CN101428222A - Catalyst for producing 1,2-propylene glycol with glycerol hydrogenolysis and preparation method thereof - Google Patents
Catalyst for producing 1,2-propylene glycol with glycerol hydrogenolysis and preparation method thereof Download PDFInfo
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- CN101428222A CN101428222A CNA200810072333XA CN200810072333A CN101428222A CN 101428222 A CN101428222 A CN 101428222A CN A200810072333X A CNA200810072333X A CN A200810072333XA CN 200810072333 A CN200810072333 A CN 200810072333A CN 101428222 A CN101428222 A CN 101428222A
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Abstract
The invention provides a catalyst for 1,2-propylene glycol synthesis via glycerol hydrogenolysis and a preparation method thereof, which belong to the field of catalysts. When being used for 1,2-PDO synthesis via glycerol hydrogenolysis, the catalyst can increase the glycerol conversion rate by 10% to 40% under the same mild conditions compared with the prior art, and the selectivity of 1,2-PDO reaches the range from 75% to 82%. The catalyst contains Cu, Zn and carbon nanotubes (CNTs), wherein the component contents are as follows: 20% to 85% of Cu, 15% to 75% of Zn and 0.5% to 15% of CNTs. The catalyst is prepared by the coprecipitation method which comprises the following steps: adding dropwise a solution of Cu metal salts, a solution of Zn metal salts and a precipitant solution at the same time into metered carbon nanotubes, allowing reactions until the precipitation is completed, calcining and drying the precipitates to obtain a catalyst precursor, activating the catalyst precursor via reduction of a low-hydrogen gaseous mixture to obtain carbon nanotubes-promoted Cu-Zn catalyst.
Description
Technical field
The present invention relates to a kind of catalyst, especially relate to a kind of glycerine hydrogenolysis system 1, CNT promoted type copper-zinc catalyst of 2-propane diols and preparation method thereof.
Background technology
1, and the 2-propane diols (1,2-PDO) be important chemical material, be widely used in chemical industry, food, medicine and cosmetics industry.Existing 1, the 2-PDO production method generally adopts expoxy propane hydration method, also can utilize 1,2-dichloropropane hydrolysis and producing, but all have problems such as bigger environmental pollution and cost be higher.Because the quick rise of petrochemical material prices such as propylene, existing production method faces the pressure of production cost, presses for exploitation new raw material sources and synthetic route.
Biomass-based polyalcohol such as glycerine and sorbierite etc. are called the novel plateform molecules that synthesizes recyclable fuel and chemicals from now on.Adopt the catalytic hydrogenolysis method, biomass polyalcohol glycerine and sorbierite etc. are converted into 1,2-PDO, 1, dihydroxylic alcohols such as 3-PDO and EG, both can increase industrial chain, increase economic efficiency, also will promote developing of relevant biomass energy chemical industry, and expand the new way and the shortage that remedies dihydroxylic alcohols output of dihydroxylic alcohols production, meet China's strategy of sustainable development.In the relevant so far patent documentation of glycerine hydrogenolysis produce diatomic alcohol, with the exploitation glycerol content be 80% or the catalyst and the catalyst system and catalyzing of the concentrated glycerin hydrogenolysis produce diatomic alcohol of above concentration in the majority.As Chinese patent ZL 95121742.9 disclosed Co-Cu-Mn-Mo catalyst at 250 ℃, H2 pressure be under the 25MPa condition reaction 6h can to make mass fraction be that 99.5% glycerol conversion yield reaches 100%, 1, the selectivity of 2-PDO reaches 87%, but this reaction needed is high pressure very, will increase investment cost.CN 101085719A discloses the Cu-Co-Al catalyst at 240 ℃, and the glycerite of 80% concentration is transformed fully, primary product 1, and 2-PDO and EG, overall selectivity can reach 95.5%; If on fixed bed reactors, adopt catalyst such as Cu-Zn or Cu-Co, under 220～260 ℃ of reaction temperatures, can make the glycerine water solution of 80% concentration realize conversion ratio greater than 95%, product 1, the 2-PDO selectivity is greater than 93%.Chinese patent CN 101012149A discloses the Cu-Zn-Mn-Al composite oxide catalysts, makes the glycerine water solution of 85% concentration reach conversion ratio more than 90% in tubular fixed-bed reactor, product 1, and the 2-PDO selectivity is greater than 85%.Chinese patent CN 101214440A discloses on the Cu-Zn-Al basis and has introduced rare earth element, thereby has improved the stability of glycerine hydrogenolysis catalyst.More than these disclosed catalyst all with 80% or the glycerine of above concentration be raw material, realized greater activity and selectivity, but when being used for dilute concentration glycerine hydrogenolysis, or conversion ratio is lower or need harsh conditions.
