CN108774135A - A kind of preparation method of 5- hydroxyl methyls - Google Patents
A kind of preparation method of 5- hydroxyl methyls Download PDFInfo
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- CN108774135A CN108774135A CN201810884027.XA CN201810884027A CN108774135A CN 108774135 A CN108774135 A CN 108774135A CN 201810884027 A CN201810884027 A CN 201810884027A CN 108774135 A CN108774135 A CN 108774135A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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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
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Abstract
The invention discloses a kind of preparation methods of 5- hydroxyl methyls, using Cu-La-Al2O3Catalyst substitutes the noble metals such as Rh and Au as catalyst, furfural prepares half contracting methanol of furfural and half contracting methanol dehydrogenation of furfural prepares methylfuroate two-step reaction and can efficiently be carried out on same reactor and catalyst, while reducing catalyst cost, half contracting methanol intermediate dehydrogenation of furfural can also be effectively catalyzed and be converted into methylfuroate, reduce reaction temperature, polymerization side reactions are avoided, the highly selective of methylfuroate is maintained.
Description
Technical field
The present invention relates to the preparing technical fields of chemical intermediate, more particularly, to a kind of preparation of 5- hydroxyl methyls
Method.
Background technology
5- hydroxyl methyls (CAS 14273-92-8) are to synthesize the important monomer of P5HV, in the PHA of synthesis mainly at
It is divided into hydroxybutyric acid (Hydroxybutyrate, HB).But the PHA of high HB contents is not only hard and crisp, and fusing point is higher, and heat is steady
Qualitative difference, this results in that when processing under conditions of temperature is higher than 10 DEG C or so of its fusing point PHA molecular weight degradations can be made, from
And limit the application of material.By introducing other monomers fusing point and the crystallization of PHA can be then reduced such as 5- hydroxyl methyls
Degree, improves its thermal stability, flexibility and ductility, material impact-resistant is made to be more easily handled.5- hydroxyl methyls can also
δ-valerolactone (δ-Valerolactone) is obtained by separating methanol, and the latter is a kind of important organic intermediate raw material and important
The intermediate of industry.δ-valerolactone is for synthesizing 5- bromine valeric acids and oligomeric peptide etc.；In pharmaceuticals industry, for synthesizing pyran pyrimidine,
Cyclenes ether, Cilostazol, witting reagents and Epothifone anticarcinogens；Especially preparing equal polyester and polyactide etc. can be with
Biodegradated polymer materal is applied to surgical sewing thread, the sustained release of drug or pesticide, cosmetics and battery industry electrolysis
Liquid etc..
The method for preparing 5- hydroxyl methyls at present is seldom, and 5 carbon compounds based on petroleum resources, such as passes through ring penta
Ketone carries out Baeyer-Villiger reactions and produces, and this method uses strong oxidizer K2S2O8, generates a large amount of acid waste water, former
Expect that cost is very high and pollutes environment.
The open loop hydrogenation reaction of industrial furan derivatives is mainly used for 1,5-PD and 1, the system of 2 pentanediols at present
It is standby.1,5-PD is a kind of widely used chemical products, may be used as new polyester, coating, adhesive, plasticizer and close
The raw material of agent is sealed, can also be used directly as cutting oil, detergent, wetting agent and special solvent.1,2- pentanediol is production
The intermediate of pesticide propiconazole can also be directly used as special solvent.Both pentanediols are all expensive fine at present
Chemicals.The synthetic method of wherein 1,5-PD includes mainly：(1) using tetrahydrofuran alcohol as raw material direct hydrogenation open loop system
Standby 1,5-PD, pressure limit is in 8MPa-42MPa, and temperature is at 120 DEG C -330 DEG C, and this method reaction temperature is high, equipment investment
Greatly, operation difficulty is also high；(2) epoxypentene alcohol is produced with cyclopentadiene photooxidation, then the 6MPa pressure at 70-100 DEG C and about
Lower Hydrogenation obtains 1,5-PD, but cyclopentadiene photooxidation preparation efficiency is low so that economy is not high；(3) penta is used first
Diacid is that raw material prepares 1,5- glutaric acid methyl esters, is then added under 150-350 DEG C and 3-5MPa under CuZnAl catalyst effect
Hydrogen prepares 1,5-PD, and conversion ratio is more than 95%, and 1,5-PD is selectively more than 95% (Chinese patent CN1565728A),
But the technological process is long, and glutaric acid cost is relatively high；(4) with substituted vinyl ethyl ether and substituted methacrylaldehyde
Reaction, generates substituted 3,4- dihydropyran, then produces glutaraldehyde by catalyzing hydrolysis, is hydrogenated to the penta 2 of substitution later
Alcohol (Chinese patent CN1072168A), catalyst is using Raney's nickel, the aluminium oxide of modified Raney's nickel, Supported Pt Nanoparticles, palladium or nickel.
