CN105646152A - Preparation method of 1, 2-benzenedimethanol - Google Patents
Preparation method of 1, 2-benzenedimethanol Download PDFInfo
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Abstract
The invention discloses a preparation method of 1, 2-benzenedimethanol. Phthalic anhydride containing halogenated alkane is adopted as the raw material, the weight content of phthalic anhydride is 5%-90%(wt), preferably 10%-70%(wt), and most preferably 20%-50%(wt), under a reaction temperature of 50-250DEG C and a reaction pressure of 0.5MPa-5MPa and in the presence of a hydrogenation catalyst, hydrogenation reaction is carried out, and the hydrogenation product is subjected to crystallization separation so as to obtain 1, 2-benzenedimethanol. The method has the advantages of simple operation process, high product yield and product purity, and low production cost, and is easy for industrial production.
Description
Technical field
The invention provides the manufacture method of a kind of manufacture method of chemical products, particularly a kind of phthalyl alcohol.
Technical background
Phthalyl alcohol is a kind of important organic fine chemicals and intermediate, is mainly used as a kind of resin additive, is used in synthetic material, is also used as the intermediate of synthetic drug simultaneously.
Phthalyl alcohol is as the alcohol of aromatic hydrocarbon side chain radical as phenmethylol, and its synthetic route has several as follows: 1) directly obtain (CN102060668B) through basic hydrolysis taking corresponding halide as raw material. 2), taking corresponding halide as raw material, first esterification generates after ester saponification under highly basic exists again and obtains (JP6426528; U53993699). 3) obtain (Wang Baoren, organic synthesis, Science Press/1981 year taking corresponding ester or acids as raw material hydrogenating reduction; CN101096335A). 4) anhydride phthalic acid direct hydrogenation is prepared phthalyl alcohol.
In above-mentioned method, the technique of the 1st kind of method is the most ripe, and in actual industrial production, application is more general. The product obtaining by this method is because containing the complete adjacent benzyl dichloride raw material of unreacted and other impurity, therefore also need the further refining finished product that just can obtain high-purity quality. In technical process in the past, adopt solvent recrystallization, centrifugation to carry out purified product more, and the solvent using mostly are again inflammable and explosive substances, in practical operation, have thus larger environmental protection and potential safety hazard.
In order to address the above problem CN102060668B, a kind of method of manufacturing phthalyl alcohol is disclosed. The main technique of the method is reaction that adjacent benzyl dichloride is hydrolyzed under alkali exists, strip and remove impurity with organic solvent, mother liquor adjusts pH to 7～7.5 through concentrated, separated salt, the cooling crude product that obtains with hydrochloric acid again, then water recrystallization, can obtain after drying finished product.
The problems such as above-mentioned first three methods adopts repeatedly recrystallization to improve product purity, therefore has operating process complexity, and product yield is low, and production cost is high, environmental pollution.
The 4th kind of relative first three methods of method, process brief introduction, can continuous operation. But in direct hydrogenation process, can produce phenyl ring and carbonyl by the side reaction of hydrogenation, cause selectivity of product low, the problems such as production cost height.
Summary of the invention
For the deficiencies in the prior art, the object of this invention is to provide that a kind of operating process is easy, product yield and product purity is high, production cost is low, be easy to the phthalyl alcohol manufacture method of suitability for industrialized production.
A kind of method of producing phthalyl alcohol of the present invention, taking the phthalic anhydride containing halogenated alkane as raw material, the weight percentage of phthalic anhydride is 5% ~ 90%(wt), preferably 10% ~ 70%(wt), most preferably 20% ~ 50%(wt), be 50 DEG C～250 DEG C in reaction temperature, reaction pressure is under the existence of 0.5MPa～5MPa and hydrogenation catalyst, carry out hydrogenation reaction, hydrogenation products makes phthalyl alcohol after Crystallization Separation.
In the inventive method, halogenated alkane is the low-carbon alkanes of monochloro generation or many chloros, comprises monochloro methane, monochlorethane, a chloropropane, a chlorobutane, dichloroethanes, dichloropropane, trichloroethanes, carbon tetrachloride. In one or more, preferably dichloroethanes or dichloropropane.
The inventive method can tank reactor discontinuous operation, also can continued operation on fixed bed reactors, preferably continued operation on fixed bed reactors.
