CN103848719A - Method for preparing 1,5-pentanediol via selective hydrogenolysis of tetrahydrofurfuryl alcohol - Google Patents
Method for preparing 1,5-pentanediol via selective hydrogenolysis of tetrahydrofurfuryl alcohol Download PDFInfo
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- CN103848719A CN103848719A CN201210516409.XA CN201210516409A CN103848719A CN 103848719 A CN103848719 A CN 103848719A CN 201210516409 A CN201210516409 A CN 201210516409A CN 103848719 A CN103848719 A CN 103848719A
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Abstract
The invention relates to a method for preparing a novel A-B/X or A/X carried catalyst of 1,5-pentanediol by performing a selective hydrogenolysis reaction on tetrahydrofurfuryl alcohol obtained from forestry and agricultural residues taken as raw materials. According to the novel A-B/X or A/X carried catalyst, wherein the component A is any one or more than one of Rh, Ir, Pt, Pd and Ru; the assistant B is any one or more than one of V, Nb and Ta; the carrier X is any one of SiO2, activated carbon, SiO2-Al2O3, titanium oxide and zirconium oxide; the carrying quantity of a precious metal A in the catalyst is between 0.5% and 10%; the molar ratio of the assistant B to the precious metal A is 0.01-1.0; the reaction pressure is between 1MPa and 20MPa; and the reaction temperature is between 50 DEG C and 150 DEG C. The novel A-B/X or A/X carried catalyst has the characteristics of moderate reaction condition, high reaction activity and good selectivity, thereby providing a novel effective way for preparing the 1,5-pentanediol by utilizing biomasses of the forestry and agricultural residues.
Description
Technical field
The present invention relates to a kind of novel method of the tetrahydrofurfuryl alcohol that by agriculture and forestry organic waste material is raw material acquisition being prepared to 1,5-PD by selectivity hydrogenolysis.Adopt specifically A-B/X or A/X loaded catalyst, compared with under mild conditions realize from the non-oil of 1,5-PD of agriculture and forestry organic waste material biomass, the renewable approach of preparing.
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 conversion obtains energy chemical has become the focus of current research.Utilize the hyperoxic feature of biomass, it optionally can be converted into end has the dibasic alcohol of hydroxyl.Because this class dibasic alcohol has 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 prior art, the production method about 1,5-PD has:
1) cyclopentadiene photochemical catalytic oxidation at normal temperatures and pressures makes epoxypentenal, through 70 ~ 100 ℃, under the condition of about 6MPa, hydrogenation obtains 1,5-PD 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 reported with 1,5-Methyl glutarate be raw material, under CuZnAl catalyst effect, produce 1,5-PD.Its temperature of reaction is 150-350 ℃, and reaction pressure is 3-5MPa.This route need to be to reaction raw materials 1, and 5-pentanedioic acid is through esterification treatment, then carries out purifying, hydrogenation, and therefore reaction process is longer.
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 petrochemical complex product as raw material, petroleum resources are had to very strong dependency.So, prepare 1,5-PD from biomass agriculture and forestry organic waste material and there is certain economic value, also can alleviate the pressure to 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, the wherein China of originating from over half.Due to the post-treatment technology to furfural of shortage, 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 to technology.Prepare 1,5-PD from furfural and not only can make full use of biomass resource, also the 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 reaction is to 1,5-pentanediol selectivity is lower by approximately 30%, primary product is 1,2-pentanediol, therefore there is no 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, take tetrahydrofurfuryl alcohol as raw material, synthetic 1,5-PD need be through three steps: first tetrahydrofurfuryl alcohol is at Al
2o
3the lower dihydropyrane that generates of effect, dihydropyrane obtains 5-hydrogenation of hydroxypentylaldehyd through hydrolysis, and last 5-hydrogenation of hydroxypentylaldehyd generates 1,5-PD under copper chromite shortening.Although the method has overcome the low problem of selectivity of product, because needs carry out separating-purifying to each step reaction product, reactions steps complexity (L.E.Schniepp, H.H.Geller, J.Am.Chem.Soc.1946,68,1646).Nearest Japanese Tomishige seminar finds the Rh/SiO that utilizes Re, W or Mo to promote
2catalyzer is catalysis tetrahydrofurfuryl alcohol hydrogenolysis 1,5-PD processed (S.Koso, I.Furikado, A.Shimao, T.Miyazawa, K.Kunimori, K.Tomishige, Chem.Comm.2009,2035 effectively; S.Koso, H.Watanabe, K.Okumura, Y.Nakagawa, K.Tomishige, Appl.Catal.B-Environ., 2012,111 – 112:27), reaction is carried out in intermittent type tank reactor.But Rh is expensive due to precious metal, limit the application of this catalyzer in industry.Therefore, need a kind of have high reactivity, highly selective and moderate catalyzer, to realize the industrial application of preparing 1,5-PD from biomass.In the periodic table of elements, Ir and Rh are congenerss, and unit price lattice are lower than Rh.This seminar finds the Ir/SiO that Re, W or Mo promote recently
2catalyzer is catalysis tetrahydrofurfuryl alcohol hydrogenolysis 1,5-PD processed effectively, and reaction is carried out (Chinese Patent Application No.: 201110221524.X), the Ir/SiO promoting with Mo in all catalyzer in intermittent type tank reactor or fixed bed moving phase reaction device
2catalyzer has best activity and selectivity.The present invention finds that the noble metal catalyst that vanadium family element promotes has the synthetic 1,5-PD activity and selectivity of good tetrahydrofurfuryl alcohol selectivity hydrogenolysis first.
