CN102911011A - Method for preparing 1,5-pentadiol by means of selective hydrogenolysis of tetrahydrofurfuryl alcohol - Google Patents
Method for preparing 1,5-pentadiol by means of selective hydrogenolysis of tetrahydrofurfuryl alcohol Download PDFInfo
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Abstract
The invention relates to a novel A-B/X or A/X supported catalyst for preparing 1,5-pentadiol by means of selective hydrogenolysis of tetrahydrofurfuryl alcohol obtained from forestry and agricultural residues. The component A refers to one or more of precious metals Ir, Pt and Pd, the auxiliary B refers to one or more of Mo, Re and W, and the carrier X refers to any one of SiO2, activated carbon and SiO2-Al2O3. The capacity of the precious metal A in the catalyst is 0.5-10%, the molar ratio of the auxiliary B to the precious metal A is 0.0-1.0, the reaction pressure is 2-20MPa, and the reaction temperature is 80-150 DEG C. The catalyst has the advantages of mild reaction conditions, high reactivity and high selectivity, and a novel effective way for preparation of 1,5-pentadiol from biomass of forestry and agricultural residues is provided.
Description
Technical field
The present invention relates to a kind of will be tetrahydrofurfuryl alcohol that raw material obtains prepares 1,5-PD by the selectivity hydrogenolysis novel method by agriculture and forestry organic waste material.Adopt specifically A-B/X or A/X loaded catalyst, in the non-oil, the renewable preparation approach that prepare 1,5-PD than realization under the mild conditions from the agriculture and forestry organic waste material biomass.
Background technology
Along with the worsening shortages of world's fossil resource, oil price constantly increases, and the renewable energy source chemical synthetic route that exploitation has high economic value added and high energy gamma source utilising efficiency is imperative.Biomass are unique reproducible carbon sources, and from unedible agricultural abandoned biomass, selectivity efficient transforms and obtains the focus that energy chemical becomes present research.Utilize the hyperoxic characteristics of biomass, it optionally can be converted into the dibasic alcohol that there is hydroxyl the end.Because this class dibasic alcohol has the normal carbon chain structure, can be used as the monomer of polyester and urethane, have broad application prospects.1,5-PD is wherein a kind of.
1,5-PD is important chemical intermediate, is widely used in the products such as polyester, urethane, softening agent, coating, spices.At present, in the prior art there be the production method about 1,5-PD:
1) at normal temperatures and pressures photochemical catalytic oxidation of cyclopentadiene makes epoxypentenal, through 70-100 ℃, approximately hydrogenation obtains 1,5-PD under the condition of 6MPa again, because problems such as the design of photooxidation reaction device, light source life and constant product quality, suitability for industrialized production is very limited;
2) Chinese patent CN1565728A has reported that with 1,5-Methyl glutarate be raw material, produces 1,5-PD under the CuZnAl catalyst effect.Its temperature of reaction is 150-350 ℃, and reaction pressure is 3-5MPa.This route need to be to reaction raw materials 1, and the 5-pentanedioic acid carry out purifying, hydrogenation, so reaction process is longer through esterification treatment again;
3) Chinese patent CN101225022A and Chinese patent CN101270032A have reported that respectively 5-glutaraldehyde hydrogenation is produced 1,5-PD with Ni based two-component loaded catalyst and loading type Ru catalyst 1.This class temperature of reaction is 60-120 ℃, and reaction pressure is 2.0-8.0MPa, and the security of the method is good, and by product is few, and shortcoming is that raw material resources are not abundant and price is high.
In sum, produce in the method for 1,5-PD, mainly take the petrochemical complex product as raw material, petroleum resources are had very strong dependency.So, have certain economic value from biomass agriculture and forestry organic waste material preparation 1,5-PD, also can alleviate the pressure to the fossil energy demand.
