CN108911949A - A kind of method that furfuryl alcohol liquid-phase catalysis selectivity hydrogenolysis prepares 1,2- pentanediol - Google Patents
A kind of method that furfuryl alcohol liquid-phase catalysis selectivity hydrogenolysis prepares 1,2- pentanediol Download PDFInfo
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Abstract
The present invention provides a kind of method of furfuryl alcohol liquid-phase catalysis selectivity hydrogenolysis preparation 1,2- pentanediol, which is characterized in that includes the following steps：Furfuryl alcohol, Cu base catalyst and reaction dissolvent are put into reaction kettle, hydrogen is filled with into reaction kettle and replace air in kettle, Hydrogen Vapor Pressure is filled with to 0.5-8MPa, stirs and be warming up to 100-180 DEG C, 1-18h of reaction obtains 1,2- pentanediol.The present invention, which prepares raw material furfuryl alcohol in the method for 1,2- pentanediol, can be entirely derived from natural plant resource, and catalytic hydrogenation reaction mild condition, used catalyst preparation method is simple, reactivity is high, have very high practicability and economy.
Description
Technical field
The present invention relates to 1,2- pentanediol technologies of preparing more particularly to a kind of furfuryl alcohol liquid-phase catalysis selectivity hydrogenolysis to prepare 1,
The method of 2- pentanediol.
Background technique
1,2- pentanediol is a kind of important fine chemistry intermediate, and unique structure has it in every field
It is widely applied.Firstly, 1,2- pentanediol is the important source material for synthesizing systemic fungicide propiconazole.Secondly, 1,2- pentanediol
With good moisture retention, can be used in the various skin care item such as face cream, eye cream, surfactant, infant care product, sunscreen product
To improve the water-resistance of product；In addition, 1,2- pentanediol, which also acts as, prepares preservative, polyester fiber, plasticizer, emulsifier
Deng.The efficient production of 1,2- pentanediol has important research significance.
The synthetic method of 1,2- pentanediol is mainly the following at present：1, n-amyl alcohol method (Hou Wei, chemical industry and work
Journey, 1996,13 (3):47-50)：Using n-amyl alcohol as raw material, n-pentene is obtained by dehydration；It is to react molten with acetic anhydride
Agent, under the catalytic action of the concentrated sulfuric acid with sodium perborate oxidation n-pentene obtain acetic acid 2- hydroxyl pentyl ester；It is obtained again through hydrolysis
To 1,2- pentanediol.This method preparation process complexity, the dosage of the catalyst concentrated sulfuric acid and rate of addition are difficult to control, and are easy to make
Increase at by-product and certain corrosivity can be generated to consersion unit.2, positive valeric acid method (fourth dogface, Anhui chemical industry, 2002,28
(5):22-3) using positive valeric acid as raw material, first existing for the phosphorus trichloride under the conditions of, bromine is added and brings it about halogenating reaction
The positive valeric acid of 2- bromo is obtained, then successively obtains 1,2- pentanediol by basic hydrolysis, acidic hydrolysis and reduction reaction.It should
Method preparation process is cumbersome, and factor in need of consideration is more in every single step reaction, bromine price is high, intermediate product is unstable, produces
Object is not readily separated, has certain pollution to environment.3, olefin oxidation method (Zhang Zhengkai, finely and specialty chemicals, 2004,12
(22):18-9)：It is that oxidizing n-pentene obtains epoxides with peroxyformic acid, then hydrolysis obtains under alkaline condition
1,2- pentanediol.This method complex process, product are not readily separated, are high to consersion unit requirement.Although the above method passes through adjusting
1, the 2- pentanediol of the available higher yields of process conditions, but generally existing complex process, expensive raw material price, to equipment
Demanding problem.Therefore, developing one has weight independent of fossil resource, environmental-friendly, low-cost process route
Want meaning.
Furfural is prepared under acid catalysed conditions by hydrolysis mainly using crop by-products such as corncobs as raw material
It obtains.China is agricultural production big country, and annual a large amount of corncob can provide sufficient raw material for production furfural.Furfuryl alcohol is
One of the downstream product that furfural is obtained by selective hydrogenation reaction, continual exploitation furfural downstream product simultaneously expand its application field tool
It is significant.Furfural or furfuryl alcohol is used to prepare concern of the 1,2- pentanediol by more and more industries for raw material in recent years.
