CN106631771A - Acrylic acid synthesis method - Google Patents
Acrylic acid synthesis method Download PDFInfo
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- CN106631771A CN106631771A CN201611245863.0A CN201611245863A CN106631771A CN 106631771 A CN106631771 A CN 106631771A CN 201611245863 A CN201611245863 A CN 201611245863A CN 106631771 A CN106631771 A CN 106631771A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
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Abstract
The invention provides an acrylic acid synthesis method, and relates to a synthesis of a chemical raw material. The synthesis method comprises the steps that trioxymethylene, tetraoxymethylene, paraformaldehyde and the like are taken as a formaldehyde source to react with acetic acid under certain reaction conditions through an alkaline solid catalyst reaction zone, and main effluent is acrylic acid; trioxymethylene, tetraoxymethylene and paraformaldehyde are dissolved by taking 1,4-dioxane, sulfolane, tetrahydrofuran, dimethylsulfoxide and the like as solvents. According to the synthesis method, the reaction raw materials do not contain water, the reaction efficiency is high, and energy sources are basically not wasted; the route process is simple, the raw materials are convenient to obtain, few by-products are generated, reaction aftertreatment is easy and convenient, and pollution to the environment is low. A new idea and method are provided for large-scale industrialized production.
Description
Technical field
The present invention relates to a kind of industrial chemicals preparation method, more particularly to a kind of acrylic acid synthetic method.
Background technology
Acrylic acid（English name：Acrylic acid）, it is simplest unsaturated carboxylic acid.High-purity acrylic acid carries feature
Penetrating odor, and have extremely strong corrosivity.It is a kind of important industrial chemicals, is widely used in the conjunction of various chemicals
Into the production with resin.Acrylic acid and acrylate industry are the important component parts of world today's petrochemical industry production field.
Synthesis of conjugated carboxylic alkeneacid mainly has：
1) 2-chloroethyl alcohol method：With 2-chloroethyl alcohol and Cyanogran. as reaction raw materials, under base catalyst existence condition, cyanogen second is firstly generated
Alcohol.In the presence of sulphuric acid, dehydration obtains acrylonitrile to cyanoethanol.Acrylonitrile is hydrolyzed again or alcoholysis, obtains acrylic acid or acrylate；
2) cyanoethanol method:This method is developed by 2-chloroethyl alcohol method, and only cyanoethanol is different with synthetic method, by oxirane
There is ring-opening reaction under hydrocyanic acid effect to generate；
3) high pressure Reppe and improvement Reppe methods:Acetylene, carbon monoxide and water in the presence of catalyst nickel salt or mantoquita,
Esterification grade acrylic acid is generated, then esterification life occurs from different alcohol, into acrylate；
4) ketenes method：Ketenes（It is obtained for raw material by acetone and acetic acid）β-propiolactone is produced with anhydrous formaldehyde reaction, in β-the third
Ester contacts isomerization with hot phosphoric acid and generates acrylic acid；
5）Formaldehyde-Acetic：There is aldol reaction in formaldehyde, directly generate acrylic acid with acetic acid；
6）Acrylonitrile hydrolysis method；
7）Ethylene process：There is oxidation and carbonylation in ethylene, raw under noble metal catalyst existence condition with carbon monoxide and oxygen
Into acrylic acid；
8）Direct oxidation of propylene method：Wherein it is divided into a step and two step direct oxidation methods again.The first step of two-step penetration method, propylene oxygen
Metaplasia further aoxidizes generation acrylic acid into acrylic aldehyde, second step, acrylic aldehyde；
9）Propane oxidation：With propane as raw material, metal-oxide is catalyst, and propane direct oxidation obtains acrylic acid；
10）Epoxyethane method：Oxirane, i.e. oxirane are inserted directly into by carbon monoxide carbonylation occurs, generate third
Acid.In 10 kinds of method for producing propenoic acid of the above, 2-chloroethyl alcohol method, cyanoethanol method, Reppe methods and ketenes method are because efficiency is low, poison
Property it is big, therefore industrial cost is higher, is progressively eliminated.Ethylene process, the catalyst stability of propane method and epoxyethane method and
Selectivity and catalyst process are still immature, there is presently no and produce must report on a large scale.Only oxidation of propylene becomes
The unique method that acrylic acid large-scale production in the world today's is adopted.
