CN103288596B - A kind of organic acid Hydrogenation is for the method for monohydroxy-alcohol or dibasic alcohol - Google Patents
A kind of organic acid Hydrogenation is for the method for monohydroxy-alcohol or dibasic alcohol Download PDFInfo
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Abstract
The present invention relates to a kind of for by the method for organic acid Hydrogenation for monohydroxy-alcohol or dibasic alcohol, adopt any one in the organic acids such as acetic acid, propionic acid, valeric acid, stearic acid, oleic acid, palmitinic acid, levulinic acid, lactic acid, succinic acid, 3-hydroxy-propionic acid to be reactant; Adopt A-B/X loaded catalyst, wherein component A is more than any one or two kinds in Ir, Pt, Pd, Rh, Ru, and auxiliary agent B is more than any one or two kinds in Mo, Re, W, and carrier X is SiO
2, gac, titanium oxide, zirconium white, SiO
2-Al
2o
3(Al
2o
3mass content 17%), any one in molecular sieve, in catalyzer, the mass loading amount of A is 0.5-10%, and the mol ratio of auxiliary agent B and A is 0.01-1.0, and reaction pressure is 2-20MPa, and temperature of reaction is 40-180 DEG C.Catalyzer of the present invention has reaction conditions gentleness, and the feature that reactive behavior is high and selectivity is good, provides a kind of new effective way preparing monohydroxy-alcohol or dibasic alcohol from biomass.
Description
Technical field
The present invention relates to a kind of for the method for organic acid Hydrogenation for monohydroxy-alcohol or dibasic alcohol.Specifically with the one in acetic acid, propionic acid, valeric acid, stearic acid, oleic acid, palmitinic acid, levulinic acid, lactic acid, succinic acid, 3-hydroxy-propionic acid and other organic acids for reactant, adopt A-B/X loaded catalyst, compared with realize under mild conditions from biomass prepare monohydroxy-alcohol and dibasic alcohol non-petroleum, renewablely prepare approach.
Background technology
Scarcity, the growth of oil price, a large amount of discharge of greenhouse gases and the society day by day of fossil resource, to the demand of the energy, require that people find the new forms of energy that can substitute fossil resource.Biomass, as unique reproducible organic carbon source, may be used for producing fuel, chemical and carbon material, become the focus of research at present.
Cellulose hydrolysis is prepared glucose and is had ripe route, the starting material also making glucose become production of chemicals to be easy to get.Glucose fermentation can obtain some important organic acids, as: acetic acid, lactic acid, succinic acid, 3-hydroxy-propionic acid, methylene-succinic acid; Utilize chemical transformation gluconate dehydratase can obtain 5 hydroxymethyl furfural (HMF), HMF is hydrolyzed further and obtains levulinic acid, and lactic acid and levulinic acid hydrogenation deoxidation can obtain propionic acid and valeric acid; In addition, animal-plant oil hydrolysis also can obtain some organic acids (as stearic acid, oleic acid, palmitinic acid), these organic acids are important biomass platform chemicals, utilize these plateform molecules can synthetic engine fuel, energy chemistry product further, thus realize biorefinery.
Selective hydrogenation is carried out to biomass organic acid, corresponding monohydroxy-alcohol or dibasic alcohol can be obtained, have broad application prospects.At present, industrial production monohydroxy-alcohol or dibasic alcohol are mainly raw material with petrochemical praduct, stronger to petroleum resources dependency.So prepare monohydroxy-alcohol from biomass or dibasic alcohol has certain economic worth, the pressure of petroleum resources also can be alleviated.