(Zhang B et al. Green Chemistry, 2012,14 (12) such as B.Zhang:3402-9.) negative using manganese-base oxide
The catalyst furfuryl alcohol hydrogenolysis of load prepares pentanediol, in the catalyst for the carried noble metal tested, Ru/MnOxIt shows
Optimal catalytic performance.In 150 DEG C, 1.5MPa H2Pressure under, the highest yield of 1,2- pentanediol is up to 42.1%, furfuryl alcohol
Conversion ratio up to 100%.Chatterjee etc. (Chatterjee et al.Catalysis Science&Technology,
2011,1,1466-1471) use Pd to be carried on MCM-41 as catalyst, tetrahydro chaff is catalyzed in supercritical carbon dioxide
Alcohol adds hydrogen to prepare pentanediol, at 80 DEG C, 14 MPa CO2, 4MPa H2Under conditions of, when using Pd/MCM-41 as catalyst, mainly
Product be 1,2- pentanediol, selectivity 77.4%.The 1,2- penta 2 of higher degree can be obtained in the above method
Alcohol, but used catalyst is noble metal catalyst, higher cost.(the Adkins et al.Journal of such as Adkins
the American Chemical Society,1931,53(3):1091-5) with CuCr2O4For catalyst, in 175 DEG C, 10-
5MPa H2Under conditions of respectively obtain 40% 1,2- pentanediol and 30% 1,5-PD, but in catalyst chromium member
Element is easy to cause damages to environment, and extensive use is also limited.
In conclusion in the preparation method of 1,2- pentanediol there is high production cost, environment is unfriendly the problems such as, therefore
Develop it is a kind of with biomass for final raw material, production cost is low, the novel preparation method of environmental-friendly 1,2- pentanediol has weight
The application background wanted.
Summary of the invention
It is an object of the present invention to for there is high production cost, environment in the preparation method of current 1,2- pentanediol
Disagreeableness problem, a kind of method for proposing furfuryl alcohol liquid-phase catalysis selectivity hydrogenolysis preparation 1,2- pentanediol, this method is a kind of
With biomass for final raw material, the preparation method that production cost is low, environmental-friendly.
To achieve the above object, the technical solution adopted by the present invention is that：A kind of furfuryl alcohol liquid-phase catalysis selectivity hydrogenolysis preparation
The method of 1,2- pentanediol, includes the following steps：
Furfuryl alcohol, Cu base catalyst and reaction dissolvent are put into reaction kettle, hydrogen is filled with into reaction kettle and is replaced in kettle
Air (displacement is multiple) is filled with Hydrogen Vapor Pressure to 0.5-8MPa, and stirring (magnetic agitation) is simultaneously warming up to 100-180 DEG C, reaction 1-
18h obtains 1,2- pentanediol.
Further, the Cu base catalyst is using Cu as active component, carrier MnOx、MnCO3、 ZrO2, in ZnO, MgO
One or more, one of auxiliary agent Mo, V, Ni, Fe, Ca, Ti or a variety of.The auxiliary agent is carried on catalyst.
Further, the carrier MnOxFor MnO2、MnO、Mn2O3、Mn3O4One of or it is a variety of.
Further, the content of the auxiliary agent is 0-50%wt, preferably 5-30%wt.
Further, the reaction dissolvent is one of methanol, ethyl alcohol, isopropanol, normal propyl alcohol, isobutyl alcohol and water or more
Kind.
Further, the mass ratio of the Cu base catalyst and furfuryl alcohol is 1:1-100, preferably 1:2-50.
Further, the mass concentration of the furfuryl alcohol is 2-100%, preferably 5-20%wt.
Further, the Hydrogen Vapor Pressure that is filled with is to 2-6MPa, stirs and is warming up to 120-160 DEG C, reacts 4-12h.
Further, by the coprecipitation or first method system of precipitating active component impregnation aids again of the Cu base catalyst
It is standby to obtain；The mass content of active component Cu is 1-100%, preferably 5-50% in the Cu base catalyst.
