CN104672185A - Method for preparing tetrahydrofurfuryl alcohol from furfural by aqueous phase hydrogenation - Google Patents
Method for preparing tetrahydrofurfuryl alcohol from furfural by aqueous phase hydrogenation Download PDFInfo
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- CN104672185A CN104672185A CN201310613486.1A CN201310613486A CN104672185A CN 104672185 A CN104672185 A CN 104672185A CN 201310613486 A CN201310613486 A CN 201310613486A CN 104672185 A CN104672185 A CN 104672185A
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- furfural
- tetrahydrofurfuryl alcohol
- hydrogenation
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 title claims abstract description 42
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000008346 aqueous phase Substances 0.000 title claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002904 solvent Substances 0.000 abstract description 10
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 30
- 230000009466 transformation Effects 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- FCAJYRVEBULFKS-UHFFFAOYSA-N 2-(oxolan-2-yl)ethanol Chemical compound OCCC1CCCO1 FCAJYRVEBULFKS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XUYPXLNMDZIRQH-LURJTMIESA-N N-acetyl-L-methionine Chemical compound CSCC[C@@H](C(O)=O)NC(C)=O XUYPXLNMDZIRQH-LURJTMIESA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Furan Compounds (AREA)
Abstract
一种糠醛水相加氢制备四氢糠醇的方法，该方法在0.5-10MPa氢气气氛中，80-180℃温度下，以水为溶剂，在镍基催化剂和碱性添加剂作用下糠醛直接转化为四氢糠醇，四氢糠醇的收率可达94%。A method for preparing tetrahydrofurfuryl alcohol by hydrogenation of furfural in aqueous phase, the method is in a hydrogen atmosphere of 0.5-10MPa, at a temperature of 80-180°C, using water as a solvent, and under the action of a nickel-based catalyst and an alkaline additive, furfural is directly converted into Tetrahydrofurfuryl alcohol, the yield of tetrahydrofurfuryl alcohol can reach 94%.
Description
Technical field
The present invention relates to a kind of preparation method of tetrahydrofurfuryl alcohol, be specifically a kind of is that raw material directly prepares the new system of tetrahydrofurfuryl alcohol by aqueous phase hydrogenation with furfural.
Background technology
Tetrahydrofurfuryl alcohol (having another name called tetrahydrofurfuryl carbinol) is a kind of excellent solvent and important Organic Chemicals, as can be used as the solvent of coating, resin and grease etc.; Also can be used as and prepare pyridine, tetrahydrofuran (THF), the raw material of Methionin etc.; Can also be used to prepare softening agent, sterilant, frostproofer, weedicide etc.
Current industrial tetrahydrofurfuryl alcohol is produced mainly through two-step approach, and the first selec-tive hydrogenation of furfural obtains furfuryl alcohol, then prepares tetrahydrofurfuryl alcohol by the method for the further selec-tive hydrogenation of furfuryl alcohol.The catalyzer that furfuryl alcohol Hydrogenation adopts for tetrahydrofurfuryl alcohol is mainly skeletal nickel catalyst, and this catalyzer can obtain higher furfuryl alcohol transformation efficiency and tetrahydrofurfuryl alcohol selectivity.As the skeletal nickel catalyst that patent CN1847234A adopts molybdenum to modify, under comparatively gentle condition, (1.5-2MPa, 30-80 DEG C) obtains the tetrahydrofurfuryl alcohol of purity 99.5%, but skeletal nickel catalyst is unstable, exposes and easily catches fire in atmosphere, poor stability.Patent CN1341483A with nickel oxide alumina alkali metal or alkaline earth metal oxide for main component is at 80-200 DEG C, under 2-8MPa pressure condition, tetrahydrofurfuryl alcohol selectivity can reach the NiCoB amorphous alloy catalyst that 97%. patent CN1789257A adopt loading type, at 110 DEG C, under 3.0MPa hydrogen pressure, furfuryl alcohol Hydrogenation, for tetrahydrofurfuryl alcohol, can obtain the yield of more than 99%, but amorphous alloy is unstable, preparation method is complicated, and this limits its application to a certain extent.
