CN108997108A - A kind of glyceric acid prepares acrylic acid - Google Patents
A kind of glyceric acid prepares acrylic acid Download PDFInfo
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- CN108997108A CN108997108A CN201810868004.XA CN201810868004A CN108997108A CN 108997108 A CN108997108 A CN 108997108A CN 201810868004 A CN201810868004 A CN 201810868004A CN 108997108 A CN108997108 A CN 108997108A
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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
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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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
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
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Abstract
The present invention relates to one kind to prepare acrylic acid from glyceric acid, first under mild reaction conditions, in water, generates 3- iodopropionic acid with hydroiodic acid and glyceric acid；Then, 3- iodopropionic acid is extracted with organic solvent；Finally, elimination reaction is occurred and is generated acrylic acid with basic catalyst or Lewis acid catalyst catalysis 3- iodopropionic acid.Reactant used in the present invention is cheap and easy to get, source green；Reaction time is short, energy-efficient；Amount of by-products is seldom, and first step product 3- iodopropionic acid yield can reach 99%, and second step product propylene acid yield can reach 99%.The method of the method extraction separates first step product, and is directly used in second step two-phase system elimination reaction.The method selectivity of product is high, and post-processing is simple, is easy to industrialize；Reaction system is simple, and cost is relatively low, has highly important application value.
Description
Technical field
The invention belongs to the field of chemical synthesis, are related to method for producing acrylic acid.
Background technique
Glyceric acid can be transformed by glycerol.Glycerol is the by-product for producing biogasoline, cheap and easy to get.Therefore sweet
Oleate conversion is that the product of higher value has great importance.
Acrylic acid is important organic synthesis raw material and synthetic resin monomer, is the very fast vinyl list of polymerization speed
Body.It is most of to manufacture the esters of acrylic acid such as methyl acrylate, ethyl ester, butyl ester, hydroxyl ethyl ester.Acrylic acid and acrylate can be with
Homopolymerization and copolymerization can also be copolymerized with monomers such as acrylonitrile, styrene, butadiene, vinyl chloride and cis-butenedioic anhydrides.These polymer are used for
Synthetic resin, adhesive, synthetic rubber, synthetic fibers, super absorbent resin etc..The approach of manufacture acrylic acid and acrylate has
Many kinds, the preparation method in traditional industry has cyanoethanol method, high pressure Reppe method, improvement Reppe method, ethylene process, acrylonitrile hydrolysis method
Deng.But these methods are since material toxicity is big, the not high factor of severe reaction conditions, yield causes it gradually by new life
Production method substitution.Propylene one-step oxidation process and two-step anodization since the 1970s (such as US 4857360, EP 239070,
CN 103736498) acrylic acid gradually has been prepared as mainstream instead of traditional production method.Propane due to
Rich reserves, cheap, it is also a kind of emerging method (such as CN 103721727, US that direct oxidation, which prepares acrylic acid,
20140243554, BR 112014028516), but since selectivity and yield be not high and propane prices are with fossil fuel
Price rises steadily, and industrialized process is very slow.Glycerol is the by-product for producing biodiesel, from sustainability
Raw material, preparing acrylic acid by glycerol is also a kind of economically viable mode (such as CN 102249890, BR 112012014145, CN
102639478).Alessandro Chieregato etc. reports a series of catalyst of uses based on W-V, in 260-330
Under the conditions of DEG C, from glycerol chemistry catalytic cracking for acrylic acid, acrylic acid yield is up to 51% (Catalysis
Today, 2012,58-65；Applied Catalysis B:Environmental, 2014,37-46；ChemSusChem,
2015,398-406).2012, Ayut Witsuthammakul etc. was reported using V-Mo-O catalyst, in 300 DEG C of temperature
Under degree, acrylic acid yield highest can obtain about 40% (Applied Catalysis A:General, 2012,109-116).2014
Year, Kaori Omata etc. is reported using H3PO4/ W-V-Nb-O catalyst, 285 DEG C at a temperature of, acrylic acid yield highest
59.2% can be obtained (The Chemical Society of Japan, 2014,435-437).2016, Xiukai Li was reported
It uses Cs (VO)0.2PMo and Cs(VO)0.2PW catalyst, 340 DEG C at a temperature of, acrylic acid yield highest can obtain 60%
(ACS Catalysis, 2016,2785-2791)；In the same year, Xiukai Li is reported using Mo-V-W-O catalyst, with two steps
Method 240 DEG C and 340 DEG C at a temperature of, obtained 90% acrylic acid yield (ACS Catalysis, 2016,143-
150).Currently, not being converted into glyceric acid first from glycerol, the report of acrylic acid is further prepared.
