CN101695657B - Method for producing lactic acid by using glycerin and special catalyst for production of lactic acid by using glycerin - Google Patents
Method for producing lactic acid by using glycerin and special catalyst for production of lactic acid by using glycerin Download PDFInfo
- Publication number
- CN101695657B CN101695657B CN200910236676A CN200910236676A CN101695657B CN 101695657 B CN101695657 B CN 101695657B CN 200910236676 A CN200910236676 A CN 200910236676A CN 200910236676 A CN200910236676 A CN 200910236676A CN 101695657 B CN101695657 B CN 101695657B
- Authority
- CN
- China
- Prior art keywords
- solution
- percentage composition
- quality percentage
- water
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a method for producing lactic acid by using glycerin and a special catalyst for the production of the lactic acid by using the glycerin. The catalyst provided by the invention is obtained by loading 0.1 to 30 mass parts of an active ingredient onto 100 mass part of carrier, wherein active ingredient is (1) Pt or (2) a composite of Pt and other noble metals. The catalyst can be used in the production of the lactic acid by using the glycerin. In the presence of the catalyst of the invention, the glycerin can be converted into the lactic acid effectively under a mild reaction condition. The catalyst of the invention has the advantages of high activity and selectively, easy preparation, low price, easy industrialization, long service life, loss prevention and good application prospective.
Description
Technical field
The present invention relates to a kind of method and special-purpose catalyst thereof that utilizes glycerine to produce lactic acid.
Background technology
Lactic acid is except being used for the production of spices and essence, in many industries such as wine brewing, food, pharmacy, daily use chemicals, aquaculture, and all is widely used in the every profession and trade such as process hides, cigarette, wool spinning.It should be noted that; Be that the PLA that obtains of polymerizable raw material is nontoxic with lactic acid; Nonirritant is a kind ofly to have good biological degradability and biocompatibility, and the macromolecular material of excellent mechanical performances and physical property; Be called as " green plastic "; Be the novel ecological green material that is expected to replace materials such as present polyvinyl chloride based on fossil resource, polypropylene, polystyrene, polyester, because its good biodegradability and biocompatibility, it has caused concern widely at biomedical sector at present.The method of commercial production lactic acid mainly is fermentation method and chemical synthesis at present.Chemical synthesis process prepares lactic acid has lactonitrile method, third rare nitrile method, propionic acid method, third rare method etc., is used for industrial only lactonitrile method (also being acetaldehyde hydrogen cyanide method) and third rare nitrile method.The main path of fermentation method is a starch in the lactic acid bacteria effect down, regulate certain pH value through ferment lactic acid, fermentation main branch homofermentation and heterofermentation.Fermentation method is simple because of its technology, and raw material is sufficient, and development early becomes the production method of lectic acid of comparative maturity, account for more than 70% of production of lactic acid, but the cycle is long, can only intermittence or semi-continuous production.Chemical synthesis can realize the large-scale continuous production of lactic acid, and synthesizing lactic acid also obtained the approval of U.S. food and drug administration (FDA), but raw material generally has toxicity, does not meet the sustainable development requirement., significant with living beings through the synthetic research that obtains lactic acid of heterogeneous catalysis approach as raw material.
Rearrangement reaction can take place by glyceraldehyde and obtain in known lactic acid under alkali condition, and glyceraldehyde is one of important products of glycerine oxidation.Glycerine is the accessory substance of inevitable association in the production of biodiesel process, and along with improving constantly of yield of biodiesel, the output of glycerine is considerable.Utilize transformation of glycerol to produce article in the middle of a series of chemicals and the chemistry, with present be that the technology of raw material is compared with ethene, benzene or other petroleum hydrocarbon, except renewable and CO
2Outside the zero-emission characteristics such as (photosynthetic results), be rich in active hydroxyl in the glycerine, be easy to replaced and synthetic many special chemical articles that in the past will just can obtain, thereby demonstrate huge advantage through very complicated hydrocarbon reaction by functional group.Therefore be raw material with glycerine, be converted into glyceraldehyde through oxidative pathway, " one kettle way (one the pot) " reaction that further obtains lactic acid is the fine biomass resource that utilizes---the important form of glycerine.This method has not only been developed the new purposes that glycerine utilizes, and also for lactic acid continuable raw material sources is provided.
Mainly contain three kinds of methods with glycerine for the raw material synthesizing lactic acid at present:
1, directly under the high temperature strong alkaline condition, transforms and obtain lactic acid
This method, under the hydrothermal condition of 1.25mol/L (mol ratio of alkali and substrate is 4: 1) NaOH, was reacted 90 minutes in 300 ℃ near-critical water not by any catalyst, and the productive rate of the lactic acid that obtains reaches 90%.The problem that this method exists is: course of reaction is temperature required higher, needs the higher hydro-thermal pressure of tolerance, and production equipment has been proposed harsh requirement.
2, the reaction of the glycerol dehydrogenase under the alkali condition obtains lactic acid
This reaction is medium with water, and the inorganic base of adding is NaOH or CaO, chooses H
2Pressure is 40bar, and reaction temperature is 200 ℃, is catalyst with Ru/C, and the reaction time is 5 hours, and can obtain glycerol conversion yield is 25-100%, and the lactic acid selectivity is 19-58%.The problem that this method exists is: need use a large amount of H in (1) reaction
2As reaction raw materials, and H
2Itself be a kind of very important energy material, its source is limited, cost is higher, and is difficult for storing and transportation; (2) higher Hydrogen Vapor Pressure, the alkaline environment under the hot conditions is higher for equipment requirements in the course of reaction, causes equipment corrosion inevitably, and increase equipment drops into expense, and operating process is dangerous.
3, glycerine oxidation rearrangement reaction obtains lactic acid under the oxidizing condition
Finding in inventor's previous work, is medium with water, and adding NaOH provides alkaline environment, chooses O
2Pressure is 15atm, and reaction temperature is 20 ℃, and under the effect of support type Au catalyst, in 2 hours reaction time, the conversion ratio that can obtain glycerine is 70%, and the selectivity of lactic acid is 46%, and obtaining the highest lactic acid yield is 32%.But the lactic acid selectivity that this method obtains is still lower, and is not high for the abundant conversion and the utilization ratio of glycerine, and the required cost of separated product is also higher.
Summary of the invention
The purpose of this invention is to provide a kind of method and special-purpose catalyst thereof that utilizes glycerine to produce lactic acid.
The catalyst that is used to utilize glycerine production lactic acid provided by the invention is carried on 100 mass parts carriers with 0.1-30 mass parts active component and obtains; Said active component is (1) or (2) as follows: (1) Pt; (2) composition of forming by other noble metal beyond Pt and the Pt.
Said other noble metal can be at least a among Pd, Rh, Ru, Au and the Ag etc.
Said active component can be the monobasic metal component that Pt constitutes; Also can be Pt with respectively with components such as Pd, Rh, Ru, Au or Ag in a kind of binary metal component of formation; Also can be Pt with respectively with components such as Pd, Rh, Ru, Au or Ag in the ternary metal component of two kinds of formations, also can be Pt with respectively with components such as Pd, Rh, Ru, Au or Ag in the multi-element metal component that constitutes more than three kinds.
Said catalyst specifically, can be carried on 100 mass parts carriers with 1-10 mass parts active component and obtain.
