CN108640827A - A method of the catalysis oxidation of aldehydes methacrylic acid processed of metering system - Google Patents
A method of the catalysis oxidation of aldehydes methacrylic acid processed of metering system Download PDFInfo
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- CN108640827A CN108640827A CN201810429288.2A CN201810429288A CN108640827A CN 108640827 A CN108640827 A CN 108640827A CN 201810429288 A CN201810429288 A CN 201810429288A CN 108640827 A CN108640827 A CN 108640827A
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- catalyst
- methacrylic acid
- methacrolein
- carbons
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- 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
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
Abstract
The present invention relates to a kind of new methods being catalyzed the oxidation of aldehydes methacrylic acid processed of metering system using gas-solid reaction.It is characterized in that this method used catalyst is C catalyst, including activated carbon, graphite, carbon nanotube, graphene oxide, redox graphene, graphene and nanometer diamond, processing can be washed by pickling or solvent or doping nitrogen, sulphur, phosphorus, boron, oxygen, molybdenum, cobalt, copper, iron, Zn-ef ficiency are modified C catalyst.When air is oxidant, the conversion ratio of methacrolein is up to 68% or more, and the selectivity of methacrylic acid is up to 92% or more.
Description
Technical field
The present invention relates to a kind of new methods of the catalysis oxidation of aldehydes methacrylic acid processed of metering system, belong to catalysis chemical industry neck
Domain.
Background technology
Methacrylic acid is a kind of important chemical intermediate, can be used for preparing important high molecular material monomer methyl
Methyl acrylate, it can also be used to prepare functional plastics, medical material, thermohardening lacquer and synthetic rubber etc..Its main producer
Method has Acetone cyanohydrin method and methacrolein oxidizing process.Since Acetone cyanohydrin method needs the sulphur of the hydrogen cyanide and strong corrosive of severe toxicity
Acid, and the solid waste such as ammonium sulfate are will produce, therefore do not met the requirement of current green chemical industry.Methacrolein oxidizing process
It is a kind of green, low, free of contamination process of energy consumption.Its used catalyst is mainly the heteropoly acid based on molybdovanaphosphoric acid
Class catalyst.It is basic element that US4803302A, which reports one kind with P, Mo, V, Cu, and the heteropoly acid for adding some other auxiliary agent is urged
Agent, the conversion ratio for obtaining methacrolein are 80% ~ 97%, and the selectivity of methacrylic acid is 80 ~ 87%.It crosses side and opens up Lang Deng
It is reported in CN200980110743.1 and organic polymer binder is added in such catalyst to help shaping of catalyst
The conversion ratio of technology, methacrolein is more than 86%, and the selectivity of methacrylic acid is more than 89%.Methacrolein is urged in heteropoly acid
High conversion rate in agent, Methacrylic acid selectivity are slightly lower.The synthesis technology of heteropolyacid catalyst is complicated, needs to use a variety of heavy
Metal, it is big to environmental pressure, and heteropolyacid catalyst is with high costs, and the service life is shorter, catalyst inactivation the reason of be heteropoly acid
Structure is thermally decomposed, it is difficult to regenerate.Therefore need to develop a kind of environmentally protective low-cost catalyst oxidation methyl third
Olefine aldehydr aoxidizes methacrylic acid processed.
Carbon materials, such as activated carbon can be used to catalytic halogenation, oxidation, oxidative dehydrogenation reaction.Activated carbon is industrially normal
It is used for purifying sewage and exhaust gas for making adsorbent, it is also possible to detach and store gas, and being capable of catalysed curing hydrogen, an oxygen
Change the oxidation of nitrogen, it can also be used to the preparation of phosgene.Carbon nanotube, nanometer diamond etc. were for being catalyzed alkanes oxidative dehydrogenation system in recent years
The reactions such as alkene, prepared by acrolein oxidation acrylic acid, show certain catalytic activity, but conversion ratio is relatively low.Carbon material is catalyzed
The oxidation of aldehydes methacrylic acid processed of metering system has not been reported.If heteropoly acid catalysis methyl can be replaced with cheap C catalyst
Prepared by acrolein oxidation methacrylic acid will undoubtedly substantially reduce the cost and energy consumption of the technique, be allowed to more meet green chemical industry
It is required that.
