CN106631758A - Method for preparing carboxylic acid by catalyzing oxygen to oxidize lignite - Google Patents
Method for preparing carboxylic acid by catalyzing oxygen to oxidize lignite Download PDFInfo
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- 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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Abstract
The invention relates to a method for preparing high-yield carboxylic acid by catalytically oxidizing lignite through an iron salt compound catalyst in a water solution. The method comprises the following steps: utilizing a mixture of soluble iron salt and inorganic acid as a catalyst system and taking oxygen as an oxidant; selectively oxidizing the lignite to prepare the high-yield carboxylic acid in the water solution; then, adopting an organic solution extracting method to separate the product carboxylic acid from the water solution of the catalyst system; circularly utilizing the water solution of the catalyst system. Compared with a traditional alkali-oxygen oxidization method, the method provided by the invention avoids the consumption of a lot of inorganic alkalis and the utilization of the inorganic acid is reduced; energy consumption in a reaction process is reduced; compared with a method for preparing the carboxylic acid by catalytically oxidizing the lignite through NaVO3, the price of the soluble iron salt is low and the method is environment-friendly.
Description
Technical field
The present invention relates to a kind of mixture with soluble ferric iron salt and mineral acid is as catalyst system, oxygen catalytic oxidation is brown
The method that coal produces carboxylic acid.
Technical background
Brown coal are a kind of important carbon-containing energy and resource, and on earth reserves enrich very much, such as Chinese brown coal storage
Measure for 130,000,000,000 tons, U.S.'s brown coal reserves be 40,700,000,000 tons, the brown coal reserves of Germany be 43,300,000,000 tons, Australia draws and raises primary mountain valley
Brown coal reserves be 160,000,000,000 tons.But brown coal high volatile, high-moisture, rich oxygen content, low-calorie feature limit brown coal
Conventional application.It is necessary to develop a kind of unconventional Land use systems of new brown coal for the These characteristics of brown coal.
It is well known that containing substantial amounts of aromatic structure and lipid structure in coal structure, and because brown coal have height oxygen-containing
Amount, this prepares carboxylic acid and provides favourable intrinsic advantage for brown coal selective oxidation.Brown coal oxidation produces carboxylic acid as a kind of new
The unconventional brown coal Land use systems of type, it is widely studied by researcher.At present the method for coal oxidation carboxylic acid mainly includes, dioxygen
Water oxidation, oxidizing acid oxidizing process, dioxygen oxidation method etc..
(K.Miura, K.Mae, H.Okutsu, the N.Mizutani.New Oxidative such as Miura in 1996
Degradation Method for Producing Fatty Acids in High Yields and High
Selectivity from Low-Rank Coals.Energy Fuels,1996,10:1196-1201) normal pressure, 80 DEG C
Under the conditions of, with H2O2For oxidant, oxidation Australia rub prestige brown coal obtain 0.52kg/kg-daf small molecule fatty acid and
Methanol.Recent Liu etc. (J.Liu, X.Y.Wei, Y.G.Wang, D.D.Zhang, T.M.Wang, J.H.Lv, J.Gui, M.Qu,
Z.M.Zong.Mild Oxidation of Xiaolongtan Lignite in Aqueous Hydrogen Peroxide-
Acetic Anhydride.Fuel,2015,142:268-273) existed as oxidant using hydrogen peroxide and acetic anhydride mixed solution
Little Longtan Brown Coal 9h is aoxidized under the conditions of temperature 50 C, 47 kinds of carboxylic acids have been obtained (including aromatic carboxylic acids and small molecule fatty acid).
Oxidizing acid is also used for brown coal oxidation and produces in the research of carboxylic acid as a kind of strong oxidizer.Early in nineteen thirty-seven
Juettner(B.Juettner.Mellitic Acid from Coals,Cokes and
Graphites.J.Am.Chem.Soc.,1937,59:208-213) with HNO3Oxidation is carried out to coal as oxidant and produces benzene
Pregnancy acid.Kinney(C.R.Kinney.The Source of Acetic Acid Obtained by Oxidation of
Coal.J.Am.Chem.Soc.,1947,69:284-289) with HNO3Oxidation is carried out to coal for oxidant and produces acetic acid, dense
The coal of different rank is aoxidized under the conditions of nitric acid, the acetic acid of different yields is obtained.Recently, Zhang etc. (H.X.Zhang,
Z.Y.Liu,Q.Y.Liu.Case Study of Quantification of Aromatic Ring Structures in
Lignite Using Sequential Oxidation.Energy Fuels,2016,30:2005-2011) adopt permanganic acid
Potassium is aoxidized as oxidant to brown coal, in KMnO4/ NaOH mass ratioes are under conditions of 7,100 DEG C of temperature, to aoxidize brown coal energy
Access the benzene carboxylic acid of 0.71mmol/g.
Above two method is expensive due to selected oxidant, there is the factors such as safety problem in operating process,
Limit their application.Oxygen obtains the attention of people as a kind of oxidant cheap and easy to get.The dioxygen oxidation method of coal
In, research is most commonly used to surely belong to alkali-dioxygen oxidation method.
(A.Okuwakl, N.Sutoh, H.Furuya, A.Amano, the T.Okabe.Production such as Okuwakl in 1984
of Oxalate by the Oxidation of Coal with Oxygen in a Concentrated Sodium
Hydroxide Solution.Ind.Eng.Chem.Prod.Res.Dev.,1984,23:648-651) in concentration 25mol/kg
Sodium hydroxide solution in, under conditions of 250 DEG C of temperature, oxygen is carried out to low-order coal by oxidant of the oxygen of 5.0MPa partial pressures
Change has obtained the volatile acid of 20%～24% carbon yield.Wang etc. (W.H.Wang, Y.C.Hou, W.Z.Wu, M.G.Niu,
W.N.Liu.Production of Benzene Polycarboxylic Acids from Lignite by Alkali-
Oxygen Oxidation.Ind.Eng.Chem.Res.,2012,51,14994-15003.W.H.Wang,Y.C.Hou,
W.Z.Wu,M.G.Niu,T.Wu.High-Temperature Alkali-Oxygen Oxidation of Lignite to
Produce Benzene Polycarboxylic Acids.Ind.Eng.Chem.Res.2013,52,680-
685.W.H.Wang,Y.C.Hou,W.Z.Wu,M.G.Niu.Simultaneous Production of Small-Molecule
Fatty Acids and Benzene Polycarboxylic Acids from Lignite by Alkali-Oxygen
Oxidation.Fuel Process.Technol., 2013,112,7-11.) alkali/coal mass ratio be 0.8～3, reaction temperature
240～300 DEG C, under the reaction condition of oxygen first pressing 5MPa, brown coal are carried out to aoxidize the benzene carboxylic for having obtained mass yield about 20%
Acid and about 40% small molecule fatty acid.