Further, coprecipitation preparation Cu base catalyst Step is as follows：Soluble copper salt is dissolved in solvent, is configured to
Concentration is the solution of 0.02-4mol/L, and one of soluble manganese salt, zirconates, zinc salt, magnesium salts or more are added according to a certain percentage
Kind, one of auxiliary agent soluble molybdenum salt, vanadic salts, molysite, calcium salt, titanium salt or a variety of is added；It is added dropwise into mixing salt solution dense
The pH of carbonate to solution that degree is 0.5-4mol/L is 7-13；Then by mixed liquor at 20-120 DEG C aging 1-8h, filter,
It is neutral for being washed with warm water to filtrate, and dry 2-20h, calcines 2h-8h at 200-800 DEG C at 100-130 DEG C；Then in 10-
30v%H2Cu base catalyst is prepared in middle reduction 1-8h.
Further, first impregnation aids preparation Cu base catalyst Step is as follows again for precipitating active component：By soluble copper salt
It is dissolved in solvent, is configured to the solution that concentration is 0.02-4mol/L, soluble manganese salt, zirconates, zinc are added according to a certain percentage
One of salt, magnesium salts are a variety of；The pH of carbonate to solution that concentration is 0.5-4mol/L is added dropwise into mixing salt solution is
7-13；Then by mixed liquor at 20-120 DEG C aging 1-8h, filter, it is neutral for being washed with warm water to filtrate, at 100-130 DEG C
Dry 2-20h；It is prepared according to a certain percentage containing one of auxiliary component Mo, V, Ni, Fe, Ca, Ti or a variety of aqueous solutions,
Catalyst after drying is impregnated in 0.5h-12h in the solution, 100-130 DEG C of dry 2-20 h is calcined at 200-800 DEG C
2h-8h；Then in 10-30v%H2Cu base catalyst is prepared in middle reduction 1-8h.
Further, the solvent for preparing Cu base catalyst is one of water, isopropanol or ethyl alcohol or a variety of, soluble gold
Category salt is one of nitrate, acetate, oxalates or sulfate or a variety of.
Further, the carbonate for preparing Cu base catalyst is one or both of sodium carbonate or magnesium carbonate.
A kind of method of furfuryl alcohol liquid phase selective hydrogenolysis preparation 1,2- pentanediol of the present invention, using copper-based catalysts, carrier
For MnOx、ZrO2, one of ZnO, MgO or a variety of, using methanol, ethyl alcohol, normal propyl alcohol, isopropanol or water etc. as solvent, anti-
Answering temperature is 100-180 DEG C, and Hydrogen Vapor Pressure reacts 1h-18h under conditions of being 0.5-8 MPa, is catalyzed furfural derivatives furfuryl alcohol hydrogen
Solution preparation 1,2- pentanediol.The present invention has the following advantages that compared with prior art：
1) raw material furfuryl alcohol of the present invention can be entirely derived from natural plant biological matter resource independent of fossil resource；
2) Cu base catalyst, cheap and easy to get used in, does not use noble metal and toxic chromium；
3) catalytic reaction condition is mild, product 1, and 2- pentanediol selectivity is high, with good application prospect.
Specific embodiment
The present invention is further described with reference to embodiments：
Embodiment 1
Present embodiment discloses a kind of Cu base catalyst, are prepared from the following steps：
Copper acetate dihydrate 2g, four acetate hydrate manganese 4.9g are weighed in 250mL volumetric flask, 100mL deionized water is added
It obtains mixed solution A and is transferred in oil bath pan to be warming up to 353K；5.4g sodium carbonate is weighed in beaker, 25mL deionization is added
Water obtains the sodium carbonate liquor B of 2mol/L；It is 8.3 or so that mixed solution B, which is slowly added dropwise into solution A to pH of mixed,
303K aging 12h；It filters, it is neutral for being washed with warm water to filtrate；383K dries 16h, and 573K calcines 2h, in 10v%H2In
573K restores 3h, can obtain Cu base catalyst 1.
Embodiment 2：
Present embodiment discloses a kind of Cu base catalyst, are prepared from the following steps：
Preparation method is substantially the same manner as Example 1, the difference is that replacing four acetate hydrate manganese with 3.62g zirconium acetate, obtains institute
Need Cu base catalyst 2.