Said carrier can be metal oxide or activated carbon.Said metal oxide specifically can be Al
2O
3, ZrO
2, TiO
2, Fe
2O
3, CeO
2Or MgO etc.
In the said active component, the shared quality percentage composition of Pt can be 0.5%-100%, specifically can be 20%-100%.
Said catalyst can adopt following arbitrary said method to prepare: infusion process, coprecipitation, deposition-precipitation method (DP method), formaldehyde reducing process and NaBH
4One stage reduction method.
Said infusion process can comprise the steps: the aqueous solution of the precursor of active component and carrier mixed, and 20-100 ℃ is stirred down, after the drying, and 150-500 ℃ of reduction 1-8h under hydrogen atmosphere.Said infusion process specifically can comprise the steps: 5-50mL solution A and 5-50mL solution B mixed, to wherein adding the 1-30g carrier; 20-100 ℃ is stirred 1-10h, and dry back is 150-500 ℃ of reduction 1-8h under hydrogen atmosphere, obtains catalyst; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.1-10% in the solution A; Said solution B, solute are one or more the compound that contains other precious metal ion beyond the Pt, and the quality percentage composition of solute is respectively 0.1-10% in the solution B;
Said coprecipitation can comprise the steps: the aqueous solution of the aqueous solution of active component precursor and ferric nitrate mixed, takes and the drip add mode with the NaOH aqueous solution, and pH value 7-11,20-90 ℃ is stirred 1-10h down, and suction filtration also washs and (to solution, do not have Cl
-Detect), after the drying, 150-500 ℃ of reduction 1-10h under hydrogen atmosphere.Said coprecipitation specifically can comprise the steps: solution A and solution B are adopted and the drip add mode, dropwise adds in the 10-400mL water, and control pH value is 7-11 in the dropping process, and 20-90 ℃ is stirred 1-10h then, and suction filtration and washing (do not have Cl to filtrating
-Detect), dry back is 150-500 ℃ of reduction 1-10h under hydrogen atmosphere, obtains catalyst; The preparation method of said solution A is following: with 5-50g Fe (NO
3)
39H
2O is dissolved in the 50-250mL water, with the quality percentage composition of 2-50mL Pt be the H of 0.1-10%
2PtCl
66H
2The quality percentage composition of the O aqueous solution and solute is that one or more compound water solutions that contain other precious metal ion beyond the Pt of 0.1-10% mix, and obtains solution A; The preparation method of said solution B is following: 5-80g NaOH is dissolved in the 50-250mL water, obtains solution B.
Said deposition-precipitation method (DP method) can comprise the steps: the aqueous solution of active component precursor and carrier mixed, slowly drip NaOH and regulate the pH value to 7-11, and suction filtration and washing (do not have Cl to solution
-Detect), after the drying, 150-500 ℃ of reductase 12-15h under hydrogen atmosphere.Said deposition-precipitation method specifically can comprise the steps: 5-50mL solution A, 5-50mL solution B and 1-30g carrier are mixed and stirring; The NaOH aqueous solution that dropwise adds 0.01-1M; Regulating the pH value is 7-11, continues to stir 2-48h, and suction filtration and washing (do not have Cl to filtrating
-Detect), dry back 150-500 ℃ of reductase 12-15h under hydrogen atmosphere obtains catalyst; Said solution A, solute are H
2PtCl
66H
20, solvent is a water, and the quality percentage composition of Pt is 0.1-10% in the solution A; Said solution B, solute are one or more the compound that contains other precious metal ion beyond the Pt, and solvent is a water, and the quality percentage composition of solute is respectively 0.1-10% in the solution B;
Said formaldehyde reducing process can comprise the steps: the aqueous solution of active component precursor and carrier mixed, adds the formalin doubly with respect to the excessive 2-50 of active component amount of substance behind the backflow 1-5h, continues backflow 1-5h, and suction filtration is also dry.Said formaldehyde reducing process specifically can comprise the steps: the 1-30g carrier is added in the 50-250mL water; Stir 10-300min; Add 5-50mL solution A and 5-50mL solution B, backflow 1-5h adds 2-100mL10-39% (quality percentage composition) formalin then; Continue backflow 1-5h, suction filtration and washing (do not have Cl to filtrating
-Detect), 90-150 ℃ of dry 2-24h obtains catalyst; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.1-10% in the solution A; Said solution B, solute are one or more the compound that contains other precious metal ion beyond the Pt, and solvent is a water, and the quality percentage composition of solute is respectively 0.1-10% in the solution B;
Said NaBH
4One stage reduction method can comprise the steps: the aqueous solution of active component precursor and carrier mixed, adds the NaBH doubly with respect to the excessive 2-50 of active component amount of substance
4The aqueous solution continues to stir 2-24h at 20-100 ℃, and suction filtration is also dry.Said NaBH
4One stage reduction method specifically can comprise the steps: the 1-30g carrier is added in the 50-500mL water, mixes with 5-50mL solution A and 5-50mL solution B, adds 2-100mL0.5-25% (quality percentage composition) NaBH
4The aqueous solution continues to stir 2-24h, and suction filtration and washing (do not have Cl to filtrating
-Detect), 90-150 ℃ of dry 2-24h obtains catalyst; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.1-10% in the solution A; Said solution B, solute are one or more the compound that contains other precious metal ion beyond the Pt, and solvent is a water, and the quality percentage composition of solute is respectively 0.1-10% in the solution B.
Said catalyst specifically can be as follows (a) or (b) or (c) or (d) or (e) or (f):
(a) Pt and Pd are carried on ZrO
2The catalyst that obtains;
(b) Pt and Pd are carried on the catalyst that activated carbon obtains;
(c) Pt and Rh are carried on Fe
2O
3The catalyst that obtains;
(d) Pt and Au are carried on CeO
2The catalyst that obtains;
(e) Pt is carried on TiO
2The catalyst that obtains;
(f) Pt, Ru and Rh are carried on Al
2O
3The catalyst that obtains.
(a) said catalyst can adopt following method to prepare: 15mL solution A and 15mL solution B is mixed, and to wherein adding 4-6g ZrO
2Carrier; 20-40 ℃ is stirred 1-3h down, and dry back 150-250 ℃ of reductase 12-4h under hydrogen atmosphere obtains Pt-Pd is carried on ZrO
2On catalyst; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.25%-0.75% in the solution A; Said solution B, solute are PdCl
2, solvent is 7.5%-12.5% (quality percentage composition) the HCl aqueous solution, the quality percentage composition of Pd is 0.5%-1% in the solution B.(a) said catalyst specifically can adopt following method to prepare: 15mL solution A and 15mL solution B is mixed, and to wherein adding 5g ZrO
2Carrier; 30 ℃ are stirred 2h down, and dry back is 200 ℃ of reduction 3h under hydrogen atmosphere, obtain Pt-Pd is carried on ZrO
2On catalyst; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.5% in the solution A; Said solution B, solute are PdCl
2, solvent is 10% (quality percentage composition) HCl aqueous solution, the quality percentage composition of Pd is 0.75% in the solution B.
