CN101767006A - Catalyst for preparing fatty alcohol with low carbon number by catalyzing and hydrolyzing glycerol and preparation method thereof - Google Patents

Catalyst for preparing fatty alcohol with low carbon number by catalyzing and hydrolyzing glycerol and preparation method thereof Download PDF

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CN101767006A
CN101767006A CN200810205072A CN200810205072A CN101767006A CN 101767006 A CN101767006 A CN 101767006A CN 200810205072 A CN200810205072 A CN 200810205072A CN 200810205072 A CN200810205072 A CN 200810205072A CN 101767006 A CN101767006 A CN 101767006A
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catalyst
hydrogenolysis
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glycerine
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CN101767006B (en
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郭岱石
胡琼
内斯劳·姆莱奇科
亚历山大·格罗斯·博文
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Bayer Technology and Engineering Shanghai Co Ltd
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Abstract

The invention relates to a catalyst for catalyzing and hydrolyzing glycerol and a preparation method thereof as well as a method for preparing fatty alcohol with low carbon number by using the catalyst to catalyze and hydrolyze the glycerol. In the invention, a supported metal-acid difunctional catalyst is used, so that the glycerol is hydrolyzed under the mild reaction condition to prepare 1-propanol, 2-propanol, propanediol, acetol and the like.

Description

The catalyst of preparing fatty alcohol with low carbon number by catalyzing and hydrolyzing glycerol and preparation method
Technical field
The present invention relates to a kind of loaded catalyst, and this Preparation of catalysts method and use this catalyst hydrogenolysis glycerine to prepare the method for fatty alcohol with low carbon number, and this catalyst is produced application in the fatty alcohol with low carbon number reaction in the glycerin catalytic hydrogenolysis.
Background technology
Along with the fast development of biodiesel manufacture technology, as the main byproduct of biodiesel processes, the output of glycerine also will be greatly improved.Therefore, efficiently be used to come from the glycerine of living beings fully, meet the trend and the requirement of environmental friendliness and sustainable development, become one of the focus of attention and research in recent years.
It is a kind of effective ways that can utilize glycerine in a large number that glycerine is prepared fatty alcohol with low carbon number through catalytic hydrogenolysis.Can prepare propane diols, ethylene glycol, propyl alcohol, ethanol and methyl alcohol by this method hydrogenolysis glycerine, can also obtain acetone and pyruvic alcohol etc., they all are important chemical material.Especially 1,2-propane diols and 1, ammediol, the target product that becomes to attach most importance to especially is because their market price is far above the price of glycerine.
US2005/0244312 and Appl.Catal.A:Gen.281 have disclosed a kind of hydrogenolysis glycerine preparation 1, the method for 2-propane diols among (2005) 225-231.This method has adopted copper chromite as catalyst, is 200 ℃ in temperature, and the 1.4MPa Hydrogen Vapor Pressure reacted 24 hours down.In the method, the conversion ratio of glycerine is 54.8wt%, 1, and the selectivity of 2-propane diols is 85%, main accessory substance is a pyruvic alcohol.This technology is batch production technology, and glycerol conversion yield is low, and the reaction time is long, complicated operation.
Chaminand etc. are at Green Chem.6, described among (2004) 359-361 a kind of improving in the hydrogenolysis glycerine products therefrom 1, ammediol and 1,2-propane diols ratio is the intermittent reaction technology of target.This process adopts support type Cu, Pd and Rh metallic catalyst, adds wolframic acid again in reaction system, and uses the sulfolane equal solvent.It is 180 ℃ that this process needs in temperature, and the 8.0MPa Hydrogen Vapor Pressure reacted 168 hours down.This process is the conditional request harshness not only, and the conversion ratio of glycerine is low, and maximum conversion also only is 32wt%.
WO2007/129560 discloses with support type Pt, Pd, Ru and Rh metallic catalyst or with the acids of tungstenic or molybdenum and is used, perhaps with adopt Al 2O 3The tungsten of load is used, and is 180 ℃ in temperature, catalytic hydrogenolysis glycerine under the 3.0-5.5MPa Hydrogen Vapor Pressure, and obtaining primary product is 1, ammediol obtains more normal propyl alcohol and isopropyl alcohol simultaneously, but this method glycerol conversion yield is still lower, is up to 23wt%.
