CN106542993A - The oxidation of one step of propane prepares acrylic acid system and method - Google Patents
The oxidation of one step of propane prepares acrylic acid system and method Download PDFInfo
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- CN106542993A CN106542993A CN201510593298.6A CN201510593298A CN106542993A CN 106542993 A CN106542993 A CN 106542993A CN 201510593298 A CN201510593298 A CN 201510593298A CN 106542993 A CN106542993 A CN 106542993A
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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
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
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Abstract
The oxidation of one step of propane prepares acrylic acid system and method, methods described includes propane selectivity oxidation reaction operation, crude acrylic acid separation circuit and vent gas treatment operation, described vent gas treatment operation includes tail gas Jing after dehydration and selectively removing carbon monoxide, circulates for selective oxidation of propane operation.The system includes vent gas treatment component, the component connection product separation assembly and raw material premix component, including the tail gas drain sump for setting gradually, removing CO reactors and compressor.Method and system provided by the present invention, by the CO with larger risk of explosion in selectively removing tail gas, and retain wherein unreacted propane and gas phase product propylene and be recycled to the system and technical flow design of production process, effective process is carried out to the tail gas that one step oxidation of propane prepares the high carbon monoxide content produced by acrylic acid process and has been recycled, be advantageously implemented selective oxidation of propane and prepare acrylic acid industrialized production.
Description
Technical field
The present invention relates to the acrylic acid system of the continuous production high value added product of one step of propane oxidation and technique, especially
Which is related to comprising vent gas treatment and the method and system for recycling, and belongs to technical field of petrochemical industry.
Background technology
Acrylic acid is important petrochemical industry, light industry and medical material, can be used to produce adsorbent, purification
Agent, fiber, pulp additive, binding agent, plastics, coating etc., and their new application is not also
Disconnected extension.
It is now widely used in and industrially prepares acrylic acid the two-stage catalysis for being that propylene is raw material to aoxidize, example
Such as EP-A575897.For cost of material, the price of propylene is higher than propane, and with propylene purposes
Expand, the price of propylene will will rise, and the gap in this price further will be increased.If instead of third
Alkene, realization prepare acrylic acid process industrialization by raw material of propane, then cost of material will be substantially reduced.Cause
This replaces direct oxidation of propylene acrylic acid to become grinding for low-carbon alkanes exploitation using propane cheap and easy to get
Study carefully one of focus.Meanwhile, the abundance of propane, it is casing-head gas, natural gas, main in refinery gas
Composition.In China, the completing of West-East National Gas Transmission Project will make the original C as liquefied gas3-C4The a large amount of mistakes of alkane
It is surplus, therefore, how there is significant economic implications and realistic meaning using these cheap alkane.
It is acrylic acid process that patent US 6,492,548 is described propane Multi-step conversion.The patent with propane is
Raw material, first converts propane to propylene, is then converted into acrylic aldehyde, and is further converted into product propylene acid.
It is apparent that containing considerable amount of acrylic aldehyde in technological process complexity, the particularly liquid product, product is increased
The detached difficulty of thing and operating cost.
In order to more preferably advance the development of acrylic acid technology of preparing, one step of propane aoxidizes acrylic acid process process processed can
The investment of acroleic acid device is substantially reduced, shortened process reduces waste and pollutant emission.At present
Jing successfully have developed the acrylic acid hybrid metal oxidation of one step of propane oxidation production of high activity, high selectivity
Thing catalyst (React.Kinet.Catal.Lett., 2009,97 (2):225-232；ZL200810012030.9).
But CO explosion limit wider range that tail gas contains during one step of existing propane oxidation acrylic acid process processed,
For 12.5%～74.2%, larger hidden peril of explosion during causing circulation of tail gas use, is there is.Therefore, it is anxious
Need to develop and incorporate energy-efficient vent gas treatment operation, and the oxidation of propane system with industrial applicibility
Propylene acid production process.
The content of the invention
An object of the present invention is to provide a kind of effective process and to recycle the propane one of reaction end gas
Step oxidation prepares acrylic acid.The one step oxidation of propane of the present invention prepares acrylic acid, including third
Alkane selective oxidation reaction operation, crude acrylic acid separation circuit and vent gas treatment operation, described vent gas treatment
Operation includes：By tail gas Jing after dehydration and selectively removing carbon monoxide (CO), circulate and select for propane
Oxidation operation.