(b) said catalyst can adopt following method to prepare: 20mL solution A and 20mL solution B is mixed, add the 2-4g absorbent charcoal carrier to it; 20-40 ℃ is stirred 1-3h, and dry back 150-250 ℃ of reductase 12-4h under hydrogen atmosphere obtains Pt-Pd is carried on the catalyst on the active carbon; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.25%-0.75% in the solution A; Said solution B, solute are PdCl
2, solvent is 7.5%-12.5% (quality percentage composition) the HCl aqueous solution, the quality percentage composition of Pd is 0.5%-1% in the solution B.(b) said catalyst specifically can adopt following method to prepare: 20mL solution A and 20mL solution B is mixed, add the 3g absorbent charcoal carrier to it; 30 ℃ are stirred 2h, and dry back is 200 ℃ of reduction 3h under hydrogen atmosphere, obtain Pt-Pd is carried on the catalyst on the active carbon; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.5% in the solution A; Said solution B, solute are PdCl
2, solvent is 10% (quality percentage composition) HCl aqueous solution, the quality percentage composition of Pd is 0.75% in the solution B.
(c) said catalyst can adopt following method to prepare: solution A and solution B are adopted and the drip add mode, dropwise add in the 150-250mL water, control pH value is 8-10 in the dropping process, and 40-60 ℃ is stirred 3-5h then, and suction filtration and washing (do not have Cl to filtrating
-Detect), dry back is 300-400 ℃ of reduction 3-5h under hydrogen atmosphere, obtains Pt-Rh is carried on Fe
2O
3On catalyst; The preparation method of said solution A is following: with 15-25g Fe (NO
3)
39H
2O is dissolved in the 150mL water, with the quality percentage composition of 10mL Pt be the H of 0.25%-0.75%
2PtCl
66H
2The quality percentage composition of the O aqueous solution and 15mL Rh is the RhCl of 0.5%-1.5%
33H
2The O aqueous solution is mixed, obtains solution A; The preparation method of said solution B is following: 30-50g NaOH is dissolved in the 100mL water, obtains solution B.(c) said catalyst specifically can adopt following method to prepare: solution A and solution B are adopted and the drip add mode, dropwise add in the 200mL water, control pH value is 9 in the process of progressively increasing, and 50 ℃ are stirred 4h then, and suction filtration and washing (do not have Cl to filtrating
-Detect), dry back is 350 ℃ of reduction 4h under hydrogen atmosphere, obtain Pt-Rh is carried on Fe
2O
3On catalyst; The preparation method of said solution A is following: with 20gFe (NO
3)
39H
2O is dissolved in the 150mL water, with the quality percentage composition of 10mL Pt be 0.5% H
2PtCl
66H
2The quality percentage composition of the O aqueous solution and 15mL Rh is 1% RhCl
33H
2The O aqueous solution is mixed, obtains solution A; The preparation method of said solution B is following: 40g NaOH is dissolved in the 100mL water, obtains solution B.
(d) said catalyst can adopt following method to prepare: with 10mL solution A, 15mL solution B and 5-7gCeO
2Mixed, the NaOH aqueous solution of adding 0.075-0.125M, regulating the pH value is 8-9, continues to stir 10-15h, suction filtration also washs and (to filtrating, does not have Cl
-Detect), dry back is 270-290 ℃ of reduction 5-7h under hydrogen atmosphere, obtains Pt-Au is carried on CeO
2On catalyst; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.25%-0.75% in the solution A; Said solution B, solute are HAuCl
4, solvent is a water; The quality percentage composition of Au is 1.25%-1.75% in the solution B.(d) said catalyst specifically can adopt following method preparation: with 10mL solution A, 15mL solution B and 6g CeO
2Mixed, the NaOH aqueous solution of adding 0.1M, regulating the pH value is 8.5, continues to stir 12h, suction filtration also washs and (to filtrating, does not have Cl
-Detect), dry back is 280 ℃ of reduction 6h under hydrogen atmosphere, obtain Pt-Au is carried on CeO
2On catalyst; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.5% in the solution A; Said solution B, solute are HAuCl
4, solvent is a water; The quality percentage composition of Au is 1.5% in the solution B.
(e) said catalyst can adopt following method to prepare: with 8-12g TiO
2Add in the 100mL water, stir 30-50min, add the 25mL solution A, backflow 2-4h adds 2-5mL 35%-39% (quality percentage composition) formalin then, continues backflow 2-4h, and suction filtration and washing (do not have Cl to filtrating
-Detect), 100-120 ℃ of dry 15-17h obtains Pt is carried on TiO
2On catalyst; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.25%-0.75% in the solution A.(e) said catalyst specifically can adopt following method to prepare: with 10g TiO
2Add in the 100mL water, stir 40min, add the 25mL solution A, backflow 3h adds 3mL 38% (quality percentage composition) formalin then, continues backflow 3h, and suction filtration and washing (do not have Cl to filtrating
-Detect), 110 ℃ of dry 16h obtain Pt is carried on TiO
2On catalyst; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.5% in the solution A.
(f) said catalyst can adopt following method to prepare: with 5-7g Al
2O
3Add in the 500mL water, mixed with 15mL solution A, 5mL solution B and 15mL solution C, add 25mL 0.5-1.5% (quality percentage composition) NaBH
4The aqueous solution continues to stir 4-6h, and suction filtration and washing (do not have Cl to filtrating
-Detect), 100-120 ℃ of dry 15-17h obtains Pt-Ru-Rh is carried on Al
2O
3On catalyst; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.25%-0.75% in the solution A; Said solution B, solute are RuCl
3, solvent is a water, the quality percentage composition of Ru is 1.25%-1.75% in the solution B; Said solution C, solute are RhCl
33H
2O, solvent is a water, the quality percentage composition of Rh is 0.5-1.5% in the solution C.(f) said catalyst specifically can adopt following method to prepare: with 6g Al
2O
3Add in the 500mL water, mixed with 15mL solution A, 5mL solution B and 15mL solution C, add 25mL 1% (quality percentage composition) NaBH
4The aqueous solution continues to stir 5h, and suction filtration and washing (do not have Cl to filtrating
-Detect), 110 ℃ of dry 16h obtain Pt-Ru-Rh is carried on Al
2O
3On catalyst; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.5% in the solution A; Said solution B, solute are RuCl
3, solvent is a water, the quality percentage composition of Ru is 1.5% in the solution B; Said solution C, solute are RhCl
33H
2O, solvent is a water, the quality percentage composition of Rh is 1% in the solution C.
More than in arbitrary described catalyst, the precursor of said active component can be the precious metal salt of solubility or contains the acid of precious metal ion.
More than arbitrary said catalyst all can be applicable to utilize glycerine to produce lactic acid.
The present invention also protects a kind of method of utilizing glycerine to produce lactic acid, is the reacting gas 0-140 ℃ of reaction 0.5-48h that in reaction system, feeds 1-15atm (1atm=101.325kPa); Said reacting gas is the gaseous mixture of oxygen or oxygen and nitrogen; Said reaction system is made up of glycerine, alkali, catalyst and water; When initial, the quality percentage composition of glycerine described in the reaction system is 0.5-50%, and the ratio of the amount of substance of said alkali and said glycerine is (0.01-16): 1, and the mass ratio of said catalyst and said glycerine is 1: (20-500).
Said alkali can be inorganic base, like NaOH, potassium hydroxide, potash, sodium carbonate etc.
In the said reacting gas, O
2Volumn concentration can be 10-100%.
The present invention has following advantage:
1, catalyst performance is good.Composite catalyst involved in the present invention has good active and selectivity under relatively low reaction temperature.The composite catalyst that wherein relates to no matter be monobasic, binary, ternary or polynary catalyst at ambient temperature, even in gentle more reaction condition and shorter reaction time, can realize that catalyzing glycerol obtains the process of lactic acid.The maximum conversion rate of glycerine can reach 100%, the highest 95% the lactic acid selectivity that gets.This catalyst has improved the efficient of reaction, has practiced thrift a large amount of energy.