This method technology path is long, and cost is higher.(5) use Ru for active component loaded catalyst, with 1,5- glutaraldehydes for raw material,
Under more mild reaction condition, 60-120 DEG C, 2MPa-8MPa, Hydrogenation is for 1,5-PD, conversion ratio and selectivity
Height, but the cost of material used in the technology is higher.
Chinese patent CN102068986, CN103265400 are related to, using furans or tetrahydrofuran derivatives as raw material, using
Catalyst containing Pt metal, Pd, Ru, Rh, Ir, Ni, Co, Cu and acid carrier prepares penta 2 by furans open loop hydrogenation method
Alcohol and middle Long-chain primary alcohols, reaction selectivity is poor, and target product yield is below 45%.Obviously, the above method cannot meet 5- hydroxyls
The production of base methyl valerate.
Chinese patent CN106278889A discloses a kind of method preparing 5- hydroxyl methyls, and this method uses matter furfural
As raw material, and partly half contracting methanol dehydrogenation of contracting methanol, furfural prepares furancarboxylic acid first to furfural with methanol generation furfural, and use is heterogeneous
Catalyst and fixed-bed process, product can be easily separated, and furfural prepares half contracting methanol of furfural and half contracting methanol dehydrogenation of furfural prepares chaff
Sour methyl esters two-step reaction can carry out on same reactor and catalyst, but must use the noble metal catalysts such as Au or Ag, at
This is higher, and heavy metal element is also easy to produce environmental pollution, is unfavorable for industrialized production.
Invention content
The object of the present invention is to provide a kind of method preparing 5- hydroxyl methyls, this method have cost of material it is low,
The feature that Atom economy is high, product yield is high, separating technology is simple.
The invention is realized by the following technical scheme：
A kind of preparation method of 5- hydroxyl methyls, includes the following steps：
A) furfural, methanol are in Cu-La-Al2O3In the presence of catalyst, methylfuroate is obtained by the reaction in air atmosphere；
B) methylfuroate that step a) is obtained is without detaching direct and hydrogen in Cu-La-Al2O3It is carried out under catalyst
Hydrogenolysis obtains the reaction solution containing 5- hydroxyl methyls, by air-distillation, recycles unreacted methanol, then using
Rectification under vacuum obtains 5- hydroxyl methyls.
Cu-La-Al of the present invention2O3Catalyst is Al2O3Carrier loaded Cu-La catalyst, the wherein weight of Cu contain
Amount is 0.1~10%, and preferably the weight content of 2~5%, La is 1~20% gross mass meter based on catalyst.
Cu-La-Al of the present invention2O3It may be used well known to a person skilled in the art method preparation, preferred catalyst
Preparation method comprises the following steps：
1)Al2O3The pretreatment of carrier：By Al2O3Wash with distilled water several times, it drains away the water, 80 degrees Celsius of dryings 1~2
Hour, it is then added in Muffle furnace, 400~500 DEG C roast 3 hours；
2) aqueous solution for configuring certain density copper nitrate and lanthanum nitrate, with 1:After step 1) processing is added in 5 solid-to-liquid ratio
Al2O3Carrier, ultrasonic immersing 3~5 hours, drains away the water, and after 80 DEG C are dried in vacuo 2 hours, is added in Muffle furnace, with 5~10
DEG C/heating rate of min is heated to 700~750 DEG C and roasts 3 hours, obtain catalyst precarsor；
3) by precursor, in-situ reducing in hydrogen to obtain the final product；Reducing condition be 0.1~1MPa of Hydrogen Vapor Pressure, preferably 0.2~
0.4MPa；The hydrogen flow rate used per 100g dehydrogenations is 0.2~10L/min, preferably 1~5L/min；Reduction temperature
120~350 DEG C, preferably 180~250 DEG C；Recovery time is 1~10 hour, preferably 2~4 hours.
