Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, and a kind of reaction conditions gentleness is provided, the synthetic method of simple dibasic alcohol of technology and polyvalent alcohol.
The invention provides the synthetic method of a kind of dibasic alcohol and polyvalent alcohol, with sucrose is raw material, may further comprise the steps: under the hydrogenolysis catalyst effect, pH value 11～14, the aqueous sucrose solution of quality percentage composition 10～50% are at first reacted 0.5h～2h under 130 ℃～150 ℃ of temperature of reaction, hydrogen pressure 6MPa～8MPa; Then 220 ℃～250 ℃ of temperature of reaction, hydrogen pressure 10MPa～13Mpa is reaction 0.5h～2h down, reaction product obtains dibasic alcohol and polyvalent alcohol after cooling, filtration, rectifying, wherein hydrogenolysis catalyst is chromium-doped or nickel-molybdenum-the copper catalyst of iron, tin, zinc, consumption is 15%～30% of a sucrose quality, dibasic alcohol comprises ethylene glycol, propylene glycol and butyleneglycol, and polyvalent alcohol comprises glycerol, sorbyl alcohol and N.F,USP MANNITOL.
The present invention is in the presence of hydrogenolysis catalyst, and glucose is reaction generation sorbyl alcohol under lower temperature of reaction and hydrogen pressure earlier; The temperature of reaction that raises then and hydrogen pressure, make the further hydrogenolysis of sorbyl alcohol of generation generate dibasic alcohol such as ethylene glycol, propylene glycol, simplified technological process, reduced operation steps, avoided the cooling, sedimentation, filtration of the treating process of sorbyl alcohol simultaneously, from the energy consumption of intermediate treatment processes such as friendship, decolouring with reduced facility investment, reduced cost.
The quality percentage composition of aqueous phase sucrose of the present invention in the aqueous solution is preferably 20～30%, and more preferably 25%.
Sucrose water of the present invention hydrocracking prepares the reaction of dibasic alcohol and polyvalent alcohol preferably to be carried out for 13～14 times in the pH value, and more preferably the pH value 13.Before the reaction beginning, with NaOH, KOH, Na2CO3Or Ca (OH)2Regulate pH value to 13 in alkali, can make the organic acids such as by product lactic acid of sucrose water hydrocracking reaction under alkaline condition, further generate organic salt, avoided itself and catalyst reaction to cause the problem of catalyst loss.
Among the present invention, the mass ratio of metallic element is a nickel in the catalyzer: molybdenum: copper: chromium (or iron, zinc)=100: 2: 5: 5, and nickel: molybdenum: copper: tin=100: 2: 5: 10.Catalyst for cracking is preferably nickel-molybdenum-copper-chromium or nickel-molybdenum-copper-tin catalyst, more preferably nickel-molybdenum-copper-chromium, and consumption is 25% of a sucrose quality.
Reaction conditions is preferably: at first reacting 1 hour under the reaction conditions of 140 ℃ of temperature of reaction, reaction pressure 7MPa, is 13 at pH then, 240 ℃ of temperature of reaction, and the reaction conditions of reaction pressure 12MPa reacted 1 hour down.
The dibasic alcohol that the hydrocracking of sucrose water makes mainly comprises ethylene glycol, propylene glycol and butyleneglycol, and wherein butyleneglycol comprises 1,2-butyleneglycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 2, isomer such as 3-butyleneglycol, polyvalent alcohol comprise glycerol, sorbyl alcohol and N.F,USP MANNITOL etc.The percentage composition of split product is under different catalysts and the reaction conditions: ethylene glycol 15～25%; Propylene glycol 40～60%; Butyleneglycol (comprising all isomer) 5～10%; Glycerol 5～15%; Sorbyl alcohol and N.F,USP MANNITOL 1～5%; Other are 2～15% years old.