Another kind method be with furfural be directly raw material one step Hydrogenation for tetrahydrofurfuryl alcohol, this is conducive to reducing costs, and increases the yield of tetrahydrofurfuryl alcohol.The skeletal nickel catalyst that Cai Tianxi etc. adopt heteropolyacid to modify is at 2.0 MPa, tetrahydrofurfuryl alcohol is prepared from furfural under 80 DEG C of conditions, the transformation efficiency of furfural and the selectivity of tetrahydrofurfuryl alcohol reach 98.1% and 98.5% (Applied Catalysis A:General1998,171:117-122) .Keiichi Tomishige etc. respectively with Ni-Pd/SiO
2for catalyzer, (40 DEG C under relatively mild conditions, 8MPaH2) carry out hydrogenation of furfural, the selectivity of tetrahydrofurfuryl alcohol reaches 96% (Catalysis Communications2010, although 12:154156). prepare tetrahydrofurfuryl alcohol by furfural and have good effect, but major part adopts unstable skeleton nickel class catalyzer, adds the danger in production process; Some have employed noble metal catalyst especially, improves cost.
Summary of the invention
The object of this invention is to provide one is prepared tetrahydrofurfuryl alcohol novel method by furfural, is solvent with water in the method, adopts nickel-base catalyst to generate tetrahydrofurfuryl alcohol by the direct step hydrogenation of furfural.
According to route provided by the present invention, hydrogenation of furfural conversion is prepared tetrahydrofurfuryl alcohol and is directly prepared by single step reaction.At present, the method preparing tetrahydrofurfuryl alcohol of most report generates furfuryl alcohol by the first hydrogenation of furfural, subsequently again to furfuryl alcohol Hydrogenation for tetrahydrofurfuryl alcohol.It is that raw material one step Hydrogenation is for tetrahydrofurfuryl alcohol with furfural that the present invention passes through direct.Effectively reduce intermediate steps, avoid the isolation andpurification of intermediate product, reduce cost.
According to method provided by the invention, the catalyzer that hydrogenation of furfural uses is metal load type catalyst.Active ingredient is Ni, auxiliary agent select in Mn, Fe, Co, Cu, Zn, La, Ce one or more.Catalyzer common mostly at present is skeleton nickel, amorphous alloy or noble metal catalyst are (see Chinese Patent Application No.: CN1847234A, CN1789257A, CN1341483A and document Catalysis Communications2010,12:154156.Applied Catalysis A:General1998,171:117-122).But skeletal nickel catalyst poor stability, easily catches fire in air; Amorphous alloy preparation method is complicated, and catalyzer is relatively unstable; And there is the problem of the aspects such as cost in noble metal catalyst.Present method adopts simple pickling process, and preparation method is ripe, simple to operate.Catalyzer is at high-temperature roasting condition compacted under, and active ingredient and carrier combine closely, and catalyst stability is strong.The hydrogen reducing rear catalyst short period of time is exposed in air and does not have a significant effect to activity.And the catalyzer that the present invention adopts is not containing precious metal, is conducive to reducing production cost.
According to method provided by the invention, reaction adopts liquid phase hydrogenating method, using water as solvent.In the liquid-phase hydrogenatin route reported in current document and patent, the alcohol that adopts as solvent (Applied Catalysis A:General1998,171:117-122) more.Using alcohol as solvent, furfural or furfuryl alcohol hydrogenation often can obtain reasonable transformation efficiency and yield.Compared with the organic solvents such as alcohol, water is the most cheap the safest solvent.Water does not burn, nontoxic, pollution-free, is that the principle that namely solvent meets Green Chemistry again reduces cost with water.But furfural and furfuryl alcohol are due to the existence of furan nucleus, relatively unstable in aqueous phase, easily generate polymerization and open-loop products.Method provided by the invention, by controlling aqueous phase hydroconversion condition, the condition such as method for preparing catalyst and auxiliary agent effectively prevent furan nucleus polymerization and open-loop products, achieves high yield in aqueous phase and prepares tetrahydrofurfuryl alcohol.