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:
Tetrahydrofurfuryl alcohol selectivity hydrogenolysis is prepared a method for 1,5-PD,
Adopt A/X or A-B/X loaded catalyst, wherein A is any or multiple in precious metal Rh, Ir, Pt, Pd, Ru; B is any or multiple in V, Nb, Ta; Carrier X is SiO
2, gac, SiO
2-Al
2o
3, any in titanium oxide, zirconium white, in loading type A-B/X catalyzer, the charge capacity of A is 0.5-10%, is preferably 2-4%, in catalyzer, the mol ratio of auxiliary agent B and A is 0.01-1.0, is preferably 0.05-0.5.
Described loaded catalyst A-B/X or A/X adopt pickling process preparation, first the soluble salt solution of A is flooded than the medium volume of the carrier X that is added to moulding in advance by metering, (80-120 ℃, 6-24 hour) is again with the soluble salt solution incipient impregnation containing auxiliary agent B element after drying, aging 6-12 hour, final drying (80-120 ℃, 6-24 hour), a 300-600 ℃ roasting 2-5 hour make.
This catalyzer before use need be in the reduction of hydrogen situ, and reductive condition is hydrogen pressure 0.1-10MPa, is preferably 2-8MPa; Hydrogen/catalyst volume air speed 800-1500h
-1, be preferably 800-1000h
-1; Reduction temperature 120-350 ℃, is 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 batch reactor reaction conditions is: tetrahydrofurfuryl alcohol concentration of aqueous solution is 5-100%, and temperature of reaction 50-150 ℃, is preferably 60-120 ℃, hydrogen pressure 1-20MPa, is preferably 2-8MPa; Reaction times 2-24 hour, is preferably 2-6 hour.
Reaction condition of carrying out in fixed bed moving phase reaction device is: tetrahydrofurfuryl alcohol concentration of aqueous solution is 5-100%, and temperature of reaction 50-150 ℃, is preferably 60-120 ℃, and hydrogen pressure 1-20MPa, is preferably 2-8MPa; Moving phase reaction device tetrahydrofurfuryl alcohol liquid material/catalyst quality air speed is 0.6-2h
-1, be preferably 0.6-1h
-1; Hydrogen/catalyst volume air speed is 600-1000h
-1, be preferably 800-1000h
-1.
When this catalyzer is prepared 1,5-PD for tetrahydrofurfuryl alcohol hydrogenolysis, reactive behavior is good, selectivity is high, and mild condition provides a kind of new biomass approach for preparing 1,5-PD.
Embodiment
Embodiment 1-13
Preparation catalyst
By containing 10% the soluble salt solution of A, be added in carrier and flood according to certain metering ratio, under room temperature aging 12 hours, then in 120 ℃ of baking ovens dry 12 hours; Take again the soluble salt solution of B component by certain B/A mol ratio, be added in the above-mentioned carrier having flooded after A component, under room temperature aging 12 hours, then at 120 ℃ dry 12 hours, at 500 ℃, roasting 3 hours in air, obtains loading type A-B/X catalyzer.The composition of catalyzer in each embodiment, the starting material kind of component A, B is in table 1.
The each catalyzer composition of table 1.