Embodiment 3：
Present embodiment discloses a kind of Cu base catalyst, are prepared from the following steps：
Preparation method is substantially the same manner as Example 1, the difference is that four acetate hydrate manganese are replaced with 3.29g zinc nitrate hexahydrate,
Cu base catalyst 3 needed for obtaining.
Embodiment 4：
Present embodiment discloses a kind of Cu base catalyst, are prepared from the following steps：
Preparation method is substantially the same manner as Example 1, the difference is that needed for replacing four acetate hydrate manganese to obtain with 1.64g magnesium nitrate
Cu base catalyst 4.
Embodiment 5：
Present embodiment discloses a kind of Cu base catalyst, are prepared from the following steps：
Preparation method is substantially the same manner as Example 1, the difference is that calcination temperature is changed to 723K, obtains required Cu base catalysis
Agent 5.
Embodiment 6：
Present embodiment discloses a kind of Cu base catalyst, are prepared from the following steps：
Preparation method is substantially the same manner as Example 1, the difference is that calcination temperature is changed to 873K, obtains required Cu base catalysis
Agent 6.
Embodiment 7：
Present embodiment discloses a kind of Cu base catalyst, are prepared from the following steps：
Copper acetate dihydrate 2g, nickel nitrate 0.91g, four acetate hydrate manganese 4.9g are weighed in 250mL volumetric flask, are added
100mL deionized water obtains mixed solution A and is transferred in oil bath pan to be warming up to 353 K；5.4g sodium carbonate is weighed in beaker, is added
Enter 25mL deionized water and obtains the sodium carbonate liquor B of 2M；Mixed solution B is slowly added dropwise and is to pH of mixed into solution A
8.3 or so, aging 12h；It filters, it is neutral for being washed with warm water to filtrate；383K dries 16h, and 573K calcines 2h, in 10v%H2
Middle 573K restores 3h, can obtain Cu base catalyst 7.
Embodiment 8：
Present embodiment discloses a kind of Cu base catalyst, are prepared from the following steps：
Preparation method is substantially the same manner as Example 7, the difference is that nickel nitrate is changed to 1.2g ferric nitrate, can obtain Cu base
Catalyst 8.
Embodiment 9：
Present embodiment discloses a kind of Cu base catalyst, are prepared from the following steps：
Preparation method is substantially the same manner as Example 7, the difference is that nickel nitrate is changed to 0.78g calcium acetate, can obtain Cu
Base catalyst 9.
Embodiment 10：
Present embodiment discloses a kind of Cu base catalyst, are prepared from the following steps：
Preparation method is substantially the same manner as Example 7, the difference is that nickel nitrate is changed to 1.18g titanium sulfate, can obtain Cu
Base catalyst 10.
Embodiment 11：
Present embodiment discloses a kind of Cu base catalyst, are prepared from the following steps：
Copper acetate dihydrate 2g, four acetate hydrate manganese 4.9g are weighed in 250mL volumetric flask, 100mL deionized water is added
It obtains mixed solution A and is transferred in oil bath pan to be warming up to 353K；5.4g sodium carbonate is weighed in beaker, 25mL deionization is added
Water obtains the sodium carbonate liquor B of 2M；It is 8.3 or so that mixed solution B, which is slowly added dropwise into solution A to pH of mixed, aging
12h；It filters, it is neutral for being washed with warm water to filtrate；383K dries 16h.It weighs, it will be before 1g catalyst using equi-volume impregnating
Body is impregnated in the aqueous solution containing 0.49g ammonium molybdate, and the dry 4h of 383K, 573K calcines 2h, in 10v%H2In 300 DEG C reduction
3h can obtain Cu base catalyst 11.
Embodiment 12：
Present embodiment discloses a kind of Cu base catalyst, are prepared from the following steps：
Preparation method is substantially the same manner as Example 11, the difference is that ammonium molybdate is changed to 0.29g ammonium metavanadate, can obtain
Cu base catalyst 12.
