CN101816936B - Method for preparing Cu-Al-containing catalyst - Google Patents
Method for preparing Cu-Al-containing catalyst Download PDFInfo
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- CN101816936B CN101816936B CN2010101375497A CN201010137549A CN101816936B CN 101816936 B CN101816936 B CN 101816936B CN 2010101375497 A CN2010101375497 A CN 2010101375497A CN 201010137549 A CN201010137549 A CN 201010137549A CN 101816936 B CN101816936 B CN 101816936B
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Abstract
The invention belongs to the technical field of a chemical catalyst, and in particular provides a method for preparing a Cu-Al-containing catalyst. The method comprising the following steps of: dissolving precursor compounds of components used for preparing the catalyst, an organic template agent and an acid in an alcohol solvent; and drying, calcining and activating the mixture to prepare the catalyst. When the catalyst is used for hydrogenation of glycerol for preparing 1,2-propylene glycol, the catalyst has the advantages of high activity and selectivity and mild reaction condition; and the catalyst preparation process is easy and feasible, is easy to repeat, and is applicable to large-scale industrial production.
Description
Technical field
The invention belongs to the chemical catalyst technical field, be specifically related to a kind of Cu-Al of containing Preparation of catalysts method and this catalyst in glycerine hydrogenation preparation 1, the application in 2-propane diols (PG) reaction.
Background technology
PG is a kind of important chemical material; Main as the intermediate of producing unsaturated polyester resin, epoxy resin, polyurethane resin etc.; In food, medicine, cosmetics and other hygienic articles, be widely used as hygroscopic agent, lubricant and solvent etc.; Also can be used as antifreezing agent, and be the food additives of U.S. FDA approval.
At present, along with some traditional energy rise in price such as oil, enjoy favor as the biodiesel of the alternative energy.Countries in the world are numerous and confused works out and pressure use biodiesel incentive policy; Make yield of biodiesel increase rapidly; But the outlet of its accessory substance crude glycerine has become the key factor that hinders the biodiesel development, because 10 tons of biodiesel of every production just produce 1 ton of glycerine.Along with the biodiesel industry heats up gradually, supply takes place and continues excess phenomenon in the glycerine market conditions, thereby the new way of seeking the glycerine utilization caused people's common concern, and the new way of seeking the glycerine utilization has become an at present international research and development focus.
Glycerine system PG reaction by biodiesel byproduct has received extensive concern at present, also for the development of PG a good opportunity to develop is provided.In order to obtain higher PG yield, research institution has carried out many explorations to hydrogenation catalyst and preparation method thereof both at home and abroad.
Reported among patent CN101428222, CN101353291, CN101362676, the CN101568510 that employing still reaction at intermittence carries out the method that glycerine hydrogenation prepares PG.Wherein, patent CN101428222 adopts the improved Cu-Zn catalyst of CNT, at 160～240 ℃; 1.0 under～4.0MPa the condition, glycerol conversion yield was near 100% o'clock, the PG selectivity is merely 75%～82%; Reaction effect is relatively poor, and this method is only applicable to the glycerine of low concentration; Though patent CN101353291 is raw material with the biodiesel base crude glycerine, the catalyst activity component is noble metal Ru or Pd, and load capacity is higher; The catalyst price is too expensive; And reaction effect is also unsatisfactory, and glycerol conversion yield is up to 92%, and the PG yield is lower than 87%; Though also be raw material among the CN101362676, and be the catalyst activity component that glycerol conversion yield is the highest to be merely 91.3% with the relatively low honest and clean metal Cu of price with the biodiesel base crude glycerine, PG yield also only 85%, reaction effect is still relatively poor; Be catalyst with Cu-Mn-Zn among the patent CN101568510, though reaction effect is better, the reaction pair glycerol concentration is had relatively high expectations, and glycerol concentration must be greater than 95%, even requires glycerol concentration greater than 99%.Above method also is not suitable for large-scale industrial production.
