CN106278889A - A kind of method preparing 5-hydroxyl methyl - Google Patents
A kind of method preparing 5-hydroxyl methyl Download PDFInfo
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- CN106278889A CN106278889A CN201510243997.8A CN201510243997A CN106278889A CN 106278889 A CN106278889 A CN 106278889A CN 201510243997 A CN201510243997 A CN 201510243997A CN 106278889 A CN106278889 A CN 106278889A
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- furfural
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
Abstract
The present invention discloses a kind of method preparing 5-hydroxyl methyl.The method uses brand-new process route, use biomass furfural wide, reproducible of originating as raw material, and furfural and methanol generate furfural partly contracting methanol, furfural half contracting methanol dehydrogenation is prepared the reaction of methylfuroate and carried out at the conditionality of same reactor, same catalyst, the selectivity of suppression furfural dimethyl acetal, improves the productivity of finished product.Have that cost of material is low, production cost is low, Atom economy is high, product yield is high, the simple feature of separating technology, and make full use of by-product hydrogen and cheap metal catalyst, environmental friendliness, cost-effective.
Description
Technical field
The invention belongs to organic synthesis field, more particularly relate to one and utilize biomass derivatives furfural to prepare
The preparation method of 5-hydroxyl methyl.
Background technology
Biomass are big etc. of increased attention, using biomass as just because of its wide material sources, reserves
Material synthesis various chemicals more environmental protection.Furfural can obtain from wastes of crops corn cob and bagasse etc.
Taking, be mass produced in China North China and Shandong one band, but major part is only with low-price export, deep processing is serious
Lack.Furfural is converted into by means of catalysis the chemicals of high added value, is possible not only to comprehensive utilization agricultural
Waste material, and the new way of a kind of environmental protection is provided for the synthesis of chemicals.
Polyhydroxyalkanoate (Polyhydroxyalkanoate, PHA), is to develop rapidly for nearly more than 20 years
The bioabsorbable polymer material got up, is present in multiple-microorganism intracellular, (5-hydroxyl penta as poly-in homopolymer
Acid), English name is poly (5-hydroxyvalerate) or P5HV.Because PHA has good simultaneously
The hot-working character of bio-compatible performance, biodegradability and plastics, can be as bio-medical material and life
Biodegradable packaging material, have become as the study hotspot that technical field of biological material in recent years is enlivened the most.PHA
Also have been used for developing biologic medical equipment, including stitching thread, prosthetic device, reparation sticking patch, suspender belt, painstaking effort
Tubular patch, orthopedic surgery pin, to adhere to Obstruct membrane, support, guiding tissue repair/regenerating unit, joint soft
Bone Defect Repari device, nerve trachea, tendon repair device, gerustmark and wound dressing.
5-hydroxyl methyl (CAS 14273-92-8) is the important monomer of synthesis P5HV, but at present
The method preparing 5-hydroxyl methyl is little, and 5 carbon compounds based on petroleum resources, as by ring penta
Ketone carry out Baeyer Villiger reaction produce (S.Zarrabi, N.O.Mahmoodi, O.Marvi,
Monatshefte f ü r Chemie-Chemical Monthly, 2010,141,889-891), the method uses
Strong oxidizer K2S2O8, producing substantial amounts of acid waste water, cost of material is the highest and pollutes environment.Therefore, urgently
Non-petroleum renewable carbon source need to be used as producing the raw material of P5HV polymer, thus reduce cost and carry
For the material being made up of Renewable resource completely.Additionally, at present the most either using pure bacterium or activated sludge as bacterium
Kind, the PHA of synthesis is mainly composed of hydroxybutyric acid (Hydroxybutyrate, HB).But high HB
The PHA of content is the hardest and crisp, and fusing point is higher, poor heat stability, and this results in and is higher than in temperature
Add under conditions of its fusing point about 10 DEG C and can make PHA molecular weight degradation man-hour, thus limit material
The application of material.By introducing other monomer, such as 5-hydroxyl methyl, then can reduce PHA fusing point and
Degree of crystallinity, improves its heat stability, pliability and ductility, makes material impact-resistant be more easily handled.