According to method provided by the invention originally, suitable reaction conditions mainly comprises reactant concn, hydrogen pressure, temperature and pH etc.Furfural aqueous solution concentration is 5-50wt%, and optimum concn is 10-20wt%; Hydrogen pressure 0.5-10MPa, optimum pressure is 2-6MPa; Temperature of reaction 80-200 DEG C, optimum temps is 120-160 DEG C, and before hydrogenation reaction, reaction system pH is 8-13, and Optimal pH is 8-9, by basic cpd NaOH, KOH, Na
2cO
3, K
2cO
3, CaO, MgO, Mg (OH)
2, Ca (OH)
2one or more carry out achieve effective control.
Route provided by the invention has the following advantages:
(1) the present invention directly prepares tetrahydrofurfuryl alcohol by hydrogenation of furfural and effectively reduces intermediate steps, avoids the isolation andpurification of intermediate product, reduces cost.
(2) catalyzer used in the present invention is not containing precious metal, and preparation method is simple, and catalyst stability is high, relatively stable in air, therefore, has very strong operability and practicality.
(3) in the present invention, furfural prepares tetrahydrofurfuryl alcohol is carry out in an aqueous medium, is different from the alcohol radical organic solvent adopted in existing document more.The present invention adopts water consumption substitution organic solvent, and security is good, meets the principle of Green Chemistry, has both been conducive to reducing production cost, is also conducive to environment protection.
Accompanying drawing explanation
Fig. 1 catalyzer transmission electron microscope photo.
Fig. 2. product gas phase color atlas; (t<6min peak is solvent peak, and wherein t=6.663min is furfural, and t=6.773min is furfuryl alcohol, and t=7.239min is tetrahydrofurfuryl alcohol, and t=9.516min is internal standard substance durene).
Embodiment
The following example will contribute to understanding the present invention, but content of the present invention is not limited thereto.
Embodiment 1
Catalyst preparing: take 4.95g Ni (NO
3)
26H
2o after adding 2.70g water stirring and dissolving.Add 10g activated alumina, fully stir into pasty state, leave standstill 15h, 120 DEG C of oven dry, then roasting 4h at 550 DEG C, at nitrogen atmosphere 500 DEG C, activate 4h. catalyzer transmission electron microscope photo before using and see Fig. 1.
Catalyzed reaction is carried out at 50ml stainless steel cauldron.By 0.1g catalyzer, 1.5g furfural, 8.5g water adds in the stainless steel autoclave with polytetrafluoro liner, then uses Na
2cO
3adjustment pH is 8-9.After off-response still, react gas reactor four times with hydrogen exchange, temperature controller controls to be warming up to 140 DEG C, and is filled with hydrogen to 4MPa, starts and stirs.Keep constant pressure in reaction process, after hydrogenation reaction terminates, after cooling pressure release, gas chromatography analysis for sampling, product chromatographic peak and ownership are shown in Fig. 2.Reaction times and the results are shown in Table 1.
Embodiment 2
0.50g Co (NO is added in nickel nitrate solution in embodiment 1
3)
26H
2o, other all the results are shown in Table 1. with embodiment 1.
Embodiment 3
Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES in embodiment 2 is changed into 2.10g Cu (NO
3)
23H
2o other all the results are shown in Table 1. with embodiment 2.
Embodiment 4
Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES in embodiment 2 is changed into 2.22g Ce (NO
3)
36H
2o other all the results are shown in Table 1. with embodiment 2.
Embodiment 5
Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES in embodiment 2 is changed into 1.37g Fe (NO
3)
39H
2o and 1.00g Co (NO
3)
26H
2o other all the results are shown in Table 1. with embodiment 2.
Embodiment 6
Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES in embodiment 2 is changed into 0.74g Ce (NO
3)
36H
2o and 0.37g La (NO
3)
36H
2o other all the results are shown in Table 1. with embodiment 2.