Missouri, USA university discloses in patent CN101410361 and has a kind ofly prepared the method for PG by glycerine through two-step reaction, earlier dehydrating glycerin is obtained hydroxypropanone-, and further hydrogenation obtains PG under the Cu-Cr catalyst action afterwards; This method process route is longer; And reaction is gas-solid phase reaction, and glycerine gasification that need boiling point is higher has increased energy consumption on the one hand; Glycerine also is easy to coking in gasification on the other hand, has reduced the yield of target product; In addition, its hydrogenation catalyst is the Cu series catalysts that contains toxic metals Cr, and environmental pollution is bigger.BASF AG describes the detailed process that is prepared PG by the glycerine hydrogenation of biodiesel byproduct in detail in patent CN101395113; Wherein to adopt the metal alloy contain Cu be catalyst to hydrogenation reaction; Catalyst is the catalyst with skeleton Raney structure of alkali extraction process preparation, also can be for adopting the pellet type catalyst of the conventional infusion process or precipitation method preparation; But hydrogenation reaction need be to carry out under 20～25MPa condition at pressure, and equipment investment is big, and the glycerine air speed is merely 0.4h
-1About, production efficiency is lower, can't be used for commercial production.Davy company adopts the Cu series catalysts of conventional method preparation to carry out glycerine hydrogenation system PG in patent WO2007010299; Though can reaction pressure be reduced to 1～3MPa; But before reaction, need glycerine be gasified in advance equally; And, adopt big excessive hydrogen to react H for obtaining desirable reaction result
2With the mol ratio of glycerine be 400: 1～600: 1; Though hydrogen can separate recirculation from product, in hydrogen compression, heating and cooling procedure, consumed lot of energy, has increased production cost.In patent WO2008012244 Davy company further to adopt containing metal Cu, Ni or Co be the catalyst of active component, but relatively poor because of hydrogenation catalyst performance, must obtain the purpose product for efficient, hydrogenation process need be passed through multistep reaction, has increased equipment investment; And still need raw material glycerine be gasified in advance H
2The problem of large usage quantity does not still obtain fine solution yet, and reaction velocity is also lower, is merely 0.1～0.5h
-1Reported among the patent CN101012149 that adopting the Cu-Zn-Mn-Al of precipitation method preparation is the method that catalyst carries out glycerine hydrogenation system PG, under 200～250 ℃, 2.5～5MPa, reacted, needed hydrogen usage very big, H
2Just can obtain reaction effect preferably with the glycerine volume ratio up to 1200, work as H
2Reduced to 800 o'clock with the glycerine volume ratio, conversion ratio is merely 83%, and energy consumption is very big.For further improving catalyst performance; All adopt the Cu system that contains rare earth element of precipitation method preparation to be catalyst among patent CN101456791 and the CN101214440; Ree content is all bigger; Be generally about 8% like CeO content among the patent CN101456791; And some expensive rare earth oxide rubidium oxides, praseodymium oxide, europium oxide, gadolinium oxide, dysprosia, yittrium oxide content even account for 3% of catalyst weight among the patent CN101214440, this makes the Catalyst Production cost increase greatly, does not have industrial application value; And reaction effect is also unsatisfactory.Patent CN101371986 has improved method for preparing catalyst; With adding a kind of material with carbon element in the catalyst precursor saline solution, make the Cu-Cr catalyst of high-specific surface area, but this catalyst is used for glycerine hydrogenation system PG reaction; Do not obtain desirable reaction effect; Though the PG selectivity can reach 100%, glycerol conversion yield only 30% still can not be used for commercial production.
In the above-mentioned patent; Catalyst adopts infusion process, the precipitation method, alkali extraction process respectively, mix novel method preparation such as material with carbon element; The catalyst reaction poor-performing; Even each research institution has carried out multiple improvement from catalytic component, reaction process etc., catalyst reaction performance or production cost all can't satisfy industrial requirements.
