of generalized case causes another to reduce.As the catalyzer of present method, have been found that nickel, rhodium and ruthenium are poorer than the effect of palladium and platinum.
As 2 of reactant or raw material, 5-DHF compounds and 2,3-DHF class product can be to contain at the most the list of 20 carbon atoms-or dicyclo, not compound that replaces or replace in our new method.2,5-DHF and 2, the example of 3-DHF compounds are the compounds with following array structure:
In the formula, each R is selected from hydrogen and C independently of one another
1-C
4Alkyl, or on behalf of formation, 2 R substituting groups can together contain the alkylidene group of 5-8 carboatomic ring.Each R is hydrogen or methyl preferably.Reactant and product preferably contain 7 carbon atoms at most.2, the specific examples of 5-dihydrofuran class reactant comprises 2,5-dihydrofuran, 2,5-dimethyl-2,5-dihydrofuran, 2,2,5-trimethylammonium-2,5-dihydrofuran, 2-methyl-2,5 dihydrofuran, 2,2,3,4,5-pentamethyl--2,5-dihydrofuran etc.In the compound that obtains by the inventive method, the most important thing is 2,3 dihydro furan.
This isomerization method can carried out in the pressure and temperature scope widely.Pressure is not the key character of present method, therefore available a little higher than or pressure below atmospheric pressure.Can use the 1-50 bars absolute, be preferably the 1-30 bars absolute, most preferred is the 1-20 bars absolute.Obviously, the pressure that vapor-phase operation requires to use is wanted synthermal matching, and reactant and product are existed with steam in reactor.The temperature of carrying out isomerization reaction can be 30-200 ℃, is preferably 40-185 ℃, most preferred for 50-175 ℃ in general, the used temperature of platinum catalyst is higher than the used temperature of palladium catalyst.
Can be used for the raising method optionally the example of epoxide and aldehydes comprise compound with following general formula.
In the formula, R
1Be hydrogen, C
1-C
3Alkyl or vinyl, R
2Be C
1-C
4Alkyl, vinyl or allyl group.The specific examples of epoxide and aldehydes comprises 3,4-epoxy-1-butylene (EpB), and oxyethane, propylene oxide, butylene oxide ring, crotonic aldehyde, acetaldehyde, propionic aldehyde, just-butyraldehyde, isobutyric aldehyde, valeral, propenal and vinyl acetaldehyde.These compounds can be to be added to 2 wittingly, in the 5-DHF charging, or are present in the charging as impurity, and for example, 1,3-butadiene can selectively be oxidized to EpB, and it changes into 2 by currently known methods again, 5-DHF.Obtain 2,5-DHF can contain trace or a small amount of crotonic aldehyde and/EpB.
Above-mentioned the epoxide of advantageous effect be can play and/or the consumption of aldehydes alters a great deal, concrete catalyzer and reaction conditions, particularly temperature depended on selectivity, and the operation and the mode that adopt, for example gas phase or liquid phase etc.In general, the consumption by volume of epoxide/aldehyde is gas part cumulative volume of entering reactor (promptly 2 in the charging of isomerization process, the diluent gas of 5-DHF reactant and any existence or liquid) 5-20,000ppmv (umbers in per 1,000,000 parts of volumes), be preferably 10-10,000ppmv, most preferred is 100-5,000ppmv.
When independent use carbon monoxide, when promptly not having one of above-mentioned epoxide or aldehyde, the carbon monoxide consumption that significantly increases catalytic selectivity alters a great deal, it depends on these factors, as concrete catalyzer and reaction conditions, temperature particularly, and the operation and the mode that adopt, for example gas phase or liquid phase.In general, the amount of carbon monoxide accounts for the 5-5000ppmv that enters gas reactor cumulative volume (promptly 2, the diluent gas of 5-DHF reactant and any existence or the volume of liquid) in isomerization reaction.Those skilled in the art can know that the carbon monoxide concentration that liquid-phase operation needs is higher than the carbon monoxide concentration of vapor-phase operation.This is that requirement has the carbon monoxide of suitable concn to be dissolved in the liquid.Therefore, liquid-phase operation is that the concentration of carbon monoxide is preferably under the 100-5000ppmv and carries out in the liquid in entering reactor.In gas phase operation, carbon monoxide concentration is preferably 10-500ppmv, and most preferred is 20-200ppmv.The carbon monoxide typical concentration is about 50ppmv in the raw material in gas phase operation.High-load carbon monoxide tends to provide to desirable 2, and the 3-DHF product has better choice.Yet, if selectivity is too high, 2, the formation speed of 3-DHF can be reduced to unacceptable level.