Catal.Commun.6, the method that (2005) 645-649 discloses adopts Pt, Pd, Rh and Ru metallic catalyst and the various solid acid of carbon load to use jointly, is 120-180 ℃ in temperature, and the 8.0MPa Hydrogen Vapor Pressure is reaction 10hr down.In the method, glycerol conversion yield is up to 40.7wt%, and product is mainly 1, ammediol, 1,2-propane diols, normal propyl alcohol and isopropyl alcohol.This method severe reaction conditions, and glycerol conversion yield is not high yet.
CN101054339 has disclosed a kind of method of utilizing glycerine to prepare normal propyl alcohol, and this method adopts multiple load type metal catalyst, can make glycerol conversion yield reach 100wt%, and the normal propyl alcohol selectivity is the highest can to reach 96.2%.This method can adopt batch (-type) or continuous process to react, and reaction temperature is 180-360 ℃, and reaction pressure is the 1.0-10.0MPa Hydrogen Vapor Pressure, and the glycerine air speed is 0.5-5.0h -1, H 2With the glycerine ratio be 3: 1-15: 1.
Catal.Commun.9 has reported a kind of support type WO among (2008) 1360-1363 3The investigation result of supporting Pt, Pd, Rh, Ru and Ir metallic catalyst once more on the carrier.This work purpose is selective glycerol ground is converted into 1, ammediol, so adopt 1,3-dimethyl-2-imidazolone is a reaction dissolvent, and with HY, AlMCM-41, TiO 2, Al 2O 3, SiO 2-Al 2O 3And ZrO 2Even load WO 3After the component as carrier.Use Pt/WO wherein 3/ ZrO 2Catalyst can access best catalytic effect, and glycerol conversion yield is 85.8%, 1, and the ammediol yield is 24.2%.Used carrier WO 3/ ZrO 2Be used as solid super-strong acid and in the acid catalysis field, carried out broad research, still WO in this work 3Effect be to improve 1, the selectivity of ammediol, rather than on purpose strengthen the acidity of catalyst because this carrier is to be prepared from 500 ℃ of roastings, the WO of this roasting temperature preparation 3/ ZrO 2Can not form and produce the necessary cubic crystalline phase ZrO of highly acid 2Structure.In addition, this method still is a batch process, and severe reaction conditions need be reacted 18hr under 170 ℃ and 8.0MPa Hydrogen Vapor Pressure, and efficient is lower.
To sum up analyze, low in the prior art ubiquity glycerol conversion yield in catalytic hydrogenolysis glycerine field, shortcomings such as severe reaction conditions, and mostly be batch production technology, be unfavorable for producing high value added products such as fatty alcohol with low carbon number at the industrial glycerine that effectively utilizes.
Summary of the invention
The objective of the invention is in order to overcome above-mentioned severe reaction conditions, glycerol conversion yield is on the low side and defective such as discontinuousization production, a kind of load type metal-bifunctional acidic catalyst of catalytic hydrogenolysis glycerine is provided, the manufacture method of this catalyst, and utilize this load type metal-bifunctional acidic catalyst hydrogenolysis glycerine to produce the continuous reaction technology of fatty alcohol with low carbon number, and, the glycerine hydrogenolysis provides a kind of new way for preparing fatty alcohol with low carbon number.Fatty alcohol with low carbon number of the present invention is that carbon number is less than 4 fatty alcohol.
For solving the problems of the technologies described above, adopt among the present invention that to have surface acid intensity be H 0The load type metal of＜-11.9 superpower acidity-bifunctional acidic catalyst (H 0Be Hammett acidity function, H 0More little, acid strength is big more; On the contrary, H 0Be worth greatly more, acid strength is more little), to relax reaction condition harsh in the prior art, improve the reactivity of glycerine in hydrogenolysis.And be applied to fixed bed reaction technology, realize serialization production.
The catalyst of catalytic hydrogenolysis glycerine of the present invention is load type metal-bifunctional acidic catalyst, and the carrier of described load type metal-bifunctional acidic catalyst is the acid carrier with acid catalysis function.
Metal of the present invention comprises one or more the combination among Rh, Pt, Cu, Pd, Ni, Co, Zn, Re, Ir, Os or the Ru, the combination of one or more among preferred Rh, Pt, Cu, Pd or the Ni.
Acid carrier of the present invention is the ZrO that tungstate radicle, molybdate or borate promote 2, TiO 2, Fe 2O 3Or SnO 2Promotion of the present invention promptly adopts inorganic acid radical to handle to metal oxide or its precursor salt, with a kind of chemical modification state of final formation inorganic acid radical at such metal oxide surface.