5-hydroxyl methyl can also obtain δ-valerolactone (δ-Valerolactone), the latter by separating methanol
It is a kind of important organic intermediate raw material and the intermediate of essential industry.δ-valerolactone is used for synthesizing 5-bromine penta
Acid and oligomeric peptide etc.；In pharmaceuticals industry, for synthesizing pyran pyrimidine, cyclenes ether, cilostazol, witting
Reagent and Epothifone anticarcinogen；Particularly preparing equal polyester and polyactide etc. can be with Biodegradable high molecular
Material, is applied to the slow release of surgical sewing thread, medicine or pesticide, cosmetics and battery industry electrolyte
Deng.
Patent US2006224013 relates to alcohols and aldehydes containing Cu and ZrO2Catalyst on occur dehydrogenation anti-
Lower member ester should be synthesized, but the alcohol used or aldehyde are confined to the micromolecular compound of only 1～4 carbon atom,
And reaction is carried out under 260 DEG C of high temperature, it is not suitable for the preparation of methylfuroate.Patent EP0189283 is open
Methyl formate is prepared in platinum group metal particularly Ru compound for catalysis methanol dehydrogenation esterification, and catalyst is prepared numerous
Trivial, react 4h yield at 180 DEG C and only have 1.5%.Chinese patent CN102068986, CN103265400
Relate to furan or tetrahydrofuran derivatives as raw material, use containing Pt metal, Pd, Ru, Rh, Ir,
Ni, Co, Cu and the catalyst of acid carrier, prepare pentanediol and middle long-chain by furan open loop hydrogenation method
Primary alconol, reaction selectivity is poor, and target product yield is below 45%.Obviously, said method can not meet 5-
The production of hydroxyl methyl.
Along with environmental conservation and chemical reaction Atom economy requirement are gradually stepped up by people, develop low one-tenth
Basis, high yield, oligosaprobic production process have become the inexorable trend of new chemical industry industrial development.
Summary of the invention
It is an object of the invention to provide a kind of method preparing 5-hydroxyl methyl, the method has raw material
This is low, Atom economy is high, product yield is high, the simple feature of separating technology.
The present invention is achieved through the following technical solutions:
The preparation method of a kind of 5-hydroxyl methyl, comprises the steps:
A) furfural, methanol, water are under the catalysis of dehydrogenation, obtain the reaction containing methylfuroate
Liquid；
B) step a) obtains the reactant liquor containing methylfuroate and hydrogen enter under the catalysis of hydrogenolysis catalyst
Row hydrogenolysis, obtains the reactant liquor containing 5-hydroxyl methyl.
The reaction equation of step a) is as follows:
The course of reaction of step b) is as follows:
Two-step reaction occurs in step a) of the present invention, and the first step generates furfural partly contracting methanol, water
Addition can suppress furfural dimethyl acetalThe generation of by-product；Second step is that dehydrogenation reaction generates
Methylfuroate.This two-step reaction completes on same reactor and dehydrogenation.
The dehydrogenation of step a) of the present invention is carrier loaded Ru, the load of described dehydrogenation
Body is the one or two or more in activated carbon, silicon dioxide, aluminium oxide, titanium dioxide and magnesium oxide；
The content of Ru is 0.1～10wt%, preferably 2～5wt%, gross mass meter based on dehydrogenation.
The reaction temperature of step a) of the present invention is 30～120 DEG C, preferably 60～100 DEG C；Mass space velocity is
0.5～3h-1, preferably 1～2h-1, in terms of furfural raw material, the mol ratio of methanol/water/furfural is
(2～8)/(0.01～0.1)/1, preferably (3～6)/(0.02～0.08)/1.
In the inventive method, Ru based dehydrogenation catalyst, catalysis furfural half contracting methanol intermediate dehydrogenation is used to turn
Turn to methylfuroate, greatly reduce reaction temperature, effectively prevent polymerization side reactions, improve methylfuroate
Selectivity.