Oxidation of propylene built up first set process units in 1969 by UCC companies in the U.S. earliest, subsequently Japan
Catalyst chemical company（MCC）In, Mitsubishi chemical company in 1970（NSKK）In 1973, and U.S.'s Celanese
（Celanese）Company established and produces acrylic acid process units with oxidation of propylene in succession in 1973.It is current in the world
The company for possessing propylene oxidation production acrylic acid process technology adopts propylene two-step oxidizing process technique.But propylene is directly derived from stone
Cerebrol is cracked, and belongs to petroleum resources downstream product.With the high speed development of World Economics, the worsening shortages of petroleum resources, environment
That what is polluted is increasingly serious, by one kind weight that coal, natural gas, biomass indirect reformer are liquid fuel and high valuable chemicals
The technical process wanted causes again the extensive concern of countries in the world.With reference to the resource characteristic of China's " rich coal, oil starvation, few gas ",
Coal chemical technology of the development with coal as waste petroleum-type product, implements oil and replaces strategy, is that relation China economy is long-term
Stable development and the key subjects of energy security, are also the inevitable choice for realizing national " with coal for replacing oil " strategy.
The content of the invention
It is an object of the invention to provide a kind of acrylic acid synthetic method, the present invention adopt metaformaldehyde, four polyformaldehyde with
And there is aldol reaction in paraformaldehyde etc., be directly synthesized acrylic acid as the source of aldehyde radical with acetic acid.1,4- dioxane,
Sulfolane, tetrahydrofuran, dimethyl sulfoxide can be used as formaldehyde as solvent, metaformaldehyde, four polyformaldehyde and paraformaldehyde etc.
Source, the by-product of reaction has methyl formate, water etc..Compared with formalin is as aldehyde radical source, reaction raw materials are not aqueous,
Reaction efficiency is high, and the energy is not wasted substantially.The path process is simple, raw material sources are convenient, and by-product is less, after simultaneous reactions
Simplicity is processed for the less pollution of environment.A kind of new thinking and method are provided for large-scale industrial production.
The purpose of the present invention is achieved through the following technical solutions：
A kind of acrylic acid synthetic method, methods described is urged with formaldehyde and acetic acid as raw material by adding alkalescence in reaction system
Agent and organic solvent, at temperature and pressure, acrylic acid synthesizing；
Including procedure below：
Equation involved by the path is as follows：
The step is：
a）To be catalyzed by alkali solid containing metaformaldehyde, four polyformaldehyde and paraformaldehyde etc. as formaldehyde source and acetic acid
Agent reaction zone, reacts under certain reaction condition, and effluent is mainly acrylic acid；
b）Solvent Isosorbide-5-Nitrae-dioxane, sulfolane, tetrahydrofuran, dimethyl sulfoxide etc. is used as solvent, dissolving metaformaldehyde, four poly- first
Aldehyde and paraformaldehyde；
c）The reaction condition is：300 ~ 400 DEG C of reaction temperature, 0.2～1.2MPa of reaction pressure, raw material metaformaldehyde, four gather
The h of the mass space velocity such as formaldehyde and paraformaldehyde 0.05～20-1；
Catalyst is a kind of composite catalyzing material, with silicon dioxide as carrier, with potassium element as load；
Preparation process is as follows：Pure lactic acid is taken in beaker, is 35% addition deionized water according to mass fraction, stirring mixing is covered
Preservative film, and it is heated to 75 DEG C, ammonium metavanadate is weighed, above-mentioned lactic acid solution is dissolved, it is sufficiently stirred for, make solution gradually become yellow
Transparent lactic acid vanadyl solution；Potassium nitrate is added, is fully dissolved after stirring, add phosphoric acid, fully reacted to bubble-free and produce, obtained
To impregnation liquid；15g20-40 mesh silica dioxide granules are taken, in being added to mixed solution, after dipping 12h required impregnating is obtained, put
Enter in baking oven and dried at 90 DEG C；Muffle furnace roasting is subsequently placed in, 300-350 DEG C is warmed up in air atmosphere and is kept 1-12 little
When, to remove lactic acid；550-650 DEG C is warmed up to, 1-12 hours are kept, required catalyst is obtained；Finally give macro-pore SiO2For
The loaded vanadium-phosphor oxide of carrier and the composite catalyst A of potassium oxide.