U.S. Pat 5,214,219 have disclosed copper zinc catalyst have been applied to glycerine hydrogenolysis preparation 1, and 2-PDO reaction, but reaction needs at 10MPa is carried out severe reaction conditions, apparatus expensive, reaction cost height under 220～280 ℃.U.S. Pat 5,276,181 adopt activated carbon supported ruthenium catalyst, under 10～15MPa, 240 ℃ of conditions, make glycerol conversion yield reach 100%, 1, and the 2-PDO selectivity reaches 75%, but exists the too high problem of equipment investment equally.In addition, U.S. Missouri university has developed by biodiesel byproduct product glycerine preparation 1, and the two-step process of 2-PDO (WO 2005/095536A2): at first, glycerine generates the intermediate product pyruvic alcohol under normal pressure; In second step, pyruvic alcohol hydrogenation under the effect of Cu-Cr catalyst generates 1, the 2-propane diols.The reaction condition gentleness, catalyst activity is higher, but chromium element toxicity height is big for environment pollution, is difficult to promote.
With the rare glycerine of by-product concentration about 30～60%, under this background,, will provide easier industrialization route undoubtedly during ester-interchange method production biodiesel if be that the catalytic material hydrogenolysis is produced dihydroxylic alcohols directly with rare glycerine.CN 101195557A discloses with Cu/SiO
2Be catalyst, under the condition about 180 ℃ of operating temperatures and operating pressure 8.0MPa, glycerine methanol solution to 5%～80% concentration range can be realized the glycerine hydrogenolysis, conversion ratio is more than 85%, but glycerine water solution for respective concentration, even adopt higher reaction pressure (～9.0MPa), glycerol conversion yield also can only reach about 40%.In addition, some disclosed bibliographical informations the result of hydrogenolysis of rare glycerol to produce diatomic alcohol.(Catalysis Communications, 2006,6:645-649 such as Tomishige for example; Applied Catalysis A:General, 2007,318:244-251; Applied Catalysis A:General, 2007,329:30-35.) developed Ru/C+Amberlys (Amberlys is a kind of macromolecule resin) catalyst system and catalyzing, the hydrogenolysis that is used for 20% rare glycerine water solution, under the reaction condition of 120 ℃ of temperature and hydrogen 8.0MPa, glycerol conversion yield is about 30%, in the product 1, the selectivity of 2-PDO is about 40%.This system is except that ruthenium comparatively the costliness, and Amberlys is decomposing more than 180 ℃ easily, thereby has limited the industrialization prospect of this catalyst system and catalyzing.Bang superfine (Catalysis Letters, 2007,117 (1-2): 62-67.) studied 20% rare glycerine water solution hydrogenolysis on the Cu-Zn catalyst, under the reaction condition of 200 ℃ and 4.2MPa, although principal product 1, the selectivity of 2-PDO is more than 80%, glycerol conversion yield only is about 25%.