The reaction temperature of step b) of the present invention is 50～150 DEG C, preferably 80～120 DEG C, reaction absolute
Pressure is 1～20MPa, preferably 4～10MPa；Hydrogen is 2～20:1 with the mol ratio of methylfuroate, preferably
5～10:1, mass space velocity is 0.5～3h-1, preferably 1～2h-1, in terms of the furfural raw material of step a).
The hydrogenolysis catalyst of step b) of the present invention is loaded catalyst, the work of described hydrogenolysis catalyst
Property component is Ag and/or Au, preferably Au, the carrier of described hydrogenolysis catalyst is Zn, In, Sn, Pb,
The metal-oxide of the one or two or more in Sb, Bi and Te, active group of described hydrogenolysis catalyst
The content divided is 1～10wt%, preferably 1～4wt%, gross mass meter based on hydrogenolysis catalyst.
The reactant liquor containing 5-hydroxyl methyl that step b) of the present invention obtains steams through normal pressure
Evaporate, reclaim unreacted methanol, obtain 5-hydroxyl methyl through rectification under vacuum the most again.
In the inventive method, described dehydrogenation and hydrogenolysis catalyst use infusion process to prepare, catalyst
Except active component, surplus is carrier.
Dehydrogenation of the present invention can use the method for well known to a person skilled in the art to prepare, and preferably adopts
Preparing by infusion process, described infusion process comprises the following steps: added by metering ratio by the soluble salt solutions of Ru
Enter the medium volume impregnation of carrier to molding in advance, be dried 6～24 hours at 80～120 DEG C, 300～600 DEG C of roastings
Burn 2～5 hours prepared dehydrogenation precursors.When used carrier is activated carbon, it is not necessary to roasting.
Described dehydrogenation precursor need to just have catalysis activity, reduction in the reduction of hydrogen situ before use
Condition is Hydrogen Vapor Pressure 0.1～1MPa, preferably 0.2～0.4MPa；Every 100g dehydrogenation uses
H2Flow velocity is 0.2～10L/min, preferably 1～5L/min；Reduction temperature 120～350 DEG C, be preferably
180～250 DEG C；Recovery time is 1～10 hour, preferably 2～4 hours.
Hydrogenolysis catalyst of the present invention can use the method for well known to a person skilled in the art to prepare, and preferably adopts
Preparing by infusion process, described infusion process comprises the following steps: pressed by the soluble salt solutions of Ag and/or Au
Metering ratio adds the medium volume impregnation of carrier to molding in advance, is dried 6～24 hours at 80～120 DEG C,
300～600 DEG C of roastings 2～obtain hydrogenolysis catalyst precursor in 5 hours.
Described hydrogenolysis catalyst precursor need to just have catalysis activity, reduction in the reduction of hydrogen situ before use
Condition is Hydrogen Vapor Pressure 0.1～1MPa, preferably 0.2～0.4MPa；Every 100g hydrogenolysis catalyst uses
H2Flow velocity is 0.2～10L/min, preferably 1～5L/min；Reduction temperature 150～450 DEG C, be preferably
200～350 DEG C；Recovery time is 1～10 hour, preferably 2～4 hours.
Heretofore described pressure is absolute pressure.
This technique compared with prior art has the advantages that
(1) use brand-new process route, use biomass furfural wide, reproducible of originating as former
Material, production cost is low, and by developing the catalyst of new high efficiency so that the high selective formation half of furfural
Acetal, the generation of suppression by-product, the selectivity 0.5～1% of furfural dimethyl acetal, with furfural molar amount；
And obtaining methylfuroate by dehydrogenation reaction height yield, the selectivity of methylfuroate is more than 95%, rubs with furfural
That gauge；In methylfuroate hydrogenolysis, ester group is unaffected, and 5-hydroxyl methyl selectivity is more than
95%, with furfural molar amount.
(2) using heterogeneous catalysis and fixed-bed process, product can be easily separated, and furfural prepares furfural half
Contracting methanol and furfural half contracting methanol dehydrogenation prepare methylfuroate two-step reaction can be on same reactor and catalyst
Efficiently carrying out, technique is simple.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, it should be noted that embodiment not structure
The restriction of paired claimed scope.
In the examples below, as without the most dated, " % " that used is " mole percent ".