Method for preparing catalyst:
Alumino nickel is added in the reaction vessel, adds entry, is heated to 50 ℃.To be dissolved with ammonium molybdate, cupric chloride, 15% hydrochloric acid soln of chromium trichloride (or tin protochloride or iron trichloride or zinc chloride) drops in the reactor.1h is stirred in continuation after dropwising, and topples over liquid.Catalyst solid washing three times, 300 ℃, reduction 5h postcooling in water or the alcoholic solvent obtains nickel-molybdenum-copper-chromium (or nickel-molybdenum-copper-Xi or nickel-molybdenum-copper-iron or nickel-molybdenum-copper-zinc) catalyzer in the nitrogen atmosphere.By the reaction of hydrochloric acid and aluminium and the replacement(metathesis)reaction of metal salt solution and aluminium, metals such as copper, chromium, tin, iron, zinc enter the alloy duct.May contain the aluminium that traces of unreacted is fallen in the catalyzer of present method preparation, but its existence does not influence catalytic performance, the present invention does not do strict the qualification to the content of aluminium.
Beneficial effect of the present invention is mainly reflected in: sucrose is reaction generation polyvalent alcohol under lower temperature of reaction and hydrogen pressure earlier; The temperature of reaction that raises then and hydrogen pressure make the further hydrogenolysis of polyvalent alcohol of generation generate dibasic alcohol such as ethylene glycol, propylene glycol, and the reaction conditions gentleness has reduced the requirement to equipment; Selected catalyzer need not to form suspension with solvent, and directly adding reaction system can catalyzed reaction carry out smoothly, has simplified technological process.
Embodiment
The present invention is described in more detail below by specific embodiment, but protection scope of the present invention is not limited to this.
Embodiment 1
A certain amount of sucrose dissolved in water, is mixed with the quality percentage composition and is 25% the aqueous solution.Getting this solution 300g joins in the autoclave of 500mL, regulate pH=13, add nickel-molybdenum-copper-chromium catalyst that 22.5g activates, close autoclave, nitrogen vacuumizes after suppressing leak test, and with hydrogen exchange 3 times, heat temperature raising then, after the question response temperature is increased to 140 ℃, charging into hydrogen to reaction pressure is that 7MPa begins catalytic hydrogenation reaction, react after 1 hour elevated temperature to 240 ℃, the reaction conditions of reaction pressure 12MPa reacted 1 hour down, high pressure liquid chromatographic analysis is used in sampling, and product is formed and content is respectively: ethylene glycol 18%, propylene glycol 50%, butyleneglycol (comprising all isomer) 9%, glycerol 10%, sorbyl alcohol and N.F,USP MANNITOL 3%, other is 10% years old.
Embodiment 2
Operate substantially the same manner as Example 1ly, different is that catalyzer is nickel-molybdenum-copper-Xi, and reaction result is as follows:
The transformation efficiency of sucrose is 100%, and different product selectivity are: ethylene glycol 15%, propylene glycol 40%, butyleneglycol (comprising all isomer) 10%, glycerol 15%, sorbyl alcohol and N.F,USP MANNITOL 5%, other 15%.
Embodiment 3
Operate substantially the same manner as Example 1ly, different is that catalyzer is nickel-molybdenum-copper-iron, and reaction result is as follows:
The transformation efficiency of sucrose is 100%, and different product selectivity are: ethylene glycol 16%, propylene glycol 48%, butyleneglycol (comprising all isomer) 9%, glycerol 12%, sorbyl alcohol and N.F,USP MANNITOL 4%, other 11%.
Embodiment 4
Operate substantially the same manner as Example 1ly, different is that catalyzer is nickel-molybdenum-copper-zinc, and reaction result is as follows:
The transformation efficiency of sucrose is 100%, and different product selectivity are: ethylene glycol 20%, propylene glycol 46%, butyleneglycol (comprising all isomer) 8%, glycerol 13%, sorbyl alcohol and N.F,USP MANNITOL 4%, other 9%.
Embodiment 5
Operate substantially the same manner as Example 1ly, the initial pH value of reaction that different is is 11, and reaction result is as follows:
The transformation efficiency of sucrose is 100%, and different product selectivity are: ethylene glycol 17%, propylene glycol 50%, butyleneglycol (comprising all isomer) 9%, glycerol 12%, sorbyl alcohol and N.F,USP MANNITOL 3%, other 9%.