A kind of described acrylic acid synthetic method, the reaction raw materials are metaformaldehyde, four polyformaldehyde and paraformaldehyde etc.
With acetic acidreaction acrylic acid synthesizing.
A kind of described acrylic acid synthetic method, the reactor of the reaction interval is fixed bed reactors, or moving bed
Reactor.
A kind of described acrylic acid synthetic method, the reaction is by containing metaformaldehyde, four polyformaldehyde and paraformaldehyde
During unstripped gas is by being loaded with the reactor of Catalyst A Catalyst.
A kind of described acrylic acid synthetic method, the reaction is in 300 ~ 400 DEG C of temperature, the MPa of reaction pressure 0.2 ~ 1.2
Under conditions of react, generate acrylic acid.
A kind of described acrylic acid synthetic method, the quality such as metaformaldehyde, four polyformaldehyde and paraformaldehyde in the raw material
Air speed is 0.05～10.0 h-1；
A kind of described acrylic acid synthetic method, the volume hundred of metaformaldehyde, four polyformaldehyde and paraformaldehyde etc. in the raw material
Content is divided to be 0.1 ~ 95%.
Description of the drawings
Fig. 1 is reaction temperature to acetic acid conversion and the impact schematic diagram of acrylic acid selectivity.
Specific embodiment
With reference to embodiment, the present invention is described in detail.
Embodiment 1
Will with Isosorbide-5-Nitrae-dioxane as solvent, metaformaldehyde and acetic acid make raw material, solid-liquid ratio is 0.3:1:1 reactor feed gas lead to
In crossing the reactor of catalyst A, reaction temperature is 300 DEG C, 320 DEG C, 340 DEG C, 360 DEG C, 380 DEG C, 400 DEG C.Reaction pressure
For 0.4 MPa, the h of response time 100.Reaction result is as shown in table 1：
The metaformaldehyde of table 1 makees raw material reaction temperature to be affected on acrylic acid selectivity
Can be seen that from upper table, with the rising of reaction temperature, raw acetic acid conversion ratio gradually increases, when temperature is up to 400 DEG C, second
Sour conversion ratio is up to 99.96%.Product propylene acid is with the rising of temperature, selectivity first increases and then decreases.When reaction temperature is
When 340 DEG C, raw acetic acid conversion ratio is 98.22%, and now product propylene acid selectivity reaches as high as 91.73%.
Embodiment 2
Will with Isosorbide-5-Nitrae-dioxane as solvent, four polyformaldehyde and acetic acid make raw material, solid-liquid ratio is 0.3:1:1 reactor feed gas lead to
In crossing the reactor of catalyst A, reaction temperature is 300 DEG C, 320 DEG C, 340 DEG C, 360 DEG C, 380 DEG C, 400 DEG C.Reaction pressure
For 0.4 MPa, the h of response time 100.Reaction result is as shown in table 2：
The polyformaldehyde of table 2 four makees raw material reaction temperature to be affected on acrylic acid selectivity
Can be seen that from upper table, with the rising of reaction temperature, raw acetic acid conversion ratio gradually increases, when temperature is up to 400 DEG C, second
Sour conversion ratio is up to 99.95%.Product propylene acid is with the rising of temperature, selectivity first increases and then decreases.When reaction temperature is
When 340 DEG C, raw acetic acid conversion ratio is 96.89%, and now product propylene acid selectivity reaches as high as 91.78%.