The content of tungsten, molybdenum or boron is 1-30wt% in the acid carrier of the present invention, preferred 10-20wt%.
Tenor of the present invention is 0.1-20wt%, preferred 2-10wt%, acid carrier content is 80-99.9wt%, preferred 90-98wt%, in the gross weight of catalyst by 100wt%.
Prepare the method for catalyst of the present invention, comprise step:
The saline admixture that a. will contain the salt of Zr, Ti, Fe or Sn or hydroxide and tungstenic, molybdenum or boron is in 600-1100 ℃ of roasting, thereby makes the ZrO that tungstate radicle, molybdate or borate promote 2, TiO 2, Fe 2O 3Or SnO 2As catalyst carrier;
B. by flooding, be total to the method for dipping, precipitation-deposition or ion-exchange, described metal is equipped on the prepared catalyst carrier;
C. the catalyst carrier that will carry described metal is then carried out roasting under 300-1000 ℃, make described load type metal-bifunctional acidic catalyst.
The time of roasting of the present invention was generally 3-5 hour.The surface acid intensity of catalyst carrier of the present invention is H 0＜-11.9.
Salt or the hydroxide that contains Zr, Ti, Fe or Sn of the present invention, with the saline admixture of tungstenic, molybdenum or boron be precursor by the saline solution that contains Zr, Ti, Fe or Sn, prepare its hydroxide by the precipitation method, with the hydroxide of prepared Zr, Ti, Fe or Sn saline solution dipping back evaporate to dryness with tungstenic, molybdenum or boron, or with the salt mechanical mixture of tungstenic, molybdenum or boron after grind and make; Perhaps with the salt that contains Zr, Ti, Fe or Sn and the salt of tungstenic, molybdenum or boron, make by sol-gel or one step of coprecipitation.
Among the step b of the present invention by the solid mixture that contains Zr or Sn under described 600-1100 ℃ sintering temperature, form and can produce highly acid tetragonal crystal structure.The sintering temperature of steps d of the present invention is preferably 350-650 ℃.
Catalytic hydrogenolysis glycerine of the present invention is produced the method for fatty alcohol with low carbon number, and described hydrogenolysis catalyst is described load type metal-bifunctional acidic catalyst.
Catalyst of the present invention or be directly used in hydrogenation reaction after roasting, or before hydrogenation reaction reduces to catalyst earlier under the condition of 0-3.0MPa and 300-600 ℃ with hydrogen or hydrogen-containing gas, eliminates surface oxide layer.
The reaction temperature of hydrogenolysis of the present invention is 100-270 ℃, preferred 180-220 ℃.The reaction pressure of hydrogenolysis of the present invention is 0.1-3.0MPa, preferred 0.6-2.6MPa.The glycerol liquids air speed of hydrogenolysis of the present invention is 0.5-2.0h -1, preferred 0.9-1.9h -1The hydrogen of hydrogenolysis of the present invention and glycerine mol ratio are 5: 1-80: 1, preferred 15: 1-60: 1.Normal propyl alcohol, isopropyl alcohol, ethanol, methyl alcohol and 1 during the organic product quality of hydrogenolysis of the present invention is formed, the total content of 2-propane diols is 32-95wt%, preferred 44-85wt%.
Hydrogenolysis of the present invention carries out in fixed bed reactors.
Load type metal of the present invention-bifunctional acidic catalyst is produced application in the fatty alcohol with low carbon number reaction in the glycerin catalytic hydrogenolysis.
Technical advantage of the present invention is, prepared a kind of load type metal-bifunctional acidic catalyst by described preparation method, the reaction that makes application this load type metal-bifunctional acidic catalyst hydrogenolysis glycerine produce fatty alcohol with low carbon number can be carried out under the reaction condition gentle more with respect to prior art.Reaction pressure can be low to moderate 0.6MPa.Under mild reaction conditions, the qualities of glycerin conversion ratio can be up to 100wt%, and product is mainly normal propyl alcohol, isopropyl alcohol and 1,2-propane diols, and can highly selective generate monohydric alcohol mixture based on propyl alcohol, and this mixture can be used as the Aalcohols fuel component and adds in the gasoline.The present invention also can pass through to regulate the composition or the reaction condition of catalyst in the catalytic hydrogenolytic cleavage, when producing described Aalcohols fuel, and coproduction 1, other products such as 2-propane diols.