Invention content
The present invention relates to a kind of method of C catalyst catalysis oxidation methacrolein methacrylic acid, catalysis used
Agent is carbons catalyst.In the method, methacrolein, air, nitrogen and water in the form of certain proportion mixed gas
Methacrylic acid is generated by the reactor equipped with carbons catalyst under certain reaction temperature and flow velocity.
Carbons catalyst include activated carbon, graphite, carbon nanotube, graphene, graphene oxide, redox graphene,
Nanometer diamond.
The dosage of carbons catalyst accounts for the 1% ~ 60% of reactor volume, can be loaded into instead by the form of powder or particle
Answer in device, catalyst loading in the reactor need according to the feed rate of reaction gas and the Temperature Distribution of reactor come
It determines.
The reactor that can be used for this method has fixed bed reactors, fluidized-bed reactor and paste state bed reactor, preferably solid
Fixed bed reactor.Catalyst shape in different reactor is different, such as column, annulus, spherical shape can be used in fixed bed reactors
The preformed catalyst of larger particles is waited, the catalyst in fluidized-bed reactor is generally smaller particle, the catalysis in slurry bed system
Dosage form state is generally tiny powder.
To these carbons catalyst（Activated carbon, graphite, carbon nanotube, graphene oxide, graphene and nanometer diamond）'s
Processing method includes carrying out pickling with nitric acid, sulfuric acid, hydrochloric acid or phosphoric acid, and the aqueous solution to washing is then washed with deionized
For neutrality, then dry；Or with 0 ~ 150oWater, ethyl alcohol, ethyl acetate, acetone, petroleum ether or the ether of C is washed, then
It is dried, preferably detergent is water.The carbons catalyst carried out after pickling and washing can be 100 ~ 1200oC is roasted, and also may not be used
It is roasted.
Carbons catalyst in the process may include a kind of in nitrogenous, sulphur, phosphorus, boron, oxygen, molybdenum, cobalt, copper, iron and zinc
Or the carbons catalyst of several elements, preferred elements are nitrogen, sulphur, phosphorus, boron, oxygen；The doping content of these elements is 0 ~ 30%, excellent
It is selected as 0.5% ~ 5%.Above-mentioned doped chemical can be made by the method for loading and adulterating in situ, and the element of doping is in carbons catalyst
In can exist in the form of oxide, carbon skeleton hetero atom, carbide.
Volume content of the methacrolein in the mixed gas of methacrolein, empty gas and water and nitrogen is 3% ~ 15%, excellent
It is selected as 3% ~ 10%；Volume content of the air in above-mentioned mixed gas is 50% ~ 80%, preferably 65% ~ 75%；Water is in above-mentioned mixing
Volume content in gas is 1% ~ 10%, preferably 2% ~ 5%；Nitrogen is balanced gas.
Reaction temperature is 200oC~400oC, preferable temperature 250 oC ~350 oC。
The time of contact of gas flow rate methacrolein and catalyst indicates, is 0.5 second ~ 5 minutes, first in preferable flow rate
The time of contact of base acrylic acid and catalyst is 1 second ~ 5 seconds.
Compared with heteropolyacid catalyst, the reaction temperature of carbon material catalysis oxidation methacrolein methacrylic acid can be low
20oC or more is of great significance to energy-saving and emission-reduction.Carbon material is at low cost, and by taking activated carbon as an example, cost is only heteropllyacids
The 1% of catalyst, it is even lower, production cost can be significantly reduced.The activity of C catalyst in the reaction is apparently higher than heteropoly acid
Catalyst, and carbon material catalysis prepares the selectivity of methacrylic acid 90% or more, even up to 99%, enormously simplifies
The separating-purifying process of methacrylic acid and other by-products.C catalyst stable structure, long lifespan will not be because of carbon distribution or decomposition
And it inactivates.
The present invention is illustrated with embodiment below, but the scope of the present invention should not be limited by the examples.
The conversion ratio computational methods of methacrolein are as follows：
C（Methacrylic acid）%=（The substance of unreacted methacrylic acid in amount-product of methacrylic acid feed material
Amount）The amount * 100% of/methacrylic acid feed material.
The selectivity of methacrylic acid calculates as follows：
S（Methacrylic acid）The amount * of the substance of the amount of the substance of methacrylic acid/conversion methacrylic acid in %=product
100%.
Description of the drawings
Fig. 1 illustrates C catalyst catalysis oxidation methacrolein methacrylic acid by taking fixed bed as an example.