Embodiment 3
Solvent will be made with Isosorbide-5-Nitrae-dioxane, metaformaldehyde and acetic acid make raw material, and solid-liquid ratio is 0.3:1:1 reactor feed gas lead to
In crossing the reactor of catalyst A, reaction pressure is respectively 0.2,0.4,0.6,0.8,1.0,1.2, MPa.Reaction temperature is
340 DEG C, the h of response time 100.Reaction result is as shown in table 3：
The metaformaldehyde of table 3 makees raw material reaction pressure to be affected on acrylic acid selectivity
From upper table it is found that with the increase of reaction pressure, acetic acid conversion increases, product propylene acid selectivity gradually increases
Plus, after tend to be steady.When reaction pressure reaches 0.4MPa, acetic acid conversion highest can reach 95.29%, and acrylic acid is selected
Property can reach 91.05%.When pressure is more than 0.4MPa, acrylic acid selectivity is varied less.
Embodiment 4
Will with Isosorbide-5-Nitrae-dioxane as solvent, four polyformaldehyde and acetic acid make raw material, solid-liquid ratio is 0.3:1:1 reactor feed gas lead to
In crossing the reactor of catalyst A, reaction pressure is respectively 0.2,0.4,0.6,0.8,1.0,1.2MPa.Reaction temperature is 340
DEG C, the h of response time 100.Reaction result is as shown in table 4：
The polyformaldehyde of table 4 four makees raw material reaction pressure to be affected on acrylic acid selectivity
From upper table it is found that with the increase of reaction pressure, acetic acid conversion increases, product propylene acid selectivity gradually increases
Plus, when reaction pressure reaches 0.4MPa, acetic acid conversion highest can reach 91.20%, and now acrylic acid selectivity is reachable
To 91.20%.When pressure is more than 0.4MPa, acrylic acid selectivity is varied less.
Embodiment 5
Will with Isosorbide-5-Nitrae-dioxane as solvent, metaformaldehyde and acetic acid make raw material, solid-liquid ratio is 0.3:1:1 reactor feed gas lead to
In crossing the reactor of catalyst A, reaction pressure is 0.4MPa.Reaction temperature be 340 DEG C, the response time be respectively 100 h,
200 h、500 h、800 h、1000 h .Reaction result is as shown in table 5：
The metaformaldehyde of table 5 makees impact of the raw material reaction time to acrylic acid selectivity
Find from upper table, with the increase in response time, raw acetic acid conversion ratio declines, and the selectivity of product propylene acid is also gradually
Decline, illustrate as the increase catalyst in response time is inactivated.Between when reacted during 100 h, acrylic acid selectivity is reached as high as
91.33%。
Embodiment 6
Make raw material so that Isosorbide-5-Nitrae-dioxane is made into solvent, four polyformaldehyde and acetic acid, solid-liquid ratio is 0.3:1:1 reactor feed gas lead to
In crossing the reactor of catalyst A, reaction pressure is 0.4MPa.Reaction temperature be 340 DEG C, the response time be respectively 100 h,
200 h、500 h、800 h、1000 h.Reaction result is as shown in table 6：
The polyformaldehyde of table 6 four makees impact of the raw material reaction time to acrylic acid selectivity
Find from upper table, with the increase in response time, raw acetic acid conversion ratio drop, acrylic acid selectivity is gradually lowered, says
The bright increase catalyst with the response time is inactivated.Between when reacted during 100 h, acrylic acid selectivity reaches as high as 91.39%.