Summary of the invention
The purpose of the present invention is to propose to a kind of glyceric acid to prepare acrylic acid, improve acrylic acid yield.
To achieve the above object, the technical solution adopted by the present invention is that:
(1) by glyceric acid and hydroiodic acid by glyceric acid: hydroiodic acid=0.001~1 molar ratio is added to high-temperature high-voltage reaction
In kettle, catalyst is not added or a certain amount of metallic catalyst is added, seal reaction kettle, reaction atmosphere is hydrogen or indifferent gas
Body is warming up to 40~200 DEG C under stirring, the reaction time is 0.5~40h, is cooled to room temperature after reaction, is extracted with organic solvent, point
From obtaining 3- iodopropionic acid.
(2) heavy-walled glass pipe is added in the organic phase and water collected step (1), by 3- iodopropionic acid: catalyst=1~1000
Basic catalyst or Lewis acid catalyst is added in molar ratio, 20~150 DEG C is risen under stirring, the reaction time is 0.5~40h, instead
Ying Hou is chilled to room temperature, collects aqueous phase reactions liquid, and separation acidification obtains acrylic acid.
Hydriodic acid concentration described in step (1) is 1%~57%.
Metallic catalyst described in step (1) can be supported on active carbon, zirconium dioxide, titanium dioxide, silica or
The precious metal catalysts such as rhodium (Rh), platinum (Pt), palladium (Pd), ruthenium (Ru) or the iridium (Ir) of the different loads amount on the carriers such as molecular sieve
Agent；Or precious metal salts or the complex such as soluble rhodium (Rh), platinum (Pt), palladium (Pd), ruthenium (Ru) or iridium (Ir).
Basic catalyst described in step (2) is that can ionize out homogeneous and multiphase alkaline matter hydroxy in water, such as
Sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide, organic amine, magnesium hydroxide, magnalium hydrotalcite, alkaline molecular sieve, calcium oxide,
Magnesia and aluminium oxide etc.；Lewis acid catalyst mainly has aluminium chloride, zinc chloride, iron chloride, stannic chloride, aluminum sulfate, barium sulfate
With molecular sieve etc..
Further, 3- iodopropionic acid and catalyst molar ratio preferably 2~60 described in step (2), it is anti-described in step (2)
Preferably 40~80 DEG C of temperature are answered, the reaction time described in step (2) is 0.01~40h, preferably 1~10h.
It is as follows that glyceric acid of the present invention prepares acrylic acid reaction equation:
Compared with prior art, the beneficial effects of the present invention are:
Acrylic acid efficiently very is prepared using biomass-based glyceric acid as raw material the present invention provides a kind of.This method
Reaction raw materials are that green is reproducible；Amount of by-products is seldom, and step (1) product 3- iodopropionic acid yield can reach 99.9%, step
(2) product propylene acid yield can reach 99.9%.The method of the method extraction separates first step product, and is directly used in second
Walk two-phase system hydrolysis.The method selectivity of product is high, and post-processing is simple, is easy to industrialize；Reaction system is simple, cost
It is lower, there is highly important application value.
Detailed description of the invention
Fig. 1: reaction front and back reaction solution1H NMR spectra；
Wherein: GA is glyceric acid, and 3-IPA is 3- iodopropionic acid.
Specific embodiment
The present invention will be described below by way of specific embodiments, but the present invention is not limited thereto.