To the problem that exists in the above patent; The present invention adopts a kind of novel method for preparing catalyst, through in catalyst preparation process, adding a kind of organic masterplate agent, afterwards through aging, roasting, activation; Make the catalyst activity height, selectivity is good; Can make glycerine hydrogenation prepare PG and be reflected under the temperate condition and carry out, and the preparation process is simple and easy to do, is applicable to large-scale industrial production.
Summary of the invention
The object of the present invention is to provide a kind of active high, selectivity is good, the preparation process simple, be convenient to suitability for industrialized production contain Cu-Al Preparation of catalysts method, and when the catalyst that this preparation method makes is used for glycerine hydrogenation and prepares the PG reaction.
The present invention provides a kind of Cu-Al of containing Preparation of catalysts method, and this catalyst is used for glycerine hydrogenation and prepares the PG reaction.Catalyst is formed general formula: Cu-A-Al, and A is one or more among Ni, Zn, Sn, Co, Fe, Mn, Ti, the W in the formula, one or more among preferred Ni, Zn, Sn, Co, Fe, the Mn; The mass content of Cu is 5～70% in the catalyst, preferred 10～60%; The mass content of A is 0～20%, preferred 1～10%; The mass content of Al is 10～95%, preferred 20～90%.The precursor compound of Cu is a kind of in copper nitrate, copper chloride, Schweinfurt green, the copper sulphate; The precursor compound of component Al is a kind of in aluminium isopropoxide, isobutanol aluminum, aluminium secondary butylate, the aluminium ethylate, and the precursor compound of component A is a kind of in its nitrate, acetate, sulfate, chloride and the hydroxide.
The Preparation of catalysts method concrete steps that the present invention proposes are following:
(a) will prepare the precursor compound of the used component of catalyst, organic masterplate agent and a kind of acid and process mixed solution, solvent is an alcohols, stirs 0.5～15 hour down at 20～150 ℃, obtains mixed slurry;
(b) mixed slurry that under 30～120 ℃ of conditions, forms in the aging step (a) 10～144 hours obtains aging material;
(c) will wear out material in the diluent gas of the gas of molecule-containing keto or molecule-containing keto in 450～800 ℃ of following roastings 2～20 hours, remove organic masterplate agent, obtain catalyst precursor;
(d) catalyst precursor that obtains is shaped to particle, and under the atmosphere of hydrogen 100～350 ℃ the reduction 0.5～20 hour, obtain said catalyst.
Preferred manufacturing procedure is: in the step (a), whipping temp is 40～120 ℃, and mixing time is 1～10 hour; In the step (b), aging temperature is 50～90 ℃, and ageing time is 24～64 hours; In the step (c), sintering temperature is 550～700 ℃, and roasting time is 4～10 hours; In the step (d), reduction temperature is 150～250 ℃, and the recovery time is 2～10 hours.
Wherein, in preparation method's step (a), precursor compound, organic masterplate agent, a kind of acid of the used component of preparation catalyst are processed the process of mixed solution; Concrete operations can be in the following several method any one: method one: the masterplate agent is dissolved in the alcohols solvent, is designated as solution A, precursor compound and a kind of acid of component Cu, A, Al is dissolved in the alcohols solvent; Be designated as solution B; Under stirring, solution B added in the solution A mix, obtain mixed slurry; Method two: the masterplate agent is dissolved in the alcohols solvent, is designated as solution A, precursor compound and a kind of acid of component Cu, A, Al is dissolved in the alcohols solvent, be designated as solution B, under stirring, solution A added in the solution B mix, obtain mixed slurry; Method three: precursor compound and a kind of acid of masterplate agent, component Cu, A, Al are dissolved in the alcohols solvent simultaneously, under stirring, mix, obtain mixed slurry.