Embodiment 7
Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES in embodiment 2 is changed into 0.42g Cu (NO
3)
23H
2o and 1.01g Zn (NO
3)
26H
2o other all the results are shown in Table 1. with embodiment 2.
Table 1 auxiliary agent is on the impact of hydrogenation of furfural performance
| Embodiment | Reaction times (h) | Furfural transformation efficiency (%) | Tetrahydrofurfuryl alcohol selectivity (%) |
[0034]
| 1 | 4.0 | 97 | 77 |
| 2 | 3.5 | 99 | 92 |
| 3 | 4.5 | 99 | 86 |
| 4 | 2.0 | 98 | 96 |
| 5 | 2.8 | 99 | 90 |
| 6 | 1.5 | 97 | 96 |
| 7 | 4.2 | 99 | 84 |
Reaction conditions: 1.5g furfural, 8.5g water, catalyzer is 20% of furfural quality, temperature: 140 DEG C, pressure: 4MPa.
Embodiment 8
By the Na in embodiment 4
2cO
3change other alkaline additive into, catalyzer and reaction characterize with embodiment 4. reaction conditions and the results are shown in Table 2.
Table 2 additive is on the impact of hydrogenation of furfural performance
| Additive | Reaction times (h) | Furfural transformation efficiency (%) | Tetrahydrofurfuryl alcohol selectivity (%) |
| K 2CO 3 | 2.5 | 97 | 89 |
| NaOH | 2.2 | 98 | 94 |
| MgO | 4.0 | 99 | 90 |
| Ca(OH) 2 | 4.0 | 98 | 91 |
Reaction conditions: 1.5g furfural, 8.5g water, catalyzer is 10% of furfural quality, temperature: 140 DEG C, pressure: 4MPa.
Embodiment 9
Change the temperature in embodiment 4, catalyzer and reaction characterize with embodiment 4, the results are shown in Table 3.
Table 3 temperature is on the impact of hydrogenation of furfural
| Temperature (DEG C) | Reaction times (h) | Furfural transformation efficiency (%) | Tetrahydrofurfuryl alcohol selectivity (%) |
[0045]
| 100 | 4.4 | 95 | 84 |
| 120 | 3.2 | 99 | 88 |
| 160 | 1.5 | 99 | 90 |
| 180 | 1.0 | 98 | 79 |
Reaction conditions: 1.5g furfural, 8.5g water, catalyst quality is 12% of furfural quality, pressure: 4MPa.
Embodiment 10
Change the pressure in embodiment 4, catalyzer and reaction characterize with embodiment 4, the results are shown in Table 4.
Table 4 hydrogen pressure is on the impact of hydrogenation of furfural
| Pressure (DEG C) | Reaction times (h) | Furfural transformation efficiency (%) | Tetrahydrofurfuryl alcohol selectivity (%) |
| 1 | 4.5 | 94 | 84 |
| 2 | 2.8 | 99 | 90 |
| 5 | 1.5 | 99 | 94 |
Reaction conditions: 1.5g furfural, 8.5g water, catalyst quality is 10% of furfural quality, temperature: 140 DEG C.
Embodiment 11
Change the furfural content in embodiment 4, catalyzer and reaction characterize with embodiment 4, the results are shown in Table 5.
Table 5 furfural content is on the impact of Hydrogenation
| Furfural content (%) | Reaction times (h) | Furfural transformation efficiency (%) | Tetrahydrofurfuryl alcohol selectivity (%) |
| 5 | 2.0 | 97 | 77 |
| 15 | 2.7 | 98 | 93 |
| 30 | 4.4 | 99 | 86 |
Reaction conditions: reaction solution total mass is 10g. catalyzer is 10% of furfural quality, temperature: 140 DEG C, pressure: 4MPa.