Summary of the invention
Purpose of the present invention is intended to provide a kind of glycerine hydrogenolysis system 1, the Catalysts and its preparation method of 2-propane diols, glycerine hydrogenolysis system 1, the catalyst of 2-propane diols is to be applicable to rare glycerine water solution hydrogenolysis system 1, the CNT of 2-PDO (CNTs) promoted type copper-zinc catalyst, and this catalyst is used for glycerine hydrogenolysis system 1, during 2-PDO, can make glycerol conversion yield improve 10%～40%, 1 than existing best catalyst under relatively mild equal conditions, the selectivity of 2-PDO reaches 75%～82%.
Glycerine hydrogenolysis system 1 of the present invention, the catalyst of 2-propane diols are CNT promoted type copper-zinc catalyst, comprise copper, zinc and CNT, and wherein, copper and zinc derive from slaine, and CNT is multi-walled carbon nano-tubes (CNTs).
Each constituent content of catalyst is Cu:40%～85% by mass percentage, Zn:15%～60%, CNTs:0.5%～15%; Be preferably Cu:45%～75%, Zn:20%～50%, CNTs:2.5%～12%.
The slaine of described copper and zinc is the nitrate of copper and zinc or the acetate of copper and zinc.
The outer tube diameter of described multi-walled carbon nano-tubes is 10～60nm, interior caliber 2～7nm, phosphorus content 〉=95%, graphite-like carbon content 〉=85%, specific area 100～200m
2/ g.
Glycerine hydrogenolysis system 1 of the present invention, the Preparation of catalysts method of 2-propane diols may further comprise the steps:
1) pre-treatment of CNT
CNT earlier through the acid solution reflow treatment, is filtered then, and deionized water is washed till neutrality, 100～160 ℃ of dry for standby;
2) coprecipitation of catalyst precursor preparation
Respectively copper, zinc slaine are mixed with the water solution A that the metal ion total concentration is 0.5～2.0M according to catalyst proportion, a kind of compound in NaOH, potassium hydroxide, sodium carbonate, sodium acid carbonate or the urea is mixed with the aqueous solution B that concentration is 0.5～2.0M; Under the mechanical agitation, solution A and solution B add in the CNT of metering simultaneously, and to keep the pH value of solution value be 6.0～8.0, separates out fully in 50～95 ℃ of following stirring reactions to precipitation, continues constant temperature and stir 3～8h, ageing 5～12h then, with sediment after filtration, the washing, behind 80～140 ℃ of vacuum drying 2～6h, be warming up to 200～350 ℃, constant temperature calcining 2～6h obtains catalyst precursor;
3) reduction activation of catalyst
With catalyst precursor under 200～300 ℃ through low hydrogen gaseous mixture reduction 1～4h, glycerine hydrogenolysis system 1, the catalyst of 2-propane diols, i.e. CNT promoted type copper-zinc catalyst.
Acid solution is preferably at least a in red fuming nitric acid (RFNA), the concentrated sulfuric acid in the described step 1.
The reflow treatment temperature is preferably 60～90 ℃ in the described step 1, and the processing time is preferably 0～36h.
Optimum reaction condition is 6.0～7.5 for keeping the pH value of solution value in the described step 2, separate out fully in 70～90 ℃ of reactions to precipitation, continue constant temperature and stir 4～6h, ageing 8～10h then, washing, the sediment that filters behind 100～120 ℃ of following vacuum drying 2～6h, are warming up to 200～350 ℃ of constant temperature calcining 2～4h.
Heating rate in the described step 2 is preferably 2～6 ℃/min.
The low hydrogen gaseous mixture is preferably and contains 5%H in the described step 3
2H
2-N
2Gaseous mixture or contain 5%H
2H
2-Ar gaseous mixture.