2, the long service life of catalyst.Composite catalyst of the present invention has very high stability under existing reaction condition, still can keep catalytic performance basically after circulating through ten times, and not have loss.
3, catalyst production cost is low.The building-up process of this catalyst is simple, can select common raw material at present for use, and is low for equipment requirements, applicable to present common commercial production condition, good application prospects arranged.
4, the present invention's noble metal component (like Pd, Ru, Rh, Au, Ag etc.) of in metal Pt, adding other helps to improve at low temperatures the catalytic activity and the selectivity of catalyst.
The invention provides a kind of method and special-purpose catalyst thereof that utilizes glycerine to produce lactic acid.Catalyst system of the present invention can be applied under the mild reaction conditions, and the glycerine high conversion obtains the process of lactic acid.Catalyst of the present invention has advantages of high activity and selectivity, is easy to preparation, and price is relatively low, is easy to industrialization, and catalyst life is long, does not have and runs off, and good application prospects is arranged.
Description of drawings
Fig. 1 is Pt-Au/CeO
2Catalyst activity is with the variation of reaction temperature; A is the conversion ratio of glycerine, and B is the selectivity of lactic acid.
Fig. 2 is Pt-Pd/ZrO
2Catalyst activity is with the variation of reaction pressure; A is the conversion ratio of glycerine, and B is the selectivity of lactic acid.
Fig. 3 is Pt/TiO
2Catalyst activity is with the variation of glycerol concentration; A is the conversion ratio of glycerine, and B is the selectivity of lactic acid.
Fig. 4 is Pt-Ru-Rh/Al
2O
3Catalyst activity is with the variation of glycerine and alkali use amount ratio; A is the conversion ratio of glycerine, and B is the selectivity of lactic acid.
Fig. 5 is Pt-Rh/Fe
2O
3Catalyst activity O
2The variation of dividing potential drop; A is the conversion ratio of glycerine, and B is the selectivity of lactic acid.
Fig. 6 is the variation of Pt-Pd/ activated-carbon catalyst activity through recycling for ten times; A is the conversion ratio of glycerine, and B is the selectivity of lactic acid.
The specific embodiment
Following embodiment is convenient to understand better the present invention, but does not limit the present invention.Experimental technique among the following embodiment like no specified otherwise, is conventional method.Used test material among the following embodiment like no specified otherwise, is to buy from routine biochemistry reagent shop and obtains.
Among the embodiment 7 to 12, reaction finishes the back according to following method, the amount of lactic acid in the assaying reaction liquid:
Adopt high performance liquid chromatography to product carry out qualitative and quantitative analysis (splitter is for Agilent 1100 Series HPLC, Beijing Agilent Co., Ltd: Alltech OA-1000 Organic Acids, with rare H
2SO
4The aqueous solution is flowing phase, flow 0.3ml/min, and UV-detector detects wavelength 195nm, 50 ℃ of operating temperatures.With lactic acid (Tianjin chemical reagent six subsidiary factories of factory, article No. is Q/12 HG 3-522-98) as standard items, the production standard curve.
Calculate glycerol conversion yield, lactic acid selectivity and lactic acid yield with method for normalizing according to the following equation.Wherein, lactic acid optionally is defined as: the growing amount of lactic acid accounts for the ratio with the generation total amount of the product of same unit representation.
In the above-mentioned formula, carbon number is meant contained carbon number in amount of substance * this material molecule.
Result in following examples is 10 mean values that repeat.
Embodiment 1, immersion process for preparing ZrO
2The Pt-Pd bimetallic catalyst of load
Solution A (15mL): solute is H
2PtCl
66H
2O, solvent are water; The quality percentage composition of Pt is 0.5% in the solution A; Contain 0.075g Pt in the solution A;
Solution B (15mL): solute is PdCl
2, solvent is the HCl aqueous solution (the quality percentage composition of HCl is 10%); The quality percentage composition of Pd is 0.75% in the solution B; Contain 0.1125g Pd in the solution B.
Solution A and solution B is mixed, to wherein adding 5g ZrO
2Carrier (Shantou Xilong Chemical Factory; Lot number 060414); Stir 2h down at 30 ℃, and dry, and 200 ℃ of reduction 3h under hydrogen atmosphere obtain being carried on ZrO again
2On Pt-Pd bimetallic loaded catalyst (Pt-Pd/ZrO
2).
Characterize through plasma emission spectrum (ICP), analyze to such an extent that the quality percentage composition of area load Pt is 1.485%, the quality percentage composition of area load Pd is 2.246%, conforms to the theoretical negative carrying capacity.
Solution A (20mL): solute is H
2PtCl
66H
2O, solvent are water; The quality percentage composition of Pt is 0.5% in the solution A; Contain 0.1g Pt in the solution A;
Solution B (20mL): solute is PdCl
2, solvent is the HCl aqueous solution (the quality percentage composition of HCl is 10%); The quality percentage composition of Pd is 0.75% in the solution B; Contain 0.15g Pd in the solution B.
Solution A and solution B is mixed, add 3g absorbent charcoal carrier (Shanghai active carbon Co., Ltd., Factory to it; Lot number 0255436); Stir 2h down at 30 ℃, and drying, 200 ℃ of reduction 3h under hydrogen atmosphere again.Obtain being carried on the Pt-Pd bimetallic loaded catalyst (Pt-Pd/ active carbon) on the active carbon.
Characterize through plasma emission spectrum (ICP), analyze to such an extent that the quality percentage composition of area load Pt is 3.323%, the quality percentage composition of area load Pd is 4.995%, conforms to the theoretical negative carrying capacity.
Embodiment 3, coprecipitation prepare Fe
2O
3The Pt-Rh bimetallic catalyst of load
Solution A: with 20g Fe (NO
3)
39H
2O is dissolved in the 150mL water, with 10mL H
2PtCl
66H
2The O aqueous solution (the quality percentage composition of Pt is 0.5%) and 15mL RhCl
33H
2The O aqueous solution (the quality percentage composition of Rh is 1%) is mixed, obtains solution A; In the solution A, contain 0.05g Pt, 0.15g Rh;
Solution B: 40g NaOH is dissolved in the 100mL water, obtains solution B.
Simultaneously solution A and solution B are adopted and the drip add mode, dropwise add in the 200mL water, during regulate the NaOH rate of addition, control pH value is 9, stirs 4h down at 50 ℃ then, suction filtration and washing do not have Cl in filtrating
-Detect, dry back is 350 ℃ of reduction 4h under hydrogen atmosphere.Obtain being carried on Fe
2O
3On Pt-Rh bimetallic catalyst (Pt-Rh/Fe
2O
3).
Characterize through plasma emission spectrum (ICP), analyze to such an extent that the quality percentage composition of area load Pt is 1.248%, the quality percentage composition of area load Rh is 3.739%, conforms to the theoretical negative carrying capacity.
Solution A (10mL): solute is H
2PtCl
66H
2O, solvent are water; The quality percentage composition of Pt is 0.5% in the solution A; Contain 0.05g Pt in the solution A;
Solution B (15mL): solute is HAuCl
4, solvent is a water; The quality percentage composition of Au is 1.5% in the solution B; Contain 0.225g Au in the solution B.