Although researcher has done substantial amounts of research to the alkali-dioxygen oxidation method of coal, still suffer from its oxidizing process
Substantial amounts of problem.Mainly include, substantial amounts of inorganic base is consumed in (1) oxidizing process, consume again in follow-up process a large amount of
Mineral acid, easily cause serious environmental pollution；(2) higher reaction temperature and oxygen pressure are needed in course of reaction,
Which again increases the energy expenditure in course of reaction.Yang etc. (F.Yang, Y.C.Hou, M.G.Niu, W.Z.Wu, D.Y.Sun,
Q.W.Wang,Z.Y.Liu.Production of Benzene Poly(carboxylic acid)s and Small-
Molecule Fatty Acids from Lignite by Catalytic Oxidation in NaVO3/H2SO4
Aqueous Solution with Molecular Oxygen.Ind.Eng.Chem.Res.,2015,54,12254-
12262.) adopt NaVO3For catalyst, oxygen catalytic oxidation brown coal, about 10% benzene carboxylic acid and little point of about 45% have been obtained
Sub- fatty acid.The problem of the consumption of a large amount of soda acids and high temperature energy consumption during alkali-dioxygen oxidation is the method overcomed, but
NaVO3There is very big harm to human body and environment as a kind of vanadium-containing compound, be unfavorable for the application of the method.
This is accomplished by a kind of method for finding suitable catalyst and catalysis oxidation, and for brown coal carboxylic acid process processed is being aoxidized
In, a large amount of acid and alkali consumptions and the energy expenditure during alkali-dioxygen oxidation, and environmental friendliness can not only be reduced.
The content of the invention
The purpose of the present invention is to carry out dioxygen oxidation to brown coal using water-soluble ferrum-based catalyst to produce carboxylic acid, with gram
The consumption of a large amount of soda acids during brown coal alkali-dioxygen oxidation, and high temperature high energy consumption issues are taken, while catalyst environment friend
It is good.
The method that a kind of oxygen catalytic oxidation brown coal that the present invention is provided produce carboxylic acid, the concrete steps that the method includes are such as
Under：
(1) granularity is less than into the brown coal of 0.1mm and containing soluble ferric iron salt and inorganic aqueous acid addition autoclave
In, it is filled with O2Or with the air of oxygen partial pressure, at a certain temperature stirring reaction certain hour, after reaction terminates, filters and divides
Separate out filtrate and residue.
(2) filtrate that step (1) is filtrated to get is transferred in separatory funnel, a certain amount of fourth is added in separatory funnel
Ketone solvent, at room temperature, extract and separate oxidation product and catalyst system aqueous solution, catalyst system aqueous solution carries out repeating profit
With.
In said method, described brown coal and the mass ratio (on the basis of water yield) of water are 1.0%～3.0%, preferably
1.2%～2.0%.
In said method, the soluble ferric iron salt is FeCl3、FeCl2、Fe2(SO4)3And FeSO4One or more.
In said method, the mineral acid is sulphuric acid either hydrochloric acid or the mixture of the two.
In said method, soluble ferric iron salt mass content in aqueous is 0.03%～0.30%, preferably
0.05～0.15%.
In said method, mineral acid mass content in aqueous be 0.25%～2.5%, preferably 1.0～
2.0%.
In said method, reaction temperature is 160 DEG C～240 DEG C, preferably 180 DEG C～220 DEG C in the step (1).
In said method, oxygen first pressing in the step (1) is 1.0MPa～5.0MPa, preferred 2.0MPa～3.5MPa.
In said method, the response time is 30min～120min, preferred 45min～90min in the step (1).
In said method, the consumption of the organic solvent butanone described in step (2) is：Butanone is 2 with the volume ratio of aqueous solution:
1～3:1, extraction temperature is room temperature.
The present invention principle be：In the case where this patent uses catalyst system and oxidizing condition, there is Fe in ferrum-based catalyst3+
With Fe2+Between variation of valence；Fe first3+Oxidation brown coal generate carboxylic acid, and itself is reduced to Fe2+；Then oxygen is by Fe2+
It is oxidized to Fe3+To complete Fe3+With Fe2+Between circulation.By the pH value for adjusting reaction temperature and solution, change iron ion
Oxidability, realizes the selective oxidation carboxylic acid of brown coal.
Compare with traditional alkali-dioxygen oxidation method, the method that the present invention is provided has advantages below：(1) present invention is provided
Method be a kind of method that oxygen catalytic oxidation brown coal produce carboxylic acid, can avoid big during traditional alkali-dioxygen oxidation
The use of amount inorganic base and mineral acid, and the method can effectively reduce the temperature and oxygen pressure of reaction with reducing energy consumption.
(2) catalyst system that this method is selected has a good circulating effect, and the characteristics of with environmental friendliness.
Specific embodiment
The present invention is further illustrated with the following example, but protection scope of the present invention is not limited to the following example.
Embodiment 1
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring.The little dragon's pools of 0.10g is brown
Coal (granularity be less than 0.075mm, quality of organic matter content for 78.9%) and 6.0mL FeCl3Mass fraction is 0.10%, H2SO4
Mass fraction is that 1.5% aqueous solution is added in reactor, reactor is closed, the sky gone out in reactor with replacement of oxygen
Gas, is then charged with the oxygen of 3.0MPa.Reactor is put in the heating mantle for heating in advance and is opened stirring, works as reaction temperature
Start timing when reaching 200 DEG C, after reaction 60min, reactor is taken out and is quenched with terminating reaction with cold water.Question response kettle drops
To room temperature, material after reaction is filtered, obtained residue and filtrate.Filtrate is settled to into 50mL, sampling carries out efficient liquid phase
Chromatography is constituted.