The activity of such catalysts evaluation is carried out in tank reactor.The rare glycerite and the catalyst of metering are joined in the autoclave, use air in nitrogen or the hydrogen exchange still behind the envelope still, feed hydrogen, be heated to reaction temperature and start and stir to required reaction pressure.The hydrogenolysis condition is: 160～240 ℃ of reaction temperatures, reaction pressure 1.0～4.0MPa, stir speed (S.S.) 200～1000rpm.After reaction was finished, the liquids and gases product adopted the gas chromatograph check and analysis that are equipped with hydrogen flame ionization detector and thermal conductivity detector (TCD) respectively.
Catalyst of the present invention is applicable to that hydrogenolysis of rare glycerol produces dihydroxylic alcohols, be particularly useful for rare glycerine water solution hydrogenolysis produce diatomic alcohol, for concentration is that rare glycerine water solution of 20～60% need not concentration, 220 ℃ of reaction temperatures and operating pressure 2.5MPa than under the temperate condition, glycerine is approaching to be transformed fully, principal product 1, and the 2-PDO selectivity reaches 75%～82%, catalyst can be reused, and having good should have prospect.
The specific embodiment
The invention will be further described below by embodiment.
Embodiment 1
Taking by weighing outer tube diameter is 10～60nm, interior caliber 2～7nm, phosphorus content 〉=95%, graphite-like carbon content 〉=85%, specific area 100～200m
2The multi-walled carbon nano-tubes 8.0g of/g pours in the round-bottomed flask, adds red fuming nitric acid (RFNA) 250mL again.Flask places 90 ℃ of oil baths, and 4h refluxes under the vigorous stirring.After reduce to room temperature, filter, be washed till neutrality with deionized water, 120 ℃ of dry for standby.
Take by weighing 75mmol copper nitrate and 25mmol zinc nitrate respectively and be dissolved in the 50mL deionized water, get solution A; Take by weighing 110mmol sodium carbonate again and be dissolved in the 55mL deionized water, get solution B.In 90 ℃ of oil baths, under the mechanical agitation solution A and B are dropwise gone into to be equipped with simultaneously in the three-necked bottle of 0.03g processing back CNTs, keeping the pH value of solution value is 6.5,20min drips off solution A (solution B is excessive).Continue to stir 5h, reduce to room temperature, standing over night.Suction filtration, washs once with small amount of ethanol to neutral with 80 ℃ of deionized water washings of 400mL again.Put 120 ℃ of following dry 4h in the baking oven, place Muffle furnace to rise to 300 ℃ with 4 ℃/min again, roasting 3h gets catalyst precursor.
Catalyst precursor is placed tube furnace, the logical 5%H that contains
2H
2-N
2Gaseous mixture, at 250 ℃ of following reductase 12 h, heating rate is 4 ℃/min, gets required catalyst 74.3%Cu-25.2%Zn-0.5%CNTs.
The catalyst activity property testing carries out in the 100mL autoclave.At first in autoclave, add 20wt% glycerine water solution 24g, add catalyst again in pure glycerin quality 6%.The envelope still, with high-purity hydrogen gas washing 3 times, after be charged to the required pressure 2.5MPa of reaction, temperature rises to 200 ℃, opens and stirs, rotating speed is 800rpm, reaction 18h.After reaction was finished, the liquids and gases product adopted the gas chromatograph check and analysis that are equipped with hydrogen flame ionization detector and thermal conductivity detector (TCD) respectively.Catalyst activity the results are shown in Table 1.
The catalyst formulation and the reaction result of table 1 20% concentration glycerine water solution hydrogenolysis produce diatomic alcohol
Embodiment 2
CNT processing, Preparation of Catalyst and method of reducing are except that the CNT addition is 0.15g, all identical with embodiment 1, the gained catalyst consist of 73.0%Cu-24.6%Zn-2.4%CNTs, its catalyst activity method of testing the results are shown in Table 1 with Comparative Examples 1.
