CN102863335A - Preparation method of diethyl succinate - Google Patents
Preparation method of diethyl succinate Download PDFInfo
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- CN102863335A CN102863335A CN2012103905764A CN201210390576A CN102863335A CN 102863335 A CN102863335 A CN 102863335A CN 2012103905764 A CN2012103905764 A CN 2012103905764A CN 201210390576 A CN201210390576 A CN 201210390576A CN 102863335 A CN102863335 A CN 102863335A
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Abstract
The invention provides a preparation method of dimethyl succinate. The method comprises the steps of mixing maleic anhydride, an alcohol compound, carbon dioxide, hydrogen and a hydrogenation catalyst and conducting esterification hydrogenation reaction to obtain the dimethyl succinate. According to the method, the maleic anhydride, the alcohol compound and hydrogen serve as raw materials, the carbon dioxide serves as a solvent and an acid catalyst, under catalysis of the hydrogenation catalyst, the esterification hydrogenation reaction is conducted, and the dimethyl succinate is obtained. The carbon dioxide serves as the solvent of the esterification hydrogenation reaction and the acid catalyst, high catalytic activity is achieved, and the reaction rate is improved; the carbon dioxide and water generated in the reaction process can form acid, and an obtained product has certain solubility in the carbon dioxide, so that the reaction can be conducted in a positive direction, and the conversion rate and the production rate of the dimethyl succinate are improved. Experimental results show that the yield rate of the obtained dimethyl succinate exceeds 99%.
Description
Technical field
The present invention relates to technical field of organic synthesis, relate in particular to a kind of preparation method of succinate.
Background technology
Succinate is the product of Succinic Acid and alcohol compound esterification, such as dimethyl succinate, dipropyl succinate, diisopropyl ester amber acid and Succinic Acid di-n-octyl etc., wherein being most widely used with dimethyl succinate (Dimethyl Succinate).Dimethyl succinate is also referred to as Succinic acid dimethylester.CAS number is 106-65-0, and molecular formula is C
4H
10O
4, have structure shown in the formula (I).Be colourless to weak yellow liquid under the dimethyl succinate room temperature, curable after the cooling, be grape wine and ether perfume (or spice) and fruital and burnt odor, 195 ℃ ~ 196 ℃ of boiling points, or 80 ℃ (1466Pa), 18 ℃ ~ 19 ℃ of fusing points, 90 ℃ of flash-points.Be slightly soluble in water (1%), be dissolved in ethanol (3%), be soluble in ether and acetone, miscible in oils.Dimethyl succinate is important synthetic perfume and organic solvent, can be used as food antiseptics, also be used as the raw material of synthetic BDO, gamma-butyrolactone, tetrahydrofuran (THF), for the synthesis of photostabilizer, high-grade paint, sterilant, medicine intermediate etc., be important industrial chemicals also.
Present industrial synthetic for dimethyl succinate, often adopting Succinic Acid and methyl alcohol is raw material, direct synthetic the making take the vitriol oil as the catalyst esterification.Yet the side reaction of this synthesis technique is many, and yield is low, and last handling process is complicated, and equipment corrosion is serious, environmental pollution is large.The reaction of Succinic Acid and methanol esterification than MALEIC ANHYDRIDE and methanol esterification reaction difficulty with slowly many.The raw material Succinic Acid itself is exactly that the hydrogenation of cis-butenedioic anhydride obtains, and slow with the methanol esterification speed of response, and reaction is difficult to carry through to the end, the refining difficulty of product separation.
In order to reduce the generation of side reaction, publication number is that the Chinese patent of CN101824627 discloses a kind of method for preparing dimethyl succinate, the method is take MALEIC ANHYDRIDE and methyl alcohol as raw material, be placed in the batch reactor, under the effect of sulfuric acid, carry out catalytic esterification, then obtain dimethyl succinate through electrochemical reduction.Although the disclosed method of this patent has reduced the generation of side reaction, it uses liquid strong acid in esterification process, easily cause equipment corrosion; And the catalyst separating difficulty, easily cause environmental pollution; Not high along transformation efficiency in the dimethyl succinate electrochemical reduction synthesis of dimethyl succinate, process is used sulfuric acid, and energy consumption is high, and consumption of organic solvent is large, and loss is large.
In order to reduce energy consumption; a kind of method of pollution-free, the dimethyl succinate that is produced on a large scale is provided; publication number is that the Chinese patent of CN102070448 discloses a kind of method for preparing the Succinic Acid methyl esters; the method is take MALEIC ANHYDRIDE and methyl alcohol as raw material; it is carried out segmentation esterification hydrogenation successive reaction; be specially and under the solid acid catalyst effect, carry out esterification, then under the effect of hydrogenation catalyst, carry out hydrogenation reaction, obtain the Succinic Acid methyl esters.Yet, esterification and hydrogenation are proceed step by step in the disclosed method of this patent, in the esterification reaction process, the existence of water is so that the activity decreased of ion exchange resin solid acid catalyst, and the ion exchange resin solid acid catalyst should not be under the temperature of reaction that the method provides long-play, make the productive rate of the Succinic Acid methyl esters that obtains lower.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of succinate, method provided by the invention has improved the transformation efficiency of synthesizing succinic acid diester, has improved the productive rate of the succinate that obtains.
The invention provides a kind of preparation method of succinate, may further comprise the steps:
With carrying out the esterification hydrogenation after MALEIC ANHYDRIDE, alcohol compound, carbonic acid gas, hydrogen and the hydrogenation catalyst mixing, obtain succinate.
Preferably, described alcohol compound is that carbonatoms is 1 ~ 10 alcohol compound.