Furfuryl alcohol selectivity hydrogenolysis preparation 1,2- pentanediol carries out in a kettle, by 0.5g furfuryl alcohol, 4.5 g isopropyls
Alcohol is separately added into Cu base catalyst described in 0.25g embodiment 1-12 in 25mL reaction kettle；Reaction kettle is closed, into reaction kettle
It is passed through hydrogen, is vented, repeated multiple times to exchange the air in kettle, it is 6MPa that hydrogen to pressure is then filled with into kettle, is closed anti-
Kettle is answered, magnetic agitation is opened, is warming up to 140 DEG C and reacts 8h；In reaction process, when Hydrogen Vapor Pressure reduces 0.5MPa, in time
Hydrogen is filled with into reaction kettle to maintain constant reaction pressure；After reaction, cooling reaction kettle takes out reaction solution to room temperature
Filter carries out gas chromatographic analysis.Furfuryl alcohol conversion ratio and 1,2- pentanediol are selectively as shown in table 1.Other Main By products are
Tetrahydrofurfuryl alcohol, 2- methylfuran, n-amyl alcohol, 1,5- pentanediol etc..
For example, in embodiment 1, the choosing of 1,2- pentanediol, n-amyl alcohol, tetrahydrofurfuryl alcohol, 2- methylfuran, 1,5- pentanediol
Selecting property is respectively 53%, 27%, 7%, 2%, 11%；1,2- pentanediol, n-amyl alcohol, tetrahydrofurfuryl alcohol, 2- methyl furan in embodiment 3
It mutters, the selectivity of 1,5- pentanediol is respectively 70%, 12%, 2%, 4%, 12%.
1 different catalysts of table are catalyzed furfuryl alcohol hydrogenolysis
| Embodiment | Catalyst | Furfuryl alcohol conversion ratio (%) | 1,2- pentanediol selectivity (%) |
| 1 | Cu/MnCO3 | 82 | 53 |
| 2 | Cu/ZrO2 | 76 | 61 |
| 3 | Cu/ZnO | 73 | 70 |
| 4 | Cu/MgO | 79 | 53 |
| 5 | Cu/MnO2 | 80 | 52 |
| 6 | Cu/Mn3O4 | 75 | 58 |
| 7 | Cu-Ni/MnCO3 | 78 | 60 |
| 8 | Cu-Fe/MnCO3 | 89 | 51 |
| 9 | Cu-Ca/MnCO3 | 92 | 43 |
| 10 | Cu-Ti/MnCO3 | 75 | 68 |
| 11 | Cu-Mo/MnCO3 | 89 | 72 |
| 12 | Cu-V/MnCO3 | 85 | 61 |
Embodiment 13-18
Embodiment 13-18 discloses different Cu load capacity and prepares the influence of 1,2- pentanediol (with Cu/ to furfuryl alcohol hydrogenolysis
MnCO3For), the specific implementation is as follows：
By 0.5g furfuryl alcohol, 4.5g isopropanol, be separately added into 0.25g active metal Cu load capacity be 1%, 5%, 10%,
20%, 50%, 100% Cu/MnCO3In 25mL reaction kettle；Reaction kettle is closed, hydrogen is passed through into reaction kettle, is vented, instead
Multiple repeatedly to exchange the air in kettle, it is 6MPa that hydrogen to pressure is then filled with into kettle, closes reaction kettle, opens magnetic force and stirs
It mixes, be warming up to 140 DEG C and react 8h；In reaction process, when Hydrogen Vapor Pressure reduces 0.5MPa, hydrogen is filled with into reaction kettle in time
Gas is to maintain constant reaction pressure；After reaction, reaction solution is filtered to room temperature, carries out gas-chromatography point by cooling reaction kettle
Analysis.Furfuryl alcohol conversion ratio and 1,2- pentanediol are selectively as shown in table 2.
The Cu/MnO of 2 difference Cu load capacity of tablexThe influence of 1,2- pentanediol is prepared to furfuryl alcohol hydrogenolysis
Embodiment 19-24
Embodiment 19-24 discloses the influence that different solvents prepare 1,2- pentanediol for furfuryl alcohol hydrogenolysis
10% Cu/MnCO3For), the specific implementation is as follows：
By 0.5g furfuryl alcohol, 4.5g solvent, 0.25g Cu/MnCO is added3In 25mL reaction kettle；Reaction kettle is closed, to anti-
It answers and is passed through hydrogen in kettle, be vented, repeated multiple times to exchange the air in kettle, it is 6MPa that hydrogen to pressure is then filled with into kettle,
Reaction kettle is closed, magnetic agitation is opened, is warming up to 140 DEG C and reacts 8h；In reaction process, when Hydrogen Vapor Pressure reduces 0.5MPa
When, it is filled with hydrogen into reaction kettle in time to maintain constant reaction pressure；After reaction, cooling reaction kettle, will be anti-to room temperature
It answers liquid to filter, carries out gas chromatographic analysis.Furfuryl alcohol conversion ratio and 1,2- pentanediol are selectively as shown in table 3.