The present invention is applied to the reaction that catalytic hydrogenolysis glycerine is produced fatty alcohol with low carbon number with load type metal-bifunctional acidic catalyst, has also opened up catalytic hydrogenolysis glycerine and has produced the frontier that fatty alcohol with low carbon number uses catalyst.
The specific embodiment
At first, a kind of preparation method according to catalyst of the present invention prepares described catalyst.Adopt ZrOCl 28H 2The O aqueous solution and 25-28% ammoniacal liquor prepare zirconium hydroxide by the precipitation method.Use (NH 4) 6W 12O 39XH 2O solution to dry and grind after the zirconium hydroxide dipping, behind the maceration extract evaporate to dryness, the gained solid is 110 ℃ of oven dry, and 823 ℃ of roastings, obtains the zirconia (WO that highly acid catalyst carrier tungstate radicle promotes x/ ZrO 2).The W content of carrier is 15wt%.Adopt H 2PtCl 66H 2O, Cu (OH) 23H 2O, RhCl 3XH 2O, Ni (NO 3) 26H 2O, Co (NO 3) 26H 2O, NH 4ReO 4, IrCl 3XH 2O, OsCl 33H 2O and RuCl 3XH 2The aqueous solution of O and PdCl 2Hydrochloric acid solution flood WO respectively x/ ZrO 2, successively through 110 ℃ of dryings and 823 ℃ of roasting process, make a series of metals-bifunctional acidic catalyst then.Tenor in every kind of catalyst is 5wt%.
Then, take by weighing the prepared catalyst of 0.5g, and be packed into tubular reactor after a certain amount of quartz sand mixes, form the beds of high 30mm, diameter 7.5mm.Before reaction beginning, catalyst activates 2hr in the 180ml/min hydrogen stream under 350 ℃ and 20bar condition.Glycerin catalytic hydrogenolysis condition is that reaction temperature is 220 ℃, and reaction pressure is 20bar, and the glycerol liquids air speed is 0.91h - 1, hydrogen and glycerine mol ratio are 30: 1.After carrying out 2hr, reaction, utilize the Agilent 6890N type gas-chromatography of equipped DM-Wax chromatographic column and hydrogen flame detector to analyze to the reactant liquor sampling.
By experiment the catalyst of load different metal is investigated.The selectivity of glycerol conversion yield and product i is calculated according to following formula.Wherein, each component concentrations is a shared percentage by weight in the organic matter summation of its place reactant liquor.
Figure G2008102050724D0000061
Figure G2008102050724D0000062
By testing and calculating as can be known Rh/WO in the various load type metals-bifunctional acidic catalyst of above preparation x/ ZrO 2Catalytic activity in the glycerine hydrogenolysis is the strongest.
Secondly, adopt RhCl 3XH 2The O aqueous solution floods different carriers respectively, successively through 110 ℃ of oven dry and 550 ℃ of roastings, makes catalyst Rh/ZrO then 2, Rh/WO 3, Rh/SiO 2, Rh/Al 2O 3, Rh/USY, Rh/TiO 2-SiO 2And Rh/Al 2O 3-SiO 2, be used for and catalyst Rh/WO x/ ZrO 2Compare.
Once more, adopt the different acid carrier MoO of following two steps preparation x/ ZrO 2, BO x/ ZrO 2, WO x/ TiO 2And WO x/ Fe 2O 31) adopts ZrOCl 28H 2O and Fe (NO 3) 39H 2The aqueous solution of O and TiCl 4Hydrochloric acid solution, carry out precipitation reaction with 25-28% ammoniacal liquor respectively, make corresponding metal hydroxide.2) adopt (NH respectively 4) 6Mo 7O 244H 2O, H 3BO 3(NH 4) 6W 12O 39XH 2The metal hydroxides that O aqueous solution dipping makes, the solid behind the evaporate to dryness is 110 ℃ of dryings, and roasting under different temperatures, makes catalyst carrier.Molybdenum in the prepared carrier, boron and W content are 15wt%.Adopt aforementioned same method that Rh (5wt%) is loaded on the prepared acid carrier, make catalyst Rh/MoO x/ ZrO 2, Rh/BO x/ ZrO 2, Rh/WO x/ TiO 2And Rh/WO x/ Fe 2O 3, in order to catalyst Rh/WO x/ ZrO 2Compare.
Then, by changing Rh content and reaction condition, investigate Rh/WO with different Rh content x/ ZrO 2Catalyst under the differential responses condition to the catalytic activity of glycerine hydrogenolysis.