On fixed bed reactors, the condition of continued operation is as follows:
50 DEG C～250 DEG C of reaction temperatures, preferably 70 DEG C-200 DEG C, most preferably 100 DEG C-180 DEG C, reaction pressure is 0.5MPa～5MPa, preferably most preferably 2.0MPa～3.0MPa of 1.0MPa～5MPa, liquor capacity air speed 0.5h-1～5.0h-1, preferably 0.5h-1～3.0h-1Most preferably 1.0h-1～2.0h-1, the mol ratio of hydrogen and phthalic anhydride is 50 ~ 1000:1, preferably most preferably 100 ~ 300:1 of 100 ~ 500:1.
The condition of tank reactor discontinuous operation is as follows: reaction temperature is 80 DEG C～200 DEG C, preferably 100 DEG C～150 DEG C, reaction pressure is 1.0MPa～4.0MPa, preferably 2.0MPa～3.0MPa, hydrogenation catalyst is 1% ~ 10% of phthalic anhydride weight, preferably 3% ~ 5%.
Catalyst described in the inventive method can adopt hydrogenation catalyst arbitrary in prior art. Preferably with A12O3Or active carbon is that one or more in carrier loaded Pd, Co, Mo, Ni, W are as catalyst.
Described in the inventive method with A12O3Or active carbon is that one or more catalyst in carrier loaded Pd, Co, Mo, Ni, W are adopted preparation with the following method:
First adopt non-polar solven, to A12O3Or active carbon carries out impregnation process, then, through washing and dry, obtain A12O3Or absorbent charcoal carrier, then adopt polar organic solvent dissolved metal salt to be mixed with maceration extract, flood above-mentioned A1 with this maceration extract2O3Or absorbent charcoal carrier, in the catalyst after dipping using the A1 as carrier2O3Or the weight of active carbon is benchmark, account for 1%～10% of catalyst carrier quality in metallic element, preferably 2%～8%, most preferably 5%～8%. Adopt non-polar organic solvent A1 after treatment2O3Or absorbent charcoal carrier and the prepared catalyst of impregnating metal salt polar organic solvent, metal is uniformly dispersed, and can effectively improve product yield and selective.
Non-polar organic solvent described in the inventive method comprises benzene,toluene,xylene, carbon tetrachloride, dichloroethanes, chloroform, carbon disulfide, bromoethane, one or more in cyclohexane, preferably one or more in dichloroethanes, chloroform, carbon tetrachloride, most preferably dichloroethanes or carbon tetrachloride.
Non-polar organic solvent processing procedure described in the inventive method is: first adopt quality 10%～100%, and preferably 20%～80%, most preferably 30%～50% non-polar solven, at 50 DEG C～200 DEG C, preferably 50 DEG C～150 DEG C, most preferably 80 DEG C～150 DEG C, to A12O3Or charcoal treatment 4h～32h, preferably most preferably 8h～12h of 8h～24h, then through washing and dry, then roasting 6 hours at 350 DEG C, then 550 DEG C of roastings 12 hours, absorbent charcoal carrier adopted inert gas shielding roasting, obtains A12O3Or absorbent charcoal carrier.
Polar organic solvent described in the inventive method is one or more in formamide, acetonitrile, methyl alcohol, ethanol, isopropyl alcohol, acetone, oxolane, MEK, n-butanol, methyl iso-butyl ketone (MIBK), sec-butyl alcohol, one or more in preferred alcohol, acetone, MEK, most preferably acetone or MEK.
Dipping process described in the inventive method is: adopt polar organic solvent dissolve the water soluble salt of above-mentioned metal and be mixed with 5%～25%, preferably 5%～20%, most preferably 10%～20% maceration extract, with this maceration extract at 30 DEG C～150 DEG C, preferably 50 DEG C～150 DEG C, flood above-mentioned A1 at most preferably 50 DEG C～80 DEG C2O3Or absorbent charcoal carrier 12h～64h, preferably 24h～56h, most preferably 24h～32h.
The inventive method has effectively improved product yield and the product purity of phthalyl alcohol, has reduced production cost, has improved operating environment.
Detailed description of the invention
Further illustrate method of the present invention and effect below by specific embodiment.
Embodiment 1
With benzene at 50 DEG C to A12O3Impregnation process 6h, then washes and is dried, and obtains A12O3Carrier, then adopt MEK to dissolve Pd salt and be mixed with mass fraction to be 5% maceration extract, at 80 DEG C, to flood above-mentioned A12O3Carrier 24h, in the catalyst after dipping using the A1 as carrier2O3Weight be benchmark, Pd accounts for 1% of catalyst carrier quality.
Embodiment 2
According to the method for embodiment 1, just benzene is changed into mass fraction and be 50% benzene carbon tetrachloride solution, then to adopt MEK to dissolve Pd salt and be mixed with mass fraction be 10% maceration extract, in the catalyst after dipping using the A1 as carrier2O3Weight be benchmark, Pd accounts for 2.5% of catalyst carrier quality.
Embodiment 3
According to the method for embodiment 1, just change benzene into dichloroethanes, after dipping, Pd accounts for 0.5% of catalyst carrier quality.
Embodiment 4
According to the method for embodiment 3, just change 100% dichloroethanes into cyclohexane, change MEK into acetone, be mixed with mass fraction and be 20% maceration extract, after dipping, Pd accounts for 5% of catalyst carrier quality.
Embodiment 5
According to the method for embodiment 1, just change treatment temperature into 100 DEG C, processing time changes 12h into, impregnation concentration changes 10% maceration extract into, Immesion active carbon carrier 16h at 100 DEG C, in catalyst after dipping, taking the weight of the active carbon as carrier as benchmark, Pd accounts for 2% of catalyst carrier quality.
Embodiment 6
With the toluene cyclohexane solution of quality 10%, at 150 DEG C to charcoal treatment 32h, then wash and be dried, obtain absorbent charcoal carrier, adopt again methyl iso-butyl ketone (MIBK) dissolve Ni salt and be mixed with 10% maceration extract, at 100 DEG C, flood above-mentioned absorbent charcoal carrier 8h, in the catalyst after dipping, taking the weight of the active carbon as carrier as benchmark, Ni accounts for 3% of catalyst carrier quality.
Embodiment 7
According to the method for embodiment 6, just by 10% toluene cyclohexane solution, change cyclohexane toluene solution into, in the catalyst after dipping, taking the weight of the active carbon as carrier as benchmark, Pd accounts for 2% of catalyst carrier quality.
Embodiment 8
In 1000m1 autoclave, drop into 30g phthalic anhydride, 70g dichloroethanes, the catalyst of 1.5g embodiment 1, uses hydrogen exchange three times, and 2.0MPa then boosts, be heated to 150 DEG C, react, when autoclave pressure drops to 1.0MPa, supplementary pressure is 2.0MPa, when autoclave pressure is not or not the time declining, be reaction and finish, reactant liquor is taken out in cooling, after Crystallization Separation, get final product to obtain finished product 26.8g 30 DEG C～50 DEG C oven dry. Product yield is 89.3%, and product purity can reach 99.5%.
Embodiment 9
In 1000m1 autoclave, drop into 50g phthalic anhydride, 50g carbon tetrachloride, the catalyst of 2.5g embodiment 2, uses hydrogen exchange three times, and 2.0MPa then boosts, be heated to 150 DEG C, react, when autoclave pressure drops to 1.0MPa, supplementary pressure is 2.0MPa, when autoclave pressure is not or not the time declining, be reaction and finish, reactant liquor is taken out in cooling, after Crystallization Separation, get final product to obtain finished product 42.5g 30 DEG C～50 DEG C oven dry. Product yield is 85%, and product purity can reach 99.5%.
Embodiment 10
According to the method for embodiment 8, just adopt the catalyst of 2.5g embodiment 3, obtain finished product 45.5g. Product yield is 84.5%, and product purity can reach 99.5%.
Embodiment 11
According to the method for embodiment 8, just adopt the catalyst of 2.0g embodiment 4, obtain finished product 40.5g. Product yield is 86.5%, and product purity can reach 99.6%.
Embodiment 12
According to the method for embodiment 8, just adopt the catalyst of 1.5g embodiment 5, obtain finished product 38.5g. Product yield is 80.5%, and product purity can reach 99.4%.
Embodiment 13
According to the method for embodiment 8, just adopt the catalyst of 3.5g embodiment 6, obtain finished product 42.5g. Product yield is 84.5%, and product purity can reach 99.6%.
Embodiment 14
According to the method for embodiment 8, just adopt the catalyst of 1.5g embodiment 7, obtain finished product 45.5g. Product yield is 86.5%, and product purity can reach 99.6%.
Embodiment 15
Be 25mm at internal diameter, fill the catalyst of 50ml embodiment 1 on the high continuous fixed bed reactors for 1.2m, the phthalic anhydride dichloroethane solution of preparation 15% mass concentration, squeezes in reactor with pump, and hydrogenation products makes phthalyl alcohol after Crystallization Separation.
Reaction condition is: 100 DEG C of reaction temperatures, reaction pressure 2.0MPa, hydrogen/phthalic anhydride mol ratio 100, LHSV1.0h-1, successive reaction 500h, product yield is 89.5% by analysis, product purity can reach 99.8%.
Embodiment 16
According to the method for embodiment 15, the phthalic anhydride dichloroethane solution of preparation 30% mass concentration, squeezes in reactor with pump, and hydrogenation products makes phthalyl alcohol after Crystallization Separation.
Reaction condition is: 150 DEG C of reaction temperatures, reaction pressure 3.0MPa, hydrogen/phthalic anhydride mol ratio 150, LHSV1.0h-1, successive reaction 500h, product yield is 93.5% by analysis, product purity can reach 99.6%.
Embodiment 17
According to the method for embodiment 15, the phthalic anhydride dichloroethane solution of preparation 60% mass concentration, squeezes in reactor with pump, and hydrogenation products makes phthalyl alcohol after Crystallization Separation.
Reaction condition is: 200 DEG C of reaction temperatures, reaction pressure 1.0MPa, hydrogen/phthalic anhydride mol ratio 200, LHSV1.0h-1, successive reaction 500h, product yield is 85.5% by analysis, product purity can reach 99.2%.
Embodiment 18
According to the method for embodiment 15, the phthalic anhydride dichloroethane solution of preparation 60% mass concentration, squeezes in reactor with pump, and hydrogenation products makes phthalyl alcohol after Crystallization Separation.
Reaction condition is: 150 DEG C of reaction temperatures, reaction pressure 2.0MPa, hydrogen/phthalic anhydride mol ratio 200, LHSV0.5h-1, successive reaction 300h, product yield is 85.5% by analysis, product purity can reach 99.2%.
Embodiment 19
According to the method for embodiment 15, the phthalic anhydride dichloroethane solution of preparation 30% mass concentration, squeezes in reactor with pump, and hydrogenation products makes phthalyl alcohol after Crystallization Separation.
Reaction condition is: 100 DEG C of reaction temperatures, reaction pressure 3.0MPa, hydrogen/phthalic anhydride mol ratio 200, LHSV1.0h-1, successive reaction 300h, product yield is 83.5% by analysis, product purity can reach 99.5%.
Embodiment 20
According to the method for embodiment 15, the phthalic anhydride dichloroethane solution of preparation 10% mass concentration, squeezes in reactor with pump, and hydrogenation products makes phthalyl alcohol after Crystallization Separation.
Reaction condition is: 150 DEG C of reaction temperatures, reaction pressure 4.0MPa, hydrogen/phthalic anhydride mol ratio 500, LHSV2.0h-1, successive reaction 300h, product yield is 87.5% by analysis, product purity can reach 99.6%.
Embodiment 21
According to the method for embodiment 15, on fixed bed reactors, fill the catalyst of 50ml embodiment 7, the phthalic anhydride chloroform soln of preparation 30% mass concentration, squeezes in reactor with pump, and hydrogenation products makes phthalyl alcohol after Crystallization Separation.
Reaction condition is: 110 DEG C of reaction temperatures, reaction pressure 3.0MPa, hydrogen/phthalic anhydride mol ratio 500, LHSV0.5h-1, successive reaction 300h, product yield is 91.5% by analysis, product purity can reach 99.8%.
Embodiment 22
According to the method for embodiment 15, the phthalic anhydride dichloromethane solution of preparation 20% mass concentration, squeezes in reactor with pump, and hydrogenation products makes phthalyl alcohol after Crystallization Separation.
Reaction condition is: 90 DEG C of reaction temperatures, reaction pressure 5.0MPa, hydrogen/phthalic anhydride mol ratio 600, LHSV1.0h-1, successive reaction 300h, product yield is 94.5% by analysis, product purity can reach 99.1%.
Embodiment 23
With benzene at 50 DEG C to A12O3Impregnation process 6h, then washes and is dried, and obtains A12O3Carrier, the Pa saline solution that preparation mass fraction is 5% floods above-mentioned A1 at 80 DEG C2O3Carrier 24h, in the catalyst after dipping using the A1 as carrier2O3Weight be benchmark, Pd accounts for 1% of catalyst carrier quality. Appreciation condition is with embodiment 22, successive reaction 300h, and product yield is 88.4% by analysis, product purity can reach 90.5%.
Embodiment 24
The Pa saline solution of alumina support direct impregnation 5%, all the other conditions are with embodiment 23, successive reaction 300h, product yield is 80.5% by analysis, product purity can reach 79.8%.
Comparative example 1
According to the method for embodiment 15, on continuous fixed bed reactors, fill the catalyst of the activated carbon supported Pd of 50ml, the phthalic anhydride toluene solution of preparation 15% mass concentration, squeezes in reactor with pump, and hydrogenation products makes phthalyl alcohol after Crystallization Separation.
Reaction condition is: 100 DEG C of reaction temperatures, reaction pressure 2.0MPa, hydrogen/phthalic anhydride mol ratio 100, LHSV1.0h-1, successive reaction 300h, product yield is 70.5% by analysis, product purity can reach 72.8%.
Comparative example 2
According to the method for embodiment 15, on fixed bed reactors, filling 50mlA1 continuously2O3The catalyst of load P d, the phthalic anhydride gamma-butyrolacton solution of preparation 15% mass concentration, squeezes in reactor with pump, and hydrogenation products makes phthalyl alcohol after Crystallization Separation.
Reaction condition is: 150 DEG C of reaction temperatures, reaction pressure 2.0MPa, hydrogen/phthalic anhydride mol ratio 200, LHSV0.5h-1, successive reaction 300h, product yield is 69.5% by analysis, product purity can reach 65.8%.
Comparative example 3
According to the method for embodiment 15, on continuous fixed bed reactors, fill the catalyst of the activated carbon supported Ni of 50ml, phthalic anhydride is happy and harmonious after, squeeze in reactor with pump, hydrogenation products makes phthalyl alcohol after recrystallization separates.
Reaction condition is: 150 DEG C of reaction temperatures, reaction pressure 2.0MPa, hydrogen/phthalic anhydride mol ratio 200, LHSV0.5h-1, successive reaction 300h, product yield is 40.5% by analysis, product purity can reach 65.8%.
Claims (22)
1. produce the method for phthalyl alcohol for one kind, it is characterized in that: taking the phthalic anhydride containing halogenated alkane as raw material, in raw material, the weight percentage of phthalic anhydride is 5% ~ 90%(wt), it is 50 DEG C～250 DEG C in reaction temperature, reaction pressure is under the existence of 0.5MPa～5MPa and hydrogenation catalyst, continued operation or carry out hydrogenation reaction in tank reactor discontinuous operation on fixed bed reactors, hydrogenation products makes phthalyl alcohol after Crystallization Separation.
2. method according to claim 1, is characterized in that: in raw material, the weight percentage of phthalic anhydride is 10% ~ 70%(wt).
3. method according to claim 1, is characterized in that: halogenated alkane is the low-carbon alkanes of monochloro generation or many chloros.
4. method according to claim 1, is characterized in that: halogenated alkane is monochloro methane, monochlorethane, a chloropropane, a chlorobutane, dichloroethanes, dichloropropane, trichloroethanes, carbon tetrachloride, in one or more.
5. method according to claim 1, is characterized in that: halogenated alkane is dichloroethanes or dichloropropane.
6. method according to claim 1, is characterized in that: on fixed bed reactors, the condition of continued operation is as follows: 50 DEG C～250 DEG C of reaction temperatures, reaction pressure is 0.5MPa～5MPa, liquor capacity air speed 0.5h-1～5.0h-1, the mol ratio of hydrogen and phthalic anhydride is 50 ~ 1000:1.
7. method according to claim 6, is characterized in that: 70 DEG C-200 DEG C of reaction temperatures, reaction pressure is 1.0MPa～5MPa, liquor capacity air speed 0.5h-1～3.0h-1, the mol ratio of hydrogen and phthalic anhydride is 100 ~ 500:1.
8. method according to claim 7, is characterized in that: 100 DEG C-180 DEG C of reaction temperatures, reaction pressure is 2.0MPa～3.0MPa, liquor capacity air speed 1.0h-1～2.0h-1, the mol ratio of hydrogen and phthalic anhydride is 100 ~ 300:1.
9. method according to claim 1, is characterized in that: the condition of tank reactor discontinuous operation is as follows: reaction temperature is 80 DEG C～200 DEG C, and reaction pressure is 1.0MPa～4.0MPa, and hydrogenation catalyst is 1% ~ 10% of phthalic anhydride weight.
10. method according to claim 9, is characterized in that: reaction temperature is 100 DEG C～150 DEG C, and reaction pressure is 2.0MPa～3.0MPa, and hydrogenation catalyst is 3% ~ 5% of phthalic anhydride weight.
11. methods according to claim 1, is characterized in that: with A12O3Or active carbon is carrier, one or more in load P d, Co, Mo, Ni, W make hydrogenation catalyst.
12. methods according to claim 11, is characterized in that: first adopt non-polar solven to A12O3Or active carbon carries out impregnation process, then, through washing and dry, obtain modification A12O3Or absorbent charcoal carrier, then adopt polar organic solvent dissolved metal salt to be mixed with maceration extract, with A1 after this maceration extract dipping modification2O3Or absorbent charcoal carrier, in the catalyst after dipping using the A1 as carrier2O3Or the weight of active carbon is benchmark, account for 1%～10% of catalyst carrier quality in the active metal of metallic element.
13. methods according to claim 12, is characterized in that: non-polar organic solvent comprises benzene,toluene,xylene, one or more in carbon tetrachloride, dichloroethanes, chloroform, carbon disulfide, bromoethane, cyclohexane.
14. methods according to claim 13, is characterized in that: non-polar organic solvent is one or more in dichloroethanes, chloroform, carbon tetrachloride.
15. methods according to claim 12, is characterized in that: non-polar organic solvent impregnation process process is: first adopt the non-polar solven of quality 10%～100%, at 50 DEG C～200 DEG C, to A12O3Or active carbon impregnation process 4h～32h, then obtain A1 through washing, dry, roasting2O3Or absorbent charcoal carrier.
16. methods according to claim 15, is characterized in that: adopt the non-polar solven of quality 20%～80%, at 50 DEG C～150 DEG C, to A12O3Or active carbon impregnation process 8h～24h.
17. methods according to claim 15, is characterized in that: adopt the non-polar solven of quality 30%～50%, at 80 DEG C～150 DEG C, to A12O3Or active carbon impregnation process 8h～12h.
18. methods according to claim 12, is characterized in that: polar organic solvent is one or more in formamide, acetonitrile, methyl alcohol, ethanol, isopropyl alcohol, acetone, oxolane, MEK, n-butanol, methyl iso-butyl ketone (MIBK), sec-butyl alcohol.
19. methods according to claim 18, is characterized in that: polar organic solvent is acetone or MEK.
20. methods according to claim 11, is characterized in that: dipping active component is: adopt the water soluble salt of polar organic solvent dissolution of metals to be also mixed with 5%～25% maceration extract, flood modification A1 with this maceration extract at 30 DEG C～150 DEG C2O3Or absorbent charcoal carrier 12h～64h.
21. methods according to claim 20, is characterized in that: adopt the water soluble salt of polar organic solvent dissolution of metals to be also mixed with 5%～20% maceration extract, flood modification A1 with this maceration extract at 50 DEG C～150 DEG C2O3Or absorbent charcoal carrier 24h～56h.
22. methods according to claim 21, is characterized in that: adopt the water soluble salt of polar organic solvent dissolution of metals to be also mixed with 10%～20% maceration extract, flood modification A1 with this maceration extract at 50 DEG C～80 DEG C2O3Or absorbent charcoal carrier 24h～32h.
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| CN109851478A (en) * | 2019-02-27 | 2019-06-07 | 武汉有机实业有限公司 | A kind of dibenzyl alcohol method of purification |
| CN113968771A (en) * | 2021-11-17 | 2022-01-25 | 大连理工大学 | Method for preparing o-xylene glycol by selective hydrogenolysis of phthalide |
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| CN113968771B (en) * | 2021-11-17 | 2022-07-19 | 大连理工大学 | Method for preparing o-xylene glycol by selective hydrogenolysis of phthalide |
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