Used masterplate agent is softex kw (CTAB), lauryl sodium sulfate (SDS), dodecyl sodium sulfate (SDBS), gathers oxireme ether-gather propylene oxide ether-gather oxireme ether-F127, gathers oxireme ether-gather in oxireme ether-P123, TPAOH, Macrogol 600 (PEG-600), the PEG400 (PEG-400) one or more of propylene oxide ether-gather in preparation method's step (a), preferred softex kw (CTAB), lauryl sodium sulfate (SDS), Chinese (F127), gathers in the oxireme ether (P123) one or more of oxireme ether-gather propylene oxide ether-gather; The mol ratio of metal ion is 0.005: 1～1.5: 1 in masterplate agent and the catalyst, preferred 0.01: 1～1: 1.Acid is a kind of in hydrochloric acid, nitric acid, acetic acid, sulfuric acid, the carbonic acid, a kind of in preferred hydrochloric acid, nitric acid, the acetic acid; Solvent alcohol is a kind of in methyl alcohol, ethanol, isopropyl alcohol, isobutanol, the tert-butyl alcohol, n-butanol, the normal propyl alcohol, a kind of in particular methanol, ethanol, isopropyl alcohol, isobutanol, the normal propyl alcohol.
At method for preparing catalyst step (c), also promptly remove the masterplate agent, obtain in the catalyst precursor step, roasting is in the diluent gas of the gas of molecule-containing keto or molecule-containing keto, to carry out, and molecular oxygen comes from pure oxygen, oxygen enrichment or air, and diluent gas is N
2, H
2A kind of among O, He or the Ar, or several kinds of mixtures of pressing arbitrary proportion wherein.The volume space velocity of the relative catalyst of roasting gas is 50～1000h
-1
At method for preparing catalyst step (d), also be the reducing catalyst presoma, obtain the step of catalyst, the atmosphere of hydrogen is pure hydrogen, hydrogen and N
2, a kind of in the mixture that is made into by arbitrary proportion of Ar or He.
When the catalyst through method for preparing was used for glycerine hydrogenation and prepares PG, raw material glycerine and hydrogen fed in the fixed bed reactors that catalyst is housed and carry out hydrogenation reaction after mixing preheating; The condition of hydrogenation reaction is: 170～220 ℃ of temperature, pressure 2～5MPa, glycerite air speed 1～3h
-1, glycerol concentration 5%～100%, H
2With the mol ratio of glycerine 3: 1～10: 1.
Optionally computing formula is following for raw material glycerol conversion yield and PG in the course of reaction:
The specific embodiment
Through specific embodiment the present invention is further described below, but protection domain does not receive the restriction of embodiment.
Embodiment 1～5
10gP123 is dissolved in the 20ml ethanol, is designated as solution A; The presoma and the 2ml hydrochloric acid of an amount of copper nitrate, aluminium isopropoxide, other components are dissolved in the 300ml ethanol, are designated as solution B.Solution A is under agitation added in the solution B, and continue down to stir 4 hours at 80 ℃; Afterwards with above-mentioned slurry be transferred in the baking oven 60 ℃ aging 36 hours, obtain aging material; Take out aging material and also place air atmosphere, 550 ℃ of roastings 6 hours obtain catalyst precursor; Further catalyst precursor is shaped to 20～40 order particles, and at 5%H
2In/Ar the gaseous mixture, 180 ℃ were reduced 4 hours, and obtained catalyst.Masterplate agent and metal ion mol ratio, catalyst composition and component A presoma are seen table 1 among the embodiment 1～5.
Table 1 embodiment 1～5 catalyst composition, presoma and masterplate agent consumption
Get catalyst 10 grams after the roasting and pack in the fixed-bed tube reactor, in above-mentioned reactor, feed raw material glycerine and hydrogen after the preheating, glycerol concentration 95%, glycerite air speed 1.5h
-1, the result that other reaction conditions and reaction were carried out after 100 hours lists in the table 2.