At last, adopt RhCl 3XH 2O and Ni (NO 3) 26H 2The mixed solution of O floods acid carrier WO altogether x/ ZrO 2, make the bimetallic loaded catalyst Rh-Ni/WO that Rh and Ni mol ratio are respectively 1: 1,3: 1 and 9: 1 x/ ZrO 2The total content of Rh and Ni is 5wt%.Adopt aforementioned same method, under the differential responses condition, investigate Rh-Ni/WO x/ ZrO 2Catalytic activity to the glycerine hydrogenolysis.
For further setting forth the present invention, see also following specific embodiment.
Embodiment 1
Adopt ZrOCl 28H 2The O aqueous solution and 25-28% ammoniacal liquor prepare zirconium hydroxide by the precipitation method.Use (NH 4) 6W 12O 39XH 2O solution to dry and grind after the zirconium hydroxide dipping, behind the maceration extract evaporate to dryness, the gained solid is 110 ℃ of oven dry, and 823 ℃ of roastings, obtains the zirconia (WO that highly acid catalyst carrier tungstate radicle promotes x/ ZrO 2).The W content of carrier is 15wt%.Adopt H 2PtCl 66H 2O, Cu (OH) 23H 2O, RhCl 3XH 2O, Ni (NO 3) 26H 2O, Co (NO 3) 26H 2O, NH 4ReO 4, IrCl 3XH 2O, OsCl 33H 2O and RuCl 3XH 2The aqueous solution of O and PdCl 2Hydrochloric acid solution flood WO respectively x/ ZrO 2, successively through 110 ℃ of dryings and 823 ℃ of roastings, make a series of metals-bifunctional acidic catalyst then.Tenor in every kind of catalyst is 5wt%.
Take by weighing the 0.5g catalyst, and be packed into tubular reactor after a certain amount of quartz sand mixes, form the beds of high 30mm, diameter 7.5mm.Before the reaction beginning, catalyst activates 2hr in the 180ml/min hydrogen stream under 350 ℃ and 20bar condition.Glycerin catalytic hydrogenolysis condition is 220 ℃, 20bar, and the glycerol liquids air speed is 0.91h -1, hydrogen and glycerine mol ratio are 30: 1.To the reactant liquor sampling, utilize the Agilent 6890N type gas-chromatography of equipped DM-Wax chromatographic column and hydrogen flame detector to analyze behind the reaction 2hr.
#1-#10 investigates the catalyst of load different metal by experiment, and experimental result is listed in table 1.
Rh/WO x/ ZrO 2The glycerine hydrogenolysis is shown the highest catalytic activity.Conversion ratio is 100wt%, is 85% to the overall selectivity of Aalcohols fuel component (methyl alcohol, ethanol, 1-propyl alcohol and 2-propyl alcohol).
The metal of table 1 load different metal-bifunctional acidic catalyst is to the catalytic activity of glycerine hydrogenolysis
Figure G2008102050724D0000091
Embodiment 2
Adopt RhCl 3XH 2The O aqueous solution floods different carriers respectively, successively through 110 ℃ of oven dry and 550 ℃ of roastings, makes catalyst Rh/ZrO then 2, Rh/WO 3, Rh/SiO 2, Rh/Al 2O 3, Rh/USY, Rh/TiO 2-SiO 2And Rh/Al 2O 3-SiO 2, be used for 1 the highest active catalyst Rh/WO with embodiment x/ ZrO 2Compare.Rh content in the prepared catalyst is 5wt%.
According to the same method of embodiment 1, #11-#17 investigates the activity of above-mentioned prepared catalyst to the glycerine hydrogenolysis by experiment, reaction condition and the results are shown in table 2.The glycerol conversion yield that obtains in the table 2 is starkly lower than use by highly acid carrier WO x/ ZrO 2The catalyst Rh/WO of preparation x/ ZrO 2Reaction result.