MAL conversion ratios, that is, MAA selectivity in Fig. 2 embodiments.
Specific implementation mode
Embodiment 1
Dry 2 millimeters of 100 milliliters of diameters after washing, high 4 millimeters of column activated carbon are packed into a diameter of 25 millimeters,
In the fixed bed reactors that length is 2000 millimeters.Other spaces are loaded by inert alumina porcelain ball in reactor.Metering system
The feed rate of aldehyde is 0.2mol/h, and air feeding rate 60L/h, water feed rate is 0.15mol/h, nitrogen feed rate
For 36L/h.Reaction pressure is 1 atmospheric pressure.Reaction temperature is set to 250 oC、270 oC、290 oC、310 oCWith 330 oC.Instead
Start sampling analysis after should carrying out 6h, liquid-like is detected with gas-chromatography fid detector, and gas sample is detected with gas-chromatography TCD
Device detects.250oWhen C, the conversion ratio of methacrolein is 30%, and the selectivity of methacrylic acid is 40%；270oWhen C, methyl-prop
The conversion ratio of olefine aldehydr is 30%, and the selectivity of methacrylic acid is 48%；290oWhen C, the conversion ratio of methacrolein is 36%, first
The selectivity of base acrylic acid is 52%；310oWhen C, the conversion ratio of methacrolein is 38%, and the selectivity of methacrylic acid is
44%；330oWhen C, the conversion ratio of methacrolein is 40%, and the selectivity of methacrylic acid is 35%；270oWhen C, methacrolein
Conversion ratio be 42%, the selectivity of methacrylic acid is 18%；290 oCAfter continuous operation 500h, the conversion of methacrolein
Rate is still maintained at 25% or more, and the selectivity of methacrylic acid is 50% or more.By-product is mainly carbon monoxide and titanium dioxide
Carbon.
Embodiment 2
Activated carbon 200g is taken, the solution of 1.2 times of the Viability charcoal volume of 85% phosphorylated ligands of 14.8g is taken, activated carbon is put into and is prepared
In phosphoric acid solution, room temperature is vigorously stirred 2 hours, after phosphoric acid solution is tightly held by activated carbon completely, 100oC is dried 24 hours.It will
Activated carbon after drying is 350 oCThe C catalyst that phosphorus load capacity is 2% is made in roasting 12 hours.
Evaluating catalyst reactor, loadings and reactant feed rate such as embodiment 1, loading catalyst are 2% phosphorus of doping
Activated carbon, evaluation temperature 290oC and 310oC。290oWhen C, the conversion ratio of methacrolein is 32%, methacrylic acid
Selectivity is 85%；310oWhen C, the conversion ratio of methacrolein is 30%, and the selectivity of methacrylic acid is 99%.310 oCEven
After reforwarding row 200h, the conversion ratio of methacrolein is still maintained at 25% or more, and the selectivity of methacrylic acid is 90% or more.
Embodiment 3
Activated carbon 200g is taken, takes boric acid 11g to be made into the solution of 1.5 times of activated carbon volume, it is molten that activated carbon is put into the boric acid prepared
In liquid, room temperature is vigorously stirred 2 hours, after phosphate aqueous solution is tightly held by activated carbon completely, 100oC is dried 24 hours.It will dry
Activated carbon afterwards is 350 oCThe C catalyst that boron load capacity is 1% is made in roasting 12 hours.
Evaluating catalyst reactor, loadings and reactant feed rate such as embodiment 1, loading catalyst are 1% boron of doping
Activated carbon, evaluation temperature 310oC.The conversion ratio of methacrolein is 18%, and the selectivity of methacrylic acid is 93%.
Embodiment 4
Dry 5 milliliters of carbon nanotubes after nitric acid treatment are packed into a diameter of 8 millimeters, the fixed bed that length is 400 millimeters
In reactor.Other spaces are loaded with quartz sand in reactor.The feed rate of methacrolein be 0.002mol/h, air into
Material rate is 0.6L/h, and water feed rate is 0.0015mol/h, and nitrogen feed rate is 0.36L/h.Reaction pressure is 1 big
Air pressure.Reaction temperature is set as 290 oC.The conversion ratio of methacrolein is 18%, and the selectivity of methacrylic acid is 35%.