In the method for the present invention, the noble metals such as Rh and Au are substituted as catalyst using Cu-La-Al catalyst, are urged in reduction
While agent cost, additionally it is possible to effectively be catalyzed half contracting methanol intermediate dehydrogenation of furfural and be converted into methylfuroate, reduce anti-
Temperature is answered, polymerization side reactions are avoided, maintains the highly selective of methylfuroate.
The reaction temperature of step a) of the present invention is 30~120 DEG C, preferably 60~100 DEG C；Mass space velocity be 0.5~
3h-1, preferably 1~2h-1, in terms of furfural raw material, the molar ratio of methanol/oxygen/furfural is (2~8)/(0.1~1)/1, preferably
(3~6)/(0.2~0.8)/1.
The reaction temperature of step b) of the present invention is 50~150 DEG C, preferably 80~120 DEG C, the pressure of reaction is 1~
20MPa, preferably 4~10MPa；The molar ratio of hydrogen and methylfuroate is 2~20:1, preferably 5~10:1, mass space velocity 0.5
~3h-1, preferably 1~2h-1, in terms of the furfural raw material of step a).Heretofore described pressure is absolute pressure.
Advantages of the present invention：
1) completely new process route is used, wide using source, reproducible biomass furfural is as raw material, production cost
It is low, and the catalyst by developing new high efficiency so that the highly selective formation hemiacetal of furfural inhibits the generation of by-product,
The selectivity 0.5~1% of furfural dimethyl acetal, with furfural molar amount；And methylfuroate is obtained by dehydrogenation reaction in high yield,
The selectivity of methylfuroate is more than 95%, with furfural molar amount；Ester group is unaffected in methylfuroate hydrogenolysis, 5- hydroxyls
Methyl valerate is selectively more than 97%, with furfural molar amount.
(2) heterogeneous catalysis and fixed-bed process, product is used to can be easily separated, furfural prepares furfural half contracting methanol and chaff
Half contracting methanol dehydrogenation of aldehyde, which prepares methylfuroate two-step reaction, efficiently to be carried out on same reactor and catalyst, simple for process.
Specific implementation mode
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
The every other embodiment that art personnel are obtained without making creative work belongs to the model that the present invention protects
It encloses.
【Embodiment 1】
1)Al2O3The pretreatment of carrier：By Al2O3Wash with distilled water several times, it drains away the water, 80 degrees Celsius of dryings 2 are small
When, it is then added in Muffle furnace and roasts 3 hours for 500 DEG C；
2) mixed aqueous solution for the copper nitrate and lanthanum nitrate that configuration quality percentage is 12.3%, with 1:5 solid-to-liquid ratio adds
Enter step 1) treated Al2O3Carrier, ultrasonic immersing 3 hours, drains away the water, and after 80 DEG C are dried in vacuo 2 hours, Muffle is added
In stove, it is heated to 700 DEG C with the heating rate of 10 DEG C/min and roasts 3 hours, obtain catalyst precarsor；
3) by catalyst precarsor, in-situ reducing, reducing condition are Hydrogen Vapor Pressure 0.3MPa in hydrogen；It is urged per 100g dehydrogenations
The hydrogen flow rate that agent uses is 3L/min；230 DEG C of reduction temperature；Recovery time is 4 hours；Up to catalyst C1, wherein base
In the gross mass meter of catalyst, the weight content that the weight content of Cu is 2%, La is 12%.