The Rh catalyst of table 2 different carriers load is to the catalytic activity of glycerine hydrogenolysis
Figure G2008102050724D0000092
Figure G2008102050724D0000101
Embodiment 3
Adopt the different acid carrier MoO of following two steps preparation x/ ZrO 2, BO x/ ZrO 2, WO x/ TiO 2And WO x/ Fe 2O 31) adopts ZrOCl 28H 2O and Fe (NO 3) 39H 2The aqueous solution of O and TiCl 4Hydrochloric acid solution, carry out precipitation reaction with 25-28% ammoniacal liquor respectively, make corresponding metal hydroxide.2) adopt (NH respectively 4) 6Mo 7O 244H 2O, H 3BO 3(NH 4) 6W 12O 39XH 2The metal hydroxides that O aqueous solution dipping makes, the solid behind the evaporate to dryness is 110 ℃ of dryings, and roasting under the different temperatures shown in the table 3, makes catalyst carrier.Molybdenum in the prepared carrier, boron and W content are 15wt%.Same method loads to Rh (5wt%) on the prepared acid carrier among the employing embodiment 2, makes catalyst Rh/MoO x/ ZrO 2, Rh/BO x/ ZrO 2, Rh/WO x/ TiO 2And Rh/WO x/ Fe 2O 3, in order to the highest active Rh/WO among the embodiment 1 x/ ZrO 2Compare.
Adopt the method among the embodiment 1, #18-#21 investigates the catalytic activity of the Rh catalyst of the different metal oxides load that molybdenum, boron and tungsten promotes to the glycerine hydrogenolysis by experiment, reaction condition and the results are shown in table 3.Rh/MoO x/ ZrO 2And Rh/WO x/ TiO 2Two kinds of catalyst have and Rh/WO x/ ZrO 2Suitable activity.
The Rh catalyst of the different metal oxides load that table 3 molybdenum, boron and tungsten promote is to the catalytic activity of glycerine hydrogenolysis
Figure G2008102050724D0000111
Embodiment 4
Adopt same method among the embodiment 1, #22-#29 investigates the Rh/WO with different Rh content and sintering temperature by experiment x/ ZrO 2Catalyst is to the catalytic activity of glycerine hydrogenolysis.Experimental result is listed in table 4.
By changing reaction condition and Rh content, when producing the Aalcohols fuel component, can obtain 1,2-propane diols, acetone and pyruvic alcohol.Wherein, under the mild reaction conditions of 10bar and 220 ℃, Rh content can realize being higher than the glycerol conversion yield of 98wt% during for 5wt%.
Rh/WO under different preparations of table 4 and the reaction condition x/ ZrO 2Catalyst is to the catalytic activity of glycerine hydrogenolysis
Figure G2008102050724D0000131
Embodiment 5
Adopt RhCl 3XH 2O and Ni (NO 3) 26H 2The mixed solution of O floods acid carrier WO altogether x/ ZrO 2, make the bimetallic loaded catalyst Rh-Ni/WO that Rh and Ni mol ratio are respectively 1: 1,3: 1 and 9: 1 x/ ZrO 2The total content of Rh and Ni is 5wt%.
Adopt same method among the embodiment 1, #30-#38 investigates Rh-Ni/WO under the differential responses condition by experiment x/ ZrO 2Catalytic activity to the glycerine hydrogenolysis the results are shown in table 5.
By to Rh/WO x/ ZrO 2Add second kind of metal Ni according to different proportion in the catalyst, can realize 1, the coproduction of 2-propane diols and Aalcohols fuel component.Be respectively 3: 1 or 9: 1 at Rh and Ni mol ratio, reaction pressure is 10-26bar, and reaction temperature is under 220 ℃ of conditions, glycerol conversion yield can be near 100wt%, 1, the selectivity of 2-propane diols can reach 22-37%, and the overall selectivity of Aalcohols fuel component can reach 44-58%.In addition, be respectively 9: 1 at Rh and Ni mol ratio, reaction pressure is 6bar, and reaction temperature is under 220 ℃ the temperate condition, also can realize the transformation of glycerol of 100wt%.
Bimetallic Rh-Ni/WO under the table 5 differential responses condition x/ ZrO 2Catalyst is to the catalytic activity of glycerine hydrogenolysis
Figure G2008102050724D0000151
Above specific embodiment is by being suitable for load type metal of the present invention-bifunctional acidic catalyst, and corresponding adjustment reaction condition, realized under mild reaction conditions, improved the qualities of glycerin conversion ratio, and highly selective generates the monohydric alcohol mixture based on propyl alcohol.Simultaneously, also realized by regulating the composition or the reaction condition of catalyst in the catalytic hydrogenolytic cleavage, when producing described Aalcohols fuel, coproduction 1, the purpose of other products such as 2-propane diols.
Though the present invention discloses preferred embodiment as above; right its is not in order to limiting the present invention, anyly has the knack of this skill person, without departing from the spirit and scope of the present invention; when can doing various changes and retouching, so protection scope of the present invention should be as the criterion with the claim scope of applying for a patent.