Table 2 embodiment 1～5 reaction condition and reaction result
Embodiment 6～11
A certain amount of organic masterplate agent is dissolved in the methyl alcohol, is designated as solution A; The nitric acid of 50g aluminium isopropoxide, 3.7g copper chloride, 0.92g zinc chloride and 5ml60% is dissolved in the 250ml methyl alcohol, is designated as solution B.Solution B is under agitation added in the solution A, and continue down to stir 5 hours at 70 ℃; Afterwards with above-mentioned slurry be transferred in the baking oven 60 ℃ aging 48 hours, obtain aging material; Take out aging material and place the air atmosphere roasting, obtain catalyst precursor; Further catalyst precursor is shaped to 20～40 order particles, and in pure hydrogen atmosphere, 150 ℃ of reduction 3h obtain catalyst 20%Cu-5%Zn-75%Al.
Used organic masterplate agent and consumption thereof, concrete roasting condition are seen table 3 among the embodiment 6～11.
Organic masterplate agent consumption and roasting condition among table 3 embodiment 6～11
Getting catalyst 5 grams after the roasting packs in the fixed-bed tube reactor; Raw material glycerine and hydrogen in above-mentioned reactor after the feeding preheating; Glycerol concentration 90%, hydrogen and glycerine mol ratio are 6: 1, the result that other reaction conditions and reaction were carried out after 100 hours lists in the table 2.
Table 4 embodiment 1～5 reaction condition and reaction result
The comparative example 1
Catalyst is formed, each component presoma is identical with embodiment 5, and just method for preparing catalyst adopts the conventional precipitation method, and promptly the precursor solution with sodium carbonate liquor and each component of catalyst reacts; Obtain sediment; Washing is to neutral, and drying, roasting, reduction obtain catalyst afterwards; Also with embodiment 5, reaction result is seen table 5 to the catalyst performance evaluation condition.
The comparative example 2
Catalyst is formed, each component presoma is identical with embodiment 6, and just method for preparing catalyst adopts conventional infusion process, promptly with Al
2O
3Be carrier, with Al
2O
3Carrier immerses in copper chloride and the liquor zinci chloridi, and drying, roasting, reduction obtain catalyst afterwards; Also with embodiment 6, reaction result is seen table 5 to the catalyst performance evaluation condition.
The comparative example 3
Catalyst composition, preparation method are identical with embodiment 1, just do not add organic masterplate agent in the catalyst preparation process, and the catalyst performance evaluation condition is also identical with embodiment 1, and reaction result is seen table 5.
The comparative example 4
Method for preparing catalyst is identical with embodiment 3 respectively, just changes organic formwork agent P123 addition in the catalyst preparation process, and the mol ratio of P123 and metal ion is 2: 1, and catalyst performance evaluation is identical with embodiment 3, and reaction result is seen table 5.
Table 5 comparative example 1～4 reaction result
Claims (8)
1. one kind is used for glycerine hydrogenation preparation 1, the 2-propane diols contain Cu-Al Preparation of catalysts method, it is characterized in that concrete steps are following:
Mixed solution is processed in precursor compound, organic formwork agent and a kind of acid that (a) will prepare the used component of catalyst, and solvent is an alcohols, stirs 0.5～15 hour down at 20～150 ℃, obtains mixed slurry;
(b) mixed slurry that under 30～120 ℃ of conditions, forms in the aging step (a) 10～144 hours obtains aging material;
(c) will wear out material in the diluent gas of the gas of molecule-containing keto or molecule-containing keto in 450～800 ℃ of following roastings 2～20 hours, remove organic formwork agent, obtain catalyst precursor;
(d) catalyst precursor that obtains is shaped to particle, and under the atmosphere of hydrogen 100～350 ℃ the reduction 0.5～20 hour, obtain said catalyst;
Said catalyst is formed general formula: Cu-A-Al; A is one or more among Ni, Zn, Sn, Co, Fe, Mn, Ti, the W in the formula; The mass content of component Cu is 5～70% in the catalyst, and the mass content of component A is 0～20%, and the mass content of component Al is 10～95%; The precursor compound of component Cu is a kind of in copper nitrate, copper chloride, Schweinfurt green, the copper sulphate; The precursor compound of component Al is a kind of in aluminium isopropoxide, isobutanol aluminum, aluminium secondary butylate, the aluminium ethylate, and the presoma of component A is a kind of in its nitrate, acetate, sulfate, chloride and the hydroxide.