The high performance liquid chromatograph for being used is Waters2695.During assay products benzene carboxylic acid, the detector for adopting is for purple
External detector, Detection wavelength 235nm, chromatographic column is C18 silicagel columns, and column temperature is 35 DEG C, and mobile phase is acetonitrile (5%) and volume integral
Number is 0.1% phosphate aqueous solution (95%), and the flow of mobile phase is 1cm3/ min, is entered, two using binary gradient elutes method
The condition of first gradient elution is：0min (5% acetonitrile, 95% phosphoric acid water) --- 10min (20% acetonitrile, 80% phosphoric acid water) ---
12min (20% acetonitrile, 80% phosphoric acid water) --- 14min (5% acetonitrile, 95% phosphoric acid water) --- 18min (5% acetonitrile, 95%
Phosphoric acid water).During assay products small molecule fatty acid, detector is Composition distribution, and chromatographic column is shodex1011 saccharide chromatographs
Post, column temperature is 55 DEG C, and mobile phase is the aqueous sulfuric acid that mass fraction is 0.1%, and the flow of mobile phase is 0.5mL/min.
The mass yield that gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter is 51.71%, wherein, formic acid
30.0%, acetic acid 9.67%, ethanedioic acid 2.28%, succinic acid 0.93%, (yield with total benzene carboxylic acid is as base for benzene carboxylic acid 8.83%
Standard, the benzene carboxylic acid is consisted of：Benzoic acid 1.36%, p-phthalic acid 3.96%, phthalic acid 1.36%, M-phthalic acid
5.55%, trimellitic acid 3.74%, benzene-1 9.51%, trimesic acid 0.90% connects benzene tetracarboxylic acid 9.29%,
Benzene tetracarboxylic acid 6.46%, inclined benzene tetracarboxylic acid 5.44%, benzene pentacarbonic acid 21.06%, mellic acid. 31.37%).
Embodiment 2
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring.The little dragon's pools of 0.06g is brown
Coal (granularity be less than 0.1mm, quality of organic matter content for 78.9%) and 6mL FeCl3Mass fraction is 0.10%, H2SO4Quality
Fraction is that 1.5% aqueous solution is added in reactor, reactor is closed, the air gone out in reactor with replacement of oxygen, so
The oxygen of 3.0MPa is filled with afterwards.Reactor is put in the heating mantle for heating in advance and is opened stirring, when reaction temperature reaches
Start timing when 200 DEG C, after reaction 60min, reactor is taken out and is quenched with terminating reaction with cold water.Question response kettle is down to room
Temperature, material after reaction is filtered, and obtains residue and filtrate.Filtrate is settled to into 50mL, sampling carries out high performance liquid chromatography
Analysis composition.Analysis condition and method are with embodiment 1.
The mass yield that gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter is 22.65%, wherein, formic acid
11.76%, acetic acid 4.87%, ethanedioic acid 0.30%, succinic acid 0.52%, benzene carboxylic acid 5.20% (composition of benzene carboxylic acid and enforcement
The benzene carboxylic acid composition of example 1 is similar).
Embodiment 3
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring.The little dragon's pools of 0.18g is brown
The FeCl of coal (granularity is less than 0.075mm, and quality of organic matter content is 78.9%, similarly hereinafter) and 6mL3Mass fraction be 0.10%,
H2SO4Mass fraction is that 1.5% aqueous solution is added in reactor, and reactor is closed, is gone out in reactor with replacement of oxygen
Air, is then charged with the oxygen of 3.0MPa.Reactor is put in the heating mantle for heating in advance and is opened stirring, when reaction temperature
Degree starts timing when reaching 200 DEG C, after reaction 60min, reactor is taken out and is quenched with terminating reaction with cold water.Question response kettle
Room temperature is down to, material after reaction is filtered, obtain residue and filtrate.Filtrate is settled to into 50mL, sampling carries out efficient liquid
Analysis of hplc is constituted.Analysis condition and method are with embodiment 1.
The mass yield that gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter is 34.68%, wherein, formic acid
21.06%, acetic acid 5.87%, ethanedioic acid 1.3%, succinic acid 0.72%, (the composition and embodiment of benzene carboxylic acid of benzene carboxylic acid 5.73%
1 benzene carboxylic acid composition is similar).
Embodiment 4
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring.The little dragon's pools of 0.10g is brown
The FeCl of coal and 6mL3Mass fraction is 0.03%, H2SO4Mass fraction is that 1.5% aqueous solution is added in reactor, will be anti-
Answer kettle closed, the air gone out in reactor with replacement of oxygen is then charged with the oxygen of 3.0MPa.Reactor is put into into heating in advance
Good heating mantle is interior and opens stirring, and timing is started when reaction temperature reaches 200 DEG C, after reaction 60min, reactor is taken out
And be quenched with terminating reaction with cold water.Question response kettle is down to room temperature, and material after reaction is filtered, and obtains residue and filtrate.
Filtrate is settled to into 50mL, sampling carries out efficient liquid phase chromatographic analysis composition.Analysis condition and method are with embodiment 1.
The mass yield that gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter is 30.44%, wherein, formic acid
13.33%, acetic acid 10.05%, ethanedioic acid 0.87%, succinic acid 0.89%, benzene carboxylic acid 5.32% (composition of benzene carboxylic acid and enforcement
The benzene carboxylic acid composition of example 1 is similar).
Embodiment 5
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring.The little dragon's pools of 0.10g is brown
The Fe of coal and 6mL2(SO4)3Mass fraction is 0.30%, H2SO4Mass fraction is that 1.5% aqueous solution is added in reactor,
Air that is reactor is closed, being gone out in reactor with replacement of oxygen, is then charged with the oxygen of 3.0MPa.Reactor is put in advance
In the heating mantle that heats and stirring is opened, timing is started when reaction temperature reaches 200 DEG C, after reacting 60min, by reactor
Take out and be quenched with terminating reaction with cold water.Question response kettle is down to room temperature, and material after reaction is filtered, and obtains residue with filter
Liquid.Filtrate is settled to into 50mL, sampling carries out efficient liquid phase chromatographic analysis composition.Analysis condition and method are with embodiment 1.