With solution A, solution B and 6g CeO
2(the general moral occasion in Beijing Science and Technology Ltd.; Lot number 090318) mixed, in the pH meter monitoring down, gentle agitation slowly adds the NaOH aqueous solution of 0.1M, and regulating pH value is 8.5, continues to stir 12h, and suction filtration and washing do not have Cl in extremely filtrating
-Detect drying and 280 ℃ of reduction 6h under hydrogen atmosphere.Obtain being carried on CeO
2On Pt-Au bimetallic catalyst (Pt-Au/CeO
2).
Characterize through plasma emission spectrum (ICP), analyze to such an extent that the quality percentage composition of area load Pt is 0.831%, the quality percentage composition of area load Au is 3.743%, conforms to the theoretical negative carrying capacity.
Solution A (25mL): solute is H
2PtCl
66H
2O, solvent are water; The quality percentage composition of Pt is 0.5% in the solution A; Contain 0.125g Pt in the solution A.
With 10g TiO
2(Chemical Reagent Co., Ltd., Sinopharm Group; Lot number 20081201) add in the 100mL water, stir 40min, dropwise add solution A, backflow 3h also is cooled to room temperature, adds 3mL 38% (quality percentage composition) formalin then, continues backflow 3h, and suction filtration and washing do not have Cl to filtrating
-Detect, filter cake is dry 16h in 110 ℃ of baking ovens.Obtain being carried on TiO
2On Pt single-metal reforming catalyst (Pt/TiO
2).
Characterize through plasma emission spectrum (ICP), analyze to such an extent that the quality percentage composition of area load Pt is 1.248%, conform to the theoretical negative carrying capacity.
Solution A (15mL): solute is H
2PtCl
66H
2O, solvent are water; The quality percentage composition of Pt is 0.5% in the solution A; Contain 0.075g Pt in the solution A.
Solution B (5mL): solute is RuCl
3, solvent is a water; The quality percentage composition of Ru is 1.5% in the solution; Contain 0.075g Ru in the solution B;
Solution C (15mL): solute is RhCl
33H
2O, solvent are water; The quality percentage composition of Rh is 1% in the solution; Contain 0.15g Rh in the solution B;
With 6g Al
2O
3(Tianjin chemical reagent three factories; Lot number 740509) add in the 500mL deionized water, mixed behind process stirring, ultrasonic (100W, the 40Hz) with solution A, solution B and solution C, stirring and adding 25mL NaBH under 20 ℃
4The aqueous solution (NaBH
4The quality percentage composition be 1%), continue about 25 ℃ (20-50 ℃ all can) and stir 5h, suction filtration and washing do not have Cl to filtrating
-Detect, filter cake is dry 16h in 110 ℃ of baking ovens.Obtain being carried on Al
2O
3On Pt-Ru-Rh trimetallic catalyst (Pt-Ru-Rh/Al
2O
3).
Characterize through plasma emission spectrum (ICP), analyze to such an extent that the quality percentage composition of area load Pt is 1.245%, the quality percentage composition of area load Ru is 1.241%, and the quality percentage composition of area load Rh is 2.494%, conforms to the theoretical negative carrying capacity.
Embodiment 7, glycerine oxidation synthesizing lactic acid
With 2g glycerine and 1.7g dissolution of sodium hydroxide in 40mL water and be transferred in three mouthfuls of round-bottomed flasks of 100mL.The Pt-Au/CeO that adds 0.15g embodiment 4 preparations
2, feeding the 1atm flow velocity is the O of 70mL/min
2, adopt different temperature reaction 3 hours.
Fig. 1 is Pt-Au/CeO
2Catalyst activity is with the variation of reaction temperature; A is the conversion ratio of glycerine, and B is the selectivity of lactic acid.Glycerol conversion yield raises with reaction temperature, and the lactic acid selectivity increases, and reaches as high as 82% lactic acid selectivity.
With 2g glycerine and 3.4g dissolution of sodium hydroxide in 40mL water and be transferred in the 100mL autoclave.The Pt-Pd/ZrO that adds 0.1g embodiment 1 preparation
2, charge into O
2And keep airtight, and be heated to 40 ℃, reacted 2 hours.Change the pressure of reaction, reaction result is as shown in Figure 2.
Fig. 2 is Pt-Pd/ZrO
2Catalyst activity is with the variation of reaction pressure; A is the conversion ratio of glycerine, and B is the selectivity of lactic acid.Glycerol conversion yield raises with reaction pressure, but the lactic acid selectivity is on a declining curve.
Embodiment 9, glycerine oxidation synthesizing lactic acid
Glycerine and NaOH are kept the ratio 1: 3 of amount of substance, and be dissolved in the 40mL water and be transferred in three mouthfuls of round-bottomed flasks of 100mL.The Pt/TiO that adds 0.05g embodiment 5 preparations
2, feeding the 1atm flow velocity is the O of 70mL/min
2, be heated to 75 ℃, reacted 1 hour.Change glycerol concentration in the reaction, reaction result is as shown in Figure 3.
Fig. 3 is Pt/TiO
2Catalyst activity is with the variation of glycerol concentration (the quality percentage composition of glycerine in the reaction system); A is the conversion ratio of glycerine, and B is the selectivity of lactic acid.Glycerol conversion yield raises with glycerol concentration and reduces, and the lactic acid selectivity does not have to change basically, has by a small margin and improves.
With 2g glycerine and a certain amount of dissolution of sodium hydroxide in 40mL water and be transferred in three mouthfuls of round-bottomed flasks of 100mL.The Pt-Ru-Rh/Al that adds 0.03g embodiment 6 preparations
2O
3, feeding the 1atm flow velocity is the O of 70mL/min
2, be heated to 60 ℃, reacted 12 hours.Change the ratio of the amount of substance of glycerine and alkali (NaOH) use amount, the result is as shown in Figure 4.
Fig. 4 is Pt-Ru-Rh/Al
2O
3Catalyst activity is with the variation of glycerine and alkali use amount ratio (ratio of amount of substance); A is the conversion ratio of glycerine, and B is the selectivity of lactic acid.Glycerol conversion yield appears with the rising of the alkali number that uses increases earlier the trend that afterwards reduces, has the concentration interval of the best, and when the alkali use was 2-8 times of amount of substance of glycerine, conversion ratio was higher.The lactic acid selectivity raises with the alkali use amount.
Embodiment 11, glycerine oxidation synthesizing lactic acid
With 2g glycerine and 1.73g dissolution of sodium hydroxide in 40mL water and be transferred in three mouthfuls of round-bottomed flasks of 100mL.The Pt-Rh/Fe that adds 0.15g embodiment 3 preparations
2O
3, (reacting gas is by O to feed the 1atm flow velocity and be the reacting gas of 70mL/min
2And N
2) form O
2Adopt different volumn concentrations), be heated to 80 ℃, reacted 6 hours.Change O in the reacting gas
2Volumn concentration, the result is as shown in Figure 5.
Fig. 5 is Pt-Rh/Fe
2O
3Catalyst activity is with O in the gas phase
2Dividing potential drop (O in the reacting gas
2Volumn concentration) variation; A is the conversion ratio of glycerine, and B is the selectivity of lactic acid.Glycerol conversion yield raises with the rising of oxygen partial pressure in the gas phase, and the lactic acid selectivity is higher on the contrary when oxygen partial pressure is low, and the high more lactic acid selectivity of partial pressure of oxygen is low more.