Claims (24)

1. catalyst that is used for catalytic hydrogenolysis glycerine, described catalyst is load type metal-bifunctional acidic catalyst, the ZrO that the carrier of described load type metal-bifunctional acidic catalyst is promoted by tungstate radicle, molybdate or borate 2, TiO 2, Fe 2O 3Or SnO 2Make.
2. catalyst as claimed in claim 1 is characterized in that, described metal comprises one or more the combination among Rh, Pt, Cu, Pd, Ni, Co, Zn, Re, Ir, Os or the Ru.
3. catalyst as claimed in claim 2 is characterized in that, described metal comprises one or more the combination among Rh, Pt, Cu, Pd or the Ni.
4. as claim 1,2 or 3 described catalyst, it is characterized in that the content of tungsten, molybdenum or boron is 1-30wt% in the described carrier, in the gross weight of carrier by 100wt%.
5. catalyst as claimed in claim 4 is characterized in that, the content of tungsten, molybdenum or boron is 10-20wt% in the described carrier, in the gross weight of carrier by 100wt%.
6. as claim 1,2 or 3 described catalyst, it is characterized in that tenor is 0.1-20wt% in the described catalyst, acid carrier content is 80-99.9wt%, in the gross weight of catalyst by 100wt%.
7. catalyst as claimed in claim 6 is characterized in that, described tenor is 2-10wt%.
8. catalyst as claimed in claim 6 is characterized in that, described acid carrier content is 90-98wt%.
9. one kind prepares the method for catalyst according to claim 1, it is characterized in that the method comprising the steps of:
The saline admixture that a. will contain the salt of Zr, Ti, Fe or Sn or hydroxide and tungstenic, molybdenum or boron is in 600-1100 ℃ of roasting, thereby makes the ZrO that tungstate radicle, molybdate or borate promote 2, TiO 2, Fe 2O 3Or SnO 2As catalyst carrier;
B. by flooding, be total to the method for dipping, precipitation-deposition or ion-exchange, described metal is equipped on the prepared catalyst carrier;
C. the catalyst carrier that will carry described metal is then carried out roasting under 300-1000 ℃, make described load type metal-bifunctional acidic catalyst.
10. as method as described in the claim 9, it is characterized in that the surface acid intensity of described catalyst carrier is H 0＜-11.9.
11., it is characterized in that the sintering temperature of described step c is 350-650 ℃ as method as described in the claim 9.
12. as method as described in the claim 9, it is characterized in that, described mixture is a precursor by the saline solution that contains Zr, Ti, Fe or Sn, prepare its hydroxide by the precipitation method, with the hydroxide of prepared Zr, Ti, Fe or Sn saline solution dipping back evaporate to dryness with tungstenic, molybdenum or boron, or with the salt mechanical mixture of tungstenic, molybdenum or boron after grind and make; Perhaps with the salt that contains Zr, Ti, Fe or Sn and the salt of tungstenic, molybdenum or boron, make by sol-gel or one step of coprecipitation.
13. one kind is used catalyst according to claim 1, the method for preparing fatty alcohol with low carbon number by catalyzing and hydrolyzing glycerol.
14., it is characterized in that the reaction temperature of described hydrogenolysis is 100-270 ℃ as method as described in the claim 13.
15., it is characterized in that the reaction temperature of described hydrogenolysis is 180-220 ℃ as method as described in the claim 14.
16., it is characterized in that the reaction pressure of described hydrogenolysis is 0.1-3.0MPa as method as described in the claim 13.
17., it is characterized in that the reaction pressure of described hydrogenolysis is 0.6-2.6MPa as method as described in the claim 16.
18., it is characterized in that the glycerol liquids air speed of described hydrogenolysis is 0.5-2.0h as method as described in the claim 13 -1
19., it is characterized in that the glycerol liquids air speed of described hydrogenolysis is 0.9-1.9h as method as described in the claim 18 -1
20., it is characterized in that the hydrogen of described hydrogenolysis and glycerine mol ratio are 5: 1-80: 1 as method as described in the claim 13.
21., it is characterized in that the hydrogen of described hydrogenolysis and glycerine mol ratio are 15: 1-60: 1 as method as described in the claim 20.