Because organic acid contains the C=O key of high degree of polarization, relatively stricter to carboxylic acid direct hydrogenation condition, the higher temperature of general needs and hydrogen pressure.Usually take first organic acid to be carried out esterification, repeated hydrogenation produces monohydroxy-alcohol or dibasic alcohol.Chinese patent CN1539551A reports to methyl lactate hydrogenation under ruthenium boron catalyzer effect, and when temperature is 150 DEG C, pressure 6MPa, reacts 1,2-PD yield after 13 hours and reach 89.9%; Chinese patent CN102059125A reports Cu, Mn, Zr oxide catalyst 3-hydroxy methyl propionate hydrogenation, and at 150 DEG C, react 20 hours under 10MPa hydrogen pressure, 3-hydroxy methyl propionate transformation efficiency is 92.31%, and 1,3-PD selectivity is 85.43%.This route needs reaction raw materials esterification treatment, then carries out purifying, hydrogenation, and reaction process is longer.If therefore organic acid can be realized having great importance compared with the direct hydrogenation under mild conditions.
Have about the method for organic acid Hydrogenation for monohydroxy-alcohol or dibasic alcohol in prior art:
1) George W.Huber etc. have investigated Ru/C, Pt/C, Pd/C, Rh/C, Ir/Al
2o
3deng catalyzer performance to 10% acetic acid hydrogenation under 110-290 DEG C, 5.17MPa hydrogen pressure, find that Ru/C reactive behavior 160 DEG C time is best, ethanol selectivity is close to 80%.But the method temperature of reaction is higher, and acetic acid conversion low (about 25%) (HakanOlcay, LijunXu, Ye Xu, George W.Huber.ChemCatChem.2010,2,1420);
2) 2%Pd/C and the 2%Ru/C catalyzer (Re charge capacity is 4%) that utilizes Re to promote such as Doan Pham Minh, to 15% succinic acid hydrogenation in tank reactor, when temperature of reaction is 160 DEG C, when pressure is 15MPa, selectivity and the yield of BDO are about 62-66%.The method is higher to butyleneglycol yield, but temperature of reaction and pressure are all harsher, is unfavorable for industrialization (Doan PhamMinh, MicheleBesson, Catherine Pinel, Patrick Fuertes, Carole Petitjean.TopCatal.2010,53,1270);
3) J ü rgen Klankermayer etc. adopt Phosphine ligands MeC (CH
2pPh
2)
3with Ru (acac)
3in conjunction with, at 160 DEG C, to levulinic acid hydrogenation under 10MPa hydrogen atmosphere, through reaction in 18 hours, levulinic acid transformed completely, and the yield of Isosorbide-5-Nitrae-pentanediol can reach 95%.Because this reaction adopts homogeneous catalysis method, product separation difficulty, and temperature of reaction is higher, so also there is certain defect (Frank M.A.Geilen, BarthelEngendahl, Andreas Harwardt, Wolfgang Marquardt, J ü rgenKlankermayer, Walter Leitner.Angew.Chem.Int.Ed.2010,49,5510);
4) Dennis J.Miller etc. study lactic acid hydrogenation in tank reactor, adopt Ru/C catalyzer, 100-170 DEG C of temperature range, and under 7-14MPa pressure, the transformation efficiency of lactic acid is close to 100%, 1, the selectivity of 2-propylene glycol can reach 90% (Zhigang Zhang, James E.Jackson, Dennis J.Miller.Applied Catalysis A:General.2001,219,89); Avelino Corma etc. utilizes Ru/TiO
2catalyzer is to lactic acid hydrogenation, and activity is three times of common Ru/C catalyzer, and can keep 1,2-PD selectivity (Ana Primo, the Patricia of 95%
avelino Corma.Chem.Commun.2011,47,3613).
To sum up, the organic acid direct hydrogenation obtained biomass prepares monohydroxy-alcohol or dibasic alcohol is feasible way, but the higher temperature of this kind of reaction needed and reaction pressure, therefore need development of new effective catalyst, to relax reaction conditions, reduce energy consumption.
Summary of the invention
The object of the invention is to provide a kind of organic acid Hydrogenation for the method for monohydroxy-alcohol or dibasic alcohol.