Experimental method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
Embodiment 1
0.75mmol glyceric acid, 100 μm of ol PdCl are sequentially added in 50mL high-temperature high-pressure reaction kettle2、10ml
57wt% hydroiodic acid seals reaction kettle, is filled with hydrogen (3000psi), stirs and quickly heats up to 170 DEG C, holding 25h.It will be anti-
It answers kettle ice-water bath to be cooled to room temperature, collect water phase and detects, glyceric acid conversion ratio 100%, 3- iodopropionic acid yield 99.9% is (about
0.75mmol).5ml aqueous phase reactions object is taken, 10ml n-hexyl alcohol is added and extracts 3- iodopropionic acid, extraction three times, and merges extractant.It takes
10ml extract liquor (the about 0.125mmol of iodopropionic acid containing 3-) and 10ml water are added in 50mL heavy-walled glass pipe, and sodium hydroxide is added
0.083g seals reaction kettle, stirs and quickly heats up to 80 DEG C, holding 10h.Reaction kettle ice-water bath is cooled to room temperature, collect,
Acidification water phase simultaneously detects, acrylic acid yield 99.9% (about 0.125mmol).
Glyceric acid conversion ratio, the detection of 3- iodopropionic acid yield and acrylic acid yield and calculation basis following methods carry out.
The detecting instrument of glyceric acid, 3- iodopropionic acid and acrylic acid concentration is 1200 series of high efficiency liquid chromatogram (RID of Agilent
Detector, Alltech OA-1000Organic Acids liquid-phase chromatographic column (300mm × 6.5mm), mobile phase are 0.005M sulphur
Aqueous acid, flow velocity 0.6ml/min, 60 DEG C of column temperature.
The conversion ratio of glyceric acid calculates:
Conversion ratio=1- (glyceric acid residue mole/investment glyceric acid mole) × 100% of glyceric acid
The calculation of yield of 3- iodopropionic acid:
The yield of 3- iodopropionic acid=(3- iodopropionic acid mole/investment glyceric acid mole) × 100%
The calculation of yield of acrylic acid:
The yield of acrylic acid=(acrylic acid mole/investment 3- iodopropionic acid mole) × 100%.
Embodiment 2
0.4mmol glyceric acid, 100 μm of ol PdCl are sequentially added in 50mL high-temperature high-pressure reaction kettle2, 10ml 1wt%
Hydroiodic acid seals reaction kettle, is filled with hydrogen (14.5psi), stirs and quickly heats up to 30 DEG C, holding 0.5h.By reaction kettle ice
Water-bath cooling is collected water phase and is detected, glyceric acid conversion ratio 11.6%, 3- iodopropionic acid yield 11.2% is (about to room temperature
0.045mmol).5ml aqueous phase reactions object is taken, 10ml n-hexyl alcohol is added and extracts 3- iodopropionic acid, extraction three times, and merges extractant.
It takes 10ml extract liquor (the about 0.0075mmol of iodopropionic acid containing 3-) and 10ml water to be added in 50mL heavy-walled glass pipe, and hydroxide is added
Sodium 0.15g seals reaction kettle, stirs and quickly heats up to 40 DEG C, holding 1h.Reaction kettle ice-water bath is cooled to room temperature, collect,
Acidification water phase simultaneously detects, acrylic acid yield 66.5% (about 0.005mmol).
Embodiment 3
3mmol glyceric acid, 100 μm of ol PdCl are sequentially added in 50mL high-temperature high-pressure reaction kettle2, 10ml30wt% hydrogen
Acid iodide seals reaction kettle, is filled with hydrogen (1500psi), stirs and quickly heats up to 60 DEG C, holding 10h.By reaction kettle ice-water bath
It is cooled to room temperature, collects water phase and detects, glyceric acid conversion ratio 59.3%, 3- iodopropionic acid yield 58.0% (about 1.74mmol).
5ml aqueous phase reactions object is taken, 10ml n-hexyl alcohol is added and extracts 3- iodopropionic acid, extraction three times, and merges extractant.Take 10ml extract liquor
(the about 0.29mmol of iodopropionic acid containing 3-) and 10ml water are added in 50mL heavy-walled glass pipe, and sodium hydroxide 0.4g is added, and sealing is anti-
Kettle is answered, stir and quickly heats up to 60 DEG C, holding 5h.Reaction kettle ice-water bath is cooled to room temperature, collected, be acidified water phase and examine
It surveys, acrylic acid yield 99.9% (about 0.29mmol).
Embodiment 4
4mmol glyceric acid, 100 μm of ol PdCl are sequentially added in 50mL high-temperature high-pressure reaction kettle2, 10ml 30wt% hydrogen
Acid iodide seals reaction kettle, is filled with hydrogen (400psi), stirs and quickly heats up to 100 DEG C, holding 10h.By reaction kettle ice-water bath
It is cooled to room temperature, collects water phase and detects, glyceric acid conversion ratio 100%, 3- iodopropionic acid yield 99.9% (about 4.0mmol).It takes
5ml aqueous phase reactions object is added 10ml n-hexyl alcohol and extracts 3- iodopropionic acid, and extraction three times, and merges extractant.Take 10ml extract liquor
(the about 0.667mmol of iodopropionic acid containing 3-) and 10ml water are added in 50mL heavy-walled glass pipe, and sodium hydroxide 0.15g is added, and seal
Reaction kettle stirs and quickly heats up to 50 DEG C, holding 2h.Reaction kettle ice-water bath is cooled to room temperature, collected, be acidified water phase and examine
It surveys, acrylic acid yield 99.9% (about 0.667mmol).
Embodiment 5
4mmol glyceric acid, 0.2g Pd/C (load capacity 5wt%), 10ml are sequentially added in 50mL high-temperature high-pressure reaction kettle
30wt% hydroiodic acid seals reaction kettle, is filled with hydrogen (400psi), stirs and quickly heats up to 100 DEG C, holding 10h.It will reaction
Kettle ice-water bath is cooled to room temperature, and is collected water phase and is detected, glyceric acid conversion ratio 100%, 3- iodopropionic acid yield 99.9% is (about
4.0mmol).10ml aqueous phase reactions object is taken, 10ml n-hexyl alcohol is added and extracts 3- iodopropionic acid, extraction three times, and merges extractant.It takes
10ml extract liquor (the about 1.33mmol of iodopropionic acid containing 3-) and 10ml water are added in 50mL heavy-walled glass pipe, and sodium hydroxide is added
0.15g seals reaction kettle, stirs and quickly heats up to 70 DEG C, holding 2h.Reaction kettle ice-water bath is cooled to room temperature, is collected, acid
Change water phase and detects, acrylic acid yield 99.9% (about 1.33mmol).
Embodiment 6
4mmol glyceric acid, 0.2g Rh/C (load capacity 5wt%), 10ml are sequentially added in 50mL high-temperature high-pressure reaction kettle
20wt% hydroiodic acid seals reaction kettle, is filled with hydrogen (400psi), stirs and quickly heats up to 80 DEG C, holding 20h.It will reaction
Kettle ice-water bath is cooled to room temperature, and is collected water phase and is detected, glyceric acid conversion ratio 100%, 3- iodopropionic acid yield 99.9% is (about
4.0mmol).5ml aqueous phase reactions object is taken, 10ml n-hexyl alcohol is added and extracts 3- iodopropionic acid, extraction three times, and merges extractant.It takes
10ml extract liquor (the about 0.667mmol of iodopropionic acid containing 3-) and 10ml water are added in 50mL heavy-walled glass pipe, and sodium hydroxide is added
0.15g seals reaction kettle, stirs and quickly heats up to 70 DEG C, holding 2h.Reaction kettle ice-water bath is cooled to room temperature, is collected, acid
Change water phase and detects, acrylic acid yield 99.9% (about 0.667mmol).
Embodiment 7
4mmol glyceric acid, 0.4g Pt/C (load capacity 2wt%), 10ml are sequentially added in 50mL high-temperature high-pressure reaction kettle
40wt% hydroiodic acid seals reaction kettle, is filled with hydrogen (400psi), stirs and quickly heats up to 100 DEG C, holding 10h.It will reaction
Kettle ice-water bath is cooled to room temperature, and is collected water phase and is detected, glyceric acid conversion ratio 100%, 3- iodopropionic acid yield 99.9% is (about
4.0mmol).5ml aqueous phase reactions object is taken, 10ml extracting n-butyl alcohol 3- iodopropionic acid is added, extraction three times, and merges extractant.It takes
10ml extract liquor (the about 1.3mmol of iodopropionic acid containing 3-) and 10ml water are added in 50mL heavy-walled glass pipe, and sodium hydroxide is added
0.15g seals reaction kettle, stirs and quickly heats up to 70 DEG C, holding 2h.Reaction kettle ice-water bath is cooled to room temperature, is collected, acid
Change water phase and detects, acrylic acid yield 99.9% (about 0.667mmol).
Embodiment 8
4mmol glyceric acid, 50 μm of ol RuCl are sequentially added in 50mL high-temperature high-pressure reaction kettle3, 10ml 10wt% hydrogen
Acid iodide seals reaction kettle, is filled with hydrogen (400psi), stirs and quickly heats up to 120 DEG C, holding 4h.By reaction kettle ice-water bath
It is cooled to room temperature, collects water phase and detects, glyceric acid conversion ratio 100%, 3- iodopropionic acid yield 99.9% (about 4.0mmol).It takes
5ml aqueous phase reactions object, is added 10ml Extraction with n-Octanol 3- iodopropionic acid, and extraction three times, and merges extractant.Take 10ml extract liquor
(the about 0.667mmol of iodopropionic acid containing 3-) and 10ml water are added in 50mL heavy-walled glass pipe, and sodium hydroxide 0.15g is added, and seal
Reaction kettle stirs and quickly heats up to 70 DEG C, holding 2h.Reaction kettle ice-water bath is cooled to room temperature, collected, be acidified water phase and examine
It surveys, acrylic acid yield 99.9% (about 0.667mmol).
Embodiment 9
4mmol glyceric acid, 100 μm of ol IrCl are sequentially added in 50mL high-temperature high-pressure reaction kettle3, 10ml 30wt% hydrogen
Acid iodide seals reaction kettle, is filled with hydrogen (400psi), stirs and quickly heats up to 100 DEG C, holding 5h.By reaction kettle ice-water bath
It is cooled to room temperature, collects water phase and detects, glyceric acid conversion ratio 100%, 3- iodopropionic acid yield 99.9% (about 4.0mmol).It takes
5ml aqueous phase reactions object is added 10ml n-hexyl alcohol and extracts 3- iodopropionic acid, and extraction three times, and merges extractant.Take 10ml extract liquor
(the about 0.667mmol of iodopropionic acid containing 3-) and 10ml water are added in 50mL heavy-walled glass pipe, and potassium hydroxide 0.30g is added, and seal
Reaction kettle stirs and quickly heats up to 60 DEG C, holding 0.5h.Reaction kettle ice-water bath is cooled to room temperature, collects, be acidified water phase simultaneously
Detection, acrylic acid yield 99.9% (about 0.667mmol).
Embodiment 10
4mmol glyceric acid, 10ml 30wt% hydroiodic acid, sealing reaction are sequentially added in 50mL high-temperature high-pressure reaction kettle
Kettle is filled with hydrogen (400psi), stirs and quickly heats up to 100 DEG C, holding 12h.Reaction kettle ice-water bath is cooled to room temperature, is received
Collection water phase simultaneously detects, glyceric acid conversion ratio 100%, 3- iodopropionic acid yield 99.9% (about 4.0mmol).5ml aqueous phase reactions object is taken,
10ml n-hexyl alcohol is added and extracts 3- iodopropionic acid, extraction three times, and merges extractant.Taking 10ml extract liquor, (iodopropionic acid containing 3- is about
It 0.667mmol) is added in 50mL heavy-walled glass pipe with 10ml water, and potassium hydroxide 0.30g is added, seal reaction kettle, stirring is simultaneously
60 DEG C are quickly heated up to, 0.5h is kept.Reaction kettle ice-water bath is cooled to room temperature, collected, be acidified water phase and detect, acrylic acid produces
Rate 99.9% (about 0.667mmol).
Embodiment 11
4mmol glyceric acid, 10ml 30wt% hydroiodic acid, sealing reaction are sequentially added in 50mL high-temperature high-pressure reaction kettle
Kettle is filled with nitrogen (400psi), stirs and quickly heats up to 100 DEG C, holding 15h.Reaction kettle ice-water bath is cooled to room temperature, is received
Collection water phase simultaneously detects, glyceric acid conversion ratio 100%, 3- iodopropionic acid yield 98% (about 3.9mmol).5ml aqueous phase reactions object is taken, is added
Enter 10ml n-hexyl alcohol extraction 3- iodopropionic acid, extraction three times, and merges extractant.Taking 10ml extract liquor, (iodopropionic acid containing 3- is about
It 0.65mmol) is added in 50mL heavy-walled glass pipe with 10ml water, and potassium hydroxide 0.30g is added, seal reaction kettle, stirred and fast
Speed is heated to 60 DEG C, keeps 0.5h.Reaction kettle ice-water bath is cooled to room temperature, collected, be acidified water phase and detect, acrylic acid yield
99.9% (about 0.65mmol).
Embodiment 12
4mmol glyceric acid, 10ml 10wt% hydroiodic acid, sealing reaction are sequentially added in 50mL high-temperature high-pressure reaction kettle
Kettle is filled with nitrogen (400psi), stirs and quickly heats up to 170 DEG C, holding 0.5h.Reaction kettle ice-water bath is cooled to room temperature,
It collects water phase and detects, glyceric acid conversion ratio 100%, 3- iodopropionic acid yield 95% (about 3.8mmol).5ml aqueous phase reactions object is taken,
10ml n-hexyl alcohol is added and extracts 3- iodopropionic acid, extraction three times, and merges extractant.Taking 10ml extract liquor, (iodopropionic acid containing 3- is about
It 0.633mmol) is added in 50mL heavy-walled glass pipe with 10ml water, and sodium hydroxide 0.05g is added, seal reaction kettle, stirring is simultaneously
80 DEG C are quickly heated up to, 1h is kept.Reaction kettle ice-water bath is cooled to room temperature, collected, be acidified water phase and detect, acrylic acid yield
99.9% (about 0.633mmol).
Embodiment 13
0.75mmol glyceric acid, 10ml 57wt% hydroiodic acid are sequentially added in 50mL high-temperature high-pressure reaction kettle, sealing is anti-
Kettle is answered, nitrogen (400psi) is filled with, stir and quickly heats up to 30 DEG C, holding 25h.Reaction kettle ice-water bath is cooled to room temperature,
It collects water phase and detects, glyceric acid conversion ratio 100%, 3- iodopropionic acid yield 90% (about 0.675mmol).Take 5ml aqueous phase reactions
Object is added 10ml n-hexyl alcohol and extracts 3- iodopropionic acid, and extraction three times, and merges extractant.Taking 10ml extract liquor, (iodopropionic acid containing 3- is about
It 0.113mmol) is added in 50mL heavy-walled glass pipe with 10ml water, and sodium hydroxide 0.27g is added, seal reaction kettle, stirring is simultaneously
40 DEG C are quickly heated up to, 10h is kept.Reaction kettle ice-water bath is cooled to room temperature, collected, be acidified water phase and detect, acrylic acid produces
Rate 99.9% (about 0.113mmol).