Embodiment 5
The preparation method of carbon nano-tube such as embodiment 2 for adulterating 1.5%P, using it as catalyst oxidation methyl methacrylaldehyde.Catalysis
Agent evaluation method such as embodiment 4.290 oC, the conversion ratio of methacrolein is 13%, and the selectivity of methacrylic acid is 95%.When
Air feeding rate is 1L/h, other reactant feed rates and reaction temperature are constant, and the conversion ratio of methacrolein is 27%,
The conversion ratio of methacrylic acid is 86%.
Embodiment 6
The mixture that graphite oxide and graphene oxide are obtained using graphite oxide legal system, it is catalyst, evaluation to take the 5mL mixtures
Method such as embodiment 4,310 oC, the conversion ratio of methacrolein is 36%, and the selectivity of methacrylic acid is 29%.When aldehyde into
Material rate increases to 0.003mol/h, other feed rates and reaction temperature are constant, and the conversion ratio of methacrolein is 15%, first
The selectivity of base acrylic acid is 35%.
Embodiment 7
The mixture 2g of graphite oxide and graphene oxide is taken, is added in 20 milliliters of solution being made by 0.15g85% phosphoric acid,
Then the solution of the 0.04g containing copper nitrate, stirring at normal temperature 2 hours, then 90 are instilled oCStirring is evaporated.100 oCLower drying 12
Hour.By the solid after drying 350 oCThe C catalyst of phosphorus and Copper-cladding Aluminum Bar is made in roasting 12 hours.
Take the 5mL catalyst, evaluation method such as embodiment 4,270 oC, the conversion ratio of methacrolein is 83%, methyl-prop
The selectivity of olefin(e) acid is 56%.
Embodiment 8
By nanometer diamond 900 oC, roast 6 hours in inert atmosphere.With 100 after cooling oCHot nitric acid treatment 6 hours, spend from
Sub- water is cleaned, and then 100 oCIt is 12 hours dry.
Treated nanometer diamond catalytic performance test method such as embodiment 4, evaluation temperature 290 oC.Methacrolein
Conversion ratio be 27%, the selectivity of methacrylic acid is 43%.
Embodiment 9
Activated carbon is added in 36% concentrated nitric acid, is stirred 24 hours at normal temperatures, is then washed with deionized water only, 100 oCIt is dry
12 hours.Phosphoric acid containing 7.4g, 11.2g sulfuric acid, 3.5g copper nitrates, 5.3g ferric nitrates 1.5 is added in 200g treated activated carbons
In the solution of times volume, it is vigorously stirred 12h, then 100 oCLower drying 24 hours.By the solid after drying 350 oCRoasting
It burns 12 hours, the C catalyst adulterated by phosphorus, sulphur, copper and ferro element is made.
To the evaluation method such as embodiment 1,270 of the catalyst oC, the conversion ratio of methacrolein is 68%, metering system
The selectivity of acid is 92%；290 oC, the conversion ratio of methacrolein is 86%, and the selectivity of methacrylic acid is 87%.310 oC,
The conversion ratio of methacrolein is 93%, and the selectivity of methacrylic acid is 75%.270 oCAfter continuous operation 200h, methyl-prop
The conversion ratio of olefine aldehydr is still maintained at 60% or more, and the selectivity of methacrylic acid is 85% or more.
Comparative example 1
By 5 milliliters of molybdovanaphosphoric acids（H4PMo11VO40, 5.6g）The particle of 20 ~ 40 mesh is made, 350oIt is flowed in air atmosphere under C
Roasting 12 hours.By the catalyst after roasting be fitted into a diameter of 8 millimeters, length be in 400 millimeters of fixed bed reactors.Reaction
Other spaces are loaded with quartz sand in device.The feed rate of methacrolein is 0.002mol/h, air feeding rate 0.6L/
H, water feed rate are 0.0015mol/h, and nitrogen feed rate is 0.36L/h.Reaction pressure is 1 atmospheric pressure.Reaction temperature
It is set to 270 oC、290 oC、310 oC、330 oCWith 350 oC。270 oC, the conversion ratio of methacrolein is 11%, metering system
The selectivity of acid is 98%；290 oC, the conversion ratio of methacrolein is 16%, and the selectivity of methacrylic acid is 91%；310 oC,
The conversion ratio of base methacrylaldehyde is 27%, and the selectivity of methacrylic acid is 90%；330 oC, the conversion ratio of methacrolein is 40%,
The selectivity of methacrylic acid is 84%；350 oC, the conversion ratio of methacrolein is 43%, and the selectivity of methacrylic acid is
27%。
Comparative example 2
It takes 5g activated carbons to be added in the aqueous solution of 20 milliliters of molybdovanaphosphoric acids containing 5g, is vigorously stirred 2 hours, 90 oCStirring is evaporated, so
Afterwards 100 oCLower drying 12 hours.By the solid after drying 350 oCRoasting 12 hours, molybdovanaphosphoric acid load capacity, which is made, is
50% activated carbon supported catalyst.