Carbon monoxide randomly can mix use with one or more above-mentioned epoxide and aldehydes to add strong selectivity.For example, at 2 of these epoxide that only contain trace and/or aldehyde, can add carbon monoxide in the 5-DHF reactant to reach the balance of desired selectivity and transformation efficiency.Obviously, the amount of mixing with one or more above-mentioned epoxide and/or aldehydes and improving the optionally carbon monoxide of catalytic process alters a great deal, depend on following these factors, as 2, the amount of epoxide/aldehyde in the 5-DHF reactant, used concrete catalyzer and reaction conditions, particularly temperature, and the operating method of using, for example gas phase or liquid phase etc.In general, the optional CO content that joins in the charging is about and is fed to that the gas feed cumulative volume (promptly accounts for 2 in the reactor, the any diluent gas or the liquid volume of the volume of 5-DHF reactant and above-mentioned epoxide and/or aldehydes and existence) 5-5,000ppmv.As mentioned above, liquid-phase operation can require the concentration of carbon monoxide to be higher than in the used carbon monoxide concentration of gas phase operation.Therefore, liquid-phase operation requirement carbon monoxide concentration of liquid in being fed to reactor is 5-5000ppmv.In gas phase operation, carbon monoxide concentration is preferably 10-200ppmv, most preferably is 20-100ppmv.The typical concentration of carbon monoxide is 25ppmv in the charging in gas phase operation.As the situation of above-mentioned epoxide/aldehydes, the effect of carbon monoxide also is a reversible, therefore, from process, remove epoxide/aldehydes and carbon monoxide, can make activity of such catalysts return to epoxide/aldehyde and the preceding existing level of carbon monoxide adding.
When using under the concentration in the best, above-mentioned epoxide, aldehydes and/or carbon monoxide can provide highly selective, and can not reduce by 2 basically, the generating rate of 3-DHF, thereby, for under the best common inlet amount of epoxide/aldehyde, having increased by 2,3-DHF to empty productive rate (STY).A special advantage of this novel method is, epoxide, and the effect of aldehyde and/or carbon monoxide is a reversible.Therefore, remove epoxide from process, aldehyde and/or carbon monoxide just can recover activity of such catalysts to adding that level that exists before epoxide/aldehyde.This phenomenon is called reversible Langmuir absorption, and it illustrates that expressly the effect of epoxide/aldehyde is a reversible, and can be controlled by the level of using epoxide/aldehyde in the process.This very ideal characteristics only make that the amount that is added to the epoxide/aldehyde in the charging by change just can improved in the range of operating parameters the performance of catalyzer as required widely.Because catalyst activity generally reduces with the consumption increase of epoxide/aldehyde, and generate desirable 2, the 3-DHF product selectivity improves with the increase of epoxide/aldehyde consumption, so, the consumption that can regulate epoxide/aldehyde in the charging is to select generating 2, the activity of 3-DHF compound and selectivity desired combined.
Usually add the performance characteristic that solid additive improves heterogeneous catalyst on the surface of active catalyst, because it is irreversible mostly, so this method out of true and wayward.Therefore, in a single day this catalyst composition forms, and its concrete operations characteristic also just forms.When feed composition changes, heat transfer condition changes, or when selectivity requires to change in concrete the application, just is starved of a kind of " adjustable " catalyst performance.
The used supported catalyst of the present invention contains palladium, platinum or their mixture, is deposited on metallic forms on the carrier of catalyzer.The consumption of the palladium of catalyzer and/or platinum composition can be 0.1-10% weight, is preferably 0.2-5.0% weight.Particularly preferably be the supported catalyst that contains 0.5-3.0% weight palladium.