The test instrunment that the present embodiment uses is: gas phase uses Shimadzu GC-2010 type gas chromatograph (hydrogen fire
Flame detector, nitrogen is as carrier gas) be analyzed, use DB-5 type capillary chromatographic column (5%Phenyl
Methyl Siloxan, 30m × 0.32mm × 0.25 μm), hydrogen flame detector (FID) detector.Enter
Sample device and detector temperature are 280 DEG C；Column temperature uses temperature programming to control: the initial 100 DEG C of holdings of column temperature
0.5 minute, 15 DEG C/min was warming up to 260 DEG C, kept 5 minutes.Column pressure 8.5868psi, flow velocity 1.5
mL/min.Sample size: 0.2 μ L.Conversion ratio and selectivity use area normalization method to calculate.
Nuclear-magnetism uses Bruker AV300 test, and 50mg sample is dissolved in the CDCl of 0.5mL3In.
Infrared use Nicolet Nexus 470 tests, and uses KBr coating method.
Embodiment 1～11: prepared by dehydrogenation
Ruthenic chloride being configured to the aqueous solution of 10wt%, adds support powder according to the ratio of table 1, stirring is mixed
Close uniformly, under room temperature, impregnate 12h, at 120 DEG C of dry 12h, roasting 4h at 500 DEG C；If carrier is alive
Property charcoal, then without roasting, prepare different activities constituent content catalyst raw powder, obtained by compression molding
The dehydrogenation precursor of molding.
Prepared by table 1 dehydrogenation
| Catalyst sequence number | Carrier | Ru content wt% |
| 1# | Activated carbon | 5 |
| 2# | SiO2 | 4 |
| 3# | Al2O3 | 5 |
| 4# | TiO2 | 3 |
| 5# | MgO | 2 |
| 6# | SiO2-Al2O3(mass ratio 1:1) | 4 |
| 7# | SiO2-TiO2(mass ratio 4:1) | 4 |
| 8# | SiO2-MgO (mass ratio 1:2) | 5 |
| 9# | TiO2-Al2O3(mass ratio 2:3) | 3 |
| 10# | MgO-Al2O3(mass ratio 3:2) | 3.5 |
| 11# | MgO-TiO2(mass ratio 1:4) | 2.5 |
Embodiment 12～22: prepared by hydrogenolysis catalyst
Substep equi-volume impregnating is used to be prepared, by the solution of the active component soluble-salt of 10wt%,
Stir to carrier than adding according to certain metering, impregnate 12 hours under room temperature, then at 120 DEG C
Baking oven is dried 12 hours；At 500 DEG C, roasting 3 hours in air, obtain catalyst raw powder, pass through tabletting
Molding obtains the hydrogenolysis catalyst precursor of molding.
Prepared by table 2 hydrogenolysis catalyst
Embodiment 23: evaluating catalyst
1# reactor is external diameter 40mm, internal diameter 20mm, the stainless steel tube of long 1000mm.50g is taken off
Hydrogen catalyst precursor is filled in 1# reactor, to catalyst precarsor in-situ reducing, reduction temperature before reaction
250 DEG C, H2Pressure is 0.2MPa, H2Flow velocity 1.5L/min, reduces 4 hours.
2# reactor is external diameter 40mm, internal diameter 20mm, the stainless steel tube of long 1000mm.By 50g hydrogen
Solve catalyst precarsor to be filled in 2# reactor, to catalyst precarsor in-situ reducing, reduction temperature before reaction
300 DEG C, H2Pressure is 0.5MPa, H2Flow velocity 1.5L/min, reduces 4 hours.
Furfural, methanol, water enter 1# reactor, analyze at 1# reactor outlet position sample；1# reacts
The reactant liquor of device and hydrogen enter 2# reactor, analyze at 2# reactor outlet position sample, reaction condition
And the results are shown in Table 3.