With 2g glycerine and 1.73g dissolution of sodium hydroxide in 40mL water and be transferred in three mouthfuls of round-bottomed flasks of 100mL.The Pt-Pd/ active carbon that adds 0.02g embodiment 2 preparations, feeding the 1atm flow velocity is the O of 70mL/min
2, be heated to 60 ℃, reacted 12 hours.After reaction finished, after catalyst filtration, drying, recovery was reused, and carries out identical operation, so repeats ten times, and the result is as shown in Figure 6.
Fig. 6 is the variation of Pt-Pd/ activated-carbon catalyst activity through recycling for ten times; A is the conversion ratio of glycerine, and B is the selectivity of lactic acid.After catalysis recycled through ten times, active and selectivity did not all have obviously to reduce, and keeps initial reaction conversion ratio and selectivity.
Claims (12)
1. following catalyst is utilizing glycerine to produce the application in the lactic acid;
Said catalyst is carried on 100 mass parts carriers with 0.1-30 mass parts active component and obtains;
Said active component is (1) or (2) as follows:
(1)Pt；
(2) composition of forming by other noble metal beyond Pt and the Pt;
Said other noble metal is at least a among Pd, Rh, Ru, Au and the Ag;
The said method of utilizing glycerine to produce lactic acid: be the reacting gas 0-140 ℃ of reaction 0.5-48h that in reaction system, feeds 1-15atm; Said reacting gas is oxygen or oxygen and nitrogen mixture; Said reaction system is made up of glycerine, alkali, said catalyst and water; When initial, the quality percentage composition of glycerine described in the reaction system is 0.5-50%, and the ratio of the amount of substance of said alkali and said glycerine is (0.01-16): 1, and the mass ratio of said catalyst and said glycerine is 1: (20-500).
2. application as claimed in claim 1 is characterized in that: said carrier is metal oxide or activated carbon; Said metal oxide is Al
2O
3, ZrO
2, TiO
2, Fe
2O
3, CeO
2Or MgO.
3. application as claimed in claim 1 is characterized in that: in the said active component, the shared quality percentage composition of Pt is 0.5-100%.
4. application as claimed in claim 1 is characterized in that: said catalyst is that following arbitrary said method prepares: infusion process, coprecipitation, deposition-precipitation method, formaldehyde reducing process and NaBH
4One stage reduction method.
5. application as claimed in claim 4 is characterized in that:
Said infusion process comprises the steps: the aqueous solution of the precursor of active component and carrier mixed, and 20-100 ℃ is stirred down, after the drying, and 150-500 ℃ of reduction 1-8h under hydrogen atmosphere;
Said coprecipitation comprises the steps: the aqueous solution of the aqueous solution of active component precursor and ferric nitrate mixed; Take and the drip add mode with the NaOH aqueous solution, pH value 7-11,20-90 ℃ is stirred 1-10h down, and suction filtration also washs; After the drying, 150-500 ℃ of reduction 1-10h under hydrogen atmosphere;
Said deposition-precipitation method comprise the steps: the aqueous solution of active component precursor and carrier mixed, add NaOH and regulate the pH value to 7-11, and suction filtration and washing, after the drying, 150-500 ℃ of reductase 12-15h under hydrogen atmosphere;
Said formaldehyde reducing process comprises the steps: the aqueous solution of active component precursor and carrier mixed, adds the formalin doubly with respect to the excessive 2-50 of active component amount of substance behind the backflow 1-5h, continues backflow 1-5h, and suction filtration is also dry;
Said NaBH
4One stage reduction method comprises the steps: the aqueous solution of active component precursor and carrier mixed, adds the NaBH doubly with respect to the excessive 2-50 of active component amount of substance
4The aqueous solution continues to stir 2-24h at 20-100 ℃, and suction filtration is also dry.
6. application as claimed in claim 5 is characterized in that:
Said infusion process comprises the steps: 5-50mL solution A and 5-50mL solution B mixed, to wherein adding the 1-30g carrier; 20-100 ℃ is stirred 1-10h, and dry back is 150-500 ℃ of reduction 1-8h under hydrogen atmosphere, obtains catalyst; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.1-10% in the solution A; Said solution B, solute are one or more the compound that contains other precious metal ion beyond the Pt, and the quality percentage composition of solute is respectively 0.1-10% in the solution B;
Said coprecipitation comprises the steps: solution A and solution B are adopted and the drip add mode; Add in the 10-400mL water; Control pH value is 7-11 in the dropping process, and 20-90 ℃ is stirred 1-10h then, suction filtration and washing; Dry back is 150-500 ℃ of reduction 1-10h under hydrogen atmosphere, obtains catalyst; The preparation method of said solution A is following: with 5-50g Fe (NO
3)
39H
2O is dissolved in the 50-250mL water, with the quality percentage composition of 2-50mL Pt be the H of 0.1-10%
2PtCl
66H
2The quality percentage composition of the O aqueous solution and solute is that one or more compound water solutions that contain other precious metal ion beyond the Pt of 0.1-10% mix, and obtains solution A; The preparation method of said solution B is following: 5-80g NaOH is dissolved in the 50-250mL water, obtains solution B;
Said deposition-precipitation method comprise the steps: 5-50mL solution A, 5-50mL solution B and 1-30g carrier are mixed and stirring; The NaOH aqueous solution that adds 0.01-1M; Regulating the pH value is 7-11, continues to stir 2-48h, suction filtration and washing; Dry back 150-500 ℃ of reductase 12-15h under hydrogen atmosphere obtains catalyst; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.1-10% in the solution A; Said solution B, solute are one or more the compound that contains other precious metal ion beyond the Pt, and solvent is a water, and the quality percentage composition of solute is respectively 0.1-10% in the solution B;
Said formaldehyde reducing process comprises the steps: the 1-30g carrier is added in the 50-250mL water, stirs 10-300min, adds 5-50mL solution A and 5-50mL solution B; Backflow 1-5h; Adding 2-100mL quality percentage composition then is the formalin of 10-39%, continues backflow 1-5h, suction filtration and washing; 90-150 ℃ of dry 2-24h obtains catalyst; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.1-10% in the solution A; Said solution B, solute are one or more the compound that contains other precious metal ion beyond the Pt, and solvent is a water, and the quality percentage composition of solute is respectively 0.1-10% in the solution B;
Said NaBH4 one stage reduction method comprises the steps: the 1-30g carrier is added in the 50-500mL water, mixes with 5-50mL solution A and 5-50mL solution B, and adding 2-100mL quality percentage composition is the NaBH of 0.5-25%
4The aqueous solution continues to stir 2-24h, suction filtration and washing, and 90-150 ℃ of dry 2-24h obtains catalyst; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.1-10% in the solution A; Said solution B, solute are one or more the compound that contains other precious metal ion beyond the Pt, and solvent is a water, and the quality percentage composition of solute is respectively 0.1-10% in the solution B.
7. like claim 2 or 3 described application, it is characterized in that: said catalyst for (a) as follows or (b) or (c) or (d) or (e) or (f):
(a) Pt and Pd are carried on ZrO
2The catalyst that obtains;
(b) Pt and Pd are carried on the catalyst that activated carbon obtains;
(c) Pt and Rh are carried on Fe
2O
3The catalyst that obtains;
(d) Pt and Au are carried on CeO
2The catalyst that obtains;
(e) Pt is carried on TiO
2The catalyst that obtains;
(f) Pt, Ru and Rh are carried on Al
2O
3The catalyst that obtains.