The catalyst support material composition is optional from many non-acid, and is traditional, the fire-resistant support of the catalyst of porous, and the reactant that these solid support material replies exist in the reaction process of using catalyzer, product, thinner and carbon monoxide come down to inert.These traditional materials can be natural, or synthetic source, preferably should be mesopore or macroporous structure, promptly surface-area is lower than 100 meters squared per gram (m
2/ g) solid support material.The apparent porosity of these solid support materials is generally greater than 20%.Usually, preferably have siliceous and/or aluminiferous combination carrier.
The specific examples of appropriate carrier is aluminum oxide (comprising the material of selling with trade mark " Alundum "), float stone, magnesium oxide, zirconium white, diatomite, Fuller's earth, silicon carbide, the porous aggregates of siliceous and/or silicon carbide, silica, the clay through selecting, artificial and natural zeolite and pottery.Be specially adapted to that the refractory support of Preparation of catalysts comprises siliceous and/or aluminum in the inventive method, if aluminum, particularly contain the material of Alpha-alumina.Use contains the carrier of Alpha-alumina, and then the tool specific surface area of preferably measuring with the B.E.T method is a 0.03-10 rice
2/ gram, the apparent porosity of measuring with traditional mercury or water absorption method is the material of 25-50% volume.The B.E.T method of measurement the specific area is by Brunauer, S., and Emmett, P.H., and Teller, E., at J.Am .Chem.Soc., 60,309-16 was once gone through in (1938).
Following material is the object lesson of operable support of the catalyst.
I. the star silica supports typically has surface-area 20-80 rice
2/ gram, the cubic capacity 0.3-0.7 milliliter (mercury) in hole/gram: the mean diameter 100-500 micron (μ) in hole, chemical constitution is essentially SiO
2
II.Norton-SN 08228, and surface-area is 0.26 meter
20.1875 inch ball of/gram, the cubic capacity in hole are 0.23 milliliter (mercury)/gram, 19 microns of the mean diameters in hole, tamped density 0.90 gram per centimeter
3, chemical constitution (weight percent): aluminum oxide-84.7, SiO
2-13.4, Fe
2O
3-0.21, TiO
2-0.47, CaO-0.21, MgO-0.12, Na
2O-0.15, K
2O-0.26.
III.Norton SA-5252, surface-area are 0.39 meter
20.1875 inch ball of/gram, 0.36 milliliter of the cubic capacity in hole (mercury)/gram, 5.4 microns of the mean diameters in hole, tamped density 0.94 gram per centimeter
3, chemical constitution (weight percent): Al
2O
3-93.1, SiO
2-5.6, Fe
2O
3-0.3, TiO
2-0.1, CaO-0.1, MgO-0.3, Na
2O-0.1, K
2O-0.1.
0.43 meter of IV.Norton 5552 aluminum oxide ring-surface-area
20.25 inch ring of/gram, 0.37 milliliter of the cubic capacity in hole (Hg)/gram, 7 microns of the mean diameters in hole, tamped density 0.80 gram per centimeter
3, chemical constitution (weight percent): Al
2O
3-93.1, SiO
2-5.6, Fe
2O
3-0.3, TiO
2-0.1, CaO-0.1, MgO-0.3, Na
2O-0.1, K
2O-0.1.
V.Norton SN-82501,0.13 meter of surface-area
20.1875 inch ball of/gram, 0.37 milliliter of the cubic capacity in hole (mercury)/gram, 32.5 microns of the mean diameters in hole, tamped density 0.88 gram per centimeter
3, chemical constitution (weight percent): Al
2O
3-85.0, SiO
2-12.0, remaining 3% is Fe
2O
3, TiO
2, CaO, MgO, Na
2O and K
2O.
Though be not preferred, operable other solid support material comprises zinc oxide, for example surface-area 3-10 rice
2/ gram and size of particles 75-250 micron; Titanium dioxide, for example, 0.5 meter of surface-area
2/ gram, size of particles 40-75 micron; Calcium oxide; Barium oxide, for example surface-area is 1 meter
2/ gram, size of particles 40-75 micron; Boron nitride; And silicon carbide.
The preferred solid support material of one class comprises the star silica supports of extruding, and this carrier has more uniform aperture and more identified that fully (1) B.E.T. surface-area is 20 meters
2-80 meters of/grams
2/ gram is preferably 70 meters
2/ gram, (2) apparent porosity is 20%-70%, is preferably 30-60%.