Embodiment 3
Taking by weighing outer tube diameter is 10～60nm, interior caliber 2～7nm, phosphorus content 〉=95%, graphite-like carbon content 〉=85%, specific area 100～200m
2The multi-walled carbon nano-tubes 8.0g of/g pours in the round-bottomed flask, adds red fuming nitric acid (RFNA) and concentrated sulfuric acid mixed liquor (volume ratio is 3:1) 250mL again.Flask places 90 ℃ of oil baths, and 4h refluxes under the vigorous stirring.After reduce to room temperature, filter, be washed till neutrality with deionized water, 120 ℃ of dry for standby.
Take by weighing 75mmol copper nitrate and 25mmol zinc nitrate respectively and be dissolved in the 200mL deionized water, get solution A; Take by weighing the 110mmol sodium acid carbonate again and be dissolved in the 220mL deionized water, get solution B.In 90 ℃ of oil baths, under the mechanical agitation solution A and B are dropwise gone into to be equipped with simultaneously in the three-necked bottle of 0.45g processing back CNTs, keeping the pH value of solution value is 6.5,20min drips off solution A (solution B is excessive).Continue to stir 5h, reduce to room temperature, standing over night.Suction filtration, washs once with small amount of ethanol to neutral with 80 ℃ of deionized water washings of 400mL again.Put 120 ℃ of following dry 4h in the baking oven, place Muffle furnace to rise to 300 ℃ with 4 ℃/min again, roasting 3h gets catalyst precursor.The catalyst precursor method of reducing is with embodiment 1, the gained catalyst consist of 69.4%Cu-23.6%Zn-7.0%CNTs, its catalyst activity method of testing the results are shown in Table 1 with embodiment 1.
Embodiment 4
CNT processing, Preparation of Catalyst and method of reducing are except that the CNT addition is 0.75g, all identical with embodiment 1, the gained catalyst consist of 66.5%Cu-22.4%Zn-11.0%CNTs, its catalyst activity method of testing the results are shown in Table 1 with Comparative Examples 1.
Embodiment 5
Taking by weighing outer tube diameter is 10～60nm, interior caliber 2～7nm, phosphorus content 〉=95%, graphite-like carbon content 〉=85%, specific area 100～200m
2The multi-walled carbon nano-tubes 8.0g of/g pours in the round-bottomed flask, adds concentrated sulfuric acid 250mL again.Flask places 90 ℃ of oil baths, and 4h refluxes under the vigorous stirring.After reduce to room temperature, filter, be washed till neutrality with deionized water, 120 ℃ of dry for standby.
Take by weighing 75mmol Schweinfurt green and 25mmol zinc acetate respectively and be dissolved in the 50mL deionized water, get solution A; Take by weighing the 110mmol dissolution of sodium hydroxide again in the 55mL deionized water, get solution B.In 90 ℃ of oil baths, under the mechanical agitation solution A and B are dropwise gone into to be equipped with simultaneously in the three-necked bottle of 1.05g processing back CNTs, keeping the pH value of solution value is 6.5,20min drips off solution A (solution B is excessive).Continue to stir 5h, reduce to room temperature, standing over night.Suction filtration, washs once with small amount of ethanol to neutral with 80 ℃ of deionized water washings of 400mL again.Put 120 ℃ of following dry 4h in the baking oven, place Muffle furnace to rise to 300 ℃ with 4 ℃/min again, roasting 3h gets catalyst precursor.The catalyst precursor method of reducing is with embodiment 1, the gained catalyst consist of 63.6%Cu-21.5%Zn-14.9%CNTs, the catalyst activity method of testing the results are shown in Table 1 with embodiment 1.
Embodiment 6
Taking by weighing outer tube diameter is 10～60nm, interior caliber 2～7nm, phosphorus content 〉=95%, graphite-like carbon content 〉=85%, specific area 100～200m
2The multi-walled carbon nano-tubes 8.0g of/g pours in the round-bottomed flask, adds red fuming nitric acid (RFNA) 250mL again.Flask places 90 ℃ of oil baths, and 4h refluxes under the vigorous stirring.After reduce to room temperature, filter, be washed till neutrality with deionized water, 120 ℃ of dry for standby.