The mass yield that gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter is 31.09%, wherein, formic acid
14.25%, acetic acid 9.65%, ethanedioic acid 0.88%, succinic acid 0.90%, benzene carboxylic acid 5.41% (composition of benzene carboxylic acid and enforcement
The benzene carboxylic acid composition of example 1 is similar).
Embodiment 6
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring.The little dragon's pools of 0.10g is brown
The FeSO of coal and 6mL4Mass fraction is 0.05%, H2SO4Mass fraction is that 1.5% aqueous solution is added in reactor, will be anti-
Answer kettle closed, the air gone out in reactor with replacement of oxygen is then charged with the oxygen of 3.0MPa.Reactor is put into into heating in advance
Good heating mantle is interior and opens stirring, and timing is started when reaction temperature reaches 200 DEG C, after reaction 60min, reactor is taken out
And be quenched with terminating reaction with cold water.Question response kettle is down to room temperature, and material after reaction is filtered, and obtains residue and filtrate.
Filtrate is settled to into 50mL, sampling carries out efficient liquid phase chromatographic analysis composition.Analysis condition and method are with embodiment 1.
The mass yield that gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter is 39.0%, wherein, formic acid
20.49%, acetic acid 9.72%, ethanedioic acid 1.05%, succinic acid 1.40%, benzene carboxylic acid 6.34% (composition of benzene carboxylic acid and enforcement
The benzene carboxylic acid composition of example 1 is similar).
Embodiment 7
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring.The little dragon's pools of 0.10g is brown
The FeCl of coal and 6mL2Mass fraction is 0.15%, H2SO4Mass fraction is that 1.5% aqueous solution is added in reactor, will be anti-
Answer kettle closed, the air gone out in reactor with replacement of oxygen is then charged with the oxygen of 3.0MPa.Reactor is put into into heating in advance
Good heating mantle is interior and opens stirring, and timing is started when reaction temperature reaches 200 DEG C, after reaction 60min, reactor is taken out
And be quenched with terminating reaction with cold water.Question response kettle is down to room temperature, and material after reaction is filtered, and obtains residue and filtrate.
Filtrate is settled to into 50mL, sampling carries out efficient liquid phase chromatographic analysis composition.Analysis condition and method are with embodiment 1.
The mass yield that gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter is 46.42%, wherein, formic acid
22.65%, acetic acid 12.25%, ethanedioic acid 1.53%, succinic acid 2.45%, benzene carboxylic acid 7.54% (composition of benzene carboxylic acid and enforcement
The benzene carboxylic acid composition of example 1 is similar).
Embodiment 8
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring.The little dragon's pools of 0.10g is brown
The FeCl of coal and 6mL3Mass fraction is 0.10%, H2SO4Mass fraction is that 1.0% aqueous solution is added in reactor, will be anti-
Answer kettle closed, the air gone out in reactor with replacement of oxygen is then charged with the oxygen of 3.0MPa.Reactor is put into into heating in advance
Good heating mantle is interior and opens stirring, and timing is started when reaction temperature reaches 200 DEG C, after reaction 60min, reactor is taken out
And be quenched with terminating reaction with cold water.Question response kettle is down to room temperature, and material after reaction is filtered, and obtains residue and filtrate.
Filtrate is settled to into 50mL, sampling carries out efficient liquid phase chromatographic analysis composition.Analysis condition and method are with embodiment 1.
The mass yield that gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter is 44.15%, wherein, formic acid
24.39%, acetic acid 9.24%, ethanedioic acid 1.11%, succinic acid 2.88%, benzene carboxylic acid 6.53% (composition of benzene carboxylic acid and enforcement
The benzene carboxylic acid composition of example 1 is similar).
Embodiment 9
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring.The little dragon's pools of 0.10g is brown
The FeCl of coal and 6mL3Mass fraction is 0.10%, H2SO4Mass fraction is that 0.25% aqueous solution is added in reactor, will
Reactor is closed, the air gone out in reactor with replacement of oxygen, is then charged with the oxygen of 3.0MPa.Reactor is put into and is added in advance
The good heating mantle of heat is interior and opens stirring, and timing is started when reaction temperature reaches 200 DEG C, after reaction 60min, reactor is taken
Go out and be quenched with terminating reaction with cold water.Question response kettle is down to room temperature, and material after reaction is filtered, and obtains residue with filter
Liquid.Filtrate is settled to into 50mL, sampling carries out efficient liquid phase chromatographic analysis composition.Analysis condition and method are with embodiment 1.
The mass yield that gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter is 25.8%, wherein, formic acid
14.3%, acetic acid 4.14%, ethanedioic acid 0.85%, succinic acid 1.08%, (the composition and embodiment of benzene carboxylic acid of benzene carboxylic acid 5.43%
1 benzene carboxylic acid composition is similar).
Embodiment 10
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring.The little dragon's pools of 0.10g is brown
The FeCl of coal and 6mL3Mass fraction is 0.10%, H2SO4Mass fraction is that 2.5% aqueous solution is added in reactor, will be anti-
Answer kettle closed, the air gone out in reactor with replacement of oxygen is then charged with the oxygen of 3.0MPa.Reactor is put into into heating in advance
Good heating mantle is interior and opens stirring, and timing is started when reaction temperature reaches 200 DEG C, after reaction 60min, reactor is taken out
And be quenched with terminating reaction with cold water.Question response kettle is down to room temperature, and material after reaction is filtered, and obtains residue and filtrate.
Filtrate is settled to into 50mL, sampling carries out efficient liquid phase chromatographic analysis composition.Analysis condition and method are with embodiment 1.
The mass yield that gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter is 41.1%, wherein, formic acid
24.3%, acetic acid 8.14%, ethanedioic acid 1.05%, succinic acid 1.18%, (the composition and embodiment of benzene carboxylic acid of benzene carboxylic acid 6.43%
1 benzene carboxylic acid composition is similar).