The second object of the present invention, is to provide a set of one step of propane oxidation to prepare acrylic acid system, including
Raw material premix component, propane selectivity oxidation reaction component, product separation assembly and vent gas treatment component, its
In, described vent gas treatment component connection product separation assembly and raw material premix component, including what is set gradually
Tail gas drain sump, removing CO reactors and compressor.
Method and system provided by the present invention, by having larger risk of explosion in selectively removing tail gas
CO, and retain wherein unreacted propane and gas phase product propylene and be recycled to the system and technique of production process
Flow scheme design, enters to the tail gas that one step oxidation of propane prepares the high carbon monoxide content produced by acrylic acid process
Effective process is gone and has recycled, be advantageously implemented selective oxidation of propane and prepare acrylic acid industrialized production.
Description of the drawings
1 width of accompanying drawing of the present invention, is that one step of the propane oxidation of the present invention prepares acrylic acid system schematic, wherein：
R-101, selective oxidation of propane reactor；R-102, removes CO reactors；M-101, premixer；
M-102, entry mixers；E-102, propane superheater；E-103, cooling section；V-104, quencher；
C-110, absorption tower；V-103, tail gas drain sump；K-101, compressor.
Specific embodiment
The specific embodiment of the present invention is described in detail below in conjunction with technical scheme and accompanying drawing.
Present invention firstly provides a kind of one step oxidation of propane prepares acrylic acid, methods described includes propane
Selective oxidation reaction operation, crude acrylic acid separation circuit and vent gas treatment operation, described vent gas treatment work
Sequence includes：By tail gas Jing after dehydration and selectively removing carbon monoxide (CO), circulate and oxygen is selected for propane
Chemical industry sequence.
In specific embodiment, described in the method for the invention described above and selectively removing carbon monoxide pass through
Catalytic selectivity reaction realize, catalyst is load type metal catalyst, its active component selected from Pt, Pd,
Ru, nanometer gold, Ni, Fe and Mn, loading are 1～5%；Carrier is selected from Al2O3、ZrO2、MgO、
FeOx、SiO2, activated carbon and MCM-41 molecular sieves.More specifically, the load type metal catalyst
Can be exemplified as but be not limited to Pt/Al2O3、Pt/ZrO2、Pt/FeOx、Pd/SiO2、Pd/FeOx、Pt-Ni/Al2O3
Or Au-Ni/Al2O3。
In the method for the invention described above, the reaction controlling bar of the selectively removing carbon monoxide (CO) addressed
Part includes：50～200 DEG C of temperature, 0.1～0.5MPa of operating pressure, reaction velocity 2000～5000L Kg-1h-1。
Those skilled in the art can be specifically suitable for according to specific catalyst choice and raw material thing proportioning.
Jing after vent gas treatment operation, carbon monoxide weight/mass percentage composition is less than 0.01%.
In another specific embodiment of the method for the invention described above, described propane selectivity oxidation reaction
Carry out under mixed metal oxide catalyst existence condition, the catalyst contain Mo, V, Sb, Te,
Any 4 kinds in Nb, Al, W, K, Co or more than 4 kinds elements.More specifically, the mixing gold
Category oxide catalyst can be exemplified as but be not limited to Mo-V-Te-Nb-O, Mo-V-Sb-Nb-O,
The mixed metal oxide catalyst of Mo-K-V-Te-Nb-O or Mo-V-Al-W-Nb-O.Described mixing gold
Category oxide catalyst is Ring-cylindrical, spherical or cylindrical.It is preferred that cylindrical catalyst.Can illustrate but not limit
In annulated column type catalyst used widely in the art, 1.5～3.0mm of internal diameter, 4.0～6.0mm of external diameter are high
3.0～5.0mm.
In the method for the invention described above, the unstripped gas in described propane selectivity oxidation reaction operation by from
The vapor of battery limit (BL), O2、N2, propane and Jing after vent gas treatment operation gained circulation with tail gas constitute, press
According to mass percent, the unstripped gas is composed of the following components：H2O 10.0～28.0%；N240.0～50.0%；
O210.0～18.0%；Propane 10.0～15.0%；CO0～0.01%；CO22.0～8.0% and propylene 1.5～5.0%.
In the method for the invention described above, described propane selectivity oxidation reaction is preferably using calandria type fixed bed
Reactor, reaction controlling condition include：300～500 DEG C of operation temperature, 0.1～0.5MPa of operating pressure, instead
Answer air speed 2000～5000L Kg-1h-1.Those skilled in the art can be according to specific catalyst choice and raw material
Thing proportioning is specifically suitable for.
On the other hand, the present invention is intended to provide the oxidation of one step of a set of propane prepares acrylic acid system, the system
Including raw material premix component, propane selectivity oxidation reaction component, product separation assembly and vent gas treatment component,
Wherein described vent gas treatment component connection product separation assembly and raw material premix component, including what is set gradually
Tail gas drain sump V-103, removes CO reactors R-102 and compressor K-101.
In the system of the invention described above, load type metal catalysis in described removing CO reactor R-102, is loaded
Agent, its active component are selected from Pt, Pd, Ru, nanometer gold, Ni, Fe and Mn, and loading is 1～5%；Carry
Body is selected from Al2O3、ZrO2、MgO、FeOx、SiO2, activated carbon and MCM-41 molecular sieves.It is described negative
Supported type metal catalyst can be illustrated but is not limited to Pt/Al2O3、Pt/ZrO2、Pt/FeOx、Pd/SiO2、Pd/FeOx、
Pt-Ni/Al2O3Or Au-Ni/Al2O3。
More specifically in embodiment, one step of the propane oxidation of the invention described above prepares acrylic acid system bag
Include：
Raw material premix component, including entry mixers M-102, which is used to receiving and mixing third from battery limit (BL)
Alkane, O2、N2, vapor and the recycled offgas from vent gas treatment component, and mixed material gas is conveyed
To propane selectivity oxidation reaction component；
Propane selectivity oxidation reaction component, for receiving the mixed material gas from entry mixers M-102
And be catalyzed propane selectivity oxidation reaction and carry out, react including the selective oxidation of propane containing cooling section E-103
Device R-101；
Product separation assembly, for receiving the product from propane selectivity oxidation reaction component, separates
Propylene acid crude, and tail gas is exported to vent gas treatment component, including the quencher V-104 being sequentially connected and
Absorption tower C-110；
Vent gas treatment component, connection product separation assembly and raw material premix component, for receiving from product point
From the tail gas of component, and the recycled offgas Jing after dehydration and removal of carbon monoxide (CO) are processed is input into raw material
Premix component；Vent gas treatment component include being sequentially connected to absorption tower C-110 and entry mixers M-102 it
Between tail gas drain sump V-103, remove CO reactors R-102 and compressor K-101.
In the system of the invention described above, described raw material premix component include entry mixers M-102 and and its
The propane superheater E-102 and premixer M-101 of connection；The propane superheater E-102 is used to receive simultaneously
The propane of heating Jing vaporization process, and it is transported to entry mixers M-102；Described premixer
M-101 is used for the O for receiving and mixing battery limit (BL) input2、N2, vapor and from vent gas treatment component loop tail
Gas, and it is transported to entry mixers M-102.
In the system of the invention described above, in described selective oxidation of propane reactor R-101, hybrid metal is loaded
Oxide catalyst, the catalyst contain appointing in Mo, V, Sb, Te, Nb, Al, W, K, Co
Meaning 4 kinds or more than 4 kinds elements.Can specifically illustrate but be not limited to Mo-V-Te-Nb-O, Mo-V-Sb-Nb-O,
The mixed metal oxide catalyst of Mo-K-V-Te-Nb-O or Mo-V-Al-W-Nb-O.Preferably
From Ring-cylindrical, spherical or cylindrical mixed metal oxide catalyst, highly preferred mode is Ring-cylindrical
Catalyst.Can illustrate but be not limited to annulated column type catalyst used widely in the art, 1.5～3.0mm of internal diameter,
4.0～6.0mm of external diameter, high 3.0～5.0mm.
Another further aspect, the present invention also include preparing third using one step of the propane oxidation described in the invention described above certainly
The system of olefin(e) acid carries out the method that acrylic acid is comprehensively produced.With regard to any excellent of the system in the invention described above
Embodiment is selected also to be of course applied for the production carried out using the system.
Present disclosure is described further in the way of specific embodiment below.
Embodiment 1
One step oxidation of propane prepares acrylic acid system, as shown in Figure 1.
The system is by raw material premix component, propane selectivity oxidation reaction component, product separation assembly and tail gas
Process assembly is constituted.Wherein：
Raw material premix component, including entry mixers M-102 and connected propane superheater E-102 and
Premixer M-101；The propane superheater E-102 is used for the propane for receiving and heating Jing vaporization process, and
It is transported to entry mixers M-102；Described premixer M-101 is defeated for receiving and mixing battery limit (BL)
The O for entering2、N2, vapor and from vent gas treatment component recycled offgas, and be transported to entry mixers
M-102；
Propane selectivity oxidation reaction component, for receiving the mixed material gas from entry mixers M-102
And be catalyzed propane selectivity oxidation reaction and carry out, included capital equipment unit is containing cooling section E-103
Selective oxidation of propane reactor R-101；
Product separation assembly, for receiving the product from propane selectivity oxidation reaction component, separates
Propylene acid crude, and tail gas is exported to vent gas treatment component, including the quencher V-104 being sequentially connected and
Absorption tower C-110；
Vent gas treatment component, connection product separation assembly and raw material premix component, for receiving from product point
From the tail gas of component, and the recycled offgas Jing after dehydration and removal of carbon monoxide (CO) are processed is input into raw material
Premix component；Vent gas treatment component include being sequentially connected to absorption tower C-110 and entry mixers M-102 it
Between tail gas drain sump V-103, remove CO reactors R-102 and compressor K-101.
Acrylic acid system is prepared using the one step oxidation of propane of the present embodiment carries out the technical process of acrylic acid production
Can be described as：Raw material propane is vaporized from battery limit (BL) feeder into propane carburator, then Jing propane superheaters
Entry mixers M-102 are entered after E-102 is overheated.Oxygen, nitrogen send into premixer from battery limit (BL) respectively
M-101, is sufficiently mixed with the vapor from battery limit (BL) and from the recycled offgas of absorption tower C-110 tower tops laggard
Enter entry mixers M-102, after being sufficiently mixed with overheated propane, be admitted to selective oxidation of propane reactor
R-101.The gaseous mixture catalyst reaction that Jing is loaded in the reactor is generated comprising acrylic acid gas
Stream, enters quencher V-104 Jing after the cooling section E-103 heat exchange of R-101 bottoms, and Jing is from absorption tower C-110
Acrylic acid aqueous solution spray chilling after, into absorption tower C-110.Washed by the desalination from tower top in tower
The component such as acrylic acid absorbed in gas is washed, in the isolated crude acrylic acid product of bottom of towe.By absorption tower C-110
The reaction end gas that tower top is discharged, a part are burned in draining into waste gas combustion furnace, are partly into tail gas dehydration
After being dehydrated in tank V-103, send in removing CO reactor R-102, Jing catalyst oxidation reactions selectivity takes off
Except CO in reaction end gas, then M-101 is returned Jing after recycle compressor K-101 compressions, Jing M-102 are fully mixed
One step oxidation reaction of propane is continued to participate in into R-101 after conjunction, one step oxidation of propane is realized and is prepared acrylic acid
Serialization.
Embodiment 2
Acrylic acid cyclic production is carried out using the system and method described in embodiment 1.
Flow is 100Kg/h, purity be 99% fresh propane it is overheated through hot device.Flow is respectively 140
The O of Kg/h and 105Kg/h2、N2With the vapor premixing (table 1) that flow is 240Kg/h, Ran Houyu
Recycled offgas (table 2) and overheated propane mixing of the tower top flow for 1040Kg/h, into reactor R-101,
Ring-cylindrical Mo-V-Te-Nb-O mixed metal oxide catalyst is loaded in reactor R-101.Reactor R-101
The feedstock quality percentage composition of entrance each component：H2O is 17.2%, N2For 46.7%, O2For 15.1%,
Propane 13.9%, CO are 0.01%, CO2For 4.5%, propylene is 2.6%.Mixed gas are in the reactor
Reaction generates acrylic acid, acetic acid, CO and CO2.380 DEG C of reaction temperature, pressure normal pressure, mixed gas outlet
420 DEG C of temperature.Whole process conversion of propane 35.5%, acrylic acid selectivity 70.1%.Reactor R-101
After acrylic acid solution spray of the exit gas (table 3) into quencher with 15%, into absorption tower, absorption tower
Pressure is 0.012MPa, 50 DEG C of bottom temperature.With the desalination water washing of the flow 100Kg/h from tower top,
Absorb, separate acrylate component, obtain the crude acrylic acid solution containing acrylic acid 20.0wt%.Gained liquid phase is produced
Thing percentage composition is shown in Table 4.