Preferably, the mol ratio of described MALEIC ANHYDRIDE and described alcohol compound is (2 ~ 6): 1.
Preferably, the quality of described hydrogenation catalyst is 0.1% ~ 10% of described MALEIC ANHYDRIDE and described alcohol compound total mass.
Preferably, the pressure of described carbonic acid gas is 1MPa ~ 14MPa.
Preferably, the pressure of described hydrogen is 0.1MPa ~ 5MPa.
Preferably, the temperature of described esterification hydrogenation is 70 ℃ ~ 160 ℃.
Preferably, the time of described esterification hydrogenation is 0.5 hour ~ 6 hours.
Preferably, described hydrogenation catalyst comprises support of the catalyst and the active ingredient that is carried on the described support of the catalyst;
Described active ingredient is one or more of Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, Cu, Zn;
Described support of the catalyst is carbon, Al
2O
3, SiO
2, TiO
2, among the ZnO one or more.
Preferably, to account for the massfraction of described hydrogenation catalyst be 0.5wt% ~ 15wt% to described active ingredient.
The invention provides a kind of preparation method of succinate, may further comprise the steps: carry out the esterification hydrogenation after MALEIC ANHYDRIDE, alcohol compound, carbonic acid gas, hydrogen and hydrogenation catalyst are mixed, obtain succinate.The present invention is take MALEIC ANHYDRIDE, alcohol compound and hydrogen as raw material, and carbonic acid gas carries out the esterification hydrogenation reaction as solvent and acid catalyst under the catalysis of hydrogenation catalyst, obtain succinate.Method provided by the invention has higher catalytic activity with solvent and the acid catalyst of carbonic acid gas as the esterification hydrogenation reaction, has improved speed of reaction; And it can also form acid with the water that generates in the reaction process, and then has promoted reaction to carry out to positive dirction; And the product that obtains has certain solubleness in carbonic acid gas, also can impel reaction to carry out to positive dirction, thereby improved the turnover ratio of succinate, improved the productive rate of succinate.Experimental result shows, the yield of the dimethyl succinate that method provided by the invention obtains is greater than 99%.
In addition, the esterification hydrogenation of method MALEIC ANHYDRIDE provided by the invention and alcohol compound can be finished in a step, has simplified production technique.And the reaction process environmental protection, be beneficial to the separation and purification of product, reduced production cost, be conducive to industrial production.
Description of drawings
Fig. 1 is the gas chromatogram of the product that obtains of the embodiment of the invention 11;
Fig. 2 is the gas chromatogram of the product that obtains of the embodiment of the invention 27.
Embodiment
The invention provides a kind of preparation method of succinate, may further comprise the steps:
With carrying out the esterification hydrogenation after MALEIC ANHYDRIDE, alcohol compound, carbonic acid gas, hydrogen and the hydrogenation catalyst mixing, obtain succinate.
The invention provides a kind of preparation method of succinate, method provided by the invention is take MALEIC ANHYDRIDE, alcohol compound and hydrogen as raw material, carbonic acid gas carries out the esterification hydrogenation reaction as solvent and acid catalyst under the catalysis of hydrogenation catalyst, obtain succinate.Method provided by the invention has higher catalytic activity with solvent and the acid catalyst of carbonic acid gas as the esterification hydrogenation reaction, has improved speed of reaction; And it can also form acid with the water that generates in the reaction process, and then has promoted reaction to carry out to positive dirction; And the product that obtains has certain solubleness in carbonic acid gas, also can impel reaction to carry out to positive dirction, thereby improved the turnover ratio of succinate, improved the productive rate of succinate.Experimental result shows, the yield of the dimethyl succinate that method provided by the invention obtains is greater than 99%.
The present invention carries out the esterification hydrogenation after MALEIC ANHYDRIDE, alcohol compound, carbonic acid gas, hydrogen and hydrogenation catalyst are mixed, and obtains succinate.After the present invention mixed above-mentioned raw materials, a step was carried out esterification and hydrogenation, obtains succinate.The present invention adopts MALEIC ANHYDRIDE (MaleicAnhydride, MAH) to be reaction raw materials, and MALEIC ANHYDRIDE also claims maleic anhydride, ten water apple acid anhydrides, has structure shown in the formula (II):
Contain two the building and anhydride bond of getting along well in the MALEIC ANHYDRIDE ring texture, and the two keys of C=C and the two key conjugation of C=O, reactive behavior is very high, so that the esterification hydrogenation that carries out take it as raw material is more prone to occur, reaction conditions is gentle, has reduced energy consumption of reaction, has reduced production cost.
The present invention does not have special restriction to the source along Succinic anhydried, adopts suitable Succinic anhydried well known to those skilled in the art to get final product, as adopting the commercial goods along Succinic anhydried.In the present invention, it is 1 ~ 10 alcohol compound that described alcohol compound is preferably carbonatoms, and more preferably carbonatoms is 1 ~ 5 alcohol compound, most preferably is methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol or Pentyl alcohol; The mol ratio of MALEIC ANHYDRIDE and described alcohol compound is (2 ~ 6): 1, more preferably (3 ~ 5): 1; It is 1MPa ~ 14MPa, more preferably 2MPa ~ 12MPa that the adding of described carbonic acid gas preferably makes its pressure; It is 0.1MPa ~ 5MPa, more preferably 2MPa ~ 4MPa that the adding of described hydrogen preferably makes its pressure; The temperature of described esterification hydrogenation is preferably 70 ℃ ~ 160 ℃, more preferably 90 ℃ ~ 150 ℃; The time of described esterification hydrogenation is preferably 0.5 hour ~ and 6 hours, more preferably 1 hour ~ 4 hours.