【Embodiment 2】
1)Al2O3The pretreatment of carrier：By Al2O3Wash with distilled water several times, it drains away the water, 80 degrees Celsius of dryings 2 are small
When, it is then added in Muffle furnace, 400 DEG C roast 3 hours；
2) mixed aqueous solution of the copper nitrate of configuration quality percentage 8.8% and lanthanum nitrate, with 1:Step is added in 5 solid-to-liquid ratio
Treated Al rapid 1)2O3Carrier, ultrasonic immersing 3 hours, drains away the water, and after 80 DEG C are dried in vacuo 2 hours, is added in Muffle furnace,
It is heated to 700 DEG C with the heating rate of 5 DEG C/min to roast 3 hours, obtains catalyst precarsor；
3) by catalyst precarsor, in-situ reducing, reducing condition are Hydrogen Vapor Pressure 0.4MPa in hydrogen；It is urged per 100g dehydrogenations
The hydrogen flow rate that agent uses is 5L/min；200 DEG C of reduction temperature；Recovery time is 2.5 hours；Up to catalyst C2, wherein
Gross mass meter based on catalyst, the weight content that the weight content of Cu is 0.2%, La is 15%.
【Embodiment 3】
1)Al2O3The pretreatment of carrier：By Al2O3Wash with distilled water several times, it drains away the water, 80 degrees Celsius of dryings 2 are small
When, it is then added in Muffle furnace, 450 DEG C roast 3 hours；
2) mixed aqueous solution of the copper nitrate of configuration quality score 10.2% and lanthanum nitrate, with 1:Step is added in 5 solid-to-liquid ratio
Treated Al rapid 1)2O3Carrier, ultrasonic immersing 5 hours, drains away the water, and after 80 DEG C are dried in vacuo 2 hours, is added in Muffle furnace,
It is heated to 700~750 DEG C with the heating rate of 5 DEG C/min to roast 3 hours, obtains catalyst precarsor；
3) by catalyst precarsor, in-situ reducing, reducing condition are Hydrogen Vapor Pressure 0.2MPa in hydrogen；It is urged per 100g dehydrogenations
The hydrogen flow rate that agent uses is 1L/min；180 DEG C of reduction temperature；Recovery time is 2 hours；It is wherein based on up to catalyst C3
The gross mass meter of catalyst, the weight content that the weight content of Cu is 10%, La is 5%.
【Embodiment 4】
Catalyst Evaluation Test carries out in the first reactor and second reactor being arranged in series, wherein first reactor
Identical catalyst is loaded with second reactor, the reaction temperature of first reactor is 60 DEG C；Mass space velocity is 1h-1, with furfural
The molar ratio of raw material meter, methanol/oxygen/furfural is 3/0.3/1.The reaction temperature of second reactor is 100 DEG C, the pressure of reaction
For 4MPa；The molar ratio of hydrogen and methylfuroate is 5:1, mass space velocity 1h-1(in terms of furfural raw material).
Concrete operations are to enter first reactor, the reaction solution and hydrogen of first reactor after furfural, methanol and air mix
Gas enters second reactor, in second reactor outlet port sampling analysis, reaction condition and the results are shown in Table 1.
Table 1
Above description has fully disclosed the specific implementation mode of the present invention.It should be pointed out that being familiar with the field
Technical staff is to any change for being done of specific implementation mode of the present invention all without departing from the range of claims of the present invention.
Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.
Claims (7)
1. a kind of preparation method of 5- hydroxyl methyls, includes the following steps：
A) furfural, methanol are in Cu-La-Al2O3In the presence of catalyst, methylfuroate is obtained by the reaction in air atmosphere；
B) methylfuroate that step a) is obtained is without detaching direct and hydrogen in Cu-La-Al2O3Hydrogenolysis is carried out under catalyst,
The reaction solution containing 5- hydroxyl methyls is obtained, by air-distillation, recycles unreacted methanol, then using decompression essence
It evaporates to obtain 5- hydroxyl methyls.
2. the preparation method of 5- hydroxyl methyls according to claim 1, which is characterized in that the Cu-La-Al2O3It urges
Agent is Al2O3Carrier loaded Cu-La catalyst, the wherein weight content of Cu are 0.1~10%, the preferably weight of 2~5%, La
Amount content is 1~20% gross mass meter based on catalyst.