1# reactor outlet material first passes through air-distillation and reclaims methanol, then uses rectification under vacuum technique, receives
Collection 2kPa, the sample of 65～66 DEG C of boiling ranges, obtain methylfuroate, purity 99.6%, carry out NMR, IR and divide
Analysis, data are as follows:
1H NMR (300MHz, CDCl3, TMS is internal standard): 3.88 (s, 3H, CH3O-),
6.69 (m, 1H, ArH), 7.15 (m, 1H, ArH), 7.56 (m, 1H, ArH).
FT-IR (KBr, σ/cm-1): 3144,3127 (Ar-H st), 2966 (C-H st), 1731 (C=O
St), 1393 (C-H δ), 1121 (C-O st).
2# reactor outlet material first passes through air-distillation and reclaims methanol, then uses rectification under vacuum technique, receives
Collection 1kPa, the sample of 78～80 DEG C of boiling ranges, obtain 5-hydroxyl methyl, purity 99.5%.Carry out
NMR, IR analyze, and data are as follows:.
1H NMR (300MHz, CDCl3, TMS is internal standard): 1.48 (m, 2H ,-CH2-),
1.68 (m, 2H ,-CH2-), 2.0 (br, 1H ,-OH), 2.25 (t, 2H ,-CH2-), 3.53 (t,
2H ,-CH2-), 3.67 (s, 3H ,-CH3O-)。
FT-IR (KBr, σ/cm-1): 3466,3456 (O-H st), 2976,2966,2939 (C-H st),
1727 (C=O st), 1396 (C-H δ), 1053 (C-O st).
Embodiment 24～33: evaluating catalyst
Using the reaction condition in table 3, remaining reaction condition is with embodiment 23.Reaction result is shown in Table 3.
Table 3 reaction condition and result
From table 3 it can be seen that the generation of furfuryl alcohol dimethyl acetal can be suppressed well by adding water, different
Ru catalyst furfural half contracting methanol dehydrogenation reaction table is revealed high activity and and methylfuroate selectivity,
Relatively low reaction temperature effectively prevent polymerization.
It addition, different hydrogenolysis catalysts shows high activity and 5-hydroxyl penta to methylfuroate hydrogenolysis
Acid methyl ester selectivity, High Temperature High Pressure is more beneficial for reaction and carries out, but temperature is too high, 5-hydroxyl methyl meeting
Excessively hydrogenolysis is methyl valerate by-product.
Embodiment 34: catalyst stability evaluation
Use 50g 3# dehydrogenation and 50g 20# hydrogenolysis catalyst to carry out study on the stability, react at string
Carrying out in the 1# reactor of connection and 2# reactor, the reaction condition of 1# reactor is: rubbing of methanol/water/furfural
That ratio=5/0.06/1, the mass space velocity of furfural is 1.5h-1, temperature 80 DEG C, normal pressure；The reaction of 2# reactor
Condition is temperature 100 DEG C, pressure 8MPa, hydrogen and mol ratio 8:1 of methylfuroate.
Carry out the continuous investigation of 1000h, furfural conversion ratio 99.2～about 100%, 5-hydroxyl methyl
Selectivity 96～about 98%, overall yield 95～97%.
The above, the only present invention preferably detailed description of the invention, but protection scope of the present invention not office
Being limited to this, any those familiar with the art, can be easily in the technical scope of present disclosure
The change expected or replacement, all should contain within protection scope of the present invention.
Claims (9)
1. the method preparing 5-hydroxyl methyl, comprises the steps:
A) furfural, methanol, water are under the catalysis of dehydrogenation, obtain the reaction containing methylfuroate
Liquid；
B) step a) obtains the reactant liquor containing methylfuroate and hydrogen enter under the catalysis of hydrogenolysis catalyst
Row hydrogenolysis, obtains the reactant liquor containing 5-hydroxyl methyl.
Method the most according to claim 1, it is characterised in that the reaction temperature of described step a) is
30～120 DEG C, preferably 60～100 DEG C.
Method the most according to claim 1, it is characterised in that the mass space velocity of described step a) is
0.5～3h-1, preferably 1～2h-1, in terms of furfural raw material.
Method the most according to claim 1, it is characterised in that methanol/water/bran in described step a)
The mol ratio of aldehyde is (2～8)/(0.01～0.1)/1, preferably (3～6)/(0.02～0.08)/1.