Embodiment 17
Catalyst activity is evaluated
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: 2g catalyst loading, to reaction tubes, reduced to catalyzer original position before reaction, and 200 ℃ of reduction temperatures, H
2pressure is 6MPa, H
2flow velocity 160mL/min, with this understanding to catalyst reduction 2 hours.After reduction finishes, be down to temperature of reaction, control H
2flow is 60mL/min, and tetrahydrofurfuryl alcohol liquid material flow velocity is 0.04mL/min, regulates pressure to required reaction pressure, reacts and takes out liquid sample after 6 hours, has the gas-chromatography of flame ion (FID) detector to analyze with being furnished with HP-INNOWAX capillary column.
(1) impact of different auxiliary agents on catalyst activity, comparative result is in table 2.
The different auxiliary agents of table 2 affect catalyst activity
Note: reaction pressure is 6MPa, temperature of reaction is 80 ℃, tetrahydrofurfuryl alcohol concentration is 20%, B/Ir mol ratio=0.1(B=V, Nb, Ta, Mo, W, Re in catalyzer), gas-phase product (methane, pentane etc.) represents with " other ".
From table 2, Ir/SiO
2itself is all lower to tetrahydrofurfuryl alcohol selectivity hydrogenolysis activity and selectivity.By to Ir/SiO
2in catalyzer, add a small amount of vanadium family element (V, Nb, Ta) and can obviously improve the activity and selectivity of this catalyzer to tetrahydrofurfuryl alcohol hydrogenolysis.With we before the Ir/SiO that promotes of the Re, the W that have applied for a patent or Mo
2catalyzer is compared, the Ir/SiO that vanadium family element promotes
2catalyzer has higher 1,5-PD selectivity.The most obvious with the promoter action of V in 3 kinds of vanadium family elements investigating.Meanwhile, we have also contrasted VO
x/ SiO
2and 4%Ir/SiO
2and VO
x/ SiO
2the activity of mechanical mixture, find that these two kinds of catalyst activities are all bad.Prove by above result, at Ir-VO
x/ SiO
2in catalyzer, between Ir species and V species, have synergy, and this synergy is to cause catalyzer to have high reactivity and basic reason optionally.
(2) to tetrahydrofurfuryl alcohol hydrogenolysis specific activity, activity rating the results are shown in Table 3 to different precious metals.
The different precious metals of table 3 are to tetrahydrofurfuryl alcohol hydrogenolysis activity influence
Note: reaction pressure is 6MPa, temperature of reaction is 80 ℃, V/A mol ratio=0.1(A=Ir, Pt, Pd, Rh, Ru in each catalyzer), tetrahydrofurfuryl alcohol concentration is 20%, gas-phase product (methane, pentane etc.) represents with " other ".
As can be seen from Table 2, Ir-VO
x/ SiO
2catalyzer is the highest to tetrahydrofurfuryl alcohol hydrogenolysis transformation efficiency, and to the yield of 1,5-PD the highest (%).Rh-VO simultaneously
x/ SiO
2catalyzer has higher selectivity to 1,5-PD, but the transformation efficiency of tetrahydrofurfuryl alcohol is lower.
(3) impact of different carriers on catalyst activity, comparative result is in table 4.
The impact of table 4 carrier on tetrahydrofurfuryl alcohol hydrogenolysis activity
Note: V/Ir mol ratio=0.1 in each catalyzer.Reaction pressure is 6MPa, and temperature of reaction is 80 ℃, and tetrahydrofurfuryl alcohol concentration is 20%, and gas-phase product (methane, pentane etc.) represents with " other ".
As can be seen from Table 4, adopt SiO
2while doing carrier with activated carbon, catalyst activity the best.
(4) Ir-VO
x/ SiO
2catalyzer, to the active contrast of different concns tetrahydrofurfuryl alcohol hydrogenolysis, the results are shown in Table 5.
Catalyst activity test under the different tetrahydrofurfuryl alcohol concentration of table 5
Note: reaction pressure is 6MPa, temperature of reaction is 80 ℃, used catalyst is 4%Ir-VO
x/ SiO
2(V/Ir mol ratio=0.1).Gas-phase product (methane, pentane etc.) represents with " other ".
With the increase of reactant tetrahydrofurfuryl alcohol concentration, Ir-VO
x/ SiO
2catalyzer increases the selectivity of 1,5-PD, but tetrahydrofurfuryl alcohol transformation efficiency declines.In the time that tetrahydrofurfuryl alcohol initial concentration is 20%, the productive rate of 1,5-PD is the highest.
(5) Ir-VO under different hydrogen pressure
x/ SiO
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
Note: temperature of reaction is 80 ℃, used catalyst is 4%Ir-VO
x/ SiO
2(V/Ir mol ratio=0.1), raw material tetrahydrofurfuryl alcohol starting point concentration is 20%.Gas-phase product (methane, pentane etc.) represents with " other ".
Even under lower pressure, Ir-VO
x/ SiO
2catalyzer also has good activity and selectivity to 1,5-PD.Under high pressure, catalyzer shows better tetrahydrofurfuryl alcohol transformation efficiency and to 1,5-PD yield.
(6) Ir-VO under differing temps
x/ SiO
2catalyzer to tetrahydrofurfuryl alcohol hydrogenolysis specific activity, the results are shown in Table 6.
Table 7 temperature of reaction is to tetrahydrofurfuryl alcohol hydrogenolysis activity influence
Note: reaction pressure is 6MPa, tetrahydrofurfuryl alcohol concentration is 20%, used catalyst is 4%Ir-VO
x/ SiO
2(V/Ir mol ratio=0.1).Gas-phase product (methane, pentane etc.) represents with " other ".
From table 7, along with the Ir-VO that improves constantly of temperature of reaction
x/ SiO
2on catalyzer, the transformation efficiency of tetrahydrofurfuryl alcohol improves constantly, and meanwhile the selectivity of 1,5-PD constantly reduces.In the time that temperature of reaction is 100 ℃, Ir-VO
x/ SiO
2on catalyzer, the productive rate of 1,5-PD reaches maximum value.
Claims (5)
1. tetrahydrofurfuryl alcohol selectivity hydrogenolysis is prepared 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 in precious metal Rh, Ir, Pt, Pd, Ru; B is any or multiple in V, Nb, Ta; Carrier X is any in SiO2, gac, SiO2-Al2O3, titanium oxide, zirconium white, and in loading type A-B/X or A/X catalyzer, the charge capacity of A is 0.5-10%, and in loading type A-B/X catalyzer, the mol ratio of auxiliary agent B and A is 0.01-1.0.
2. method according to claim 1, is characterized in that: described loaded catalyst A-B/X or A/X adopt pickling process preparation;
Loaded catalyst A/X preparation: first the soluble salt solution of A is flooded than the medium volume of the carrier X that is added to moulding in advance by metering, aging 6-12 hour, final drying also makes in 300-600 ℃ of roasting 2-5 hour;
Loaded catalyst A-B/X preparation: first the soluble salt solution of A is flooded than the medium volume of the carrier X that is added to moulding in advance by metering, after drying again with the soluble salt solution incipient impregnation containing auxiliary agent B element, aging 6-12 hour, final drying also makes in 300-600 ℃ of roasting 2-5 hour.
3. method according to claim 1, it is characterized in that: this catalyzer before use need be 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 1-10 hour.
4. method according to claim 1, is characterized in that: reaction is carried out in batch reactor, and tetrahydrofurfuryl alcohol aqueous solution mass concentration is 5-100%, temperature of reaction 50-150 ℃, hydrogen pressure 1-20MPa, 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 tetrahydrofurfuryl alcohol aqueous solution mass concentration is 5-100%, temperature of reaction 50-150 ℃, hydrogen pressure 1-20MPa; Moving phase reaction device tetrahydrofurfuryl alcohol liquid material/catalyst quality air speed is 0.6-2h-1, and hydrogen/catalyst volume air speed is 600-1000h-1.
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Cited By (7)
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CN108187674A (en) * | 2016-12-08 | 2018-06-22 | 中国科学院大连化学物理研究所 | Tantalum base catalyst and its application in the reaction of tetrahydrofurfuryl alcohol 1,5- pentanediols |
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WO2018170932A1 (en) | 2017-03-23 | 2018-09-27 | 万华化学集团股份有限公司 | Catalyst for preparing 1,5-pentanediol via hydrogenolysis of tetrahydrofurfuryl alcohol, method and application thereof |
CN109438325A (en) * | 2018-12-05 | 2019-03-08 | 兰州大学 | A kind of method of ring valeryl imines catalytic hydrogenation synthesis octahydro pentamethylene [C] pyrroles |
CN110560053A (en) * | 2019-09-30 | 2019-12-13 | 成都欣华源科技有限责任公司 | Supported catalyst and preparation method thereof, and method for preparing alcohol by aldehyde hydrogenation |
CN111434382A (en) * | 2019-01-15 | 2020-07-21 | 天津大学 | Carrier-supported vanadium oxide promoted Rh-based catalyst and preparation method and application thereof |
CN113877583A (en) * | 2021-11-11 | 2022-01-04 | 中国石油大学(华东) | Catalyst in process for producing 1, 5-pentanediol by biological furfuryl alcohol hydrogen ring-opening, preparation and application |
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