The actual physics form of support of the catalyst is not a particularly important.The form of support of the catalyst is to almost not influence of catalyst activity, but consideration from practicality, as conduct heat, whether mass transfer easy, because the efficient of gas-liquid-solid contact falls in the pressure of fluid flow restriction, life of catalyst etc., the then preferred carrier of determining shape that uses, star for example, sphere, the ball shape, extrudate, ring, saddle type etc.
Carry out method of the present invention and can in reactor, feed 2 in vapour phase, the 5-DHF reactant, the epoxide of one or more above-mentioned discussion and/or aldehydes or carbon monoxide, and/or a kind of mixture of inert gasiform thinner, this reactor contains one or more catalyzer of one or more layers above-mentioned discussion.If in operating process, in reactor, do not feed inert diluent, can be reduced at the separation of reactant/product from reactor behind the downstream.Use thinner with and consumption depend on many factors, wherein the concrete design or the structure that comprise reactor are because the heat that isomerization process produces must be removed from reactor.The example of operable thinner comprises helium, argon, krypton, neon, carbonic acid gas, nitrogen and/or one or more C
1-C
8Paraffinic hydrocarbons.Thinner: 2, the volume ratio of 5-DHF reactant can be 1: 10-1: 0.02, and more typical volume ratio is 1: 1-1: 0.1.With United States Patent (USP) 3,651, the method difference of discussing in 092, method of the present invention preferably substantially do not have hydrogen and carry out under existing, and for example, are not wittingly hydrogen to be joined 2, in 5-DHF reactant and/or the optional thinner.
Gas hourly space velocity (GHSV) used in the vapor-phase operation of present method generally is 100-10,000, and preferably 200-8000, most preferably 300-5000.GHSV is gas (reactant the adds used any thinner) volume that per hour the feeds reactor volume divided by the catalyzer that exists in the reactor.When other process parameter is identical, 2 of charging, the 5-DHF reactant is to requirement product 2, and the transformation efficiency of 3-DHF is inversely proportional to used GHSV.Like this, desired transformation efficiency has determined used GHSV.
Present method also can be operated in liquid phase.One of pattern of liquid-phase operation comprises, in reactor, feed and contain liquid 2, the 5-DHF reactant, epoxide, aldehyde and/or atmospheric CO and be the biphase liquid mixture of the inert diluent of liquid under present method condition contain one or more catalyzer of one layer or more in the reactor.Be called in the pattern of overflow bed operation one, liquid mixture is on catalyzer, for example with upward to flowing.Thinner suitable in this liquid-phase operation is 2 of present method, and the 3-DHF product can send in the liquid-phase operation of present method 2,5-DHF: 2, and the typical weight ratio of 3-DHF is 1: 10-1: 0.1.
In another liquid-phase operation pattern, will contain 2, the 5-DHF reactant, the mixture of atmospheric CO and the steam state inert diluent of choosing wantonly is passed into liquid inert diluent or reaction medium, and for example paraffinic hydrocarbon in mineral oil, therein, is suspended with catalyzer.Product 2,3-DHF removes from liquid reaction medium as steam.
Further specify method of the present invention by the following examples.The method of embodiment has been used the reactor that is made of the Pyrex Glass tubing of once-through vapour phase.The catalyst charge place is fixed on the desired location by the Pyrex frit.Geometrical shape of selecting reactor (10 millimeters internal diameters) and granules of catalyst (0.4-0.8 mm dia) are with the real kinetics and the catalytic performance of maintenance and assaying reaction.The thermopair (nickel chromium triangle/alumel) that is loaded in the stainless steel sleeve is embedded in the catalyst bed to measure real temperature of reaction.Reactor is equipped with the supported catalyst of 1.0-2.0 gram.