Claims (9)
1. a kind of glyceric acid prepares acrylic acid, it is characterized in that as follows:
(1) by glyceric acid and hydroiodic acid by glyceric acid: hydroiodic acid=0.001~1 molar ratio is added in high-temperature high-pressure reaction kettle,
Other catalyst are not added or metallic catalyst is added, seal reaction kettle, reaction atmosphere is hydrogen or inert gas, under stirring
40~200 DEG C are warming up to, the reaction time is 0.5~40h, is chilled to room temperature after reaction, is extracted with organic solvent, separates, obtains 3-
Iodopropionic acid；
(2) heavy-walled glass pipe is added in the organic phase and water collected step (1), by 3- iodopropionic acid: catalyst=1~1000 mole
Than basic catalyst or Lewis acid catalyst is added, 20~150 DEG C are risen under stirring, the reaction time is 0.5~40h, reaction
Afterwards, it is chilled to room temperature, collects aqueous phase reactions liquid, separation acidification obtains acrylic acid.
2. a kind of glyceric acid according to claim 1 prepares acrylic acid, it is characterized in that hydrogen iodine described in step (1)
Acid concentration is 1%~57%.
3. a kind of glyceric acid according to claim 1 prepares acrylic acid, it is characterized in that metal described in step (1)
Catalyst is the different loads amount being supported on active carbon, zirconium dioxide, titanium dioxide, silica or molecular sieve carrier
Rhodium, platinum, palladium, ruthenium or iraurite metal catalyst；Or rhodium, platinum, palladium, ruthenium or iridium metal salt or complex.
4. a kind of glyceric acid according to claim 1 prepares acrylic acid, it is characterized in that glycerol described in step (1)
The molar ratio 0.01~0.5 of acid and hydroiodic acid.
5. a kind of glyceric acid according to claim 1 prepares acrylic acid, it is characterized in that reaction described in step (1)
The pressure of atmosphere is 14.5~4000psi.
6. a kind of glyceric acid according to claim 1 prepares acrylic acid, it is characterized in that reaction described in step (1)
Temperature is 30~170 DEG C, and the reaction time is 0.5~25h.
7. a kind of glyceric acid according to claim 1 prepares acrylic acid, it is characterized in that alkalinity described in step (2)
Catalyst is that can ionize out homogeneous and multiphase alkaline matter hydroxy in water；Lewis acid catalyst is aluminium chloride, chlorination
Zinc, iron chloride, stannic chloride, aluminum sulfate, barium sulfate or molecular sieve.
8. a kind of glyceric acid according to claim 7 prepares acrylic acid, it is characterized in that alkalinity described in step (2)
Catalyst is sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide, organic amine, magnesium hydroxide, magnalium hydrotalcite, alkali molecules
Sieve, calcium oxide, magnesia or aluminium oxide.
9. a kind of glyceric acid according to claim 1 prepares acrylic acid, it is characterized in that 3- iodine described in step (2)
Propionic acid and catalyst molar ratio are 2~60, and reaction temperature is 40~80 DEG C, and the reaction time is 1~10h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810868004.XA CN108997108A (en) | 2018-08-01 | 2018-08-01 | A kind of glyceric acid prepares acrylic acid |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810868004.XA CN108997108A (en) | 2018-08-01 | 2018-08-01 | A kind of glyceric acid prepares acrylic acid |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160031789A1 (en) * | 2014-07-31 | 2016-02-04 | Basf Se | Process for preparing acrylic acid from methanol and acetic acid |
| CN108329202A (en) * | 2018-03-16 | 2018-07-27 | 南昌大学 | A kind of method that glyceric acid prepares 3- iodopropionic acids |
-
2018
- 2018-08-01 CN CN201810868004.XA patent/CN108997108A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160031789A1 (en) * | 2014-07-31 | 2016-02-04 | Basf Se | Process for preparing acrylic acid from methanol and acetic acid |
| CN108329202A (en) * | 2018-03-16 | 2018-07-27 | 南昌大学 | A kind of method that glyceric acid prepares 3- iodopropionic acids |
Non-Patent Citations (1)
| Title |
|---|
| 姜俊: "潜在生物质平台分子3-碘丙酸的催化转化", 《第十一届全国环境催化与环境材料学术会议论文集》 * |
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Application publication date: 20181214 |