Embodiment 11
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring.The little dragon's pools of 0.10g is brown
The FeCl of coal and 6mL3Mass fraction is 0.10%, H2SO4Mass fraction is that 2.0% aqueous solution is added in reactor, will be anti-
Answer kettle closed, the air gone out in reactor with replacement of oxygen is then charged with the oxygen of 3.0MPa.Reactor is put into into heating in advance
Good heating mantle is interior and opens stirring, and timing is started when reaction temperature reaches 200 DEG C, after reaction 60min, reactor is taken out
And be quenched with terminating reaction with cold water.Question response kettle is down to room temperature, and material after reaction is filtered, and obtains residue and filtrate.
Filtrate is settled to into 50mL, sampling carries out efficient liquid phase chromatographic analysis composition.Analysis condition and method are with embodiment 1.
The mass yield that gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter is 46.1%, wherein, formic acid
26.8%, acetic acid 8.64%, ethanedioic acid 1.55%, succinic acid 1.68%, (the composition and embodiment of benzene carboxylic acid of benzene carboxylic acid 7.43%
1 benzene carboxylic acid composition is similar).
Embodiment 12
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring.The little dragon's pools of 0.10g is brown
The FeCl of coal and 6mL3The aqueous solution that mass fraction is 0.10%, HCl mass fractions are 1.5% is added in reactor, will be anti-
Answer kettle closed, the air gone out in reactor with replacement of oxygen is then charged with the oxygen of 3.0MPa.Reactor is put into into heating in advance
Good heating mantle is interior and opens stirring, and timing is started when reaction temperature reaches 180 DEG C, after reaction 60min, reactor is taken out
And be quenched with terminating reaction with cold water.Question response kettle is down to room temperature, and material after reaction is filtered, and obtains residue and filtrate.
Filtrate is settled to into 50mL, sampling carries out efficient liquid phase chromatographic analysis composition.Analysis condition and method are with embodiment 1.
The mass yield that gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter is 43.2%, wherein, formic acid
26.3%, acetic acid 7.64%, ethanedioic acid 1.15%, succinic acid 1.08%, (the composition and embodiment of benzene carboxylic acid of benzene carboxylic acid 7.03%
1 benzene carboxylic acid composition is similar).
Embodiment 13
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring.The little dragon's pools of 0.10g is brown
The FeCl of coal and 6mL3Mass fraction is 0.10%, H2SO4Mass fraction is that 1.5% aqueous solution is added in reactor, will be anti-
Answer kettle closed, the air gone out in reactor with replacement of oxygen is then charged with the oxygen of 3.0MPa.Reactor is put into into heating in advance
Good heating mantle is interior and opens stirring, and timing is started when reaction temperature reaches 220 DEG C, after reaction 60min, reactor is taken out
And be quenched with terminating reaction with cold water.Question response kettle is down to room temperature, and material after reaction is filtered, and obtains residue and filtrate.
Filtrate is settled to into 50mL, sampling carries out efficient liquid phase chromatographic analysis composition.Analysis condition and method are with embodiment 1.
The mass yield that gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter is 45.55%, wherein, formic acid
28.3%, acetic acid 8.64%, ethanedioic acid 1.03%, succinic acid 1.15%, (the composition and embodiment of benzene carboxylic acid of benzene carboxylic acid 7.43%
1 benzene carboxylic acid composition is similar).
Embodiment 14
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring.The little dragon's pools of 0.10g is brown
The FeCl of coal and 6mL3Mass fraction is 0.10%, H2SO4Mass fraction is that 1.5% aqueous solution is added in reactor, will be anti-
Answer kettle closed, the air gone out in reactor with replacement of oxygen is then charged with the oxygen of 3.0MPa.Reactor is put into into heating in advance
Good heating mantle is interior and opens stirring, and timing is started when reaction temperature reaches 160 DEG C, after reaction 60min, reactor is taken out
And be quenched with terminating reaction with cold water.Question response kettle is down to room temperature, and material after reaction is filtered, and obtains residue and filtrate.
Filtrate is settled to into 50mL, sampling carries out efficient liquid phase chromatographic analysis composition.Analysis condition and method are with embodiment 1.
The mass yield that gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter is 27.93%, wherein, formic acid
16.28%, acetic acid 5.26%, ethanedioic acid 1.52%, succinic acid 0.58%, benzene carboxylic acid 4.29% (composition of benzene carboxylic acid and enforcement
The benzene carboxylic acid composition of example 1 is similar).
Embodiment 15
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring.The little dragon's pools of 0.12g is brown
The FeCl of coal and 6mL3Mass fraction is 0.10%, H2SO4Mass fraction is that 1.5% aqueous solution is added in reactor, will be anti-
Answer kettle closed, the air gone out in reactor with replacement of oxygen is then charged with the oxygen of 3.0MPa.Reactor is put into into heating in advance
Good heating mantle is interior and opens stirring, and timing is started when reaction temperature reaches 200 DEG C, after reaction 60min, reactor is taken out
And be quenched with terminating reaction with cold water.Question response kettle is down to room temperature, and material after reaction is filtered, and obtains residue and filtrate.
Filtrate is settled to into 50mL, sampling carries out efficient liquid phase chromatographic analysis composition.Analysis condition and method are with embodiment 1.
The mass yield that gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter is 42.45%, wherein, formic acid
26.2%, acetic acid 6.26%, ethanedioic acid 1.02%, succinic acid 0.68%, (the composition and embodiment of benzene carboxylic acid of benzene carboxylic acid 8.29%
1 benzene carboxylic acid composition is similar).
Embodiment 16
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring.The little dragon's pools of 0.072g is brown
The FeCl of coal and 6mL3Mass fraction is 0.10%, H2SO4Mass fraction is that 1.5% aqueous solution is added in reactor, will be anti-
Answer kettle closed, the air gone out in reactor with replacement of oxygen is then charged with the oxygen of 3.0MPa.Reactor is put into into heating in advance
Good heating mantle is interior and opens stirring, and timing is started when reaction temperature reaches 200 DEG C, after reaction 60min, reactor is taken out
And be quenched with terminating reaction with cold water.Question response kettle is down to room temperature, and material after reaction is filtered, and obtains residue and filtrate.
Filtrate is settled to into 50mL, sampling carries out efficient liquid phase chromatographic analysis composition.Analysis condition and method are with embodiment 1.