The present invention is achieved by the following technical solutions:
Organic acid Hydrogenation is for a method for monohydroxy-alcohol or dibasic alcohol, and adopt A-B/X loaded catalyst, wherein A is more than any one or two kinds in Ir, Pt, Pd, Rh, Ru; B is more than any one or two kinds in Mo, Re, W; Carrier X is SiO
2, gac, titanium oxide, zirconium white, SiO
2-Al
2o
3(wherein Al
2o
3mass content 17%), any one in molecular sieve, in loading type A-B/X catalyzer, the mass loading amount of A is 0.5-10%, and be preferably 2-4%, the mol ratio of auxiliary agent B and A is 0.1-1.0, preferably 0.05-0.5.
The organic acid adopted is following any one: acetic acid, propionic acid, valeric acid, stearic acid, oleic acid, palmitinic acid, levulinic acid, lactic acid, succinic acid, 3-hydroxy-propionic acid and other organic acids; Corresponding product monohydroxy-alcohol or dibasic alcohol are respectively: ethanol, propyl alcohol, amylalcohol, stearyl alcohol, hexadecanol, Isosorbide-5-Nitrae-pentanediol, 1,2-PD, BDO, 1,3-PD and other alcohols.
Loaded catalyst A-B/X adopts pickling process preparation, first by the soluble salt solutions of A by metering than being added to the medium volume impregnation of carrier X, (drying conditions: 80-120 DEG C, 6-24 hour) is again with the soluble salt solutions incipient impregnation containing auxiliary agent B after drying, aging 6-12 hour, dry (drying conditions: 80-120 DEG C, 6-24 hour) in 300-600 DEG C of roasting 2-5 hour; This catalyzer need reduce at hydrogen situ before use, and reductive condition is hydrogen pressure 0.1-10MPa, is preferably 2-8MPa; Hydrogen/catalyst volume air speed 1000-3000 hour
-1, be preferably 2000-3000 hour
-1; Reduction temperature 120-350 DEG C, is preferably 180-250 DEG C; 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: aqueous solutions of organic acids mass concentration is 5-100%, temperature of reaction 40-180 DEG C, is preferably 60-100 DEG C, hydrogen pressure 2-20MPa, is preferably 2-8MPa; Reaction times 2-24 hour, is preferably 2-6 hour.
Reaction condition of carrying out in fixed bed moving phase reactor is: aqueous solutions of organic acids mass concentration is 5-100%, temperature of reaction 40-180 DEG C, is preferably 60-100 DEG C, hydrogen pressure 2-20MPa, is preferably 2-8MPa; Moving phase reactor organic acid liquid material/catalyst quality air speed is 0.5-3 hour
-1, be preferably 1-2 hour
-1; Hydrogen/catalyst volume air speed is 500-2000 hour
-1, be preferably 800-1000 hour
-1.
This catalyzer is used for the organic acid hydrogenation that obtains of Wood Adhesives from Biomass, and reactive behavior is good, selectivity is high, mild condition, for preparing monohydroxy-alcohol and dibasic alcohol provides a kind of new biomass approach.
Embodiment
Embodiment 1-8
Preparation catalyst
By the soluble salt solutions of 10% (massfraction) containing A, be added in carrier according to certain metering ratio and flood, aged at room temperature 12 hours, then in 120 DEG C of baking ovens dry 12 hours; Take the soluble salt solutions of B component again by certain B/A mol ratio, be added to and above-mentionedly flooded in the carrier after component A, in aged at room temperature 12 hours, then at 120 DEG C dry 12 hours, roasting 3 hours in air at 500 DEG C; This catalyzer needs to reduce under hydrogen before use, reduction temperature 200 DEG C, H
2pressure is 6MPa, H
2flow velocity 160mL/min, with this understanding to catalyst reduction 2 hours, 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.
Note: in each embodiment, the mass loading amount of A is 4%, B/A mol ratio is 0.13, adopts carrier X to be SiO
2.
Embodiment 9-11
Catalyst activity is evaluated
Evaluating catalyst of the present invention carries out in fixed bed moving phase reactor, and reactor is the stainless steel tube of external diameter 6mm, long 360mm.Experimentation is as follows: by 2g catalyst loading in reaction tubes, to catalyzer in-situ reducing before reaction, is down to temperature of reaction, control H after reduction terminates
2flow is 60mL/min, and organic acid solution stream speed is 0.04mL/min, reaction pressure 6MPa, reacts sampling analysis after 6 hours.