8. application as claimed in claim 7 is characterized in that:
In (a) of claim 7, said Preparation of catalysts method is following: 15mL solution A and 15mL solution B is mixed, and to wherein adding 4-6g ZrO
2Carrier; 20-40 ℃ is stirred 1-3h down, and dry back 150-250 ℃ of reductase 12-4h under hydrogen atmosphere obtains Pt and Pd are carried on ZrO
2On catalyst; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.25%-0.75% in the solution A; Said solution B, solute are PdCl
2, solvent is the HCl aqueous solution of 7.5%-12.5% for the quality percentage composition, the quality percentage composition of Pd is 0.5%-1% in the solution B;
In (b) of claim 7, said Preparation of catalysts method is following: 20mL solution A and 20mL solution B is mixed, add the 2-4g absorbent charcoal carrier to it; 20-40 ℃ is stirred 1-3h, and dry back 150-250 ℃ of reductase 12-4h under hydrogen atmosphere obtains Pt and Pd are carried on the catalyst on the active carbon; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.25%-0.75% in the solution A; Said solution B, solute are PdCl
2, solvent is the HCl aqueous solution of 7.5%-12.5% for the quality percentage composition, the quality percentage composition of Pd is 0.5%-1% in the solution B;
In (c) of claim 7; Said Preparation of catalysts method is following: solution A and solution B are adopted and the drip add mode, add in the 150-250mL water, control pH value is 8-10; 40-60 ℃ is stirred 3-5h then; Suction filtration and washing, dry back be 300-400 ℃ of reduction 3-5h under hydrogen atmosphere, obtains Pt and Rh are carried on Fe
2O
3On catalyst; The preparation method of said solution A is following: with 15-25g Fe (NO
3)
39H
2O is dissolved in the 150mL water, with the quality percentage composition of 10mL Pt be the H of 0.25%-0.75%
2PtCl
66H
2The quality percentage composition of the O aqueous solution and 15mL Rh is the RhCl of 0.5%-1.5%
33H
2The O aqueous solution is mixed, obtains solution A; The preparation method of said solution B is following: 30-50g NaOH is dissolved in the 100mL water, obtains solution B;
In (d) of claim 7, said Preparation of catalysts method is following: with 10mL solution A, 15mL solution B and 5-7g CeO
2Mixed, the NaOH aqueous solution of adding 0.075-0.125M, regulating the pH value is 8-9, continues to stir 10-15h, and suction filtration also washs, and dry back is 270-290 ℃ of reduction 5-7h under hydrogen atmosphere, obtains Pt and Au are carried on CeO
2On catalyst; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.25%-0.75% in the solution A; Said solution B, solute are HAuCl
4, solvent is a water; The quality percentage composition of Au is 1.25%-1.75% in the solution B;
In (e) of claim 7, said Preparation of catalysts method is following: with 8-12g TiO
2Add in the 100mL water, stir 30-50min, add the 25mL solution A; Backflow 2-4h, adding 2-5mL quality percentage composition then is the formalin of 35%-39%, continues backflow 2-4h; Suction filtration and washing, 100-120 ℃ of dry 15-17h obtains Pt is carried on TiO
2On catalyst; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.25%-0.75% in the solution A;
In (f) of claim 7, said Preparation of catalysts method is following: with 5-7g Al
2O
3Add in the 500mL water, mixed with 15mL solution A, 5mL solution B and 15mL solution C, adding 25mL quality percentage composition is the NaBH of 0.5-1.5%
4The aqueous solution continues to stir 4-6h, suction filtration and washing, and 100-120 ℃ of dry 15-17h obtains Pt, Ru and Rh are carried on Al
2O
3On catalyst; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.25%-0.75% in the solution A; Said solution B, solute are RuCl
3, solvent is a water, the quality percentage composition of Ru is 1.25%-1.75% in the solution B; Said solution C, solute are RhCl
33H
2O, solvent is a water, the quality percentage composition of Rh is 0.5-1.5% in the solution C.
9. application as claimed in claim 8 is characterized in that:
In (a) of claim 7, said Preparation of catalysts method is following: 15mL solution A and 15mL solution B is mixed, and to wherein adding 5g ZrO
2Carrier; 30 ℃ are stirred 2h down, and dry back is 200 ℃ of reduction 3h under hydrogen atmosphere, obtain Pt and Pd are carried on ZrO
2On catalyst; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.5% in the solution A; Said solution B, solute are PdCl
2, solvent is 10% the HCl aqueous solution for the quality percentage composition, the quality percentage composition of Pd is 0.75% in the solution B;
In (b) of claim 7, said Preparation of catalysts method is following: 20mL solution A and 20mL solution B is mixed, add the 3g absorbent charcoal carrier to it; 30 ℃ are stirred 2h, and dry back is 200 ℃ of reduction 3h under hydrogen atmosphere, obtain Pt and Pd are carried on the catalyst on the active carbon; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.5% in the solution A; Said solution B, solute are PdCl
2, solvent is 10% the HCl aqueous solution for the quality percentage composition, the quality percentage composition of Pd is 0.75% in the solution B;
In (c) of claim 7, said Preparation of catalysts method is following: solution A and solution B are adopted and the drip add mode, add in the 200mL water; Control pH value is 9, and 50 ℃ are stirred 4h then, suction filtration and washing; Dry back is 350 ℃ of reduction 4h under hydrogen atmosphere, obtain Pt and Rh are carried on Fe
2O
3On catalyst; The preparation method of said solution A is following: with 20g Fe (NO
3)
39H
2O is dissolved in the 150mL water, with the quality percentage composition of 10mL Pt be 0.5% H
2PtCl
66H
2The quality percentage composition of the O aqueous solution and 15mL Rh is 1% RhCl
33H
2The O aqueous solution is mixed, obtains solution A; The preparation method of said solution B is following: 40g NaOH is dissolved in the 100mL water, obtains solution B;
In (d) of claim 7, said Preparation of catalysts method is following: with 10mL solution A, 15mL solution B and 6g CeO
2Mixed, the NaOH aqueous solution of adding 0.1M, regulating the pH value is 8.5, continues to stir 12h, and suction filtration also washs, and dry back is 280 ℃ of reduction 6h under hydrogen atmosphere, obtain Pt and Au are carried on CeO
2On catalyst; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.5% in the solution A; Said solution B, solute are HAuCl
4, solvent is a water; The quality percentage composition of Au is 1.5% in the solution B;
In (e) of claim 7, said Preparation of catalysts method is following: with 10g TiO
2Add in the 100mL water, stir 40min, add the 25mL solution A, backflow 3h adds 3mL quality percentage composition and is 38% formalin then, continues backflow 3h, suction filtration and washing, and 110 ℃ of dry 16h obtain Pt is carried on TiO
2On catalyst; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.5% in the solution A;
In (f) of claim 7, said Preparation of catalysts method is following: with 6g Al
2O
3Add in the 500mL water, mixed with 15mL solution A, 5mL solution B and 15mL solution C, adding 25mL quality percentage composition is 1% NaBH
4The aqueous solution continues to stir 5h, suction filtration and washing, and 110 ℃ of dry 16h obtain Pt, Ru and Rh are carried on Al
2O
3On catalyst; Said solution A, solute are H
2PtCl
66H
2O, solvent is a water, the quality percentage composition of Pt is 0.5% in the solution A; Said solution B, solute are RuCl
3, solvent is a water, the quality percentage composition of Ru is 1.5% in the solution B; Said solution C, solute are RhCl
33H
2O, solvent is a water, the quality percentage composition of Rh is 1% in the solution C.