Method the most according to claim 1, it is characterised in that the dehydrogenation of described step a)
For carrier loaded Ru, the carrier of described dehydrogenation is activated carbon, silicon dioxide, aluminium oxide, dioxy
Change the one or two or more in titanium and magnesium oxide；The content of Ru is 0.1～10wt%, preferably
2～5wt%, gross mass meter based on dehydrogenation.
Method the most according to claim 1, it is characterised in that the reaction temperature of described step b) is
50～150 DEG C, preferably 80～120 DEG C, the absolute pressure of reaction is 1～20MPa, preferably 4～10MPa.
Method the most according to claim 1, it is characterised in that hydrogen and furancarboxylic acid in described step b)
The mol ratio of methyl ester is 2～20:1, preferably 5～10:1.
Method the most according to claim 1, it is characterised in that the mass space velocity of described step b) is
0.5～3h-1, preferably 1～2h-1, in terms of the furfural raw material of step a).
Method the most according to claim 1, it is characterised in that the hydrogenolysis catalyst of described step b)
Agent is loaded catalyst, and the active component of described hydrogenolysis catalyst is Ag and/or Au, preferably Au, institute
The carrier stating hydrogenolysis catalyst is the one or two or more in Zn, In, Sn, Pb, Sb, Bi and Te
Metal-oxide, the content of the active component of described hydrogenolysis catalyst is 1～10wt%, preferably
1～4wt%, gross mass meter based on hydrogenolysis catalyst.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108774135A (en) * | 2018-08-06 | 2018-11-09 | 朱友富 | A kind of preparation method of 5- hydroxyl methyls |
| CN108929224A (en) * | 2018-08-06 | 2018-12-04 | 朱友富 | A method of preparation 5- hydroxyl methyl is catalyzed using bifunctional catalyst |
| CN113831312A (en) * | 2020-06-24 | 2021-12-24 | 中国石油化工股份有限公司 | Method for preparing delta-cyclopentanolide |
| CN115894420A (en) * | 2021-08-18 | 2023-04-04 | 中国石油化工股份有限公司 | Method for preparing delta-cyclopentanolide |
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| EP1048638A1 (en) * | 1999-04-27 | 2000-11-02 | Kvaerner Process Technology Limited | Process for the recovery of pentane-1,5-diol |
| CN102068986A (en) * | 2011-01-06 | 2011-05-25 | 华东理工大学 | Catalyst used in ring-opening hydrogenation reaction of furan derivative |
| CN103265400A (en) * | 2013-05-28 | 2013-08-28 | 华东理工大学 | Environment-friendly novel method for preparing primary alcohol from furan or tetrahydrofuran derivatives |
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| EP1048638A1 (en) * | 1999-04-27 | 2000-11-02 | Kvaerner Process Technology Limited | Process for the recovery of pentane-1,5-diol |
| CN102068986A (en) * | 2011-01-06 | 2011-05-25 | 华东理工大学 | Catalyst used in ring-opening hydrogenation reaction of furan derivative |
| CN103265400A (en) * | 2013-05-28 | 2013-08-28 | 华东理工大学 | Environment-friendly novel method for preparing primary alcohol from furan or tetrahydrofuran derivatives |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108774135A (en) * | 2018-08-06 | 2018-11-09 | 朱友富 | A kind of preparation method of 5- hydroxyl methyls |
| CN108929224A (en) * | 2018-08-06 | 2018-12-04 | 朱友富 | A method of preparation 5- hydroxyl methyl is catalyzed using bifunctional catalyst |
| CN113831312A (en) * | 2020-06-24 | 2021-12-24 | 中国石油化工股份有限公司 | Method for preparing delta-cyclopentanolide |
| CN113831312B (en) * | 2020-06-24 | 2023-06-09 | 中国石油化工股份有限公司 | Method for preparing delta-cyclopentalactone |
| CN115894420A (en) * | 2021-08-18 | 2023-04-04 | 中国石油化工股份有限公司 | Method for preparing delta-cyclopentanolide |
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| CN106278889B (en) | 2019-01-29 |
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