CN101380576B - Catalyst for hydrogenolysis of rare glycerol to produce diatomic alcohol and preparation method thereof - Google Patents
Catalyst for hydrogenolysis of rare glycerol to produce diatomic alcohol and preparation method thereof Download PDFInfo
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- CN101380576B CN101380576B CN200810071932XA CN200810071932A CN101380576B CN 101380576 B CN101380576 B CN 101380576B CN 200810071932X A CN200810071932X A CN 200810071932XA CN 200810071932 A CN200810071932 A CN 200810071932A CN 101380576 B CN101380576 B CN 101380576B
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Abstract
The invention discloses a catalyst used for hydrogenolysis of dilute glycerol to prepare dihydric alcohol and a preparation method thereof, and relates to a catalyst to prepare dihydric alcohol. The catalyst comprises nickel, metal A and boracium, wherein, A is iron, cobalt or copper and the like. The content of the components is as follows: 1% to 70% of nickel, 2% to 60% of metal A and 20% to 50% of boracium. The components are dissolved in water, methanol or ethanol and prepared into the saturated solution with the concentration of 0.1mol/L; the solution is cooled by stirring; a reducing agent is dissolved in water, methanol or ethanol and prepared into the solution with the concentration of 0.5 to 4.0mol/L; the reducing agent is added into metal salt mixed solution cooled by water-ice by stirring, then the mixed solution is stirred and put statically to obtain the mixture. A solid obtained by pumping filtration is washed to be neutral and leached and dehydrated to obtain catalyst precursor, and the catalyst precursor is dried to remove water and ethanol. Pre-reduction activation treatment is carried out in gas mixture with low concentration of hydrogen to obtain a powdered catalyst.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method with rare glycerin catalytic hydrogenolysis produce diatomic alcohol.
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.
Ethylene glycol (EG) is another kind of important Organic Chemicals, has in Chemical Manufacture and daily life very and uses widely.It is mainly used in and produces polyester fiber, antifreezing agent, unsaturated polyester resin, lubricant, plasticizer, non-ionic surface active agent and explosive, also as the solvent and the suspension media of ammonium pertorate, and the raw material of electrolytic capacitor production and production EG, be the indispensable chemical industry alcohols of industry such as coating, soup, brake-fluid and printing ink.At present, the unique method of producing EG both at home and abroad is that epoxyethane water is legal, but the technological process of this method is long, equipment is many, energy consumption is high, thereby production cost is also high, also exist simultaneously equipment perishable with problem such as contaminated environment.
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, ZL 95121742.9 disclosed Co-Cu-Mn-Mo catalyst at 250 ℃, H
2Pressure 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 high pressure will increase investment cost very much.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%.Publication number is that the application for a patent for invention of 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%.Publication number is that the application for a patent for invention of CN 101214440A discloses on the Cu-Zn-Al basis and introduces 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.
The rare glycerine of by-product concentration about 30～60% will be produced during ester-interchange method production biodiesel, under this background,, easier industrialization route will be provided undoubtedly directly as if being that the catalytic material hydrogenolysis is produced dihydroxylic alcohols with rare glycerine.Publication number is that the application for a patent for invention of CN101195557A 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 ranges 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.For example, (Catalysis Communications, 2006,6:645-649 such as Tomishige; Applied Catalysis A:General, 2007,318:244-251) 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%, and 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 Catalysts and its preparation method of hydrogenolysis of rare glycerol to produce diatomic alcohol, when this catalyst is used for the hydrogenolysis of low concentration glycerine water solution, under temperate condition, make transformation of glycerol near complete, principal product 1,2-propane diols and ethylene glycol overall selectivity reach 60～85%.