3 different solvents of table prepare the influence of 1,2- pentanediol to furfuryl alcohol hydrogenolysis
Embodiment 25-29
Embodiment 25-29 discloses influence of the differential responses temperature for furfuryl alcohol hydrogenolysis preparation 1,2- pentanediol, specific real
It is as follows to apply situation：
By 0.5g furfuryl alcohol, 4.5g isopropanol, it is separately added into 0.25g 10%Cu/MnCO3In 25mL reaction kettle；It closes
Reaction kettle is passed through hydrogen into reaction kettle, emptying, repeated multiple times to exchange the air in kettle, and hydrogen is then filled with into kettle extremely
Pressure is 6MPa, close reaction kettle, open magnetic agitation, be warming up to respectively 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C simultaneously
React 8h；In reaction process, when Hydrogen Vapor Pressure reduces 0.5MPa, it is filled with hydrogen into reaction kettle in time to maintain reaction pressure
It is constant；After reaction, reaction solution is filtered to room temperature, carries out gas chromatographic analysis by cooling reaction kettle.Furfuryl alcohol conversion ratio and
1,2- pentanediol is selectively as shown in table 4.
4 differential responses temperature of table prepares the influence of 1,2- pentanediol to furfuryl alcohol hydrogenolysis
Embodiment 30-35
Embodiment 30-35 discloses influence of the differential responses pressure to furfuryl alcohol hydrogenolysis preparation 1,2- pentanediol, specific implementation
Situation is as follows：
By 0.5g furfuryl alcohol, 4.5g isopropanol, it is separately added into 0.25g 10%Cu/MnCO3In 25mL reaction kettle；It closes
Reaction kettle is passed through hydrogen into reaction kettle, emptying, repeated multiple times to exchange the air in kettle, is then filled with respectively into kettle
Hydrogen to pressure is 0.5MPa, 1MPa, 2MPa, 4MPa, 6MPa, 8MPa, closes reaction kettle, opens magnetic agitation, is warming up to
140 DEG C and react 8h；In reaction process, when Hydrogen Vapor Pressure reduces 0.5MPa, it is filled with hydrogen into reaction kettle in time to maintain
Constant reaction pressure；After reaction, reaction solution is filtered to room temperature, carries out gas chromatographic analysis by cooling reaction kettle.Furfuryl alcohol turns
Rate and 1,2- pentanediol are selectively as shown in table 5.
5 different hydrogen pressure of table prepares the influence of 1,2- pentanediol to furfuryl alcohol hydrogenolysis
Embodiment 36-42
Embodiment 36-42 discloses influence of the reaction time to furfuryl alcohol hydrogenolysis preparation 1,2- pentanediol, and situation is embodied
It is as follows：
By 0.5g furfuryl alcohol, 4.5g isopropanol, 0.25g 10%Cu/MnCO3In 25mL reaction kettle；Reaction kettle is closed, to
It is passed through hydrogen in reaction kettle, is vented, it is repeated multiple times to exchange the air in kettle, then respectively to being filled with hydrogen into kettle to pressure
For 6MPa, reaction kettle is closed, magnetic agitation is opened, is warming up to 140 DEG C, reacts 1h, 2h, 4h, 6h, 8h, 12h, 18h respectively；Instead
During answering, when Hydrogen Vapor Pressure reduces 0.5MPa, it is filled with hydrogen into reaction kettle in time to maintain constant reaction pressure；Reaction
After, reaction solution is filtered, carries out gas chromatographic analysis by cooling reaction kettle to room temperature.Furfuryl alcohol conversion ratio and 1,2- penta 2
Alcohol is selectively as shown in table 6.