Embodiment 7
By the reactor feed gas of Isosorbide-5-Nitrae-dioxane, metaformaldehyde and acetic acid by there is the reactor of catalyst A in, reaction pressure
For 0.4 MPa.Reaction temperature is 340 DEG C, and the solid-liquid ratio for changing Isosorbide-5-Nitrae-dioxane, metaformaldehyde and acetic acid is 0.1:1:1、
0.2:1:1、0.3:1:1、0.4:1:1、0.5:1:1、0.6:1:1.Reaction result is as shown in table 7：
Table 7 changes 1,4- dioxane and impact of the raw material solid-liquid ratio to acrylic acid selectivity
Find from upper table, during with Isosorbide-5-Nitrae-dioxane as solvent, with the increase of solid-liquid ratio, conversion ratio tends to after gradually increasing
Steadily, acrylic acid selectivity first increases, after tend to be steady.When solid-liquid ratio is 0.3:1:It is optimal solid-liquid ratio when 1, now acetic acid
Conversion ratio is 99.65%, and product propylene acid selectivity is up to 91.33%.
Embodiment 8
By the reactor feed gas of sulfolane, metaformaldehyde and acetic acid by there is the reactor of catalyst A in, reaction pressure is
0.4MPa.Reaction temperature is 340 DEG C, and it is 0.1 to change sulfolane, metaformaldehyde, the solid-liquid ratio of acetic acid:1:1、0.2:1:1、
0.3:1:1、0.4:1:1、0.5:1:1、0.6:1:1.Reaction result is as shown in table 8：
Table 8 changes sulfolane and impact of the raw material solid-liquid ratio to acrylic acid selectivity
Find from upper table, when making solvent with sulfolane, with the increase of solid-liquid ratio, acetic acid conversion tends to flat after gradually increasing
Surely, acrylic acid selectivity is continuously increased, after tend to be steady.When solid-liquid ratio is 0.3:1:It is optimal solid-liquid ratio when 1, now acetic acid
Conversion ratio is 99.73%, and product propylene acid selectivity is up to 91.44%.
Embodiment 9
By the reactor feed gas of tetrahydrofuran, metaformaldehyde and acetic acid by there is the reactor of catalyst A in, reaction pressure is
0.4MPa.Reaction temperature is 340 DEG C, and the solid-liquid ratio for changing tetrahydrofuran, metaformaldehyde and acetic acid is 0.1:1:1、0.2:1:1、
0.3:1:1、0.4:1:1、0.5:1:1、0.6:1:1.Reaction result is as shown in table 9：
Table 9 changes tetrahydrofuran and impact of the raw material solid-liquid ratio to acrylic acid selectivity
Find from upper table, when making solvent with tetrahydrofuran, with the increase of solid-liquid ratio, acetic acid conversion tends to after gradually increasing
Steadily, acrylic acid selectivity is continuously increased, after tend to be steady.When solid-liquid ratio is 0.4:1:It is optimal solid-liquid ratio when 1.Acetic acid turns
Up to 99.67%, now acrylic acid selectivity is up to 91.52% for rate.
Embodiment 10
By the reactor feed gas of dimethyl sulfoxide, metaformaldehyde and acetic acid by there is the reactor of catalyst A in, reaction pressure is
0.4 MPa.Reaction temperature is 340 DEG C, and the solid-liquid ratio for changing dimethyl sulfoxide, metaformaldehyde and acetic acid is 0.1:1:1、0.2:1:1、
0.3:1:1、0.4:1:1、0.5:1:1、0.6:1:1.Reaction result is as shown in table 10：
Table 10 changes dimethyl sulfoxide and impact of the raw material solid-liquid ratio to acrylic acid selectivity
From upper table find, when making solvent with dimethyl sulfoxide, with the increase of solid-liquid ratio, acetic acid selectivity first increases, after tend to
Steadily.Acrylic acid selectivity first increases and tends to be steady afterwards.When solid-liquid ratio is 0.3:1:It is optimal solid-liquid ratio when 1.Acetic acid conversion
Up to 99.72%, now acrylic acid selectivity is up to 91.51%.