Take by weighing 50mmol copper nitrate and 50mmol zinc nitrate respectively and be dissolved in the 50mL deionized water, get solution A; Take by weighing 110mmol urea again and be dissolved in the 55mL deionized water, get solution B.In 90 ℃ of oil baths, under the mechanical agitation solution A and B are dropwise gone into to be equipped with simultaneously in the three-necked bottle of 0.15g processing back CNTs, keeping the pH value of solution value is 6.5,20min drips off solution A (solution B is excessive).Continue to stir 5h, reduce to room temperature, standing over night.Suction filtration, washs once with small amount of ethanol to neutral with 80 ℃ of deionized water washings of 400mL again.Put 120 ℃ of following dry 4h in the baking oven, place Muffle furnace to rise to 300 ℃ with 4 ℃/min again, roasting 3h gets catalyst precursor.The catalyst precursor method of reducing is with embodiment 1, the gained catalyst consist of 48.0%Cu-49.6%Zn-2.4%CNTs, its catalyst activity method of testing the results are shown in Table 1 with embodiment 1.
Embodiment 7～9
Taking by weighing outer tube diameter is 10～60nm, interior caliber 2～7nm, phosphorus content 〉=95%, graphite-like carbon content 〉=85%, specific area 100～200m
2The multi-walled carbon nano-tubes 8.0g of/g pours in the round-bottomed flask, adds red fuming nitric acid (RFNA) 250mL again.Flask places 90 ℃ of oil baths, reflux respectively under the vigorous stirring 0h, 12h and 24h, after reduce to room temperature, filter, be washed till neutrality with deionized water, 120 ℃ of oven dry obtain three kinds of CNTs, and are standby.
Preparation of Catalyst and method of reducing obtain composition and are 73.0%Cu-24.6%Zn-11.0%CNTs with embodiment 4, but three kinds of different catalyst of CNTs treatment conditions, its catalyst activity method of testing the results are shown in Table 2 with embodiment 1.
The reaction result of various Preparation of Catalyst conditions of table 2 and 20% concentration glycerine water solution hydrogenolysis produce diatomic alcohol
Embodiment 10 and 11
CNT processing, method for preparing catalyst are with embodiment 4.Catalyst precursor places tube furnace, the logical 5%H that contains
2H
2-N
2Gaseous mixture, at 200 ℃ and 300 ℃ of following reductase 12 h, heating rate is 4 ℃/min respectively, obtains the catalyst 73.0%Cu-24.6%Zn-11.0%CNTs of different reduction temperature preparations, its catalyst activity method of testing the results are shown in Table 2 with embodiment 1.
Embodiment 12 and 13
CNT processing, Preparation of Catalyst and method of reducing divided by 110mmol potassium hydroxide be dissolved in the 55mL deionized water join outside the solution B, with embodiment 2, the gained catalyst consists of 73.0%Cu-24.6%Zn-2.4%CNTs.The catalyst activity test condition is respectively 180 ℃ and 220 ℃ except that reaction temperature, and all the other the results are shown in Table 3 with embodiment 1.
The result of table 3 catalyst 73.0%Cu-24.6%Zn-2.4%CNTs under the differential responses condition
Embodiment 14 and 15
CNT processing, Preparation of Catalyst and method of reducing are with embodiment 2, and catalyst consists of 73.0%Cu-24.6%Zn-2.4%CNTs.The catalyst activity test condition is except that reaction pressure is respectively 2.0MPa and 3.0MPa, and all the other the results are shown in Table 3 with embodiment 1.
Embodiment 16
CNT processing, Preparation of Catalyst and method of reducing are with embodiment 2, and catalyst consists of 73.0%Cu-24.6%Zn-2.4%CNTs.The catalyst activity test condition is except that transferring to reactant liquor pH 12 with 2M NaOH solution, and all the other the results are shown in Table 3 with Comparative Examples 1.
Embodiment 17
CNT processing, Preparation of Catalyst and method of reducing are with embodiment 2, and catalyst consists of 73.0%Cu-24.6%Zn-2.4%CNTs.The catalyst activity test condition adds the 50wt% glycerine water solution 9.6g except that using, and all the other the results are shown in Table 3 with embodiment 1.
Comparative Examples 1
Take by weighing 75mmol copper nitrate and 25mmol zinc nitrate respectively and be dissolved in the 50mL deionized water, get solution A; Take by weighing 110mmol sodium carbonate again and be dissolved in the 55mL deionized water, get solution B.In 90 ℃ of oil baths, under the mechanical agitation solution A and B are dropwise gone in the three-necked bottle of 250mL simultaneously, keeping the pH value of solution value is 6.5,20min drips off solution A (solution B is excessive).Continue to stir 5h, reduce to room temperature, standing over night.Suction filtration, washs once with small amount of ethanol to neutral with 80 ℃ 400mL deionized water washings again.Put 120 ℃ of following dry 4h in the baking oven, place Muffle furnace to rise to 300 ℃ with 4 ℃/min again, roasting 3h gets catalyst precursor.
Catalyst precursor places tube furnace, the logical 5%H that contains
2H
2-N
2Gaseous mixture, at 250 ℃ of following reductase 12 h, heating rate is 4 ℃/min, gets required catalyst 75.5%Cu-24.5%Zn.
The catalyst activity property testing carries out in the 100mL autoclave.At first in autoclave, add 20wt% glycerine water solution 24g, add catalyst again in pure glycerin quality 6%.The envelope still, with high-purity hydrogen gas washing 3 times, after be charged to the required pressure 2.5MPa of reaction, temperature rises to 200 ℃, opens and stirs, rotating speed is 800rpm, reaction 18h.After reaction was finished, the liquids and gases product adopted the gas chromatograph check and analysis that are equipped with hydrogen flame ionization detector and thermal conductivity detector (TCD) respectively.Catalyst activity the results are shown in Table 1.
Claims (10)
1. glycerine hydrogenolysis system 1, and the catalyst of 2-propane diols is characterized in that comprising copper, zinc and CNT, and wherein, copper and zinc derive from slaine, and CNT is a multi-walled carbon nano-tubes.
2. glycerine hydrogenolysis system 1 as claimed in claim 1, the catalyst of 2-propane diols is characterized in that each constituent content of catalyst is Cu:40～85%, Zn:15～60%, CNTs:0.5～15% by mass percentage.
3. glycerine hydrogenolysis system 1 as claimed in claim 2, the catalyst of 2-propane diols is characterized in that each constituent content of catalyst is Cu:45～75%, Zn:20～50%, CNTs:2.5～12% by mass percentage.
4. glycerine hydrogenolysis system 1 as claimed in claim 1, the catalyst of 2-propane diols, the slaine that it is characterized in that copper and zinc are the nitrate of copper and zinc or the acetate of copper and zinc.
5. the described glycerine of claim 1 hydrogenolysis system 1, the Preparation of catalysts method of 2-propane diols is characterized in that may further comprise the steps:
1) pre-treatment of CNT
CNT earlier through the acid solution reflow treatment, is filtered then, and deionized water is washed till neutrality, 100～160 ℃ of dry for standby;
2) coprecipitation of catalyst precursor preparation
Respectively copper, zinc slaine are mixed with the water solution A that the metal ion total concentration is 0.5～2.0M according to catalyst proportion, a kind of compound in NaOH, potassium hydroxide, sodium carbonate, sodium acid carbonate or the urea is mixed with the aqueous solution B that concentration is 0.5～2.0M; Under the mechanical agitation, solution A and solution B add in the CNT of metering simultaneously, and to keep the pH value of solution value be 6.0～8.0, separates out fully in 50～95 ℃ of following stirring reactions to precipitation, continues constant temperature and stir 3～8h, ageing 5～12h then, with sediment after filtration, the washing, behind 80～140 ℃ of vacuum drying 2～6h, be warming up to 200～350 ℃, constant temperature calcining 2～6h obtains catalyst precursor;
3) reduction activation of catalyst
With catalyst precursor under 200～300 ℃ through low hydrogen gaseous mixture reduction 1～4h, glycerine hydrogenolysis system 1, the catalyst of 2-propane diols, i.e. CNT promoted type copper-zinc catalyst.