In the present invention, described esterification hydriding process can represent with reaction equation shown in the formula (III):
Wherein, in the formula (III), R-OH is that carbonatoms is 1 ~ 10 alcohol compound, and R is that carbonatoms is 1 ~ 10 alkyl.
Method provided by the invention is with carbonic acid gas and the hydrogenation catalyst catalyzer as the esterification hydrogenation, and the present invention does not have special restriction to the source of described carbonic acid gas, adopts carbonic acid gas well known to those skilled in the art to get final product.The present invention does not have special restriction to described hydrogenation catalyst yet, adopts hydrogenation catalyst well known to those skilled in the art to get final product.In the present invention, described hydrogenation catalyst preferably includes support of the catalyst and the active ingredient that is carried on the described support of the catalyst;
Described active ingredient is one or more of Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, Cu, Zn;
Described support of the catalyst is carbon, Al
2O
3, SiO
2, TiO
2, among the ZnO one or more.
The hydrogenation catalyst that the present invention adopts is preferably loaded catalyst, preferably include support of the catalyst and be carried on active ingredient on the described support of the catalyst, described active ingredient is preferably one or more of Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, Cu, Zn; More preferably Pd and/or Ni; Described support of the catalyst is preferably carbon, Al
2O
3, SiO
2, TiO
2, among the ZnO one or more, more preferably carbon, Al
2O
3, SiO
2, TiO
2, a kind of among the ZnO; In the present invention, described carbon is preferably gac; The quality optimization of described active ingredient is 0.5% ~ 15% of described catalyzer total mass, more preferably 5% ~ 10%.
In the present invention, the hydrogenation catalyst that obtains is named in " active ingredient/support of the catalyst " described mode, when if active ingredient is two or more, adopt "-" to separate between the active ingredient, separate with "/" between active ingredient and the support of the catalyst, namely adopt " the first active ingredient-second active ingredient-...-Di N active ingredient/support of the catalyst " name, when if support of the catalyst is two or more, adopt "/" to separate between the support of the catalyst, also adopt "/" to separate between support of the catalyst and the active ingredient, namely adopt " active ingredient/the first support of the catalyst/the second support of the catalyst/... the/the N support of the catalyst " name.Be Pd such as active ingredient, support of the catalyst is carbon, the catalyzer called after " Pd/C " that obtains; For another example, active ingredient is Cu, and support of the catalyst is ZnO and Al
2O
3, the catalyzer called after " Cu/ZnO/Al that obtains
2O
3"; For another example, active ingredient is Pd and Fe, and support of the catalyst is SiO
2, the catalyzer called after " Pd-Fe/SiO that obtains
2".
The present invention does not have special restriction to the preparation method of described hydrogenation catalyst, adopts pickling process well known to those skilled in the art, improvement pickling process or coprecipitation method to prepare hydrogenation catalyst and all can.
In the present invention, the detailed process of described pickling process is: the soluble salt of active ingredient is disperseed, obtain the dispersion liquid of active ingredient; Described dispersion liquid is mixed with support of the catalyst, reduce after dipping is abundant, obtain catalyzer.The present invention does not have special restriction to described soluble salt, adopt the soluble salt of active ingredient well known to those skilled in the art to get final product, when being Pd such as active ingredient, the soluble salt of described active ingredient can be Palladous chloride, when if active ingredient is Ni, the soluble salt of described active ingredient can be nickelous nitrate, if when active ingredient is Cu, the soluble salt of described active ingredient can be cupric nitrate.The present invention does not have special restriction to the mass concentration of active ingredient in the described dispersion liquid, and the concentration of the active ingredient that adopts when adopting employing pickling process well known to those skilled in the art to prepare supported catalyst gets final product.The present invention carries out drying after dispersion liquid and support of the catalyst are mixed, and then preferably reduces under hydrogen atmosphere, obtains catalyzer.
In the present invention, the detailed process of described coprecipitation method is: the soluble salt of active ingredient and the presoma of support of the catalyst or support of the catalyst are mixed to get mixing solutions, then to wherein adding precipitation agent, are precipitated; Reduce after the precipitation that obtains worn out, obtain hydrogenation catalyst.In the present invention, the soluble salt of described active ingredient can be the described soluble salt of the described pickling process of technique scheme; Described the present invention does not have special restriction to the presoma of described support of the catalyst, and the presoma of the support of the catalyst that adopts when adopting coprecipitation method well known to those skilled in the art to prepare supported catalyst gets final product, in the present invention, if support of the catalyst is Al
2O
3, then the presoma of described support of the catalyst can be aluminum nitrate; If support of the catalyst is ZnO, then the presoma of described support of the catalyst can be zinc nitrate; In the present invention, described precipitation agent can be selected according to the kind of active ingredient, and when being Cu such as soluble component, described precipitation agent can be carbonate; The present invention preferably keeps stirring in precipitation process, and the final pH of solution is preferably 7 ~ 8, thereby is precipitated; Described aging temperature is preferably 40 ℃ ~ 60 ℃, more preferably 45 ℃ ~ 55 ℃; The described aging time is preferably 2h ~ 8h, more preferably 3h ~ 5h;
The present invention finishes behind described precipitation aging, preferably described precipitation is filtered, and the filter cake that obtains is carried out drying under 70 ℃ ~ 90 ℃, more preferably 75 ℃ ~ 85 ℃; After finishing drying, the present invention will obtain dry filter cake roasting under 300 ℃ ~ 400 ℃ air atmosphere, more preferably 330 ℃ ~ 380 degrees centigrade, obtain hydrogenation catalyst.