6 reaction time of table prepares the influence of 1,2- pentanediol to furfuryl alcohol hydrogenolysis
Embodiment 43-48
Embodiment 43-48 discloses influence of the furfuryl alcohol concentration to furfuryl alcohol hydrogenolysis preparation 1,2- pentanediol, and situation is embodied
It is as follows：
Using isopropanol as solvent, being separately added into mass fraction is 2%, 5%, 10%, 50%, 80%.100% furfuryl alcohol is molten
Liquid, 0.25g 10%Cu/MnCO3In 25mL reaction kettle；Reaction kettle is closed, hydrogen is passed through into reaction kettle, is vented, it is repeatedly more
It is secondary to exchange the air in kettle, then respectively to be filled with into kettle hydrogen to pressure be 6MPa, close reaction kettle, open magnetic force stir
It mixes, is warming up to 140 DEG C, react 8h；In reaction process, when Hydrogen Vapor Pressure reduces 0.5MPa, hydrogen is filled with into reaction kettle in time
Gas is to maintain constant reaction pressure；After reaction, reaction solution is filtered to room temperature, carries out gas-chromatography point by cooling reaction kettle
Analysis.Furfuryl alcohol conversion ratio and 1,2- pentanediol are selectively as shown in table 7.
7 furfuryl alcohol concentration of table prepares the influence of 1,2- pentanediol to furfuryl alcohol hydrogenolysis
Embodiment 49-54
Embodiment 49-54 discloses influence of the catalyst amount to furfuryl alcohol hydrogenolysis preparation 1,2- pentanediol, and feelings are embodied
Condition is as follows：
0.5g furfuryl alcohol, 4.5g isopropanol are transferred in 25mL reaction kettle；Be separately added into 0.005g, 0.05g, 0.1g,
0.25g, 0.5g 10%Cu/MnCO3Reaction kettle is closed, hydrogen is passed through into reaction kettle, is vented, it is repeated multiple times to exchange in kettle
Air, then respectively to be filled with into kettle hydrogen to pressure be 6MPa, close reaction kettle, open magnetic agitation, be warming up to 140
DEG C, react 8h；In reaction process, when Hydrogen Vapor Pressure reduces 0.5MPa, it is filled with hydrogen into reaction kettle in time to maintain to react
Pressure is constant；After reaction, reaction solution is filtered to room temperature, carries out gas chromatographic analysis by cooling reaction kettle.Furfuryl alcohol conversion ratio
And 1,2- pentanediol is selectively as shown in table 8.
8 catalyst amount of table prepares the influence of 1,2- pentanediol to furfuryl alcohol hydrogenolysis
Embodiment 55
Present embodiment discloses a kind of methods of furfuryl alcohol hydrogenolysis preparation 1,2- pentanediol, and steps are as follows for specific experiment：
By 10g furfuryl alcohol, 15g isopropanol, 5g 10%Cu/MnCO3It is transferred in 50mL reaction kettle；Reaction kettle is closed, to anti-
It answers and is passed through hydrogen in kettle, be vented, it is repeated multiple times to exchange the air in kettle, be then to being filled with hydrogen to pressure into kettle respectively
6MPa closes reaction kettle, opens magnetic agitation, is warming up to 140 DEG C, reacts 10h；In reaction process, when Hydrogen Vapor Pressure reduces
When 0.5MPa, it is filled with hydrogen into reaction kettle in time to maintain constant reaction pressure；After reaction, reaction kettle is cooled down to room
Temperature filters reaction solution, carries out gas chromatographic analysis.According to gas chromatographic analysis as a result, the conversion ratio of furfuryl alcohol is 75%, wherein
The selectivity of 1,2- pentanediol is 43%.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, those skilled in the art should understand that：Its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of method of furfuryl alcohol liquid-phase catalysis selectivity hydrogenolysis preparation 1,2- pentanediol, which is characterized in that include the following steps：
Furfuryl alcohol, Cu base catalyst and reaction dissolvent are put into reaction kettle, hydrogen is filled with into reaction kettle and replace air in kettle,
Hydrogen Vapor Pressure is filled with to 0.5-8MPa, stirs and is warming up to 100-180 DEG C, 1-18h of reaction obtains 1,2- pentanediol.