Embodiment 6
Operate substantially the same manner as Example 1ly, different is that reaction conditions is: at first 130 ℃ of temperature of reaction, and the reaction 1 hour down of the reaction conditions of reaction pressure 8MPa; Then, 220 ℃ of temperature of reaction, the reaction conditions of reaction pressure 13MPa reacted 1 hour down, and reaction result is as follows:
The transformation efficiency of sucrose is 100%, and different product selectivity are: ethylene glycol 15%, propylene glycol 49.5%, butyleneglycol (comprising all isomer) 8%, glycerol 13.5%, sorbyl alcohol and N.F,USP MANNITOL 4.5%, other 9.5%.
Embodiment 7
Operate substantially the same manner as Example 1ly, different is that reaction conditions is: at first 150 ℃ of temperature of reaction, and the reaction 1 hour down of the reaction conditions of reaction pressure 6MPa; Then, 250 ℃ of temperature of reaction, the reaction conditions of reaction pressure 10MPa reacted 1 hour down, and reaction result is as follows:
The transformation efficiency of sucrose is 100%, and different product selectivity are: ethylene glycol 19%, propylene glycol 55%, butyleneglycol (comprising all isomer) 6%, glycerol 8%, sorbyl alcohol and N.F,USP MANNITOL 2%, other 10%.
Embodiment 8
Operate substantially the same manner as Example 1ly, different is that the aqueous phase concentration of sucrose is 10%, and catalyst levels is 4.5g, and reaction result is as follows:
The transformation efficiency of sucrose is 100%, and different product selectivity are: ethylene glycol 20%, propylene glycol 60%, butyleneglycol (comprising all isomer) 8%, glycerol 9%, sorbyl alcohol and N.F,USP MANNITOL 1%, other 2%.
Embodiment 9
Operate substantially the same manner as Example 1ly, different is that the aqueous phase concentration of sucrose is 50%, and catalyst levels is 37.5g, and the initial pH value of reaction is 14, and reaction result is as follows:
The transformation efficiency of sucrose is 100%, and different product selectivity are: ethylene glycol 18%, propylene glycol 47%, butyleneglycol (comprising all isomer) 9%, glycerol 12%, sorbyl alcohol and N.F,USP MANNITOL 5%, other 9%.
Embodiment 10
Operate substantially the same manner as Example 1, at first reaction 0.5 hour under 140 ℃, 7MPa reaction conditions that different is, reaction 0.5 hour under 240 ℃, 12MPa reaction conditions then, reaction result is as follows:
The transformation efficiency of sucrose is 100%, and different product selectivity are: ethylene glycol 15%, propylene glycol 45%, butyleneglycol (comprising all isomer) 10%, glycerol 15%, sorbyl alcohol and N.F,USP MANNITOL 5%, other 10%.
Embodiment 11
Operate substantially the same manner as Example 1, at first reaction 2 hours under 140 ℃, 7MPa reaction conditions that different is, reaction 2 hours under 240 ℃, 12MPa reaction conditions then, reaction result is as follows:
The transformation efficiency of sucrose is 100%, and different product selectivity are: ethylene glycol 25%, propylene glycol 58%, butyleneglycol (comprising all isomer) 6%, glycerol 5%, sorbyl alcohol and N.F,USP MANNITOL 1%, other 5%.
Embodiment 12
Operate substantially the same manner as Example 1, at first reaction 0.5 hour under 140 ℃, 7MPa reaction conditions that different is, reaction 2 hours under 240 ℃, 12MPa reaction conditions then, reaction result is as follows:
The transformation efficiency of sucrose is 100%, and different product selectivity are: ethylene glycol 21%, propylene glycol 56%, butyleneglycol (comprising all isomer) 5%, glycerol 7%, sorbyl alcohol and N.F,USP MANNITOL 3%, other 8%.