Embodiment 11
Will be with Isosorbide-5-Nitrae-dioxane, paraformaldehyde and acetic acid, solid-liquid ratio is 0.3:1:1 reactor feed gas are by there is catalyst A
Reactor in, reaction temperature is 300 DEG C, 320 DEG C, 340 DEG C, 360 DEG C, 380 DEG C, 400 DEG C.Reaction pressure is 0.4 MPa, instead
100 h between seasonable.Reaction result is as shown in table 11：
The paraformaldehyde of table 11 makees impact of the raw material reaction temperature to acrylic acid selectivity
Can be seen that from upper table, with the rising of reaction temperature, raw acetic acid conversion ratio gradually increases, when temperature is up to 400 DEG C, second
Sour conversion ratio is up to 99.96%.Product propylene acid is with the rising of temperature, selectivity first increases and then decreases.When reaction temperature is
When 340 DEG C, raw acetic acid conversion ratio is 98.59%, and now product propylene acid selectivity reaches as high as 92.56%.
Embodiment 12
Will be with Isosorbide-5-Nitrae-dioxane, paraformaldehyde and acetic acid as reaction raw materials, solid-liquid ratio is 0.3:1:1 reactor feed gas pass through
In having the reactor of catalyst A, reaction pressure is respectively 0.2,0.4,0.6,0.8,1.0,1.2 MPa.Reaction temperature is 340
DEG C, the h of response time 100.Reaction result is as shown in table 12：
The paraformaldehyde of table 12 makees impact of the raw material reaction pressure to acrylic acid selectivity
From upper table it is found that with the increase of reaction pressure, acetic acid conversion increases, product propylene acid selectivity gradually increases
Plus, when reaction pressure reaches 0.4 MPa, acetic acid conversion highest can reach 96.77%, and now acrylic acid selectivity is also most
Height, can reach 91.20%.When pressure is more than 0.4MPa, acrylic acid selectivity change is little.
Embodiment 13
Will be with Isosorbide-5-Nitrae-dioxane, paraformaldehyde and acetic acid as reaction raw materials, solid-liquid ratio is 0.3:1:1 reactor feed gas pass through
In having the reactor of catalyst A, reaction pressure is 0.4 MPa.Reaction temperature be 340 DEG C, the response time be respectively 100 h, 200
h、500 h、800 h、1000 h.Reaction result is as shown in table 13：
The paraformaldehyde of table 13 makees impact of the raw material reaction time to acetic acid selectivity
Find that, with the increase in response time, raw acetic acid conversion ratio is gradually reduced from upper table, the selectivity of product propylene acid
It is gradually reduced.Illustrate with the increase in response time, catalyst inactivation.Between when reacted during 100 h, acetic acid conversion is reachable
99.53%, acrylic acid selectivity is up to 91.05%.
The above, is only several embodiments of the application, any type of restriction is not done to the application, although this Shen
Please disclosed as above with preferred embodiment, but and be not used to limit the application, any those skilled in the art are not taking off
In the range of technical scheme, make a little variation using the technology contents of the disclosure above or modification is equal to
Effect case study on implementation, belongs in the range of technical scheme.