The invention provides a kind of preparation method of succinate, may further comprise the steps: carry out the esterification hydrogenation after MALEIC ANHYDRIDE, alcohol compound, carbonic acid gas, hydrogen and hydrogenation catalyst are mixed, obtain succinate.The present invention is take MALEIC ANHYDRIDE, alcohol compound and hydrogen as raw material, and carbonic acid gas carries out the esterification hydrogenation reaction as solvent and acid catalyst under the catalysis of hydrogenation catalyst, obtain succinate.Method provided by the invention has higher catalytic activity with solvent and the acid catalyst of carbonic acid gas as the esterification hydrogenation reaction, has improved speed of reaction; And it can also form acid with the water that generates in the reaction process, and then has promoted reaction to carry out to positive dirction; And the product that obtains has certain solubleness in carbonic acid gas, also can impel reaction to carry out to positive dirction, thereby improved the turnover ratio of succinate, improved the productive rate of succinate.Experimental result shows, the yield of the dimethyl succinate that method provided by the invention obtains is greater than 99%.
In addition, the esterification hydrogenation of method MALEIC ANHYDRIDE provided by the invention and alcohol compound can be finished in a step, has simplified production technique.And the reaction process environmental protection, be beneficial to the separation and purification of product, reduced production cost, be conducive to industrial production.
In order to further specify the present invention, below in conjunction with embodiment the preparation method of succinate provided by the invention is described in detail, but they can not be interpreted as limiting the scope of the invention.
Embodiment 1
It is the diluted hydrochloric acid aqueous solution of 1mol/L that the Palladous chloride of 0.1g is placed the 0.2mL volumetric molar concentration, stirs 2h so that Palladous chloride fully disperses, and obtains palladium chloride aqueous solution; Absorbent charcoal carrier 0.2g after calcining pretreatment is impregnated in the described palladium chloride aqueous solution, at room temperature fully floods, spend the night, then 60 ℃ of lower dryings, at last 150 ℃ of reduction under hydrogen atmosphere get load P d/C catalyzer.
Embodiment 2
The nickelous nitrate of 0.28g is placed 1mL water, stir 1h, obtain nickel nitrate aqueous solution; Alumina carrier 1g after calcining pretreatment is impregnated in the described aqueous nitric acid, and at room temperature abundant dipping spends the night, then 60 ℃ lower dry, at last in retort furnace with 450 ℃ of calcinings, then reduction obtains loading type Ni/Al under hydrogen atmosphere
2O
3Catalyzer.
Embodiment 3
The water of getting 0.5g cupric nitrate, 0.15g zinc nitrate and 0.18g aluminum nitrate and 5mL is hybridly prepared into mixing solutions, be that the sodium carbonate solution of 0.6mol/L is added drop-wise in the above-mentioned salts solution slowly with volumetric molar concentration, keep in the precipitation process stirring, making the final pH value of solution is 7 ~ 8, stir and aging 4h under 50 ℃, then filter, the filter cake that obtains is dry under 80 ℃, and roasting obtains Cu/ZnO/Al under 350 degree air atmospheres at last
2O
3Catalyzer.
Embodiment 4
The iron nitrate of 0.2g is dissolved in the 0.5mL water, obtains iron nitrate aqueous solution, the silica supports 0.5g after calcining pretreatment is impregnated into described iron nitrate aqueous solution, fully flood under the room temperature, spend the night, then lower dry at 60 ℃; It is the diluted hydrochloric acid aqueous solution of 1mol/L that the Palladous chloride of 0.05g is placed the 0.5mL volumetric molar concentration, stirs 1.5h so that Palladous chloride fully disperses, and obtains palladium chloride aqueous solution; Then the solid impregnating that above-mentioned drying is obtained again is to described palladium chloride aqueous solution, and impregnation drying is calcined under last 450 ℃, and reduction obtains Pd-Fe/SiO under hydrogen atmosphere at last
2Catalyzer.
Embodiment 5
The nickelous nitrate of 0.3g is dissolved in the 0.8mL water, obtains nickel nitrate aqueous solution, the titania support 0.8g after calcining pretreatment is impregnated into described nickel nitrate aqueous solution, fully flood under the room temperature, spend the night, then lower dry at 60 ℃; The iridium chloride of 0.05g is placed 0.5mL water, stir 1h so that iridium chloride fully disperses, obtain the iridium chloride aqueous solution; Then above-mentioned solid impregnating is arrived described palladium chloride aqueous solution, then impregnation drying is calcined under 450 ℃, and reduction obtains Ni-Ir/TiO under hydrogen atmosphere at last
2Catalyzer.
Embodiment 6
The Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES of 0.3g is dissolved in the 2mL water, obtains cobalt nitrate aqueous solution, the absorbent charcoal carrier 1.8g after calcining pretreatment is impregnated into described iron nitrate aqueous solution, fully flood under the room temperature, spend the night, then lower dry at 60 ℃; The Platinic chloride of 0.2g is placed 1.5mL water, obtain chloroplatinic acid aqueous solution; Then the solid impregnating that above-mentioned drying is obtained again is to described chloroplatinic acid aqueous solution, and impregnation drying is calcined under last 450 ℃, and reduction obtains the Pt-Co/C catalyzer under hydrogen atmosphere at last.
Embodiment 7
It is the diluted hydrochloric acid aqueous solution of 0.5mol/L that the ruthenium chloride of 0.035g is placed the 0.5mL volumetric molar concentration, stirs 2h so that ruthenium chloride fully disperses, and obtains ruthenium chloride aqueous solution; Absorbent charcoal carrier 0.5g after calcining pretreatment is impregnated in the described ruthenium chloride aqueous solution, at room temperature fully floods, spend the night, then 60 ℃ of lower dryings, reduction obtains Ru/SiO under hydrogen atmosphere at last
2Catalyzer.