10. application as claimed in claim 1 is characterized in that: the precursor of said active component is the precious metal salt of solubility or the acid that contains precious metal ion.
11. application as claimed in claim 1 is characterized in that: said alkali is inorganic base; Said alkali is NaOH, potassium hydroxide, potash or sodium carbonate.
12., it is characterized in that like claim 1 or 11 described application: in the said reacting gas, O
2Volumn concentration be 10-100%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910236676A CN101695657B (en) | 2009-10-27 | 2009-10-27 | Method for producing lactic acid by using glycerin and special catalyst for production of lactic acid by using glycerin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910236676A CN101695657B (en) | 2009-10-27 | 2009-10-27 | Method for producing lactic acid by using glycerin and special catalyst for production of lactic acid by using glycerin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101695657A CN101695657A (en) | 2010-04-21 |
| CN101695657B true CN101695657B (en) | 2012-10-10 |
Family
ID=42140804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910236676A Active CN101695657B (en) | 2009-10-27 | 2009-10-27 | Method for producing lactic acid by using glycerin and special catalyst for production of lactic acid by using glycerin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101695657B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8669397B2 (en) * | 2009-06-13 | 2014-03-11 | Rennovia, Inc. | Production of adipic acid and derivatives from carbohydrate-containing materials |
| CA2763177C (en) | 2009-06-13 | 2017-08-01 | Thomas R. Boussie | Production of glutaric acid and derivatives from carbohydrate-containing materials |
| US9770705B2 (en) | 2010-06-11 | 2017-09-26 | Rennovia Inc. | Oxidation catalysts |
| CN101914650B (en) * | 2010-06-29 | 2012-07-04 | 同济大学 | Method for reducing oxidation state iron into simple substance iron by using glycerol |
| US9085521B2 (en) | 2011-03-30 | 2015-07-21 | University Of Kansas | Catalyst system and process for converting glycerol to lactic acid |
| AT511965B1 (en) | 2011-10-11 | 2013-04-15 | Amitava Dipl Ing Dr Kundu | PROCESS FOR THE PREPARATION OF MILKY ACID |
| LV14490B (en) | 2011-12-23 | 2012-05-20 | Rīgas Tehniskā Universitāte | Selective catalysts for producing lactic acid from glycerol |
| FR2999571B1 (en) * | 2012-12-19 | 2015-02-27 | Novance | TRANSFORMATION OF GLYCEROL BY HETEROGENEOUS CATALYSIS |
| FR3011838B1 (en) | 2013-10-15 | 2015-11-13 | Pivert | SUPPORTED BIMETALLIC CATALYST AND USE THEREOF FOR SELECTIVE GLYCEROL OXIDATION |
| CN104549211B (en) * | 2015-01-27 | 2016-11-23 | 陕西师范大学 | A kind of support type Er2o3catalyst and the application in catalyzing cellulose hydrolysis lactic acid thereof |
| CN106810436B (en) * | 2015-11-30 | 2020-06-30 | 中国科学院大连化学物理研究所 | Method for preparing lactic acid by catalytic oxidation of glycerol |
| CN110628274A (en) * | 2019-10-12 | 2019-12-31 | 谢海峰 | For removing H2CO and HCHO paint and preparation method thereof |
-
2009
- 2009-10-27 CN CN200910236676A patent/CN101695657B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| Claudia L.Bianchi et al..Selective oxidation of glycerol with oxygen using mono and bimetallic catalysts based on Au,Pd and Pt metals.《Catalysis Today》.2005,第102-103卷(第**期),203-212. * |
| ClaudiaL.Bianchietal..SelectiveoxidationofglycerolwithoxygenusingmonoandbimetalliccatalystsbasedonAu Pd and Pt metals.《Catalysis Today》.2005 |
| Erin P.Maris et al..Hydrogenolysis of glycerol over carbon-supported Ru and Pt catalysts.《Journal of Catalysis》.2007,第249卷328-337. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101695657A (en) | 2010-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101695657B (en) | Method for producing lactic acid by using glycerin and special catalyst for production of lactic acid by using glycerin | |
| Katryniok et al. | Selective catalytic oxidation of glycerol: perspectives for high value chemicals | |
| CN101549292B (en) | Catalyst for synthesizing cyclohexene by hydrogenation of benzene ring and preparing method thereof | |
| CN102091624B (en) | Catalyst for preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol and preparation method thereof | |
| CN102924233B (en) | Method for preparing propylene glycol by glycerin hydrogenolysis | |
| CN115254100A (en) | For CO 2 Preparation and application of metal oxide doped type monatomic catalyst for preparing ethanol by hydrogenation | |
| CN107552056B (en) | Catalyst for preparing carbon monoxide by carbon dioxide hydrogenation, preparation method and application thereof | |
| CN103191731A (en) | Au-Pd bimetallic catalyst for preparing methyl formate by selective oxidation of methanol as well as preparation method and application thereof | |
| CN102728380A (en) | Catalyst used for preparing 1,3-propylene glycol through glycerin hydrogenolysis, preparation method thereof, and application thereof | |
| CN109926056A (en) | It is a kind of using carbon nanotube as the catalyst of carrier, preparation method and application | |
| CN104276951B (en) | A kind of aqueous catalysis Oxidation of Lactic ester prepares the method for pyruvate | |
| CN111408392A (en) | Cobalt-nitrogen co-doped porous carbon material catalyst and preparation method and application thereof | |
| CN105771974A (en) | Catalyst for producing hydrogen by catalyzing decomposition of formate at room temperature | |
| CN104923218A (en) | Catalyst for itaconic acid hydrogenation as well as preparation method and use of catalyst, and method for preparing high value-added products from itaconic acid | |
| CN103145545A (en) | Method of preparing propanoldiacid through catalytic oxidation of glycerol | |
| CN107286006A (en) | A kind of method that catalyzed alcoholysis lignin prepares Acetovanillone and acetosyringone | |
| CN114950505B (en) | Catalyst for preparing beta-phenethyl alcohol by hydrogenation of styrene oxide, and preparation method and application thereof | |
| CN108069850A (en) | A kind of method for being catalyzed lactic acid oxidative dehydrogenation and preparing pyruvic acid | |
| CN112569945B (en) | Metal-loaded dolomite catalyst for preparing ethanol by glycerol dehydration and preparation thereof | |
| CN102649057A (en) | Catalyst for preparing oxalate through coupling reaction of CO (carbon monoxide) | |
| CN108404919A (en) | Copper C catalyst and preparation method thereof for esters liquid-phase hydrogenatin synthetic fatty alcohol | |
| CN101837288B (en) | Active carbon supported magnesium oxide catalyst for synthetic aromatic alcohol and application thereof | |
| CN101502805B (en) | Catalyst for preparing acetic anhydride as well as preparation method and application | |
| CN101058073A (en) | Method for preparing nickel nanometer line network particle catalyst | |
| CN104888778B (en) | A kind of Cu/MgO catalyst of catalysis glucose hydrogenolysis and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |