CN109174183A - The method for preparing oxalic acid with POMs/HAP catalysis of solid catalyst glycerol - Google Patents

The method for preparing oxalic acid with POMs/HAP catalysis of solid catalyst glycerol Download PDF

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Publication number
CN109174183A
CN109174183A CN201810992613.6A CN201810992613A CN109174183A CN 109174183 A CN109174183 A CN 109174183A CN 201810992613 A CN201810992613 A CN 201810992613A CN 109174183 A CN109174183 A CN 109174183A
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hap
poms
pmo
oxalic acid
glycerol
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Inventor
王晓红
李鸣
李一鸣
李月
张雪艳
李宗航
孙宁悦
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Northeastern University China
Northeast Normal University
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Northeast Normal University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

A method of the composite catalyst catalytic air oxidation glycerol being immobilized on hydroxyapatite (HAP) with polyoxometallate (POMs) prepares oxalic acid, it is related to purposes of the POMs/HPA composite catalyst in biomass orientation conversion, the composition of composite catalyst are as follows: H4PMo11VO40/ HAP (n%) (n represents loading of the POMs in HAP).POMs/HAP composite catalyst is added in glycerine water solution, is passed through air at 80-120 DEG C, under certain time, is centrifugated catalyst.The conversion ratio of glycerol can reach 60% -91%, and the yield of oxalic acid can reach 60% -85%.

Description

The method for preparing oxalic acid with POMs/HAP catalysis of solid catalyst glycerol
Technical field
The present invention relates to the use that complex solid catalyst is formed on HAP is supported on containing the phosphomolybdic acid that vanadium metal replaces On the way, it relates generally to be prepared as the new technical field of oxalic acid in the by-product glycerin selective conversion of biodiesel.
Technical background
Science and technology have made huge strides for modern society, the earth for causing petroleum resources increasingly in short supply therefrom and constantly deteriorating Environment forces national governments actively to seek suitable alternative energy source and green chemical technology, how preferably to realize that resource is whole Environmental protection is taken into account on the basis of conjunction as important issue.Biomass refer in nature one cut with life, having of can growing Body, including all plants, animal, microorganism and their waste.Biomass source is very extensive, and reserves quite may be used It sees, also therefore becomes a kind of green, Sustainable type energy.Biodiesel is with its environmental protection, reproducibility and excellent usability A current big hot spot can be become, quilt is it is believed that be second of biological liquid fuel.Biodiesel is edible from palm oil etc. It is acted on the alcohol of oil, animal oil etc. and short chain, every biodiesel for preparing 1mol generates the glycerol of 3mol.Therefore in biodiesel Production process in, generate a large amount of by-products --- crude glycerine.Especially fast-developing production technology more results in glycerol A large amount of accumulation.From 1992 600000 tons, with annual 3.75% amount of increase increased to 2010 hundred million tons of 1.1-1.5 (reference Document H.Fukuda, A.Kondo and H.Noda, J.Biosci.Bioeng.92 (2001) 405-416).Therefore glycerol Price " is as low as zero ", the chemicals for how converting glycerol into higher utility value just become very urgent problems and by Extensive concern.
Glycerol contains there are three active hydroxyl, can pass through the chemical products of different chemical reaction preparation high added values, comprising: Methacrylaldehyde, dihydroxyacetone (DHA) (DHA), glyceric acid, glyceraldehyde, oxalic acid (OA) and lactic acid (LA) etc..But because glycerol oxygen It is sufficiently complex to change reaction process, selective glycerol is oxidized to desired product is still a very huge challenge.
Oxalic acid is a kind of simple organic dibasic acid, and distinctive physicochemical properties make oxalic acid in industry, agricultural, medicine The fields such as industry are all widely used, and are good rust remover, bleaching agent, colour developing dyeing auxiliaries and catalyst, especially dilute Extensive application in soil extraction extraction.The method for preparing oxalic acid of domestic report mainly has at present: (1) sodium formate method technique at Ripe, quality is stablized, but process flow is complicated, be adapted only to large enterprises' production (bibliography, Chen Huanzhang, oxalic acid production technology overview, Ningxia chemical industry, 1994,2,21-24)；(2) it is raw material nitric acid as oxidant that nitric acid oxidation method, which is using sugar or starch, but yield is low, Nitric acid consumption is big, causes serious environmental problem, while consuming starch and glucose (bibliography, Ji Qingrong, carbohydrate Catalysis oxidation oxalic acid, chemistry world, 1988,29,491)；(3) fibrous matter produces oxalic acid, but yield through alkali or acid processing Low, severe reaction conditions, industrialization that energy consumption is high is difficult, and (bibliography, Guo Xueyang, cornstalk produce the research of oxalic acid, natural gas Chemical industry, 1990,4:38-43. Wang Jianhuas, sweet potato vine produce oxalic acid process study, chemistry world, and 1994,35,515- 517)；(4) sawdust is waste oxalic acid, is the new approach (ginseng that oxalic acid production has been started using hydrolysis-oxidation-technology for hydrolyzing Examine document, Wang Qiao, Zhang Liping, Song Yanwei, Sun little Yan, Yanan University's journal (natural science edition), 2002,22,44-46)； (5) Zeng et al. utilizes Co0.30/Mg3Glycerol is aoxidized in the presence of Al-s catalyst oxygen and alkali, 100% conversion produces 24.4% Oxalic acid (bibliography, Jin X, Zhao M, Zeng C, et al.Oxidation of Glycerol to Dicarboxylic Acids Using Cobalt Catalysts, ACS Catalysis, 2016,6,4576-4583)；(6) Clark et al. is utilized Pd- starbon is catalyst, H2O2For oxidant, glycerol conversion yield reaches 100%, oxalic acid yield 60% (bibliography, Luque R,Budarin V,Clark J H,et al.Glycerol transformations on polysaccharide Derived mesoporous materials, Applied Catalysis B Environmental, 2008,82 (3-4), 157-162).It can be seen that being influenced from the oxalic acid technology of preparing of glycerol by many factors: the use of alkali causes Certain environmental problem also creates salt rather than sour, simultaneous reactions although the oxalic acid of certain yield can be prepared simultaneously System generates a large amount of alkali wasteliquid and needs to handle, and improves the preparation cost of glycerol.Therefore development is catalyzed under the conditions of non-alkaline The technology that glycerol is oxidized to oxalic acid is extremely urgent.It is catalyst selective glycerol oxidation preparation grass using noble metal such as Pd etc. Acid, H2O2For oxidant, one side price is high, and the oxidability of another aspect hydrogen peroxide brings by force side reaction more.Therefore develop Oxygen especially air is that the new invention of oxidant is the key that from glycerol to oxalic acid.
It is a kind of metal oxygen cluster compound that polyoxometallate (Polyoxometalates, POMs)-, which is also referred to as polyacid, In types of applications, the application of catalytic field is most important.In recent years, using the strong oxidizing property of POMs and certain acidity, Be successfully applied to catalysis DIRECT OXIDATION OF ETHYLENE TO ACETIC ACID ethyl ester (bibliography I.V.Kozhevnikov, Chem.Rev., 1998,98,171-198), industrialization has been realized in Japan.POMs performance strong oxidizing property will appear as quickly in a mild condition Reversible polyelectron oxidationreduction transformation, and its oxidation-reduction quality can be and changing its chemical composition in very large range Adjustment.POMs shows the relationship between substrate oxygen: E in oxidation catalysis reaction simultaneouslySubstrate<Epom<E O2, therefore can lead to Cross the POMs that suitable oxidation catalysis reaction is found to the adjustment of POMs composition.Most study is saturation Kiggin structure at present The general structure of heteropoly acid molecule can be expressed as YxH3-x[PM12O40]·nH2O, wherein P is center atom, and M is can with atom To select Mo and W, Y is gegenion, H2O is the crystallization water, and n is crystallization water number.One octahedron of removal can from saturation POMs To prepare single vacant POMs, occur a vacancy in total, metal can be generated with Action of Metal Ions and replaced Type POMs still keeps structure with Keggin, general formula K5PM11LO39(M=Co2+,Fe2+,Mn2+, Cu2+,Ni2+, V5+).Pass through gold Belong to one tungsten atom of ionic compartmentation, the redox property of adjustable entire POMs, and the oxidation reaction of glycerol can be regulated and controled And the distribution of product.
The chemical formula of hydroxyapatite is Ca10(PO4)6(OH)2It (HAP), is a kind of common alkalescent catalyst carrier. With stable skeleton structure and certain ion-exchange capacity, by H4PMo11VO40It is immobilized on available POMs/ on HAP On the one hand HAP composite catalyst shows certain redox ability, solid alkaline is on the one hand provided, in glycerol oxidation reaction Middle offer active site and alkaline environment, while the proportion of POMs and HAP can regulate and control efficiently to realize that glycerol prepares oxalic acid.
About POMs/HAP composite catalyst involved in this patent, it is oxidant using air, selective glycerol is turned Turn to oxalic acid, conversion ratio and selectivity are all up to 85% or more, be a kind of new glycerol conversion and prepare the strategy of oxalic acid can be with It solves glycerol orientation and is converted into technical problem present in oxalic acid:
1, the substitution precious metals pd composite catalyst that non-alkali systems use in the world realizes that efficient glycerol is oxidized to oxalic acid, Reduce the cost of catalyst；Do not generate alkaline waste water；
2, a kind of catalysis oxidation glycerol provided by the invention prepares the POMs/HAP composite catalyst of oxalic acid, while showing one Fixed redox ability and solid alkaline environment guarantees the efficient and highly selective completion of glycerol oxidation reaction；
3, process for synthetic catalyst is simple, catalytic activity is high, oxalic acid yield is high；It is simultaneously oxidant using air, reduces Reaction cost saves mass energy；Reaction condition is mild, and under the conditions of 80 DEG C, 8 hours can achieve 90% conversion substantially The yield of rate, oxalic acid is up to 85%.One kettle way can complete the tandem reaction of oxidation scission of link and dehydrogenation, save intermediate product Separation process simplifies reaction step.
4, heterogeneous catalysis centrifuge separation is recoverable, while hydroxyapatite structure stabilizing mechanical intensity is big, Activated centre H4PMo11VO40It does not fall off, improves the service life of catalyst.Greatly reduce the use cost of catalyst.
The H of different POMs loadings is synthesized by design4PMo11VO40/ HAP (n%) can achieve excellent redox Property and alkali solid catalyst, realize glycerol to oxalic acid orientation conversion, it is practical.
Summary of the invention
It is selected the object of the present invention is to provide a kind of preparation method with POMs/HAP composite catalyst and in catalyzing glycerol Property oxidation prepares the application of oxalic acid.
A kind of POMs/HAP composite catalyst the present invention relates to offer is that there is one kind structure with Keggin POMs to be supported on Compound on hydroxyapatite, general formula H4PMo11VO40/ HAP (n%), n=5,10,15,20,25 and 30, represent POMs Loading in HPA.
The K5PW11MO39/ HPA composite catalyst is preferred are as follows:
(1)H4PMo11VO40/ HAP (5%)
(2)H4PMo11VO40/ HAP (10%)
(3)H4PMo11VO40/ HAP (15%)
(4)H4PMo11VO40/ HAP (20%)
(5)H4PMo11VO40/ HAP (25%)
(6)H4PMo11VO40/ HAP (30%)
H provided by the invention4PMo11VO40The synthetic method of/HAP composite catalyst is as follows:
1:5-50 weighs HAP and H in mass ratio4PMo11VO40It is added separately in the dehydrated alcohol of 10-100mL, flows back Reaction 10-is for 24 hours.Filtering, obtained solid are washed 2-4 times with dehydrated alcohol, dry 3h under the conditions of 110 DEG C.Obtain different POMs The H of loading4PMo11VO40/ HAP composite catalyst.Its yield is 90%.
The catalyst of oxalic acid is prepared with a kind of catalyzing glycerol oxidation provided by the invention, catalyzing glycerol is oxidized to the side of oxalic acid Method is as follows:
In a high pressure reaction kettle, the glycerine water solution containing 0.05-5.0g/mL is added, while H is added4PMo11VO40/HAP Composite catalyst, substrate glycerol and catalyst quality ratio are 100:1-20.When this mixture is heated to 50-120 DEG C, it is passed through Pressure is the air of 0.1-5Mbar, and reaction carries out 1-5 hours.After reaction, catalyst centrifuge separation is used for next time Reaction.Product high-efficient liquid phase color spectral test, the conversion ratio of glycerol can reach 60% -91%, and the yield of oxalic acid can reach 60% -85%.
H provided by the invention4PMo11VO40The synthesis preferred method of/HAP composite catalyst is as follows:
1:5-35 weighs HAP and H in mass ratio4PMo11VO40It is added separately in the dehydrated alcohol of 10-50mL, reflux is anti- Answer 12-20h.Filtering, obtained solid are washed 2-4 times with dehydrated alcohol, dry 3h under the conditions of 110 DEG C.Obtain different POMs loads The H of carrying capacity4PMo11VO40/ HAP composite catalyst.Its yield is 90%.
H provided by the invention4PMo11VO40The synthesis best approach of/HAP composite catalyst is as follows:
1:5-30 weighs HAP and H in mass ratio4PMo11VO40It is added separately in the dehydrated alcohol of 40mL, back flow reaction 14h.Filtering, obtained solid dry 3h under the conditions of washing 3 times, 110 DEG C with dehydrated alcohol.Obtain different POMs loadings H4PMo11VO40/ HAP (n%) composite catalyst (n=5,10,15,20,25 and 30).Its yield is 90%.
H provided by the invention4PMo11VO40The preferred method of/HAP composite catalyst catalyzing glycerol conversion is as follows:
In a high pressure reaction kettle, the glycerine water solution containing 0.1-2.5g/mL is added, while H is added4PMo11VO40/HAP Composite catalyst, substrate glycerol and catalyst quality ratio are 100:3-15.When this mixture is heated to 50-100 DEG C, it is passed through Pressure is the air of 0.4-4Mbar, and reaction carries out 2-4 hours.After reaction, catalyst centrifuge separation is used for next time Reaction.Product high-efficient liquid phase color spectral test, the conversion ratio of glycerol can reach 70% -91%, and the yield of oxalic acid can reach 70% -85%.
H provided by the invention4PMo11VO40The best approach that/HAP composite catalyst catalyzing glycerol is oxidized to oxalic acid is as follows:
In a high pressure reaction kettle, the glycerite containing 0.5g/mL is added, while H is added4PMo11VO40/ HAP is compound to be urged Agent, substrate glycerol and catalyst quality ratio are 100:3.When this mixture is heated to 80 DEG C, being passed through pressure is 0.5 bar Oxygen, reaction carry out 3 hours.After reaction, catalyst centrifuge separation is used for next secondary response.Product efficient liquid phase Chromatography is examined, and the conversion ratio of glycerol and the yield of lactic acid can achieve 90% and 85% respectively.
Specific embodiment
Embodiment 1
1:5 weighs HAP and H in mass ratio4PMo11VO40It is added separately in the dehydrated alcohol of 30mL, back flow reaction is for 24 hours. Filtering, obtained solid are washed 2-4 times with dehydrated alcohol, dry 3h under the conditions of 110 DEG C.Obtain K5PW11CoO39Loading is 5% H4PMo11VO40/ HAP composite catalyst.Its yield is 90%.
Embodiment 2
In a high pressure reaction kettle, the glycerine water solution containing 0.05g/mL is added, while H is added4PMo11VO40/HAP (5%) composite catalyst, substrate glycerol and catalyst quality ratio are 100:1.When this mixture is heated to 50 DEG C, it is passed through Pressure is the air of 0.1Mbar, and reaction carries out 1 hour.After reaction, catalyst centrifuge separation is used for next secondary response. Product high-efficient liquid phase color spectral test, the conversion ratio of glycerol reach 75%, and the yield of oxalic acid reaches 65%.
Embodiment 3
In a high pressure reaction kettle, the glycerine water solution containing 5.0g/mL is added, while H is added4PMo11VO40/HAP (30%) composite catalyst, substrate glycerol and catalyst quality ratio are 100:20.When this mixture is heated to 120 DEG C, lead to Enter the air that pressure is 5Mbar, reaction carries out 5 hours.After reaction, catalyst centrifuge separation is used for next secondary response. Product high-efficient liquid phase color spectral test, the conversion ratio of glycerol reach 91%, and the yield of oxalic acid can reach 85%.

Claims (2)

1. a kind of POMs solid-carrying type solid catalyst for preparing oxalic acid for air oxidation glycerol, it is characterised in that it is containing vanadium Substituted phosphomolybdic acid compound as catalytic active center, and be immobilized on basic hydroxide group apatite (HAP) formed it is compound Solid catalyst；The general formula of above-described compound is；
H4PMo11VO40/ HAP (n%)
N=5,10,15,20,25 and 30, represent loading of the POMs in HPA.
2. a kind of POMs/HAP (n%) catalyst for preparing oxalic acid for catalysis oxidation glycerol as described in claim 1, described Compound it is preferred are as follows:
(1)H4PMo11VO40/ HAP (5%)
(2)H4PMo11VO40/ HAP (10%)
(3)H4PMo11VO40/ HAP (15%)
(4)H4PMo11VO40/ HAP (20%)
(5)H4PMo11VO40/ HAP (25%)
(6)H4PMo11VO40/ HAP (30%).
CN201810992613.6A 2018-08-28 2018-08-28 The method for preparing oxalic acid with POMs/HAP catalysis of solid catalyst glycerol Pending CN109174183A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014056005A1 (en) * 2011-10-11 2014-04-17 Amitava Kundu Method for producing lactic acid
CN104045544A (en) * 2014-06-27 2014-09-17 江苏大学 Method for preparing lactic acid through catalyzing glycerol by supported copper catalyst
CN104045545A (en) * 2014-06-27 2014-09-17 江苏大学 Method for preparing lactic acid through catalyzing glycerol by supported catalyst
CN104475156A (en) * 2014-12-10 2015-04-01 湖南师范大学 Method for synthesizing immobilized polyoxometallate material by one step
CN107056602A (en) * 2017-05-05 2017-08-18 江苏大学 A kind of method that Hydroxyapatite-Supported nickel catalysis high concentration glycerine produces lactic acid
CN107088438A (en) * 2017-05-04 2017-08-25 东北师范大学 The method for preparing lactic acid with the selective conversion of catalyzing glycerol containing molybdenum heteropolyacid

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014056005A1 (en) * 2011-10-11 2014-04-17 Amitava Kundu Method for producing lactic acid
CN104045544A (en) * 2014-06-27 2014-09-17 江苏大学 Method for preparing lactic acid through catalyzing glycerol by supported copper catalyst
CN104045545A (en) * 2014-06-27 2014-09-17 江苏大学 Method for preparing lactic acid through catalyzing glycerol by supported catalyst
CN104475156A (en) * 2014-12-10 2015-04-01 湖南师范大学 Method for synthesizing immobilized polyoxometallate material by one step
CN107088438A (en) * 2017-05-04 2017-08-25 东北师范大学 The method for preparing lactic acid with the selective conversion of catalyzing glycerol containing molybdenum heteropolyacid
CN107056602A (en) * 2017-05-05 2017-08-18 江苏大学 A kind of method that Hydroxyapatite-Supported nickel catalysis high concentration glycerine produces lactic acid

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
LINGQIN SHEN ET AL.: "Glycerol valorization to lactic acid catalyzed by hydroxyapatite-supported palladium particles", 《J.CHEM.TECHNOL.BIOTECHNOL.》 *
MEILIN TAO ET AL.: "Hetropolyacid-Catalyzed Oxidation of Glycerol into Lactic Acid under Mild Base-Free Conditions", 《CHEM.SUS.CHEM.》 *
谢劲松: "《甘油》", 29 February 1984, 轻工业出版社 *

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