Embodiment 8
The rhodium chloride of 0.02g is dissolved in the 1.2mL water, obtains the rhodium chloride aqueous solution, the zinc oxide carrier 0.8g after calcining pretreatment is impregnated into the described rhodium chloride aqueous solution, fully flood under the room temperature, spend the night, then lower dry at 60 ℃; The nickelous nitrate of 0.5g is joined in the 0.8mL water, obtain nickel nitrate aqueous solution; Arrive described nickel nitrate aqueous solution at the solid impregnating that then above-mentioned drying is obtained, impregnation drying, last 450 ℃ of calcinings, then reduction obtains the Ni-Rh/ZnO catalyzer.
Embodiment 9
The iron nitrate of 0.5g is dissolved in the 1.5mL water, obtains iron nitrate aqueous solution, the absorbent charcoal carrier 2g after calcining pretreatment is impregnated into described iron nitrate aqueous solution, fully flood under the room temperature, spend the night, then lower dry at 60 ℃; The nickelous nitrate of 0.58g is dissolved in the 1.8mL water, obtains nickel nitrate aqueous solution; Then the solid impregnating that above-mentioned drying is obtained again arrives described nickel nitrate aqueous solution, impregnation drying, and last 450 ℃ of calcinings, then reduction obtains the Ni-Fe/C catalyzer under hydrogen atmosphere.
Embodiment 10
The 0.4g iron nitrate is dissolved in the 1.6mL water, obtains iron nitrate aqueous solution, the alumina carrier 1.2g after calcining pretreatment is impregnated into described iron nitrate aqueous solution, fully flood under the room temperature, spend the night, then lower dry at 60 ℃; The Platinic chloride of 0.05g is placed 1.2mL water, obtain chloroplatinic acid aqueous solution; Arrive described chloroplatinic acid aqueous solution at the solid impregnating that then above-mentioned drying is obtained, impregnation drying, last 450 ℃ of calcinings, then reduction obtains Pt-Fe/Al under hydrogen atmosphere
2O
3Catalyzer.
Embodiment 11
In the 50mL reactor, add the Pd/C catalyzer that mol ratio is the MALEIC ANHYDRIDE of 6:1 and embodiment 1 preparation that methyl alcohol, mass ratio are MALEIC ANHYDRIDE and methyl alcohol total mass 0.2%, to wherein adding CO
2, making its pressure is 2MPa, again to wherein adding H
2, making its pressure is 0.6MPa, carries out esterification hydrogenation 2h under 90 ℃, obtains product.
The present invention carries out gas chromatographic analysis with the reaction product that obtains, the result as shown in Figure 1, Fig. 1 is the gas chromatogram of the product that obtains of the embodiment of the invention 11, as seen from Figure 1, the product that the present embodiment obtains is dimethyl succinate.And the present invention calculated the yield of the dimethyl succinate that obtains, and the result is greater than 99%.
Embodiment 12
In the 100mL reactor, add the Ni/Al that mol ratio is the MALEIC ANHYDRIDE of 4:1 and embodiment 2 preparations that methyl alcohol, mass ratio are MALEIC ANHYDRIDE and methyl alcohol total mass 5%
2O
3Catalyzer is to wherein adding CO
2, making its pressure is 10MPa, again to wherein adding H
2, making its pressure is 3MPa, carries out esterification hydrogenation 1h under 160 ℃, obtains product.
The present invention carries out gas chromatographic analysis with the reaction product that obtains, and the result shows, the product that the present embodiment obtains is dimethyl succinate.And the present invention calculated the yield of the dimethyl succinate that obtains, and the result is greater than 99%.
Embodiment 13
The MALEIC ANHYDRIDE that adds mol ratio in the 150mL reactor and be 5:1 and methyl alcohol, mass ratio are the Cu/ZnO/Al that 1% embodiment 3 of MALEIC ANHYDRIDE and methyl alcohol total mass prepares
2O
3Catalyzer is to wherein adding CO
2And to make its pressure be 4MPa, again to wherein adding H
2And to make its pressure be 5MPa, carries out esterification hydrogenation 3h under 150 ℃, obtains product.
The present invention carries out gas chromatographic analysis with the reaction product that obtains, and the result shows, the product that the present embodiment obtains is dimethyl succinate.And the present invention calculated the yield of the dimethyl succinate that obtains, and the result is greater than 99%.
Embodiment 14
In the 200mL reactor, add the Pd-Fe/SiO that mol ratio is the MALEIC ANHYDRIDE of 3:1 and embodiment 4 preparations that methyl alcohol, mass ratio are MALEIC ANHYDRIDE and methyl alcohol total mass 0.2%
2Catalyzer is to wherein adding CO
2Making its pressure is 8MPa, again to wherein adding H
2Making its pressure is 4MPa, carries out esterification hydrogenation 1h under 100 ℃, obtains product.
The present invention carries out gas chromatographic analysis with the reaction product that obtains, and the result shows, the product that the present embodiment obtains is dimethyl succinate.And the present invention calculated the yield of the dimethyl succinate that obtains, and the result is greater than 99%.
Embodiment 15
In the 200mL reactor, add the Pd-Fe/SiO that mol ratio is the MALEIC ANHYDRIDE of 3:1 and embodiment 4 preparations that methyl alcohol, mass ratio are MALEIC ANHYDRIDE and methyl alcohol total mass 0.5%
2Catalyst levels is to wherein adding CO
2Making its pressure is 8MPa, again to wherein adding H
2Making its pressure is 4MPa, carries out esterification hydrogenation 1h under 100 ℃, obtains product.
The present invention carries out gas chromatographic analysis with the reaction product that obtains, and the result shows, the product that the present embodiment obtains is dimethyl succinate.And the present invention calculated the yield of the dimethyl succinate that obtains, and the result is greater than 99%.
Embodiment 16
In the 200mL reactor, add the Pd-Fe/SiO that mol ratio is the MALEIC ANHYDRIDE of 3:1 and embodiment 4 preparations that methyl alcohol, mass ratio are MALEIC ANHYDRIDE and methyl alcohol total mass 1%
2Catalyst levels is to wherein adding CO
2Making its pressure is 8MPa, again to wherein adding H
2Making its pressure is 4MPa, carries out esterification hydrogenation 1h under 100 ℃, obtains product.
The present invention carries out gas chromatographic analysis with the reaction product that obtains, and the result shows, the product that the present embodiment obtains is dimethyl succinate.And the present invention calculated the yield of the dimethyl succinate that obtains, and the result is greater than 99%.
Embodiment 17
In the 250mL reactor, add the Ni-Ir/TiO that mol ratio is the MALEIC ANHYDRIDE of 4.5:1 and embodiment 5 preparations that methyl alcohol, mass ratio are MALEIC ANHYDRIDE and methyl alcohol total mass 0.1%
2Catalyzer is to wherein adding CO
2Making its pressure is 6MPa, again to wherein adding H
2Making its pressure is 1MPa, carries out esterification hydrogenation 1.5h under 140 ℃, obtains product.
The present invention carries out gas chromatographic analysis with the reaction product that obtains, and the result shows, the product that the present embodiment obtains is dimethyl succinate.And the present invention calculated the yield of the dimethyl succinate that obtains, and the result is greater than 99%.
Embodiment 18
In the 250mL reactor, add the Ni-Ir/TiO that mol ratio is the MALEIC ANHYDRIDE of 4.5:1 and embodiment 5 preparations that methyl alcohol, mass ratio are MALEIC ANHYDRIDE and methyl alcohol total mass 1%
2Catalyzer is to wherein adding CO
2Making its pressure is 6MPa, again to wherein adding H
2Making its pressure is 1MPa, carries out esterification hydrogenation 1.5h under 140 ℃, obtains product.
The present invention carries out gas chromatographic analysis with the reaction product that obtains, and the result shows, the product that the present embodiment obtains is dimethyl succinate.And the present invention calculated the yield of the dimethyl succinate that obtains, and the result is greater than 99%.
Embodiment 19
In the 250mL reactor, add the Ni-Ir/TiO that mol ratio is the MALEIC ANHYDRIDE of 4.5:1 and embodiment 5 preparations that methyl alcohol, mass ratio are MALEIC ANHYDRIDE and methyl alcohol total mass 5%
2Catalyzer is to wherein adding CO
2Making its pressure is 6MPa, again to wherein adding H
2Making its pressure is 1MPa, carries out esterification hydrogenation 1.5h under 140 ℃, obtains product.
The present invention carries out gas chromatographic analysis with the reaction product that obtains, and the result shows, the product that the present embodiment obtains is dimethyl succinate.And the present invention calculated the yield of the dimethyl succinate that obtains, and the result is greater than 99%.
Embodiment 20
In the 500mL reactor, add the Pt-Co/C catalyzer that mol ratio is the MALEIC ANHYDRIDE of 5.5:1 and embodiment 6 preparations that methyl alcohol, mass ratio are MALEIC ANHYDRIDE and methyl alcohol total mass 0.4%, to wherein adding CO
2Making its pressure is 3MPa, again to wherein adding H
2Making its pressure is 0.8MPa, carries out esterification hydrogenation 2.5h under 110 ℃, obtains product.
The present invention carries out gas chromatographic analysis with the reaction product that obtains, and the result shows, the product that the present embodiment obtains is dimethyl succinate.And the present invention calculated the yield of the dimethyl succinate that obtains, and the result is greater than 99%.
Embodiment 21
In the 500mL reactor, add the Pt-Co/C catalyzer that mol ratio is the MALEIC ANHYDRIDE of 5.5:1 and embodiment 6 preparations that methyl alcohol, mass ratio are MALEIC ANHYDRIDE and methyl alcohol total mass 1%, to wherein adding CO
2Making its pressure is 3MPa, again to wherein adding H
2Making its pressure is 0.8MPa, carries out esterification hydrogenation 2.5h under 110 ℃, obtains product.
The present invention carries out gas chromatographic analysis with the reaction product that obtains, and the result shows, the product that the present embodiment obtains is dimethyl succinate.And the present invention calculated the yield of the dimethyl succinate that obtains, and the result is greater than 99%.
Embodiment 22
In the 500mL reactor, add the Pt-Co/C catalyzer that mol ratio is the MALEIC ANHYDRIDE of 5.5:1 and embodiment 6 preparations that methyl alcohol, mass ratio are MALEIC ANHYDRIDE and methyl alcohol total mass 5%, to wherein adding CO
2Making its pressure is 3MPa, again to wherein adding H
2Making its pressure is 0.8MPa, carries out esterification hydrogenation 2.5h under 110 ℃, obtains product.
The present invention carries out gas chromatographic analysis with the reaction product that obtains, and the result shows, the product that the present embodiment obtains is dimethyl succinate.And the present invention calculated the yield of the dimethyl succinate that obtains, and the result is greater than 99%.
Embodiment 23
In the 1000mL reactor, add the Ru/SiO that mol ratio is the MALEIC ANHYDRIDE of 3.5:1 and embodiment 7 preparations that methyl alcohol, mass ratio are MALEIC ANHYDRIDE and methyl alcohol total mass 0.2%
2Catalyzer is to wherein adding CO
2Making its pressure is 5MPa, again to wherein adding H
2Making its pressure is 2MPa, carries out esterification hydrogenation 2h under 130 ℃, obtains product.
The present invention carries out gas chromatographic analysis with the reaction product that obtains, and the result shows, the product that the present embodiment obtains is dimethyl succinate.And the present invention calculated the yield of the dimethyl succinate that obtains, and the result is greater than 99%.
Embodiment 24
In the 100mL reactor, add the Ni-Rh/ZnO catalyzer that mol ratio is the MALEIC ANHYDRIDE of 5.5:1 and embodiment 8 preparations that methyl alcohol, mass ratio are MALEIC ANHYDRIDE and methyl alcohol total mass 0.1%, to wherein adding CO
2Making its pressure is 12MPa, again to wherein adding H
2Making its pressure is 5MPa, carries out esterification hydrogenation 4h under 120 ℃, obtains product.
The present invention carries out gas chromatographic analysis with the reaction product that obtains, and the result shows, the product that the present embodiment obtains is dimethyl succinate.And the present invention calculated the yield of the dimethyl succinate that obtains, and the result is greater than 99%.
Embodiment 25
In the 100mL reactor, add the Ni-Rh/ZnO catalyzer that mol ratio is the MALEIC ANHYDRIDE of 5.5:1 and embodiment 8 preparations that methyl alcohol, mass ratio are MALEIC ANHYDRIDE and methyl alcohol total mass 1%, to wherein adding CO
2Making its pressure is 12MPa, again to wherein adding H
2Making its pressure is 5MPa, carries out esterification hydrogenation 4h under 120 ℃, obtains product.
The present invention carries out gas chromatographic analysis with the reaction product that obtains, and the result shows, the product that the present embodiment obtains is dimethyl succinate.And the present invention calculated the yield of the dimethyl succinate that obtains, and the result is greater than 99%.
Embodiment 26
In the 100mL reactor, add the Ni-Rh/ZnO catalyzer that mol ratio is the MALEIC ANHYDRIDE of 5.5:1 and embodiment 8 preparations that methyl alcohol, mass ratio are MALEIC ANHYDRIDE and methyl alcohol total mass 5%, to wherein adding CO
2Making its pressure is 12MPa, again to wherein adding H
2Making its pressure is 5MPa, carries out esterification hydrogenation 4h under 120 ℃, obtains product.
The present invention carries out gas chromatographic analysis with the reaction product that obtains, and the result shows, the product that the present embodiment obtains is dimethyl succinate.And the present invention calculated the yield of the dimethyl succinate that obtains, and the result is greater than 99%.
Embodiment 27
In the 50mL reactor, add the Ni-Fe/C catalyzer that mol ratio is the MALEIC ANHYDRIDE of 4:1 and embodiment 9 preparations that ethanol, mass ratio are MALEIC ANHYDRIDE and total ethanol quality 5%, to wherein adding CO
2Making its pressure is 4MPa, again to wherein adding H
2Making its pressure is 4MPa, carries out esterification hydrogenation 2h under 130 ℃, obtains product.
The present invention carries out gas chromatographic analysis with the reaction product that obtains, the result as shown in Figure 2, Fig. 2 is the gas chromatogram of the product that obtains of the embodiment of the invention 27, as seen from Figure 2, the product that the present embodiment obtains is diethyl succinate.And the present invention calculated the yield of the diethyl succinate that obtains, and the result is greater than 99%.
Embodiment 28
In the 50mL reactor, add the Ni-Fe/C catalyzer that mol ratio is the MALEIC ANHYDRIDE of 4:1 and embodiment 9 preparations that ethanol, mass ratio are MALEIC ANHYDRIDE and total ethanol quality 8%, to wherein adding CO
2Making its pressure is 4MPa, again to wherein adding H
2Making its pressure is 4MPa, carries out esterification hydrogenation 2h under 130 ℃, obtains product.
The present invention carries out gas chromatographic analysis with the reaction product that obtains, and the result shows, the product that the present embodiment obtains is diethyl succinate.And the present invention calculated the yield of the diethyl succinate that obtains, and the result is greater than 99%.
Embodiment 29
In the 50mL reactor, add the Pt-Fe/Al that mol ratio is the MALEIC ANHYDRIDE of 5:1 and embodiment 10 preparations that propyl alcohol, mass ratio are MALEIC ANHYDRIDE and propyl alcohol total mass 0.5%
2O
3Catalyzer is to wherein adding CO
2Making its pressure is 8MPa, and to make its pressure be 1MPa to wherein adding H2, carries out esterification H-H reaction 1h under 110 ℃, obtains product.
The present invention carries out gas chromatographic analysis with the reaction product that obtains, and the result shows, the product that the present embodiment obtains is dipropyl succinate.And the present invention calculated the yield of the dipropyl succinate that obtains, and the result is greater than 99%.
Embodiment 30
In the 50mL reactor, add the Pt-Fe/Al that mol ratio is the MALEIC ANHYDRIDE of 5:1 and embodiment 10 preparations that propyl alcohol, mass ratio are MALEIC ANHYDRIDE and propyl alcohol total mass 1%
2O
3Catalyzer is to wherein adding CO
2Making its pressure is 8MPa, to wherein adding H
2Making its pressure is 1MPa, carries out esterification H-H reaction 1h under 110 ℃, obtains product.
The present invention carries out gas chromatographic analysis with the reaction product that obtains, and the result shows, the product that the present embodiment obtains is dipropyl succinate.And the present invention calculated the yield of the dipropyl succinate that obtains, and the result is greater than 99%.