22. as method as described in the claim 13, it is characterized in that, described hydrogenolysis catalyst, reduces to catalyst earlier under reaction temperature 300-600 ℃ the condition and is used further to hydrogenation reaction after handling at reaction pressure 0-3.0MPa with hydrogen or hydrogen-containing gas before preparation back end hydrogenation reaction.
23., it is characterized in that described hydrogenolysis carries out in fixed bed reactors as method as described in the claim 13.
24. load type metal-bifunctional acidic catalyst is produced application in the fatty alcohol with low carbon number reaction in the glycerin catalytic hydrogenolysis according to claim 1.
CN 200810205072 2008-12-30 2008-12-30 Catalyst for preparing fatty alcohol with low carbon number by catalyzing and hydrolyzing glycerol and preparation method thereof Expired - Fee Related CN101767006B (en)

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CN105669373A (en) * 2014-11-17 2016-06-15 中国科学院大连化学物理研究所 Method for hydrocracking polyols
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
CN107096564A (en) * 2017-06-05 2017-08-29 扬州大学 The supporting Pts of SAPO 34 and WOx a kind of catalyst and preparation method thereof
CN107913722A (en) * 2017-10-31 2018-04-17 张家港美景荣化学工业有限公司 Metal/solid acid catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation
CN109225329A (en) * 2018-09-26 2019-01-18 浙江恒澜科技有限公司 A kind of catalyst and its application preparing 1,3- propylene glycol for hydrogenolysis of glycerin
CN109748777A (en) * 2018-12-26 2019-05-14 大连理工大学 A kind of method that 1,2,6- hexanetriol catalytic hydrogenolysis prepares 1,6-HD
CN111054339A (en) * 2018-10-16 2020-04-24 中国石油化工股份有限公司 Catalyst composition for preparing glycol
CN111054338A (en) * 2018-10-16 2020-04-24 中国石油化工股份有限公司 Catalyst for preparing biomass-based ethylene glycol
CN113227327A (en) * 2018-12-31 2021-08-06 耐思特公司 Method for the catalytic production of propanol
CN113831248A (en) * 2020-06-24 2021-12-24 中国石油化工股份有限公司 Method for preparing 3-hydroxy propionate derivatives

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Cited By (16)

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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
CN105669373A (en) * 2014-11-17 2016-06-15 中国科学院大连化学物理研究所 Method for hydrocracking polyols
CN105669373B (en) * 2014-11-17 2017-09-15 中国科学院大连化学物理研究所 A kind of method of polyalcohol hydrogenolysis
CN105478141B (en) * 2015-11-19 2018-02-06 合肥工业大学 Pt nanometer alloy catalysts and its production and use
CN105478141A (en) * 2015-11-19 2016-04-13 合肥工业大学 Pt nanometer alloy catalyst, and preparation method and application thereof
CN107096564A (en) * 2017-06-05 2017-08-29 扬州大学 The supporting Pts of SAPO 34 and WOx a kind of catalyst and preparation method thereof
CN107913722A (en) * 2017-10-31 2018-04-17 张家港美景荣化学工业有限公司 Metal/solid acid catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation
CN107913722B (en) * 2017-10-31 2020-03-27 张家港美景荣化学工业有限公司 Metal/solid acid catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation
CN109225329A (en) * 2018-09-26 2019-01-18 浙江恒澜科技有限公司 A kind of catalyst and its application preparing 1,3- propylene glycol for hydrogenolysis of glycerin
CN111054338A (en) * 2018-10-16 2020-04-24 中国石油化工股份有限公司 Catalyst for preparing biomass-based ethylene glycol
CN111054339A (en) * 2018-10-16 2020-04-24 中国石油化工股份有限公司 Catalyst composition for preparing glycol
CN109748777A (en) * 2018-12-26 2019-05-14 大连理工大学 A kind of method that 1,2,6- hexanetriol catalytic hydrogenolysis prepares 1,6-HD
CN109748777B (en) * 2018-12-26 2020-09-11 大连理工大学 Method for preparing 1, 6-hexanediol by catalytic hydrogenolysis of 1,2, 6-hexanetriol
CN113227327A (en) * 2018-12-31 2021-08-06 耐思特公司 Method for the catalytic production of propanol
CN113831248A (en) * 2020-06-24 2021-12-24 中国石油化工股份有限公司 Method for preparing 3-hydroxy propionate derivatives
CN113831248B (en) * 2020-06-24 2023-11-10 中国石油化工股份有限公司 Method for preparing 3-hydroxy propionate derivative

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