Embodiment 9
Acetic acid hydrogenation ethanol activity rating
1) temperature of reaction is on the impact of acetic acid hydrogenation activity, and Activity evaluation is in table 2.
Table 2. temperature of reaction is to acetic acid hydrogenation activity influence
Note:
4%Ir-MoO
x/ SiO
2(Mo/Ir=0.13, x=0 ~ 3) catalyzer, 10% acetic acid solution (mass concentration), gas-phase product methane, ethane and a small amount of acetaldehyde represent with " other ".
As can be seen from Table 2,4%Ir-MoO
x/ SiO
2(Mo/Ir=0.13, x=0 ~ 3) catalyzer has good low temperature active, and when temperature of reaction is 100 DEG C, the yield of ethanol is the highest (47.2%).
2) different auxiliary agent is to the contrast of acetic acid hydrogenation activity, and Activity evaluation is in table 3.
The different auxiliary agent of table 3. is to acetic acid hydrogenation activity influence
Note: in each catalyzer, Ir mass loading amount is 4%, B/Ir=0.13 (B=Mo, Re, Co, W), x=0 ~ 3, y=0 ~ 3.5, z=0 ~ 1.33,10% acetic acid solution (mass concentration), and temperature of reaction is 100 DEG C.
Experimental result shows, the interpolation of Mo, Re, W is to Ir/SiO
2catalyzer has promoter action in various degree, wherein obvious with the promoter action of Mo.
3) different precious metal is to acetic acid hydrogenation activity influence, and reaction result is in table 4.
The different precious metal of table 4. is to acetic acid hydrogenation active testing
Note: in each catalyzer, A mass loading amount is 4%, Mo/A=0.13 (A=Ir, Pt, Pd, Ru, Rh), x=0 ~ 3,10% acetic acid solution (mass concentration), and temperature of reaction is 100 DEG C.
As can be seen from Table 4, when adopting precious metal Rh, acetic acid hydrogenation is active best with selectivity, and acetic acid yield is up to 86.6%, and Pt, Ir also have higher hydrogenation capability to acetic acid simultaneously.
Embodiment 10
Levulinic acid Hydrogenation Isosorbide-5-Nitrae-pentanediol activity rating
1) 4%Ir-MoO
x/ SiO
2under (Mo/Ir=0.13, x=0 ~ 3) catalyzer, levulinic acid Hydrogenation is active for Isosorbide-5-Nitrae-pentanediol
Table 5.4%Ir-MoO
x/ SiO
2levulinic acid hydrogenation activity under (Mo/Ir=0.13, x=0 ~ 3) catalyzer
Note: 10% levulinic acid solution (mass concentration), gas-phase product (pentane etc.) represents with " other ".
As can be seen from Table 5,4%Ir-MoO
x/ SiO
2(Mo/Ir=0.13, x=0 ~ 3) catalyzer has good activity to levulinic acid hydrogenation, and at 60 DEG C, levulinic acid transforms completely, when 80 DEG C, reaches 52.8% to the yield of Isosorbide-5-Nitrae pentanediol.
2) 4%Rh-MoO
x/ SiO
2under (Mo/Rh=0.13, x=0 ~ 3) catalyzer, levulinic acid Hydrogenation is active for Isosorbide-5-Nitrae-pentanediol
Table 6.4%Rh-MoO
x/ SiO
2levulinic acid Hydrogenation under (Mo/Rh=0.13, x=0 ~ 3) catalyzer
Note: 10% levulinic acid solution (mass concentration).
Reaction result shows, Rh is better to the selective hydrogenation behavior of levulinic acid, and have good low temperature active, at 100 DEG C, the yield of Isosorbide-5-Nitrae-pentanediol, up to 75.3%, is better than Ir catalyzer.