The Preparation of catalysts method of described a kind of hydrogenolysis of rare glycerol to produce diatomic alcohol, the catalyst of described a kind of hydrogenolysis of rare glycerol to produce diatomic alcohol consist of nickel, metal A and boron, wherein metal A is an iron, cobalt or copper, by mass percentage, each components contents is nickel 2%～60%, metal A 6%～55% and boron 26%～43% in the catalyst; Nickel and metal A derive from its slaine, and described slaine is acetate or chlorate; Boron element is from reducing agent NaBH
4Or KBH
4
Described preparation method may further comprise the steps:
1) each component in the catalyst is taken by weighing by mass percentage, distinguish in water-soluble or methyl alcohol or the ethanol, in molar ratio, being configured to concentration is extremely saturated solution of 0.1mol/L, stirs, and cools off in frozen water;
2) reducing agent is dissolved in water or methyl alcohol or the ethanol, in molar ratio, is configured to the solution that concentration is 0.5～4.0mol/L;
3) stirring adds reducing agent down in the slaine mixed liquor of ice-water bath cooling, produces to there being bubble, stirs, and leaves standstill, and gets mixture;
4) with step 3) gained mixture through the solid that suction filtration obtains, be washed with water to after washing lotion is neutrality, with ethanol drip washing dehydration, obtain catalyst precursor again;
5), remove and anhydrate and ethanol with the catalyst precursor drying;
6) with dried catalyst precursor under 250～400 ℃, prereduction activation processing under low hydrogen mixture gas atmosphere, powder catalyst.
In step 1), each component in the catalyst is taken by weighing by mass percentage, distinguish in water-soluble or methyl alcohol or the ethanol, in molar ratio, preferably being configured to concentration is that 0.5mol/L is to saturated solution.
In step 2) in, reducing agent is dissolved in water or methyl alcohol or the ethanol, in molar ratio, preferably be configured to the solution that concentration is 2.0～4.0mol/L.
In step 3), the time of stirring is preferably 10～60min.
In step 5), dry temperature is preferably 80～120 ℃, and the dry time is preferably 2～12h.
In step 6), described low hydrogen gaseous mixture is preferably and contains 5%H
2H
2-N
2Gaseous mixture or contain 5%H
2H
2-Ar gaseous mixture, the time of prereduction activation processing is preferably 2～12h.
Described reducing agent can be selected from NaBH
4Or KBH
4
The activity of such catalysts evaluation is carried out in tank reactor.The rare glycerite and the catalyst fines of metering are joined in the autoclave, use behind the envelope still to feed hydrogen in high purity nitrogen or the hydrogen exchange still behind the air, be heated to reaction temperature and start stirring reaction to reaction pressure.The hydrogenolysis condition is: 180～220 ℃ of reaction temperatures, reaction pressure 2.0～5.0MPa, stir speed (S.S.) 500～1000rpm/min.After reaction was finished, the liquids and gases product adopted the gas chromatographic detection analysis that is 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, under temperate condition (as, 200 ℃ of operating temperatures, operating pressure 2.0MPa) glycerol conversion yield is near 100%, principal product 1,2-PDO and EG overall selectivity reach 60%～85%, and catalyst can be reused, and having good should have prospect.
The specific embodiment
The invention will be further described below by embodiment.
Embodiment 1
Accurately take by weighing 0.01mol nickel acetate and 0.01mol cobalt acetate and be dissolved in the 40mL water and mix, join in the 150mL flask, in ice-water bath, slowly splash into the NaBH of 4.0mol/L under the mechanical agitation
4Solution until there not being bubble to produce, stops to drip, and after continuing to stir 20min, uses the deionized water filtering and washing, with the absolute ethyl alcohol dehydration, obtains the black precursor at last; The black precursor is placed vacuum drying chamber vacuum drying 5h under 100 ℃ of conditions, and dried precursor is with containing 5%H
2H
2-N
2Gaseous mixture is handled 12h 250 ℃ of following pre-activated and is obtained the black catalyst fines, and catalyst consists of 36%Ni-37%Co-27%B.
The test of catalyst activity is carried out in the 100mL autoclave, at first in autoclave, add the 20mL glycerine water solution, then drop into catalyst in pure glycerin quality 5%, be charged to the required pressure of reaction for several times with the high-purity hydrogen gas washing, hydrogenation reaction 12h under 200 ℃, 2.0MPa, after reaction was finished, the liquids and gases product adopted gas-chromatography FID and TCD check and analysis respectively, and the catalyst formulation and the reaction result of 20% concentration glycerine water solution hydrogenolysis produce diatomic alcohol see Table 1.