The mass yield that gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter is 40.58%, wherein, formic acid
22.29%, acetic acid 7.26%, ethanedioic acid 1.53%, succinic acid 1.58%, benzene carboxylic acid 7.92% (composition of benzene carboxylic acid and enforcement
The benzene carboxylic acid composition of example 1 is similar).
Embodiment 17
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring.The little dragon's pools of 0.10g is brown
The FeCl of coal and 6mL3Mass fraction is 0.10%, H2SO4Mass fraction is that 1.5% aqueous solution is added in reactor, will be anti-
Answer kettle closed, the air gone out in reactor with replacement of oxygen is then charged with the oxygen of 3.0MPa.Reactor is put into into heating in advance
Good heating mantle is interior and opens stirring, and timing is started when reaction temperature reaches 240 DEG C, after reaction 60min, reactor is taken out
And be quenched with terminating reaction with cold water.Question response kettle is down to room temperature, and material after reaction is filtered, and obtains residue and filtrate.
Filtrate is settled to into 50mL, sampling carries out efficient liquid phase chromatographic analysis composition.Analysis condition and method are with embodiment 1.
The mass yield that gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter is 25.15%, wherein, formic acid
14.28%, acetic acid 5.2%, ethanedioic acid 0.52%, succinic acid 0.88%, (the composition and embodiment of benzene carboxylic acid of benzene carboxylic acid 4.27%
1 benzene carboxylic acid composition is similar).
Embodiment 18
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring.The little dragon's pools of 0.10g is brown
The FeCl of coal and 6mL3Mass fraction is 0.10%, H2SO4Mass fraction is that 1.5% aqueous solution is added in reactor, will be anti-
Answer kettle closed, the air gone out in reactor with replacement of oxygen is then charged with the oxygen of 1.0MPa.Reactor is put into into heating in advance
Good heating mantle is interior and opens stirring, and timing is started when reaction temperature reaches 200 DEG C, after reaction 60min, reactor is taken out
And be quenched with terminating reaction with cold water.Question response kettle is down to room temperature, and material after reaction is filtered, and obtains residue and filtrate.
Filtrate is settled to into 50mL, sampling carries out efficient liquid phase chromatographic analysis composition.Analysis condition and method are with embodiment 1.
The mass yield that gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter is 23.53%, wherein, formic acid
10.31%, acetic acid 4.63%, ethanedioic acid 2.0%, succinic acid 0.94%, (the composition and embodiment of benzene carboxylic acid of benzene carboxylic acid 5.65%
1 benzene carboxylic acid composition is similar).
Embodiment 19
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring.The little dragon's pools of 0.10g is brown
The FeCl of coal and 6mL3Mass fraction is 0.10%, H2SO4Mass fraction is that 1.5% aqueous solution is added in reactor, will be anti-
Answer kettle closed, the air gone out in reactor with replacement of oxygen is then charged with the oxygen of 5.0MPa.Reactor is put into into heating in advance
Good heating mantle is interior and opens stirring, and timing is started when reaction temperature reaches 200 DEG C, after reaction 60min, reactor is taken out
And be quenched with terminating reaction with cold water.Question response kettle is down to room temperature, and material after reaction is filtered, and obtains residue and filtrate.
Filtrate is settled to into 50mL, sampling carries out efficient liquid phase chromatographic analysis composition.Analysis condition and method are with embodiment 1.
The mass yield that gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter is 32.9%, wherein, formic acid
18.3%, acetic acid 6.36%, ethanedioic acid 1.05%, succinic acid 0.63%, (the composition and embodiment of benzene carboxylic acid of benzene carboxylic acid 6.56%
1 benzene carboxylic acid composition is similar).
Embodiment 20
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring.The little dragon's pools of 0.10g is brown
The FeCl of coal and 6mL3Mass fraction is 0.10%, H2SO4Mass fraction is that 1.5% aqueous solution is added in reactor, will be anti-
Answer kettle closed, the air gone out in reactor with replacement of oxygen is then charged with the oxygen of 3.0MPa.Reactor is put into into heating in advance
Good heating mantle is interior and opens stirring, and timing is started when reaction temperature reaches 200 DEG C, after reaction 30min, reactor is taken out
And be quenched with terminating reaction with cold water.Question response kettle is down to room temperature, and material after reaction is filtered, and obtains residue and filtrate.
Filtrate is settled to into 50mL, sampling carries out efficient liquid phase chromatographic analysis composition.Analysis condition and method are with embodiment 1.
The mass yield that gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter is 34.4%, wherein, formic acid
20.35%, acetic acid 5.96%, ethanedioic acid 1.84%, succinic acid 0.74%, benzene carboxylic acid 5.51% (composition of benzene carboxylic acid and enforcement
The benzene carboxylic acid composition of example 1 is similar).
Embodiment 21
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring.The little dragon's pools of 0.10g is brown
The FeCl of coal and 6mL3Mass fraction is 0.10%, H2SO4Mass fraction is that 1.5% aqueous solution is added in reactor, will be anti-
Answer kettle closed, the air gone out in reactor with replacement of oxygen is then charged with the oxygen of 3.0MPa.Reactor is put into into heating in advance
Good heating mantle is interior and opens stirring, and timing is started when reaction temperature reaches 200 DEG C, after reaction 120min, reactor is taken
Go out and be quenched with terminating reaction with cold water.Question response kettle is down to room temperature, and material after reaction is filtered, and obtains residue with filter
Liquid.Filtrate is settled to into 50mL, sampling carries out efficient liquid phase chromatographic analysis composition.Analysis condition and method are with embodiment 1.
The mass yield that gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter is 31.87%, wherein, formic acid
17.98%, acetic acid 5.98%, ethanedioic acid 0.80%, succinic acid 0.81%, benzene carboxylic acid 6.30% (composition of benzene carboxylic acid and enforcement
The benzene carboxylic acid composition of example 1 is similar).
Embodiment 22
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring.The little dragon's pools of 0.10g is brown
The FeCl of coal and 6mL3Mass fraction is 0.10%, H2SO4Mass fraction is that 1.5% aqueous solution is added in reactor, will be anti-
Answer kettle closed, the air gone out in reactor with replacement of oxygen is then charged with the oxygen of 2.0MPa.Reactor is put into into heating in advance
Good heating mantle is interior and opens stirring, and timing is started when reaction temperature reaches 200 DEG C, after reaction 45min, reactor is taken out
And be quenched with terminating reaction with cold water.Question response kettle is down to room temperature, and material after reaction is filtered, and obtains residue and filtrate.