2. the method for furfuryl alcohol liquid-phase catalysis selectivity hydrogenolysis preparation 1,2- pentanediol according to claim 1, which is characterized in that
The Cu base catalyst is using Cu as active component, carrier MnOx、MnCO3、ZrO2, one of ZnO, MgO or a variety of, auxiliary agent
For one of Mo, V, Ni, Fe, Ca, Ti or a variety of.
3. the method for furfuryl alcohol liquid-phase catalysis selectivity hydrogenolysis preparation 1,2- pentanediol according to claim 2, which is characterized in that
The carrier MnOxFor MnO2、MnO、Mn2O3、Mn3O4One of or it is a variety of.
4. the method for furfuryl alcohol liquid-phase catalysis selectivity hydrogenolysis preparation 1,2- pentanediol according to claim 2, which is characterized in that
The content of the auxiliary agent is 0-50%wt.
5. the method for furfuryl alcohol liquid-phase catalysis selectivity hydrogenolysis preparation 1,2- pentanediol according to claim 1, which is characterized in that
The reaction dissolvent is one of methanol, ethyl alcohol, isopropanol, normal propyl alcohol, isobutyl alcohol and water or a variety of.
6. the method for furfuryl alcohol liquid-phase catalysis selectivity hydrogenolysis preparation 1,2- pentanediol according to claim 1, which is characterized in that
The mass ratio of the Cu base catalyst and furfuryl alcohol is 1:1–100.
7. the method for furfuryl alcohol liquid-phase catalysis selectivity hydrogenolysis preparation 1,2- pentanediol according to claim 1, which is characterized in that
The Hydrogen Vapor Pressure that is filled with is stirred and is warming up to 120-160 DEG C, react 4-12h to 2-6MPa.
8. the method for furfuryl alcohol liquid-phase catalysis selectivity hydrogenolysis preparation 1,2- pentanediol according to claim 1, which is characterized in that
The method that the Cu base catalyst precipitates active component impregnation aids again by coprecipitation or first is prepared；Cu base catalysis
The mass content of active component Cu is 1-100%wt in agent.
9. the method for furfuryl alcohol liquid-phase catalysis selectivity hydrogenolysis preparation 1,2- pentanediol according to claim 1, which is characterized in that
It is as follows that coprecipitation prepares Cu base catalyst Step：Soluble copper salt is dissolved in solvent, being configured to concentration is 0.02-4mol/L
Solution, one of soluble manganese salt, zirconates, zinc salt, magnesium salts or a variety of are added according to a certain percentage, it is soluble that auxiliary agent is added
One of molybdenum salt, vanadic salts, molysite, calcium salt, titanium salt are a variety of；The carbon that concentration is 0.5-4mol/L is added dropwise into mixing salt solution
The pH of hydrochlorate to solution is 7-13；Then by mixed liquor at 20-120 DEG C aging 1-8h, filter, washed with warm water to filtrate and be
Neutrality, dry 2-20h, calcines 2h-8h at 200-800 DEG C at 100-130 DEG C；Then in 10-30v%H2Middle reduction 1-8h,
Cu base catalyst is prepared.
10. the method for furfuryl alcohol liquid-phase catalysis selectivity hydrogenolysis preparation 1,2- pentanediol, feature exist according to claim 1
In first precipitating active component, impregnation aids preparation Cu base catalyst Step is as follows again：Soluble copper salt is dissolved in solvent, is prepared
The solution for being 0.02-4mol/L at concentration, be added according to a certain percentage one of soluble manganese salt, zirconates, zinc salt, magnesium salts or
It is a variety of；It is 7-13 that the pH of carbonate to solution that concentration is 0.5-4mol/L is added dropwise into mixing salt solution；Then by mixed liquor
The aging 1-8h at 20-120 DEG C is filtered, and being washed with warm water to filtrate is neutral, dry 2-20h at 100-130 DEG C；According to one
Certainty ratio is prepared containing one of auxiliary component Mo, V, Ni, Fe, Ca, Ti or a variety of aqueous solutions, by the catalyst after drying
It is impregnated in 0.5h-12h in the solution, 100-130 DEG C of dry 2-20h calcines 2h-8h at 200-800 DEG C；Then in 10-
30v%H2Cu base catalyst is prepared in middle reduction 1-8h.
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