The evaluation method of the catalyst such as comparative example 1, evaluation temperature 290 oC、310 oC、330 oCWith 350 oC。
290 oC, the conversion ratio of methacrolein is 24%, and the selectivity of methacrylic acid is 94%；310 oC, the conversion ratio of base methacrylaldehyde
It is 51%, the selectivity of methacrylic acid is 68%；330 oC, the conversion ratio of methacrolein is 79%, the selection of methacrylic acid
Property is 24%；350 oC, the conversion ratio of methacrolein is 80%, and the selectivity of methacrylic acid is 23%.
Claims (9)
1. a kind of method by the oxidation of aldehydes methacrylic acid processed of metering system, it is characterised in that used catalyst is catalyzed for carbons
Agent, methacrolein, air（Or oxygen）, nitrogen and water in the form of certain proportion mixed gas in certain reaction temperature and stream
Methacrylic acid is generated by the reactor equipped with carbons catalyst under speed.
2. according to the method described in claim 1, it is characterized in that carbons catalyst includes activated carbon, graphite, carbon nanotube, stone
Black alkene, graphene oxide, redox graphene, nanometer diamond.
3. according to the method described in claim 2, it is characterized in that the processing method of the carbons catalyst includes with nitric acid, sulphur
Acid, hydrochloric acid or phosphoric acid carry out pickling, and it is neutrality that the aqueous solution to washing, which is then washed with deionized, is then dried；Or with 0
~150oWater, ethyl alcohol, ethyl acetate, acetone, petroleum ether or the ether of C is washed, and is then dried, after carrying out pickling and washing
Carbons catalyst can be 100 ~ 1200oC is roasted, also can be without roasting.
4. according to the method described in claim 2, it is characterized in that the carbons catalyst include nitrogenous, sulphur, phosphorus, boron, oxygen,
The doping content of the carbons catalyst of one or more of molybdenum, cobalt, copper, iron and zinc element, these elements is 0 ~ 30%.
5. method according to claim 1, it is characterised in that the dosage of carbons catalyst accounts for the 1% ~ 60% of reactor volume.
6. method according to claim 1, it is characterised in that the reactor that can be used for this method has fixed bed reactors, fluidisation
Bed reactor and paste state bed reactor.
7. method according to claim 1, it is characterised in that methacrolein is in methacrolein, empty gas and water and nitrogen
Volume content in mixed gas is 3% ~ 15%, and volume content of the air in above-mentioned mixed gas is 50% ~ 80%, and water is above-mentioned
Volume content in mixed gas is 1% ~ 10%, and nitrogen is balanced gas.
8. method according to claim 1, it is characterised in that reaction temperature 200oC~400oC。
9. method according to claim 1, it is characterised in that the time of contact of gas flow rate methacrolein and catalyst
It indicates, is 0.5 second ~ 5 minutes.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110655079A (en) * | 2019-09-24 | 2020-01-07 | 万华化学（宁波）有限公司 | Method for preparing phosgene |
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| CN104001543A (en) * | 2014-06-09 | 2014-08-27 | 中国科学院过程工程研究所 | Catalyst for preparing methacrylic acid by oxidation of methylacrolein and preparation method of catalyst |
| CN104001542A (en) * | 2014-06-09 | 2014-08-27 | 中国科学院过程工程研究所 | Preparation method of catalyst for preparing methacrylic acid through oxidation of methylacrolein |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110655079A (en) * | 2019-09-24 | 2020-01-07 | 万华化学（宁波）有限公司 | Method for preparing phosgene |
| CN110655079B (en) * | 2019-09-24 | 2023-03-03 | 万华化学（宁波）有限公司 | Method for preparing phosgene |
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Application publication date: 20181012 |