Be blown into helium through remaining on preset temperature, be generally 20 ℃ 2, the 5-DHF liquid reservoir, with 2,5-DHF steam and helium are added in the charging, make 2,5-DHF: the volume ratio of helium changed between 1: 20 to 1: 4.From each steam-fluid balance saturex that remains on proper temperature and flow velocity, also add EpB or crotonic aldehyde, make the concentration of the EpB/ crotonic aldehyde in the charging reach requirement.Application is connected to the mass of the electron flow director of the gas supply device that contains the 1000ppmv carbon monoxide in helium, and carbon monoxide is infeeded in the charging.By controlling 2,5-DHF, above-mentioned epoxide/aldehydes, the flow rate of gas of carbon monoxide/helium mixture is to determine the actual amount of carbon monoxide in the charging in total the flowing of helium and carbon monoxide.In these cases, general 2,5-DHF concentration used concentration when in charging, not adding carbon monoxide.Be used for 2 of each embodiment, 5-DHF is highly purified, and does not contain the organic composition that other can detect.All air-flows are carried by mass flow controller.
Gas chromatographic analysis adopts the gas sampling valve of in-line to carry out, and this makes can be to all analyzing at catalyst bed air-flow up and down.All reactor feeds and discharging pipeline all heat at 100 ℃, to prevent the condensation of charging and/or discharging material.The logical comparison that air-flow above the catalyst bed and following is formed is to measure transformation efficiency.Carry out gas chromatogram with 10 feet (3.05 meters) long Pyrex glass column (2 millimeters internal diameters) and separate, the Carbowax 20M (20%) that it is carrier that the Pyrex glass column is equipped with the red diatomite chromatogram W with pickling.The nonselective by product that generates in this process is mainly furans and tetrahydrofuran (THF), and both amounts are almost equal.Embodiment 1-4 and comparative example C-1 and C-2
According to above-mentioned vapor-phase process, consist of 2 in 90 ℃ of temperature of reaction and feeding gas, the EpB and the carbon monoxide of 5-DHF and helium and different amounts do not contain EpB and/or carbon monoxide in the comparative example, make 2, and 5-DHF is converted into 2,3-DHF.Used catalyzer (1.25 gram) is made up of the palladium that with the silicon-dioxide extrudate is 1.0% weight of carrier.The gaseous mixture of forming with the helium of the hydrogen of 20% volume and 80% volume was 225 ℃ of on-the-spot disposal catalyzer 2.0 hours.2 of feeding gas, 5-DHF: the ratio of the cumulative volume of helium is 1: 15.2,5-DHF is added in the reactor with the speed of per minute 0.043 gram.The time that the experiment of embodiment 1-4 and comparative example C-1 and C-2 is carried out answers sufficiently long to reach steady state condition.
What obtain in these embodiments the results are shown in Table I, and wherein, the value of " EpB " and " CO " respectively does for oneself in the unstripped gas 3, the ppmv concentration of 4-epoxy-1-butylene and carbon monoxide, and " 2,5-DHF Conv " are 2,5-DHF molar percentage transformation efficiency is defined as:
And " 2,3-DHF Select " be to select to be converted into 2, and the molar percentage of 3-DHF is defined as:
Table I
2，5-DHF 2，3-DHF
Embodiment
EpB
CO
Conv
Select
C-1 0 25 98.0 91.7
1 220 25 76.2 96.8
2 630 25 59.4 97.9
3 1400 25 46.5 97.5
C-2 0 0 100.0 79.0
4 800 0 60.0 96.8
Table I shows the epoxide of various content, and as 3,4-epoxy-1-butylene (EpB) is being added with and is not adding under the carbon monoxide in the presence of palladium catalyst, and to 2,5-DHF is converted into 2, the influence of 3-DHF.Reach 97-98% in the selectivity level that is added with or do not add 2,3 dihydro furan under the carbon monoxide.EpB and carbon monoxide be added-time not, and selectivity is lower, and in the presence of EpB and carbon monoxide mixtures, compares with the situation of having only carbon monoxide, and selectivity is improved.Because EpB is the same with carbon monoxide, work with identical reversible manner.So, when the EpB of q.s exists, can from charging, remove carbon monoxide
Embodiment 5-10 and comparative example C-3 and C-4
The method that the foregoing description is used is used among embodiment 5-10 and comparative example C-3 and the C-4, and different is the crotonic aldehyde of use different amounts, rather than EpB.The used fresh catalyst charge (1.25 gram) of embodiment 5-10 and comparative example C-3 and C-4 is to use the aforesaid method activatory.These embodiment obtained the results are shown in Table II, and wherein " Croton " is the ppmv concentration of crotonic aldehyde in the unstripped gas, and " CO ", " 2,5-DHF Conv " and " 2,3-DHFSelect " have the given meaning in front.