Furfural is the product (common hemicellulose has: cereal shell, bagasse, corn cob, sunflower seed shell etc.) of crop by-product hydrolysis of hemicellulose.World's furfural annual production is larger, and annual approximately 280,000 tons, wherein half originates from China.Owing to lacking the post-treatment technology to furfural, the furfural major part that China produces exports to foreign countries, and profit is lower, therefore has to be developed furfural effectively to be utilized technology.Not only can take full advantage of biomass resource from furfural preparation 1,5-PD, also alternative production line take oil as raw material obtains the chemical of high value.Furfural 1,5-PD processed can be realized by following two kinds of methods:
1) furfural obtains furfuralcohol through preliminary hydrogenation, furfuralcohol direct hydrogenation under copper chromite catalysis obtains 1,5-PD, and this reacts 1,5-pentanediol selectivity is low by approximately 30%, primary product is 1,2-pentanediol, does not therefore have industrial value (H.Adkins, R.Connor, J.Am.Chem.Soc.1931,53,1091);
2) prepare 1,5-PD by furfural complete hydrogenation product tetrahydrofurfuryl alcohol.In initial report, synthetic 1,5-PD needed through three steps take tetrahydrofurfuryl alcohol as raw material: at first tetrahydrofurfuryl alcohol is at Al
2O
3Effect is lower to generate dihydropyrane, and dihydropyrane obtains the 5-hydrogenation of hydroxypentylaldehyd, through hydrolysis, and last 5-hydrogenation of hydroxypentylaldehyd, generates 1,5-PD under the copper chromite shortening.Although the method has overcome the low problem of selectivity of product, carry out separating-purifying owing to need to each be gone on foot reaction product, reactions steps complicated (L.E.Schniepp, H.H.Geller, J.Am.Chem.Soc.1946,68,1646).Nearest Japanese Tomishige seminar finds the Rh/SiO that utilizes Re or Mo to promote
2Catalyzer is catalysis tetrahydrofurfuryl alcohol hydrogenolysis system 1 effectively, 5-pentanediol (S.Koso, I.Furikado, A.Shimao, T.Miyazawa, K.Kunimori, K.Tomishige, Chem.Comm.2009,2035), reaction is carried out in the intermittent type tank reactor, and reaction pressure is 8MPa, 120 ℃ of temperature of reaction.But because precious metal Rh is expensive, limited the application of this catalyzer in industry.Therefore, need a kind of high reactivity, highly selective and moderate catalyzer, to realize from the industrial application of biomass preparation 1,5-PD.
Summary of the invention
The object of the present invention is to provide a kind of tetrahydrofurfuryl alcohol to select hydrogenolysis to prepare the method for 1,5-PD.
The present invention is achieved by the following technical solutions:
A kind of tetrahydrofurfuryl alcohol selectivity hydrogenolysis prepares the method for 1,5-PD,
Adopt A/X or A-B/X loaded catalyst, wherein A is any or multiple among precious metal Ir, Pt, the Pd; B is any or multiple among Mo, Re, the W; Carrier X is SiO
2, gac, SiO
2-Al
2O
3In any, the charge capacity of A is 0.5-10% in the loading type A-B/X catalyzer, is preferably 2-4%, the mol ratio of auxiliary agent B and A is 0.0-1.0 in the catalyzer, is preferably 0.05-0.5.
Described loaded catalyst A-B/X or A/X adopt the pickling process preparation, at first the soluble salt solution with A floods than the medium volume of the carrier X that is added in advance moulding by metering, (80-120 ℃, 6-24 hour) is again with the soluble salt solution incipient impregnation that contains the auxiliary agent B element after drying, aging 6-12 hour, final drying (80-120 ℃, 6-24 hour), 300-600 ℃ roasting 2-5 hour made.
This catalyzer needs before use in the reduction of hydrogen situ, and reductive condition is hydrogen pressure 0.1MPa-10MPa, is preferably 2-8MPa; Hydrogen/catalyst volume air speed 800-1500h
-1, be preferably 800-1000h
-1Reduction temperature 120-350 ℃, be preferably 180-250 ℃; Recovery time is 1-10 hour, is preferably 2-4 hour.
The reactive mode that the method adopts is intermittent type still reaction or the reaction of fixed bed moving phase, wherein the batch reactor reaction conditions is: the tetrahydrofurfuryl alcohol concentration of aqueous solution is 5-100%, temperature of reaction 80-150 ℃, is preferably 100-140 ℃, hydrogen pressure 2-20MPa is preferably 2-8MPa; Reaction times 2-24 hour, be preferably 2-6h.