Filtrate is settled to into 50mL, sampling carries out efficient liquid phase chromatographic analysis composition.Analysis condition and method are with embodiment 1.
The mass yield that gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter is 43.8%, wherein, formic acid
26.98%, acetic acid 6.9%, ethanedioic acid 1.30%, succinic acid 1.32%, (the composition and embodiment of benzene carboxylic acid of benzene carboxylic acid 7.30%
1 benzene carboxylic acid composition is similar).
Embodiment 23
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring.The little dragon's pools of 0.10g is brown
The FeCl of coal and 6mL3Mass fraction is 0.10%, H2SO4Mass fraction is that 1.5% aqueous solution is added in reactor, will be anti-
Answer kettle closed, the air gone out in reactor with replacement of oxygen is then charged with the oxygen of 3.5MPa.Reactor is put into into heating in advance
Good heating mantle is interior and opens stirring, and timing is started when reaction temperature reaches 200 DEG C, after reaction 90min, reactor is taken out
And be quenched with terminating reaction with cold water.Question response kettle is down to room temperature, and material after reaction is filtered, and obtains residue and filtrate.
Filtrate is settled to into 50mL, sampling carries out efficient liquid phase chromatographic analysis composition.Analysis condition and method are with embodiment 1.
The mass yield that gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter is 47.7%, wherein, formic acid
28.4%, acetic acid 7.92%, ethanedioic acid 1.58%, succinic acid 1.95%, (the composition and embodiment of benzene carboxylic acid of benzene carboxylic acid 7.85%
1 benzene carboxylic acid composition is similar).
Embodiment 24
The present embodiment is tested for the reuse of catalyst system.Catalyst system is reused 3 times, in product extraction point
The butanone used during is 2 with the volume ratio of aqueous solution.Concrete operations are as follows：
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring, product carboxylic acid extract and separate
Experiment is carried out in separatory funnel.By the little Longtan Brown Coals of 0.10g and the FeCl of 6.0mL3Mass fraction is 0.12%, H2SO4Quality
Fraction is that 1.7% aqueous solution is added in reactor, reactor is closed, the air gone out in reactor with replacement of oxygen, so
The oxygen of 3.0MPa is filled with afterwards.Reactor is put in the heating mantle for heating in advance and is opened stirring, when reaction temperature reaches
Start timing when 200 DEG C, after reaction 60min, reactor is taken out and is quenched with terminating reaction with cold water.Question response kettle is down to room
Temperature, material after reaction is filtered, and obtains residue and filtrate.The filtrate is transferred in separatory funnel, then into funnel
The butanone of 6mL is added, at room temperature fully shaking 15min, then stands 60min, solution is thoroughly layered；By upper organic phase
Remove；Repeat butanone extraction experiments 1 time (total butanone consumption is 2 with the volume ratio of aqueous solution).Finally by lower floor's reaction solution
In being transferred to test tube, using N2Purging, removes the butanone of the residual in solution.Solution after purging is added water and is settled to 6mL use
In catalyst system recycling next time.2 butanone extracts are merged, after sampling, constant volume, using high performance liquid chromatography
Analysis composition analysis, analysis condition and method are with embodiment 1.Above-mentioned catalyst system is carried out into recycling experiment.
The experimental result that the catalyst system reuses three times is as follows：
The mass yield of first time catalyst system circulation gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter
For 50.91%, wherein, formic acid 30.05%, acetic acid 9.47%, ethanedioic acid 2.08%, succinic acid 0.78%, benzene carboxylic acid 8.53%
(composition of benzene carboxylic acid is similar with the benzene carboxylic acid of embodiment 1 composition).
The mass yield of second catalyst system circulation gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter
For 51.11%, wherein, formic acid 30.22%, acetic acid 9.38%, ethanedioic acid 1.89%, succinic acid 1.17%, benzene carboxylic acid 8.45%
(composition of benzene carboxylic acid is similar with the benzene carboxylic acid of embodiment 1 composition).
The mass yield of third time catalyst system circulation gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter
For 50.85%, wherein, formic acid 30.13%, acetic acid 9.11%, ethanedioic acid 1.71%, succinic acid 1.11%, benzene carboxylic acid 8.79%
(composition of benzene carboxylic acid is similar with the benzene carboxylic acid of embodiment 1 composition).
Embodiment 25
The present embodiment is tested for the reuse of catalyst system.Catalyst system is reused 3 times, in product extraction point
The butanone used during is 3 with the volume ratio of aqueous solution.Concrete operations are as follows：
Brown coal oxidation experiment is carried out in the 25mL high-temperature high-pressure reaction kettles with magneton stirring, product carboxylic acid extract and separate
Experiment is carried out in separatory funnel.By the little Longtan Brown Coals of 0.10g and the FeCl of 6.0mL3Mass fraction is 0.10%, H2SO4Quality
Fraction is that 1.5% aqueous solution is added in reactor, reactor is closed, the air gone out in reactor with replacement of oxygen, so
The oxygen of 3.0MPa is filled with afterwards.Reactor is put in the heating mantle for heating in advance and is opened stirring, when reaction temperature reaches
Start timing when 200 DEG C, after reaction 60min, reactor is taken out and is quenched with terminating reaction with cold water.Question response kettle is down to room
Temperature, material after reaction is filtered, and obtains residue and filtrate.The filtrate is transferred in separatory funnel, then into funnel
The butanone of 6mL is added, at room temperature fully shaking 15min, then stands 60min, solution is thoroughly layered；By upper organic phase
Remove；Repeat butanone extraction experiments 2 times (total butanone consumption is 3 with the volume ratio of aqueous solution).Finally by lower floor's reaction solution
In being transferred to test tube, using N2Purging, removes the butanone of the residual in solution.Solution after purging is added water and is settled to 6mL use
In catalyst system recycling next time.3 butanone extracts are merged, after sampling, constant volume, using high performance liquid chromatography
Analysis composition analysis, analysis condition and method are with embodiment 1.Above-mentioned catalyst system is carried out into recycling experiment.