Table II
2，5-DHF 2，3-DHF
Embodiment
Croton
CO
Conv
Select
C-3 0 0 100.0 31.6
5 620 0 68.7 95.6
6 1380 0 55.5 96.0
7 1970 0 49.5 96.2
C-4 0 55 88.9 93.3
8 530 55 68.4 94.9
9 1040 55 58.1 95.7
10 2070 55 44.2 95.9
Table II shows, in the presence of fresh pretreated and activatory palladium catalyst with hydrogen and helium mixture, when being added with or do not add carbon monoxide, the different crotonic aldehydes of measuring are to 2, and 5-DHF is converted into 2, the influence of 3-DHF.Comparative example C-3 shows that in the presence of no crotonic aldehyde or carbon monoxide, the selectivity that generates 2,3 dihydro furan is very low.Comparative example C-4 proves to have only carbon monoxide to exist, and can improve selectivity.But, when carbon monoxide mixes with crotonic aldehyde (embodiment 8-10) or when the crotonic aldehyde of a large amount replaces carbon monoxide (embodiment 5-7) together slightly, can make selectivity that bigger raising is arranged.These data show, carbon monoxide and crotonic aldehyde have similar influence to the performance of catalyzer.Like this, can be used as feed impurities or additive is offset by the amount of crotonic aldehyde, to reach to 2,3 dihydro furan transformation efficiency and the desired balance of the best optionally as the actual amount of the carbon monoxide of charging additive.
Embodiment 11-18 and comparative example C-5 and C-6
Be used in supported catalyst 1.25 grams that contain 1.0% weight palladium composition on the silicon-dioxide extrudate, with 2,5-DHF is converted into 2 according to above-mentioned vapor-phase process, 3-DHF.Consisting of of unstripped gas: by 2,5-DHF: the helium volume ratio be 1: 15 2,5-DHF and helium, and the carbon monoxide of different amounts, and in the comparative example, do not contain carbon monoxide.With 2,5-DHF sends into reactor with the speed of per minute 0.043 gram.The experiment that comprises embodiment 11-18 and comparative example C-5 and C-6 is carried out the sufficiently long time to reach steady state condition.
What obtain among these embodiment the results are shown in Table III, and wherein " Rxn Temp " is with being embedded in temperature of reaction that the thermopair in the catalyst charge measures degree centigrade to represent; " CO ", " 2,5-DHF Conv " and " 2,3-DHF Select " have the meaning that provides above; " ProdRate " is that " 2, the generation speed of 3-DHF " are measuring of total output, be defined as that every gram catalyzer per hour produces 2, the gram number of 3-DHF.
Table III
Rxn 2，5-DHF 2，3-DHF Prod
Embodiment
Temp
CO
Conv
Select
Rate
C-5 90.9 0 100 72.5 1.45
11 90.8 10 99.3 88.3 1.75
12 90.6 25 98.2 91.5 1.80
13 90.2 50 96.0 94.7 1.80
14 90.2 100 88.4 96.2 1.70
15 90.0 205 44.0 98.0 0.86
C-6 82 0 98.5 69.0 1.36
16 82 35 64.2 94.6 1.22
17 82 134 30.2 96.5 0.58
18 82 490 7.2 98.0 0.14
Table III shows, even carbon monoxide on the 490ppmv level, is being united with the 1.0%Pd/ SiO 2 catalyst when using 2,5-DHF is converted into 2, and 3-DHF still has the effect of promotor.In the presence of high-load carbon monoxide, demonstrate 98% 2, the selectivity level of 3-DHF.When carbon monoxide did not exist, then comparative example 5 and comparative example's 6 proof selectivity were much lower.Embodiment 11-14 shows, carbon monoxide content at 10-100ppmv to obtaining very ideal space time yield.Obviously, use the carbon monoxide of higher concentration, can produce very high selectivity but lower transformation efficiency, need usually to reclaim and recirculation unreacted 2,5-DHF.