Claims (7)
1. a kind of acrylic acid synthetic method, it is characterised in that methods described with formaldehyde and acetic acid as raw material, by reaction system
Middle addition base catalyst and organic solvent, at temperature and pressure, acrylic acid synthesizing；
Including procedure below：
Equation involved by the path is as follows：
；The step is：
Will be containing metaformaldehyde, four polyformaldehyde and paraformaldehyde etc. as formaldehyde source and acetic acid, by alkali solid catalyst
Reaction zone, reacts under certain reaction condition, and effluent is mainly acrylic acid；
b）Solvent Isosorbide-5-Nitrae-dioxane, sulfolane, tetrahydrofuran, dimethyl sulfoxide etc. is used as solvent, dissolving metaformaldehyde, four poly- first
Aldehyde and paraformaldehyde；
c）The reaction condition is：300 ~ 400 DEG C of reaction temperature, 0.2～1.2MPa of reaction pressure, raw material metaformaldehyde, four gather
The h of the mass space velocity such as formaldehyde and paraformaldehyde 0.05～20-1；
Catalyst is a kind of composite catalyzing material, with silicon dioxide as carrier, with potassium element as load；
Preparation process is as follows：Pure lactic acid is taken in beaker, is 35% addition deionized water according to mass fraction, stirring mixing is covered
Preservative film, and it is heated to 75 DEG C, ammonium metavanadate is weighed, above-mentioned lactic acid solution is dissolved, it is sufficiently stirred for, make solution gradually become yellow
Transparent lactic acid vanadyl solution；Potassium nitrate is added, is fully dissolved after stirring, add phosphoric acid, fully reacted to bubble-free and produce, obtained
To impregnation liquid；15g20-40 mesh silica dioxide granules are taken, in being added to mixed solution, after dipping 12h required impregnating is obtained, put
Enter in baking oven and dried at 90 DEG C；Muffle furnace roasting is subsequently placed in, 300-350 DEG C is warmed up in air atmosphere and is kept 1-12 little
When, to remove lactic acid；550-650 DEG C is warmed up to, 1-12 hours are kept, required catalyst is obtained；Finally give macro-pore SiO2For
The loaded vanadium-phosphor oxide of carrier and the composite catalyst A of potassium oxide.
2. a kind of acrylic acid synthetic method according to claim 1, it is characterised in that the reaction raw materials are trimerization first
Aldehyde, four polyformaldehyde and paraformaldehyde etc. and acetic acidreaction acrylic acid synthesizing.
3. a kind of acrylic acid synthetic method according to claim 1, it is characterised in that the reactor of the reaction interval is
Fixed bed reactors, or moving-burden bed reactor.
4. a kind of acrylic acid synthetic method according to claim 1, it is characterised in that the reaction will be containing trimerization first
During the unstripped gas of aldehyde, four polyformaldehyde and paraformaldehyde is by being loaded with the reactor of Catalyst A Catalyst.
5. a kind of acrylic acid synthetic method according to claim 1, it is characterised in that the reaction is in temperature 300 ~ 400
DEG C, react under conditions of the MPa of reaction pressure 0.2 ~ 1.2, generate acrylic acid.
6. a kind of acrylic acid synthetic method according to claim 1, it is characterised in that metaformaldehyde in the raw material, four
The mass space velocity such as polyformaldehyde and paraformaldehyde is 0.05～10.0 h-1。
7. a kind of acrylic acid synthetic method according to claim 1, it is characterised in that metaformaldehyde in the raw material, four
The volumn concentration of polyformaldehyde and paraformaldehyde etc. is 0.1 ~ 95%.
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| CN111849587A (en) * | 2020-08-14 | 2020-10-30 | 德杰(浙江)润滑科技有限公司 | Preparation method and process of lubricating oil additive |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102652922A (en) * | 2012-03-23 | 2012-09-05 | 太原理工大学 | Supported phosphorus-vanadium-cesium-lanthanum catalyst and application thereof |
| CN103611522A (en) * | 2013-07-09 | 2014-03-05 | 中国科学院过程工程研究所 | Catalyst for synthesizing acrylic acid (ester) by taking formaldehyde and acetic acid as raw materials and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102652922A (en) * | 2012-03-23 | 2012-09-05 | 太原理工大学 | Supported phosphorus-vanadium-cesium-lanthanum catalyst and application thereof |
| CN103611522A (en) * | 2013-07-09 | 2014-03-05 | 中国科学院过程工程研究所 | Catalyst for synthesizing acrylic acid (ester) by taking formaldehyde and acetic acid as raw materials and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111849587A (en) * | 2020-08-14 | 2020-10-30 | 德杰(浙江)润滑科技有限公司 | Preparation method and process of lubricating oil additive |
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