The experimental result that the catalyst system reuses three times is as follows：
The mass yield of first time catalyst system circulation gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter
For 51.85%, wherein, formic acid 30.11%, acetic acid 9.77%, ethanedioic acid 2.16%, succinic acid 0.95%, benzene carboxylic acid 8.86%
(composition of benzene carboxylic acid is similar with the benzene carboxylic acid of embodiment 1 composition).
The mass yield of second catalyst system circulation gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter
For 51.33%, wherein, formic acid 30.24%, acetic acid 9.55%, ethanedioic acid 2.04%, succinic acid 1.05%, benzene carboxylic acid 8.45%
(composition of benzene carboxylic acid is similar with the benzene carboxylic acid of embodiment 1 composition).
The mass yield of third time catalyst system circulation gained carboxylic acid is calculated on the basis of the initial brown coal content of organic matter
For 51.55%, wherein, formic acid 30.3%, acetic acid 9.17%, ethanedioic acid 1.97%, succinic acid 1.17%, benzene carboxylic acid 8.94%
(composition of benzene carboxylic acid is similar with the benzene carboxylic acid of embodiment 1 composition).
Claims (7)
1. a kind of method that oxygen catalytic oxidation brown coal prepare carboxylic acid, what the method included comprises the following steps that：
(1) granularity is less than into the brown coal of 0.1mm and is added in autoclave containing soluble ferric iron salt and inorganic aqueous acid, filled
Enter O2Or with the air of oxygen partial pressure, at a certain temperature stirring reaction certain hour, after reaction terminates, filters to isolate filter
Liquid and residue；
(2) filtrate that step (1) is filtrated to get is transferred in separatory funnel, adds a certain amount of butanone molten in separatory funnel
Agent, at room temperature, extract and separate oxidation product and catalyst system aqueous solution, catalyst system aqueous solution is reused；
Wherein, brown coal and the mass ratio of water are 1.0%～3.0% in step (1)；
Soluble ferric iron salt described in step (1) is FeCl3、FeCl2、Fe2(SO4)3And FeSO4One or more, this can
Dissolubility iron salt mass content in aqueous is 0.03%～0.30%；
Step (1) mineral acid is sulphuric acid or hydrochloric acid, mineral acid mass content in aqueous is 0.25%～
2.5%；
Oxygen first pressing described in step (1) is 1.0MPa～5.0MPa；
Reaction temperature described in step (1) is 160 DEG C～240 DEG C；
Response time described in step (1) is 30min～120min；
The consumption of the extractant butanone described in step (2) is：Butanone is 2 with the volume ratio of aqueous solution:1～3:1.
2. method according to claim 1, it is characterised in that brown coal are 1.2%～2.0% with the mass ratio of water.
3. method according to claim 1, it is characterised in that soluble ferric iron salt mass content in aqueous is
0.05%～0.15%.
4. method according to claim 1, it is characterised in that mineral acid mass content in aqueous is 1.0～
2.0%.
5. method according to claim 1, it is characterised in that reaction temperature is 180 DEG C～220 DEG C.
6. method according to claim 1, it is characterised in that oxygen first pressing is 2.0MPa～3.5MPa.
7. method according to claim 1, it is characterised in that the response time is 45min～90min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107513013A (en) * | 2017-09-14 | 2017-12-26 | 北京化工大学 | A kind of method that lignite oxidation for suppressing carbon dioxide generation prepares chemicals |
| CN113801007A (en) * | 2021-09-28 | 2021-12-17 | 太原师范学院 | Method for preparing benzene carboxylic acid and micromolecular fatty acid by mild catalytic oxidation of lignite |
| CN113801008A (en) * | 2021-09-28 | 2021-12-17 | 太原师范学院 | Method for preparing benzene carboxylic acid and micromolecular fatty acid by synergistically catalyzing and oxidizing lignite |
| CN114644553A (en) * | 2022-03-24 | 2022-06-21 | 西咸新区青氢华屹能源科技有限公司 | Method for preparing formic acid by photo-induced iron catalysis of biomass |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224537A (en) * | 2013-04-17 | 2013-07-31 | 河南理工大学 | Method for degrading coal by using Fenton reaction |
| CN103319324A (en) * | 2012-03-20 | 2013-09-25 | 北京化工大学 | Method for preparing benzene carboxylic acids by alkali-oxygen oxidation of brown coals |
-
2016
- 2016-10-08 CN CN201610877972.8A patent/CN106631758B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319324A (en) * | 2012-03-20 | 2013-09-25 | 北京化工大学 | Method for preparing benzene carboxylic acids by alkali-oxygen oxidation of brown coals |
| CN103224537A (en) * | 2013-04-17 | 2013-07-31 | 河南理工大学 | Method for degrading coal by using Fenton reaction |
Non-Patent Citations (1)
| Title |
|---|
| FAN YANG ET AL.,: "Production of Benzene Poly(carboxylic acid)s and Small-Molecule Fatty Acids from Lignite by Catalytic Oxidation in NaVO3/H2SO4 Aqeous Solution with Molecular Oxygen", 《IND.ENG.CHEM.RES.》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107513013A (en) * | 2017-09-14 | 2017-12-26 | 北京化工大学 | A kind of method that lignite oxidation for suppressing carbon dioxide generation prepares chemicals |
| CN113801007A (en) * | 2021-09-28 | 2021-12-17 | 太原师范学院 | Method for preparing benzene carboxylic acid and micromolecular fatty acid by mild catalytic oxidation of lignite |
| CN113801008A (en) * | 2021-09-28 | 2021-12-17 | 太原师范学院 | Method for preparing benzene carboxylic acid and micromolecular fatty acid by synergistically catalyzing and oxidizing lignite |
| CN114644553A (en) * | 2022-03-24 | 2022-06-21 | 西咸新区青氢华屹能源科技有限公司 | Method for preparing formic acid by photo-induced iron catalysis of biomass |
| CN114644553B (en) * | 2022-03-24 | 2023-08-22 | 西咸新区青氢华屹能源科技有限公司 | Method for preparing formic acid by catalyzing biomass through light-induced iron |
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