3. the preparation method of 5- hydroxyl methyls according to claim 1, which is characterized in that the preparation of the catalyst
Method comprises the following steps：
1)Al2O3The pretreatment of carrier：By Al2O3Wash with distilled water several times, it drains away the water, 80 degrees Celsius of dryings 1~2 hour,
It is then added in Muffle furnace, 400~500 DEG C roast 3 hours；
2) aqueous solution for configuring certain density copper nitrate and lanthanum nitrate, with 1:Step 1) is added in 5 solid-to-liquid ratio, and treated
Al2O3Carrier, ultrasonic immersing 3~5 hours, drains away the water, and after 80 DEG C are dried in vacuo 2 hours, is added in Muffle furnace, with 5~10
DEG C/heating rate of min is heated to 700~750 DEG C and roasts 3 hours, obtain catalyst precarsor；
3) by precursor, in-situ reducing in hydrogen to obtain the final product.
4. the preparation method of 5- hydroxyl methyls according to claim 3, which is characterized in that in step 3), restore item
Part is 0.1~1MPa of Hydrogen Vapor Pressure, preferably 0.2~0.4MPa；The hydrogen flow rate used per 100g dehydrogenations for 0.2~
10L/min, preferably 1~5L/min；120~350 DEG C of reduction temperature, preferably 180~250 DEG C；Recovery time is 1~10 small
When, preferably 2~4 hours.
5. the preparation method of 5- hydroxyl methyls according to claim 1, it is characterised in that：In the step a), instead
It is 30~120 DEG C, preferably 60~100 DEG C to answer temperature；Mass space velocity is 0.5~3h-1, preferably 1~2h-1, in terms of furfural raw material,
The molar ratio of methanol/oxygen/furfural is (2~8)/(0.1~1)/1, preferably (3~6)/(0.2~0.8)/1.
6. the preparation method of 5- hydroxyl methyls according to claim 1, it is characterised in that：In the step b), instead
It is 50~150 DEG C to answer temperature, and preferably 80~120 DEG C, the pressure of reaction is 1~20MPa, preferably 4~10MPa；Hydrogen and furancarboxylic acid
The molar ratio of methyl esters is 2~20:1, preferably 5~10:1, mass space velocity is 0.5~3h-1, preferably 1~2h-1, with step a's)
Furfural raw material meter.
7. the preparation method of 5- hydroxyl methyls according to claim 6, it is characterised in that：The pressure is exhausted
Pressure.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113831312A (en) * | 2020-06-24 | 2021-12-24 | 中国石油化工股份有限公司 | A kind of method for preparing δ-cyclovalerolactone |
| CN115894420A (en) * | 2021-08-18 | 2023-04-04 | 中国石油化工股份有限公司 | A kind of method for preparing delta-cyclopentalactone |
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| CN1911507A (en) * | 2006-08-17 | 2007-02-14 | 复旦大学 | Nanometer copper base catalyst for preparing 1,3-propanediol by hydrogenation of 3-hydroxy methyl propionate and its preparation method |
| 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 |
| CN105363459A (en) * | 2014-08-27 | 2016-03-02 | 中国石油化工股份有限公司 | Ester hydrogenation copper catalyst |
| CN106278889A (en) * | 2015-05-13 | 2017-01-04 | 万华化学集团股份有限公司 | A kind of method preparing 5-hydroxyl methyl |
| CN106365957A (en) * | 2016-08-25 | 2017-02-01 | 宁波博撷化学科技有限公司 | Preparation method of 1,2-pentanediol |
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| CN1911507A (en) * | 2006-08-17 | 2007-02-14 | 复旦大学 | Nanometer copper base catalyst for preparing 1,3-propanediol by hydrogenation of 3-hydroxy methyl propionate and its preparation method |
| 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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| CN113831312A (en) * | 2020-06-24 | 2021-12-24 | 中国石油化工股份有限公司 | A kind of method for preparing δ-cyclovalerolactone |
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| CN115894420A (en) * | 2021-08-18 | 2023-04-04 | 中国石油化工股份有限公司 | A kind of method for preparing delta-cyclopentalactone |
| CN115894420B (en) * | 2021-08-18 | 2024-06-11 | 中国石油化工股份有限公司 | Method for preparing delta-cyclopentalactone |
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