Table 1
Embodiment 2～7
Accurately take by weighing 0.001mol nickel acetate and 0.019mol cobalt acetate respectively and be dissolved in the 40mL water and mix, join in the 150mL flask, in ice-water bath, slowly splash into the NaBH of 2.0mol/L under the mechanical agitation
4Solution until there not being bubble to produce, stops to drip, and after continuing to stir 20min, uses the deionized water filtering and washing, with the absolute ethyl alcohol dehydration, obtains the black precursor at last; The black precursor is placed vacuum drying chamber vacuum drying 2h under 80 ℃ of conditions, and dried precursor is with containing 5%H
2H
2-N
2Gaseous mixture is handled 12h 250 ℃ of following pre-activated and is obtained black catalyst fines 3%Ni-55%Co-42%B.The consumption that changes nickel acetate and cobalt acetate method is according to this prepared catalyst 6%Ni-52%Co-42%B, 10%Ni-50%Co-40%B, 12%Ni-46%Co-42%B, 29%Ni-29%Co-42%B and the 58%Ni-42%B of different compositions respectively.The gained catalyst adopts still reaction respectively, and hydrogenation reaction 12h carries out activity rating under 200 ℃, 2.0MPa, the results are shown in Table 1.
Embodiment 8～10
Accurately take by weighing 0.005mol nickel acetate and 0.02mol iron chloride respectively and be dissolved in the 50mL ethanol and mix, join in the 150mL flask, in ice-water bath, slowly splash into the NaBH of 2.0mol/L under the mechanical agitation
4Solution until there not being bubble to produce, stops to drip, and after continuing to stir 20min, uses the deionized water filtering and washing, with the absolute ethyl alcohol dehydration, obtains the black precursor at last; The black precursor is placed vacuum drying chamber vacuum drying 10h under 80 ℃ of conditions, and dried precursor is with containing 5%H
2H
2-Ar gaseous mixture is handled 12h 250 ℃ of following pre-activated and is obtained black catalyst fines 12%Ni-45%Fe-43%B.Method is prepared the different catalyst of forming respectively and is prepared different catalyst 29%Ni-28%Fe-43%B of composition and 47%Ni-11%Fe-42%B according to this respectively according to this.Last gained catalyst adopts still reaction respectively, and hydrogenation reaction 12h carries out activity rating under 200 ℃, 2.0MPa, the results are shown in Table 1.
Embodiment 11
Accurately take by weighing 0.01mol nickel acetate and 0.01mol copper acetate and be dissolved in the 80mL methyl alcohol and mix, join in the 150mL flask, splash into the KBH of 2.0mol/L under in ice-water bath, stirring
4Solution produces until no bubble, stops to drip, and after continuing to stir 20min, uses the deionized water filtering and washing, with the absolute ethyl alcohol dehydration, obtains the black precursor at last; The black precursor is placed vacuum drying chamber vacuum drying 2h under 120 ℃ of conditions, and dried precursor is with containing 5%H
2H
2-N
2Gaseous mixture is handled 12h 250 ℃ of following pre-activated and is obtained the black catalyst fines.Last gained catalyst 28%Ni-32%Cu-40%B adopts still reaction, and hydrogenation reaction 12h carries out activity rating under 200 ℃, 2.0MPa, the results are shown in Table 1.
Embodiment 12～16
Catalyst 8%Ni-50%Co-42%B preparation method is with embodiment 1.Dry catalyst precursor is through containing 5%H
2H
2-N
2Gaseous mixture is respectively at 250～450 ℃ of following prereduction activation processing 2～12h.Gained catalyst hydrogenation reaction 12h under 200 ℃, 2.0MPa carries out activity rating, and the reaction result of catalyst prereduction activation temperature and 20% concentration glycerine water solution hydrogenolysis produce diatomic alcohol sees Table 2.