Reaction condition of carrying out in fixed bed moving phase reaction device is: the tetrahydrofurfuryl alcohol concentration of aqueous solution is 5-100%, temperature of reaction 80-150 ℃, be preferably 100-140 ℃, and hydrogen pressure 2-20MPa is preferably 2-8MPa; Liquid material/the catalyst quality air speed is 0.6-2h to moving phase reaction device tetrahydrofurfuryl alcohol
-1, be preferably 0.6-1h
-1Hydrogen/catalyst volume air speed is 600-1000h
-1, be preferably 800-1000h
-1
When this catalyzer prepared 1,5-PD for the tetrahydrofurfuryl alcohol hydrogenolysis, reactive behavior was good, selectivity is high, and mild condition is for the preparation 1,5-PD provides a kind of new biomass approach.
Embodiment
Embodiment 1-8
Preparation catalyst
10% the soluble salt solution that will contain A is added in the carrier according to certain metering ratio and floods, and under the room temperature aging 12 hours, then in 120 ℃ of baking ovens dry 12 hours; Take by weighing again the soluble salt solution of B component by certain B/A mol ratio, be added in the above-mentioned carrier that has flooded after the A component, under room temperature aging 12 hours, then lower dry 12 hours at 120 ℃, roasting is 3 hours in 500 ℃ of lower air, obtains loading type A-B/X catalyzer.The composition of catalyzer among each embodiment, the starting material kind of component A, B sees Table 1.
Each catalysis of table 1. forms
Embodiment 8
Catalyst activity is estimated
Evaluating catalyst of the present invention carries out in fixed bed moving phase reaction device, and reactor is external diameter 6mm, the stainless steel tube of long 360mm.Experimentation is as follows: the 2g catalyst loading to reaction tubes, is reduced 200 ℃ of reduction temperatures, H to the catalyzer original position before the reaction
2Pressure is 6MPa, H
2Flow velocity 160mL/min is with this understanding to catalyst reduction 2 hours.Reduction is down to temperature of reaction after finishing, control H
2Flow is 60mL/min, and tetrahydrofurfuryl alcohol liquid material flow velocity is 0.04mL/min, regulates pressure to required reaction pressure, reacts sampling analysis after 6 hours.
(1) different precious metals to tetrahydrofurfuryl alcohol hydrogenolysis specific activity, activity rating the results are shown in Table 2.
The different precious metals of table 2 are to tetrahydrofurfuryl alcohol hydrogenolysis activity influence
Annotate: reaction pressure is 6MPa, Mo/A=0.13 in each catalyzer (A=Ir, Pt, Pd), and tetrahydrofurfuryl alcohol concentration is 20%, gas-phase product (methane, pentane etc.) represents with " other ".
As can be seen from Table 2, Ir-Mo/SiO
2Catalyzer is the highest to tetrahydrofurfuryl alcohol hydrogenolysis transformation efficiency, and to the yield the highest (50.3%) of 1,5-PD.While Pt-Mo/SiO
2, Pd-Mo/SiO
2Catalyzer has higher selectivity to 1,5-PD, but the transformation efficiency of tetrahydrofurfuryl alcohol is lower.
(2) different auxiliary agents are on the impact of catalyst activity, and comparative result sees Table 3.
The different auxiliary agents of table 3 affect catalyst activity
Annotate: reaction pressure is 6MPa, and tetrahydrofurfuryl alcohol concentration is 20%, B/Ir=0.13 in each catalyzer (B=Mo, Re, W).
As can be seen from Table 3, when Mo made auxiliary agent, catalyst activity was best, Re, when W makees auxiliary agent 1,5-PD was also had higher selectivity, but transformation efficiency is lower.
(3) different carriers is on the impact of catalyst activity, and comparative result sees Table 4.
Table 4 carrier is on the impact of tetrahydrofurfuryl alcohol hydrogenolysis activity
Annotate: reaction pressure is 6MPa, and tetrahydrofurfuryl alcohol concentration is 20%, Mo/Ir=0.13 in each catalyzer.
As can be seen from Table 4, adopt SiO
2When doing carrier with activated carbon, catalyst activity is best.
(4) Ir-Mo/SiO
2Catalyzer the results are shown in Table 5 to the active contrast of different concns tetrahydrofurfuryl alcohol hydrogenolysis.
Catalyst activity property testing under the different tetrahydrofurfuryl alcohol concentration of table 5
Annotate: reaction pressure is 6MPa, and catalyst system therefor is 4%Ir-Mo/SiO
2(Mo/Ir=0.13).
With the increase of reactant concn, this catalyzer increases the selectivity of 1,5-PD, shows good catalytic activity.
(5) Ir-Mo/SiO under the different hydrogen pressure
2Catalyzer to tetrahydrofurfuryl alcohol hydrogenolysis specific activity the results are shown in Table 6.
Table 6 hydrogen pressure is to tetrahydrofurfuryl alcohol hydrogenolysis activity influence
Annotate: tetrahydrofurfuryl alcohol concentration is 20%, and catalyst system therefor is 4%Ir-Mo/SiO
2(Mo/Ir=0.13).
Even under lower pressure, this catalyzer also has good selectivity to 1,5-PD.
Under high pressure, then show preferably the tetrahydrofurfuryl alcohol transformation efficiency and to the 1,5-PD yield.
Embodiment 12
The catalyst stability test
To 4%Ir-Mo/SiO
2(Mo/Ir=0.13) catalyzer has been done stability test, the results are shown in Table 7.
The test of table 7 catalyst stability
Annotate: reaction pressure 6MPa, tetrahydrofurfuryl alcohol concentration is 20%, catalyst system therefor is 4%Ir-Mo/SiO
2(Mo/Ir=0.13).
This catalyzer is behind 24 hours active testings, and transformation efficiency and selectivity tend towards stability, and with the carrying out of reaction, catalyzer increases gradually to the selectivity of 1,5-PD, illustrates that this catalyzer has satisfactory stability.
Claims (5)
1. a tetrahydrofurfuryl alcohol selectivity hydrogenolysis prepares the method for 1,5-PD, it is characterized in that:
Adopt A-B/X or A/X loaded catalyst, wherein A is any or multiple among precious metal Ir, Pt, the Pd; B is any or multiple among Mo, Re, the W; Carrier X is SiO
2, gac, SiO
2-Al
2O
3In any, the charge capacity of A is 0.5-10% in the loading type A-B/X catalyzer, the mol ratio of auxiliary agent B and A is 0.0-1.0 in the catalyzer.
2. method according to claim 1, it is characterized in that: described loaded catalyst A-B/X or A/X adopt the pickling process preparation, at first the soluble salt solution with A floods than the medium volume of the carrier X that is added in advance moulding by metering, after drying again with the soluble salt solution incipient impregnation that contains the auxiliary agent B element, aging 6-12 hour, final drying also made in 300-600 ℃ of roasting 2-5.
3. method according to claim 1 is characterized in that: this catalyzer needs before use in the reduction of hydrogen situ, and reductive condition is that hydrogen pressure is 0.1-10MPa, hydrogen/catalyst volume air speed 800-1500h
-1, reduction temperature 120-350 ℃, the recovery time is 1-10h.
4. method according to claim 1 is characterized in that: reaction is carried out in batch reactor, and the tetrahydrofurfuryl alcohol concentration of aqueous solution is 5-100%, and temperature of reaction 80-150 ℃, hydrogen pressure 2-20MPa, reaction times 2-24 hour.
5. method according to claim 1 is characterized in that: reaction is carried out in fixed bed moving phase reaction device, and the tetrahydrofurfuryl alcohol concentration of aqueous solution is 5-100%, and temperature of reaction 80-150 ℃, hydrogen pressure 2-20MPa; Liquid material/the catalyst quality air speed is 0.6-2h to moving phase reaction device tetrahydrofurfuryl alcohol
-1, hydrogen/catalyst volume air speed is 600-1000h
-1
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Cited By (10)
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|---|---|---|---|---|
| CN103265400A (en) * | 2013-05-28 | 2013-08-28 | 华东理工大学 | Environment-friendly novel method for preparing primary alcohol from furan or tetrahydrofuran derivatives |
| CN103977796A (en) * | 2014-05-18 | 2014-08-13 | 华东理工大学 | Catalyst used in preparation of long-chain alkane through catalytic hydrodeoxygenation of biomass |
| JP2015003892A (en) * | 2013-06-24 | 2015-01-08 | 宇部興産株式会社 | Method for producing polyol compound |
| CN108620127A (en) * | 2017-03-23 | 2018-10-09 | 万华化学集团股份有限公司 | A kind of catalyst and preparation method and applications of tetrahydrofurfuryl alcohol hydrogenolysis 1,5- pentanediols |
| CN109590013A (en) * | 2018-12-21 | 2019-04-09 | 广东工业大学 | A kind of biomass loaded catalyst and preparation method thereof adding hydrogen for open loop |
| CN109896921A (en) * | 2017-12-07 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of method that Containing Sulfur molybdenum catalyst is used for tetrahydrofurfuryl alcohol catalytic hydrogenation 1,5- pentanediol |
| CN110102296A (en) * | 2019-05-16 | 2019-08-09 | 广东工业大学 | A kind of catalyst and preparation method thereof for synthesizing 1,5-PD |
| CN111229204A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | Application of bimetallic catalyst in preparation of 1, 5-pentanediol from tetrahydrofurfuryl alcohol |
| CN112657485A (en) * | 2020-11-24 | 2021-04-16 | 中国科学院广州能源研究所 | Method for preparing tetrahydrofurfuryl alcohol and pentanediol by furfuryl alcohol hydrogenation |
| CN113024350A (en) * | 2021-03-19 | 2021-06-25 | 中国科学院兰州化学物理研究所 | Method for preparing 1, 5-pentanediol or 1, 6-hexanediol by utilizing bio-based furan compound |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265400A (en) * | 2013-05-28 | 2013-08-28 | 华东理工大学 | Environment-friendly novel method for preparing primary alcohol from furan or tetrahydrofuran derivatives |
| JP2015003892A (en) * | 2013-06-24 | 2015-01-08 | 宇部興産株式会社 | Method for producing polyol compound |
| CN103977796A (en) * | 2014-05-18 | 2014-08-13 | 华东理工大学 | Catalyst used in preparation of long-chain alkane through catalytic hydrodeoxygenation of biomass |
| CN108620127A (en) * | 2017-03-23 | 2018-10-09 | 万华化学集团股份有限公司 | A kind of catalyst and preparation method and applications of tetrahydrofurfuryl alcohol hydrogenolysis 1,5- pentanediols |
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| CN109896921B (en) * | 2017-12-07 | 2022-02-01 | 中国科学院大连化学物理研究所 | Method for preparing 1, 5-pentanediol by using molybdenum sulfide-containing catalyst for catalytic hydrogenation of tetrahydrofurfuryl alcohol |
| CN109896921A (en) * | 2017-12-07 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of method that Containing Sulfur molybdenum catalyst is used for tetrahydrofurfuryl alcohol catalytic hydrogenation 1,5- pentanediol |
| CN111229204A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | Application of bimetallic catalyst in preparation of 1, 5-pentanediol from tetrahydrofurfuryl alcohol |
| CN109590013A (en) * | 2018-12-21 | 2019-04-09 | 广东工业大学 | A kind of biomass loaded catalyst and preparation method thereof adding hydrogen for open loop |
| CN109590013B (en) * | 2018-12-21 | 2022-02-15 | 广东工业大学 | Biomass supported catalyst for ring-opening hydrogenation and preparation method thereof |
| CN110102296A (en) * | 2019-05-16 | 2019-08-09 | 广东工业大学 | A kind of catalyst and preparation method thereof for synthesizing 1,5-PD |
| CN112657485A (en) * | 2020-11-24 | 2021-04-16 | 中国科学院广州能源研究所 | Method for preparing tetrahydrofurfuryl alcohol and pentanediol by furfuryl alcohol hydrogenation |
| CN112657485B (en) * | 2020-11-24 | 2023-10-13 | 中国科学院广州能源研究所 | Method for preparing tetrahydrofurfuryl alcohol and pentanediol through furfuryl alcohol hydrogenation |
| CN113024350A (en) * | 2021-03-19 | 2021-06-25 | 中国科学院兰州化学物理研究所 | Method for preparing 1, 5-pentanediol or 1, 6-hexanediol by utilizing bio-based furan compound |
| CN113024350B (en) * | 2021-03-19 | 2022-06-14 | 中国科学院兰州化学物理研究所 | Method for preparing 1, 5-pentanediol or 1, 6-hexanediol by utilizing bio-based furan compound |
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Application publication date: 20130206 |