Claims (6)
1. prepared a method for tetrahydrofurfuryl alcohol by furfural, it is characterized in that: in hydrogen atmosphere, water is reaction medium, and furfural hydrogenation under catalyzer and alkaline additive effect generates tetrahydrofurfuryl alcohol;
Furfural aqueous phase Hydrogenation is metal carrying catalyst for the catalyzer that tetrahydrofurfuryl alcohol uses,
Furfural aqueous phase Hydrogenation selects Ni for tetrahydrofurfuryl alcohol active ingredient, and contain in catalyzer or do not contain auxiliary agent, auxiliary agent is one or two or more kinds in Mn, Fe, Co, Zn, La, Ce;
Activity component load quantity is the 1-20% of catalyzer total mass, and auxiliary agent charge capacity and active ingredient mol ratio are 0-1;
Furfural aqueous phase Hydrogenation is NaOH, KOH, Na for the alkaline additive that tetrahydrofurfuryl alcohol uses
2cO
3, K
2cO
3, CaO, MgO, Mg (OH)
2, Ca (OH)
2in one or more than two kinds.
2. in accordance with the method for claim 1, it is characterized in that: catalyst levels is the 5-50% of furfural quality.
3. in accordance with the method for claim 1, it is characterized in that: furfural aqueous phase Hydrogenation for tetrahydrofurfuryl alcohol use the carrier of catalyzer for Al
2o
3.
4. in accordance with the method for claim 1, it is characterized in that: the hydrogenation reaction of furfural is carried out in water medium, and furfural aqueous solution concentration is 5-50%.
5. in accordance with the method for claim 1, it is characterized in that: the hydrogen pressure of the hydrogenation reaction of furfural is 0.5-10MPa, and temperature of reaction is 80-200 DEG C, and the reaction times is 0.5-6h.
6. in accordance with the method for claim 1, it is characterized in that: the hydrogenation reaction alkaline additive consumption of furfural makes the initial pH of reaction solution be 9-14.
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Cited By (12)
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|---|---|---|---|---|
| CN105348235A (en) * | 2015-12-15 | 2016-02-24 | 林康艺 | Method for preparing furfuryl alcohol by catalyzing furfural |
| CN105903481A (en) * | 2016-04-27 | 2016-08-31 | 中国科学院合肥物质科学研究院 | Sulfonyl-functionalized carbon-based metal catalyst and application thereof |
| CN106694012A (en) * | 2017-01-13 | 2017-05-24 | 中国石油化工股份有限公司 | Catalyst containing rare earth element and preparation method thereof |
| CN106732706A (en) * | 2017-01-13 | 2017-05-31 | 中国石油化工股份有限公司 | Furfuraldehyde hydrogenation catalyst containing rare earth element and preparation method thereof |
| CN107413344A (en) * | 2017-05-18 | 2017-12-01 | 北京化工大学 | A kind of preparation method of confinement structure hexahedron pattern nano nickel base catalyst and its application of catalytic hydrogenation |
| CN109225254A (en) * | 2018-09-18 | 2019-01-18 | 中国科学院广州能源研究所 | A kind of PtNi/C bimetallic catalyst and preparation method thereof |
| CN109833897A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A method of for produce furfuryl alcohol catalyst and its preparation and production furfuryl alcohol |
| CN110240578A (en) * | 2018-03-08 | 2019-09-17 | 华东师范大学 | A kind of method for preparing tetrahydrofurfuryl alcohol by hydrogenation and supported nickel catalyst |
| CN110496614A (en) * | 2018-05-16 | 2019-11-26 | 中国科学院大连化学物理研究所 | Metal catalyst, its preparation method and its application in aqueous phase catalytic furfural hydrogenation to prepare furfuryl alcohol |
| CN113061122A (en) * | 2021-03-15 | 2021-07-02 | 昆明理工大学 | Preparation method of 2, 5-dihydroxymethyl tetrahydrofuran |
| CN114591271A (en) * | 2022-03-22 | 2022-06-07 | 大连理工大学 | A kind of method for preparing tetrahydrofurfuryl alcohol by one-step hydrogenation of furfural under low temperature condition |
| CN118649686A (en) * | 2024-08-19 | 2024-09-17 | 广东工业大学 | A MOFs-derived porous carbon-coated bifunctional metal nanocatalyst and its preparation method and application |
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