Embodiment 11
Other biological matter organic acid is at 4%Rh-MoO
x/ SiO
2hydrogenation test under (Mo/Rh=0.13, x=0 ~ 3) catalyzer
Table 7. other biological matter organic acid is at 4%Rh-MoO
x/ SiO
2under (Mo/Rh=0.13, x=0 ~ 3) catalyzer, Hydrogenation is for monohydroxy-alcohol or dibasic alcohol
Note: temperature of reaction is 100 DEG C, a, c, d, gas-phase product propane, ethane etc.; B, gas-phase product butane and a small amount of tetrahydrofuran (THF), butyrolactone etc.; E, gas-phase product pentane, butane etc.; F, tetrahydrofuran solution; G, the alkane that carbon number is less than 15; H, the alkane that carbon number is less than 17.
As can be seen from Table 7,4%Rh-MoO
x/ SiO
2(Mo/Rh=0.13, x=0 ~ 3) catalyzer has higher activity to lactic acid, succinic acid, 3-hydroxy-propionic acid, propionic acid and valeric acid, palmitinic acid, stearic acid, oleic acid Hydrogenation for corresponding dibasic alcohol or monohydroxy-alcohol, is good biomass organic acid hydrogenation catalyst.
Claims (7)
1. organic acid Hydrogenation is for a method for monohydroxy-alcohol or dibasic alcohol, it is characterized in that: adopt A-B/X loaded catalyst, wherein A is more than any one or two kinds in Ir, Pt, Pd, Rh, Ru; B is more than any one or two kinds in Mo, W; Carrier X is SiO
2, gac, Al
2o
3mass content is the SiO of 17%
2-Al
2o
3, titanium oxide, zirconium white, any one in molecular sieve, in loading type A-B/X catalyzer, the mass loading amount of A is 0.5-10%, and the mol ratio of auxiliary agent B and A is 0.01-1.
2. method according to claim 1, is characterized in that: the organic acid adopted is following any one: acetic acid, propionic acid, valeric acid, stearic acid, oleic acid, palmitinic acid, levulinic acid, lactic acid, succinic acid, 3-hydroxy-propionic acid; Corresponding product monohydroxy-alcohol or dibasic alcohol are respectively: ethanol, propyl alcohol, amylalcohol, stearyl alcohol, hexadecanol, Isosorbide-5-Nitrae-pentanediol, 1,2-PD, BDO, 1,3-PD.
3. method according to claim 1, it is characterized in that: loaded catalyst A-B/X adopts pickling process preparation, first by the soluble salt solutions of A by required metering than being added to the medium volume impregnation of carrier X, after drying again with the soluble salt solutions incipient impregnation containing auxiliary agent B, aging 6-12 hour, in 300-600 DEG C of roasting 2-5 hour after drying; This catalyzer need reduce at hydrogen situ before use, and reductive condition is hydrogen pressure 0.1-10MPa, hydrogen/catalyst volume air speed 1000-3000 hour
-1, reduction temperature 120-350 DEG C, the recovery time is 1-10 hour.
4. method according to claim 1, is characterized in that: react and carry out in batch reactor, and aqueous solutions of organic acids mass concentration is 5-100%, temperature of reaction 40-180 DEG C, hydrogen pressure 2-20MPa, reaction times 2-24 hour.
5. method according to claim 4, it is characterized in that: temperature of reaction is preferably 60-100 DEG C, hydrogen pressure is preferably 2-8MPa; Reaction times is preferably 2-6 hour.
6. method according to claim 1, is characterized in that: react and carry out in fixed bed moving phase reactor, and aqueous solutions of organic acids mass concentration is 5-100%, temperature of reaction 40-180 DEG C, hydrogen pressure 2-20MPa; Moving phase reactor organic acid soln/catalyst quality air speed is 0.5-3 hour
-1, hydrogen/catalyst volume air speed is 500-2000 hour
-1.
7. method according to claim 6, it is characterized in that: temperature of reaction is preferably 60-100 DEG C, hydrogen pressure is preferably 2-8MPa; Moving phase reactor organic acid liquid material/catalyst quality air speed is preferably 1-2 hour
-1; Hydrogen/catalyst volume air speed is preferably 800-1000 hour
-1.
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