Embodiment 31
In the 50mL reactor, add the Pt-Fe/Al that mol ratio is the MALEIC ANHYDRIDE of 5:1 and embodiment 10 preparations that propyl alcohol, mass ratio are MALEIC ANHYDRIDE and propyl alcohol total mass 5%
2O
3Catalyzer is to wherein adding CO
2Making its pressure is 8MPa, to wherein adding H
2Making its pressure is 1MPa, carries out esterification H-H reaction 1h under 110 ℃, obtains product.
The present invention carries out gas chromatographic analysis with the reaction product that obtains, and the result shows, the product that the present embodiment obtains is dipropyl succinate.And the present invention calculated the yield of the dipropyl succinate that obtains, and the result is greater than 99%.
As seen from the above embodiment, the invention provides a kind of preparation method of succinate, may further comprise the steps: carry out the esterification hydrogenation after MALEIC ANHYDRIDE, alcohol compound, carbonic acid gas, hydrogen and hydrogenation catalyst are mixed, obtain succinate.The present invention is take MALEIC ANHYDRIDE, alcohol compound and hydrogen as raw material, and carbonic acid gas carries out the esterification hydrogenation reaction as solvent and acid catalyst under the catalysis of hydrogenation catalyst, obtain succinate.Method provided by the invention has higher catalytic activity with solvent and the acid catalyst of carbonic acid gas as the esterification hydrogenation reaction, has improved speed of reaction; And it can also form acid with the water that generates in the reaction process, and then has promoted reaction to carry out to positive dirction; And the product that obtains has certain solubleness in carbonic acid gas, also can impel reaction to carry out to positive dirction, thereby improved the turnover ratio of succinate, improved the productive rate of succinate.Experimental result shows, the yield of the succinate that method provided by the invention obtains is greater than 99%.
In addition, the esterification hydrogenation of method MALEIC ANHYDRIDE provided by the invention and alcohol compound can be finished in a step, has simplified production technique.And the reaction process environmental protection, be beneficial to the separation and purification of product, reduced production cost, be conducive to industrial production.
The above only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. the preparation method of a succinate may further comprise the steps:
With carrying out the esterification hydrogenation after MALEIC ANHYDRIDE, alcohol compound, carbonic acid gas, hydrogen and the hydrogenation catalyst mixing, obtain succinate.
2. method according to claim 1 is characterized in that, described alcohol compound is that carbonatoms is a kind of in 1 ~ 10 the alcohol compound.
3. method according to claim 1 is characterized in that, the mol ratio of described MALEIC ANHYDRIDE and described alcohol compound is (2 ~ 6): 1.
4. method according to claim 1 is characterized in that, the quality of described hydrogenation catalyst is 0.1% ~ 10% of described MALEIC ANHYDRIDE and described alcohol compound total mass.
5. method according to claim 1 is characterized in that, the pressure of described carbonic acid gas is 1MPa ~ 14MPa.
6. method according to claim 1 is characterized in that, the pressure of described hydrogen is 0.1MPa ~ 5MPa.
7. method according to claim 1 is characterized in that, the temperature of described esterification hydrogenation is 70 ℃ ~ 160 ℃.
8. method according to claim 1 is characterized in that, the time of described esterification hydrogenation is 0.5 hour ~ 6 hours.
9. method according to claim 1 is characterized in that, described hydrogenation catalyst comprises support of the catalyst and the active ingredient that is carried on the described support of the catalyst;
Described active ingredient is one or more of Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, Cu, Zn;
Described support of the catalyst is carbon, Al
2O
3, SiO
2, TiO
2, among the ZnO one or more.
10. method according to claim 1 is characterized in that, the massfraction that described active ingredient accounts for described hydrogenation catalyst is 0.5wt% ~ 15wt%.
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| CN112121817A (en) * | 2020-09-22 | 2020-12-25 | 万华化学集团股份有限公司 | Sulfonic acid modified carrier supported solid acid catalyst and preparation method and application thereof |
| CN113522323A (en) * | 2021-08-20 | 2021-10-22 | 南昌大学 | Eu-P-W composite catalyst and preparation method and application thereof |
| CN115445636A (en) * | 2021-06-08 | 2022-12-09 | 中国科学院大连化学物理研究所 | Monoatomic dispersed palladium-based catalyst, and preparation method and application thereof |
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| CN103611546A (en) * | 2013-12-12 | 2014-03-05 | 中国科学院新疆理化技术研究所 | Bimetal catalyst for synthesizing butanedioic-acid dialkyl ester and preparation method thereof |
| CN112121817A (en) * | 2020-09-22 | 2020-12-25 | 万华化学集团股份有限公司 | Sulfonic acid modified carrier supported solid acid catalyst and preparation method and application thereof |
| CN112121817B (en) * | 2020-09-22 | 2022-04-26 | 万华化学集团股份有限公司 | Sulfonic acid modified carrier supported solid acid catalyst and preparation method and application thereof |
| CN115445636A (en) * | 2021-06-08 | 2022-12-09 | 中国科学院大连化学物理研究所 | Monoatomic dispersed palladium-based catalyst, and preparation method and application thereof |
| CN115445636B (en) * | 2021-06-08 | 2023-12-12 | 中国科学院大连化学物理研究所 | Monoatomic dispersed palladium-based catalyst and preparation method and application thereof |
| CN113522323A (en) * | 2021-08-20 | 2021-10-22 | 南昌大学 | Eu-P-W composite catalyst and preparation method and application thereof |
| CN113522323B (en) * | 2021-08-20 | 2022-06-24 | 南昌大学 | Eu-P-W composite catalyst and preparation method and application thereof |
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