Embodiment 19-25
Embodiment 19-25 has used the used method of front embodiment and catalyzer (1.25 gram), the gas feed that different are to use be by three kinds different 2,5-DHF: the helium volume ratio is formed.These embodiment obtain the results are shown in Table IV, wherein, and " Rxn Temp ", " CO ", " 2,5-DHFConv " and " 2,3-DHF Select " have the meaning that provides above, and " DHF: He " is for feeding 2 of gas reactor, 5-DHF: helium volume ratio.
Table IV
Rxn 2, and 5-DHF 2,3-DHF
Embodiment Temp CO DHF: He Conv Select
19 86 91 1∶19 80 97.7
20 86 130 1∶19 76 98.2
21 93 90 1∶10 90 94.0
22 90 111 1∶10 82 96.0
23 88 115 1∶5 66 96.8
24 93 115 1∶5 80 94.9
25 97 115 1: 5 93 91.0
Embodiment 26-28 and comparative example C-7 and C-8
The method that repetition is discussed in embodiment 11-18 and comparative example C-5 and C-6, different is, the palladium catalysts on the supported catalyst replacement vector of being made up of the platinum on the silicon-dioxide extrudate of 1.0% weight with 1.2 grams.The resulting Table V that the results are shown in of these embodiment, wherein, " Rxn Temp ", " CO ", " 2,5-DHF Conv ", " 2,3-DHFSelect " and " Prod Rate " have the meaning that provides above.
Table V
Rxn 2, and 5-DHF 2,3-DHF Prod
Embodiment Temp CO Conv Select Rate
C-7 144 0 34.3 82.9 0.57
C-8 168 0 54.5 77.2 0.82
26 144 50 21 85.4 0.36
27 144 100 19.8 89.3 0.35
28 168 50 54.1 80.2 0.87
Table V shows that carbon monoxide has favorable influence to the selectivity of 2,3 dihydro furan under two groups of temperature (144 ℃ and 168 ℃), but the activity of platinum catalyst is lower than palladium catalyst.As in the catalytic isomerization situation of palladium, non-selective product is furans and tetrahydrofuran (THF), and both are equivalent almost.
Comparative example C-9-C-14
The method that repetition is discussed in embodiment 11-18 and comparative example C-5 and C-6, different is, the palladium catalyst on the alternative carrier of forming with the nickel on the silica/alumina by 50.0% weight of 2.2 grams of supported catalyst.The gaseous mixture of forming by the helium of the hydrogen of 40% volume and 60% volume at 250 ℃ by catalyzer 2 hours deactivated catalyst on the spot.What obtain in these embodiments the results are shown in Table VI, wherein, and " Rxn Temp ", " CO ", " 2,5-DHF Conv ", " 2,3-DHF Select " and " Prod Rate " have top given meaning.
Table VI
Rxn 2，5-DHF 2，3-DHF Prod
Embodiment
Temp
CO
Conv
Select
Rate
C-9 104 0 63.3 82.2 0.55
C-10 104 25 61.5 85.1 0.55
C-11 104 50 57.3 85.4 0.52
C-12 104 100 47.0 86.0 0.43
C-13 86 0 44.2 88.0 0.41
The present invention is described in detail by concrete preferred embodiment, still, can be understood as, and within the spirit and scope of the present invention, can carry out changes and improvements.
Claims (10)
1. prepare 2, the method of 3-dihydrofuran compounds, this method comprises makes 2 at elevated temperatures, 5-dihydrofuran compounds contacts with palladium on the carrier or platinum catalyst with the incoming mixture of a certain amount of following substances that selectivity is increased, described these materials are: a kind of aldehyde, and it is selected from the alkanal that contains 2-5 carbon atom and contains the chain olefine aldehydr of 3 or 4 carbon atoms; A kind of epoxide, it is selected from the 1 hydrocarbon and 3 that contains 2-5 carbon atom, 4-epoxy-1-butylene; Carbon monoxide; Or two or more these aldehyde, the mixture of epoxide or carbon monoxide.
2. the process of claim 1 wherein that this method is carried out under 30-200 ℃ temperature, raw mix contains 10-10, the epoxide of 000ppm volume, aldehyde or their mixture and 2,5-dihydrofuran and 2,3 dihydro furan compounds, both respectively contain 7 carbon atoms at the most the back.