2. preparation method according to claim 1; It is characterized in that described organic formwork agent is softex kw, lauryl sodium sulfate, dodecyl sodium sulfate, gathers oxireme ether-gather propylene oxide ether-gather oxireme ether-P123, gathers oxireme ether-gather in oxireme ether-F127, TPAOH, Macrogol 600 (PEG-600), the PEG400 (PEG-400) one or more of propylene oxide ether-gather that the mol ratio of metal ion is 0.005: 1～1.5: 1 in template and the catalyst.
3. preparation method according to claim 1 is characterized in that described acid is a kind of in hydrochloric acid, nitric acid, acetic acid, sulfuric acid, the carbonic acid; Solvent alcohol is a kind of in methyl alcohol, ethanol, isopropyl alcohol, isobutanol, the tert-butyl alcohol, n-butanol, the normal propyl alcohol.
4. preparation method according to claim 1 is characterized in that: in the step (a), whipping temp is 40～120 ℃, and mixing time is 1～10 hour; In the step (b), aging temperature is 50～90 ℃, and ageing time is 24～64 hours; In the step (c), sintering temperature is 550～700 ℃, and roasting time is 4～10 hours; In the step (d), reduction temperature is 150～250 ℃, and the recovery time is 2～10 hours.
5. preparation method according to claim 1; It is characterized in that organic formwork agent is softex kw, lauryl sodium sulfate, gathers oxireme ether-gather propylene oxide ether-gather oxireme ether-F127, gathers oxireme ether-gather among oxireme ether-P123 one or more of propylene oxide ether-gather that the mol ratio of metal ion is 0.01: 1～1: 1 in template and the catalyst; Acid is a kind of in hydrochloric acid, nitric acid, the acetic acid; Solvent alcohol is a kind of in methyl alcohol, ethanol, isopropyl alcohol, isobutanol, the normal propyl alcohol.
6. preparation method according to claim 1 is characterized in that molecular oxygen comes from pure oxygen, oxygen enrichment or air, and diluent gas is N
2, H
2A kind of among O, He or the Ar or its are pressed the mixture of arbitrary proportion.
7. preparation method according to claim 1, the atmosphere that it is characterized in that hydrogen is pure hydrogen, hydrogen and N
2, a kind of in the mixture that is made into by arbitrary proportion of Ar or He.
8. the Application of Catalyst of preparation method's preparation according to claim 1; It is characterized in that catalyst is used for glycerine hydrogenation preparation 1; The process of 2-propane diols is: raw material glycerine and hydrogen feed in the fixed bed reactors that catalyst is housed and carry out hydrogenation reaction after mixing preheating; The condition of hydrogenation reaction is: 170～220 ℃ of temperature, pressure 2～5MPa, glycerite air speed 1～3h
-1, glycerite concentration 5%～100%, H
2With the mol ratio of glycerine 3: 1～10: 1.
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| CN103657730B (en) * | 2012-09-20 | 2016-03-02 | 中国石油化工股份有限公司 | The Catalysts and its preparation method of preparing 1,2-dihydroxypropane by glycerine hydrogenation |
| CN104549347B (en) * | 2013-10-15 | 2017-11-28 | 中国石油化工股份有限公司 | Glycerine hydrogenation prepares catalyst of 1,2 propane diols and its preparation method and application |
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| CA2642592A1 (en) * | 2006-03-03 | 2007-09-07 | Basf Se | Process for the preparation of 1,2-propanediol |
| CN100432034C (en) * | 2007-02-07 | 2008-11-12 | 南京工业大学 | Method for continuously preparing 1, 2-propylene glycol by catalytic hydrogenation of glycerol |
| CN101371986A (en) * | 2008-05-15 | 2009-02-25 | 大连理工大学 | Method for preparing Cu-Cr metallic oxide with high specific surface area and application |
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