Table 2
Embodiment 17～25
Catalyst 8%Ni-50%Co-42%B preparation process is with embodiment 1, and process contains 5%H under 250 ℃
2H
2-N
2Prereduction activation processing 12h.Embodiment 17～18 is differential responses temperature (180 ℃, 220 ℃), and 2.0MPa reaction 12h down carries out the activity rating result; Embodiment 19～20 for differential responses pressure (3.0MPa, 4.0MPa), 200 ℃ down reaction 12h carry out the activity rating result; Embodiment 21 is 200 ℃, and 2.0MPa reaction 6h down carries out the activity rating result; Embodiment 22～23 is that initial 20% glycerite adopts NaOH solution to regulate pH=12, at 200 ℃, reacts 6h respectively under the 2.0MPa and 12h carries out the activity rating result; Embodiment 24～25 is 40% and 60% at 200 ℃ for initial glycerol concentration, and 2.0MPa reaction 12h down carries out the activity rating result.The reaction result of the various hydrogenolysis of rare glycerol to produce diatomic alcohol of catalyst sees Table 3 under the various reaction conditions.
Table 3
Embodiment 26～29
Embodiment 26～29 is catalyst 8%Ni-50%Co-42%B recycling situation, and catalyst is concrete access times of hydrogenation reaction 12h and reaction result under 200 ℃, 2.0MPa.Catalyst is as shown in table 4 to the repeated use result of 20% concentration glycerine water solution hydrogenolysis produce diatomic alcohol.
Table 4
Claims (6)
1. the Preparation of catalysts method of a hydrogenolysis of rare glycerol to produce diatomic alcohol, it is characterized in that, the catalyst of described a kind of hydrogenolysis of rare glycerol to produce diatomic alcohol consist of nickel, metal A and boron, wherein metal A is an iron, cobalt or copper, by mass percentage, each components contents is nickel 2%～60%, metal A 6%～55% and boron 26%～43% in the catalyst; Nickel and metal A derive from its slaine, and described slaine is acetate or chlorate; Boron element is from reducing agent NaBH
4Or KBH
4Described preparation method may further comprise the steps:
1) each component in the catalyst is taken by weighing by mass percentage, distinguish in water-soluble or methyl alcohol or the ethanol, in molar ratio, being configured to concentration is extremely saturated solution of 0.1mol/L, stirs, and cools off in frozen water;
2) reducing agent is dissolved in water or methyl alcohol or the ethanol, in molar ratio, is configured to the solution that concentration is 0.5～4.0mol/L;
3) stirring adds reducing agent down in the slaine mixed liquor of ice-water bath cooling, produces to there being bubble, stirs, and leaves standstill, and gets mixture;
4) with step 3) gained mixture through the solid that suction filtration obtains, be washed with water to after washing lotion is neutrality, with ethanol drip washing dehydration, obtain catalyst precursor again;
5), remove and anhydrate and ethanol with the catalyst precursor drying;
6) with dried catalyst precursor under 250～400 ℃, prereduction activation processing under low hydrogen mixture gas atmosphere, powder catalyst, described low hydrogen gaseous mixture is for containing 5%H
2H
2-N
2Gaseous mixture or contain 5%H
2H
2-Ar gaseous mixture, the time of prereduction activation processing is 2～12h.
2. the Preparation of catalysts method of a kind of hydrogenolysis of rare glycerol to produce diatomic alcohol as claimed in claim 1 is characterized in that in step 1), and described concentration is that 0.5mol/L is to saturated solution.
3. the Preparation of catalysts method of a kind of hydrogenolysis of rare glycerol to produce diatomic alcohol as claimed in claim 1 is characterized in that in step 2) in, described concentration is the solution of 2.0～4.0mol/L.
4. the Preparation of catalysts method of a kind of hydrogenolysis of rare glycerol to produce diatomic alcohol as claimed in claim 1 is characterized in that in step 3), and the time of stirring is 10～60min.
5. the Preparation of catalysts method of a kind of hydrogenolysis of rare glycerol to produce diatomic alcohol as claimed in claim 1 is characterized in that in step 5), and dry temperature is 80～120 ℃, and the dry time is 2～12h.
6. the Preparation of catalysts method of a kind of hydrogenolysis of rare glycerol to produce diatomic alcohol as claimed in claim 1 is characterized in that described reducing agent is selected from NaBH
4Or KBH
4
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