6. glycerine hydrogenolysis system 1 as claimed in claim 5, the Preparation of catalysts method of 2-propane diols is characterized in that acid solution in the step 1) is at least a in red fuming nitric acid (RFNA), the concentrated sulfuric acid.
7. glycerine hydrogenolysis system 1 as claimed in claim 5, the Preparation of catalysts method of 2-propane diols is characterized in that the reflow treatment temperature is 60～90 ℃ in the step 1), the processing time is 0～36h.
8. glycerine hydrogenolysis system 1 as claimed in claim 5, the Preparation of catalysts method of 2-propane diols, it is characterized in that step 2) in reaction condition be 6.0～7.5 for keeping the pH value of solution value, separate out fully in 70～90 ℃ of reactions to precipitation, continue constant temperature and stir 4～6h, ageing 8～10h then behind 100～120 ℃ of following vacuum drying 2～6h, is warming up to 200～350 ℃ of constant temperature calcining 2～4h with washing, the sediment that filters.
9. glycerine hydrogenolysis system 1 as claimed in claim 5, the Preparation of catalysts method of 2-propane diols is characterized in that step 2) in heating rate be 2～6 ℃/min.
10. glycerine hydrogenolysis system 1 as claimed in claim 5, the Preparation of catalysts method of 2-propane diols is characterized in that the low hydrogen gaseous mixture is for containing 5%H in the step 3)
2H
2-N
2Gaseous mixture or contain 5%H
2H
2-Ar gaseous mixture.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101898946A (en) * | 2010-06-29 | 2010-12-01 | 江苏大学 | Method for hydrogenolysis catalysis of glycerin |
| CN101898946B (en) * | 2010-06-29 | 2013-04-17 | 江苏大学 | Method for hydrogenolysis catalysis of glycerin |
| CN103170338A (en) * | 2011-12-23 | 2013-06-26 | 北京石油化工学院 | Catalyst for 1,2-propylene glycol and preparation method of catalyst |
| CN103170338B (en) * | 2011-12-23 | 2017-10-31 | 北京石油化工学院 | A kind of catalyst for being used for 1,2 propane diols and preparation method thereof |
| US9447011B2 (en) | 2012-11-21 | 2016-09-20 | University Of Tennessee Research Foundation | Methods, systems and devices for simultaneous production of lactic acid and propylene glycol from glycerol |
| CN107029765A (en) * | 2017-04-07 | 2017-08-11 | 厦门大学 | A kind of method of the phosphide catalyst of hydrogenolysis of glycyl alcohol monohydric alcohol |
| CN108435185A (en) * | 2018-04-18 | 2018-08-24 | 佛山市飞程信息技术有限公司 | A kind of catalyst preparing benzaldehyde for catalysis oxidation benzyl alcohol |
| CN115364856A (en) * | 2022-09-20 | 2022-11-22 | 西北工业大学 | Catalyst for preparing mannitol by fructose hydrogenation and preparation method thereof |
| CN115364856B (en) * | 2022-09-20 | 2023-11-07 | 西北工业大学 | Catalyst for preparing mannitol by fructose hydrogenation and preparation method thereof |
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| CN101428222B (en) | 2011-09-07 |
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