3. the method for claim 1, wherein, this method is carried out under 40-185 ℃ temperature, raw mix contains 3 of 100-5000ppm volume, 4-epoxy-1-butylene or crotonic aldehyde and 2,5-dihydrofuran and 2,3 dihydro furan compounds, both respectively contain the back at the most 7 carbon atoms and have following general formula:
Wherein, each R is independently selected from hydrogen and methyl.
4. the method for claim 3, wherein, raw mix also contains the carbon monoxide of 10-200ppm volume.
5. the process of claim 1 wherein that unstripped gas contains 2, the 5-dihydrofuran, inert diluent, and 10-10,3 of 000ppm volume, 4-epoxy-1-butylene or crotonic aldehyde, they contact with the palladium catalyst on the carrier under temperature 30-200 ℃.
6. the process of claim 1 wherein that unstripped gas contains 2, the 5-dihydrofuran, inert diluent, 3 of 100-5000ppm volume, the carbon monoxide of 4-epoxy-1-butylene or crotonic aldehyde and 10-200ppm volume, they contact with the palladium catalyst on the carrier under 30-200 ℃ temperature.
7. the method for claim 1, wherein unstripped gas contains 2, the 5-dihydrofuran, inert diluent, 3 of 100-5000ppm volume, the carbon monoxide of 4-epoxy-1-butylene or crotonic aldehyde and 20-200ppm volume, their palladium catalysts on the carrier that contains 0.5-3.0% weight palladium on the catalyst support material that coexists under 50-175 ℃ the temperature contact.
8. the process of claim 1 wherein that unstripped gas contains 2, the 5-dihydrofuran, inert diluent, and 10-500ppm volume carbon monoxide, they contact with the palladium catalyst on the carrier under temperature 30-200 ℃.
9. the process of claim 1 wherein that raw material liq contains 2, the 5-dihydrofuran, the carbon monoxide of inert diluent and 100-5000ppm volume, they contact with the palladium catalyst on the carrier under temperature 30-200 ℃.
10. the method for claim 1, wherein unstripped gas contains 2,5-dihydrofuran, inert diluent, with 20-200ppm volume carbon monoxide, their palladium catalysts on the carrier that contains 0.5-3.0% weight palladium on the catalyst support material that coexists under temperature 50-175 ℃ contact.
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|---|---|---|---|
| CN 96192692 CN1179154A (en) | 1995-01-31 | 1996-01-18 | Preparation of 2, 3 -dihydrofurans compounds |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/381,594 | 1995-01-31 | ||
| US08/381,595 | 1995-01-31 | ||
| CN 96192692 CN1179154A (en) | 1995-01-31 | 1996-01-18 | Preparation of 2, 3 -dihydrofurans compounds |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633754A (en) * | 2012-03-28 | 2012-08-15 | 南开大学 | Method for preparing high-purity 2, 5-dihydrofuran by modified nano alumina catalyst |
| CN114349616A (en) * | 2022-01-10 | 2022-04-15 | 上海巽田科技股份有限公司 | Method for preparing cyclopropane formaldehyde |
| CN114685404A (en) * | 2020-12-25 | 2022-07-01 | 南通泰禾化工股份有限公司 | Preparation method of 2, 3-dihydrofuran intermediate for preparing cyclopropanecarboxaldehyde |
-
1996
- 1996-01-18 CN CN 96192692 patent/CN1179154A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633754A (en) * | 2012-03-28 | 2012-08-15 | 南开大学 | Method for preparing high-purity 2, 5-dihydrofuran by modified nano alumina catalyst |
| CN102633754B (en) * | 2012-03-28 | 2014-02-05 | 南开大学 | Method for preparing high-purity 2, 5-dihydrofuran by modified nano alumina catalyst |
| CN114685404A (en) * | 2020-12-25 | 2022-07-01 | 南通泰禾化工股份有限公司 | Preparation method of 2, 3-dihydrofuran intermediate for preparing cyclopropanecarboxaldehyde |
| CN114349616A (en) * | 2022-01-10 | 2022-04-15 | 上海巽田科技股份有限公司 | Method for preparing cyclopropane formaldehyde |
| CN114349616B (en) * | 2022-01-10 | 2023-12-26 | 上海巽田科技股份有限公司 | Process for preparing cyclopropanecarboxaldehyde |
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