Table 1
Table 2
Table 3
Table 4
In above-mentioned production process, mainly contain in the reaction end gas that C-110 tower top in absorption tower is discharged propane, third
The compositions such as alkene, oxygen, carbon monoxide, carbon dioxide, nitrogen and water vapour.It is determined that for the tail gas of circulation
Consumption, remainder tail gas drain into burned waste gas device burning disposal as waste gas.For the tail gas Jing of circulation
Tail gas drain sump V-103 60 DEG C operation temperature and 0.01MPa pressure under processed, into removing
CO reactor R-102.Pt/FeO is loaded in the removing CO reactor R-102xCatalyst.The removing
The charging percentage composition of CO reactor R-102 entrance each components：N2For 64.2%, O2For 15.1%, third
Alkane 13.9%, CO are 3.2%, CO2For 2.4%, propylene is 1.2%.Reaction end gas are anti-in removing CO
Answer Jing catalyst oxidation selectivity in device R-102 to remove CO therein, reduce risk of explosion, and propane and third
Alkene content is basically unchanged.130 DEG C of reaction temperature, pressure normal pressure.Reactor outlet gas, i.e. recycled offgas group
Into and proportioning be shown in Table 2.
The recycled offgas is returned in premixer M-101 with the flow of 1040Kg/h Jing after compressor compression,
Fresh propane, oxygen, nitrogen and water vapour with battery limit (BL) source is sufficiently mixed, anti-into selective oxidation of propane
Answer device R-101, realize that the successive reaction and tail gas of acrylic acid production are recycled.
Claims (12)
1. one step oxidation of propane prepares acrylic acid, including propane selectivity oxidation reaction operation, thick third
Olefin(e) acid separation circuit and vent gas treatment operation, described vent gas treatment operation include：Tail gas Jing is dehydrated and is selected
After selecting property removal of carbon monoxide, circulate for selective oxidation of propane operation.
2. method according to claim 1, it is characterised in that described selectively removing carbon monoxide
Realize that catalyst is load type metal catalyst by catalytic selectivity reaction, active component selected from Pt, Pd,
Ru, nanometer gold, Ni, Fe and Mn, loading are 1～5%；Carrier is selected from Al2O3、ZrO2、MgO、
FeOx、SiO2, activated carbon and MCM-41 molecular sieves.
3. method according to claim 2, it is characterised in that described selectively removing carbon monoxide
(CO) 50～200 DEG C of reaction temperature, 0.1～0.5MPa of operating pressure, 2000～5000L of reaction velocity
Kg-1h-1。
4. method according to claim 1, it is characterised in that described tail gas Jing processes latter oxidation
Carbon weight/mass percentage composition is less than 0.01%.
5. method according to claim 1, it is characterised in that described propane selectivity oxidation reaction
Carry out under mixed metal oxide catalyst existence condition, the catalyst contain Mo, V, Sb, Te,
Any 4 kinds in Nb, Al, W, K, Co or more than 4 kinds elements.
6. method according to claim 1, it is characterised in that described propane selectivity oxidation reaction
Unstripped gas in operation is by the vapor from battery limit (BL), O2、N2, propane and Jing after vent gas treatment operation gained
Circulation with tail gas constitute, according to mass percent, the unstripped gas is composed of the following components：H2O
10.0～28.0%；N240.0～50.0%；O210.0～18.0%；Propane 10.0～15.0%；CO0～0.01%；
CO22.0～8.0% and propylene 1.5～5.0%.
7. method according to claim 6, it is characterised in that described propane selectivity oxidation reaction
Using calandria type fixed bed reactor, 300～500 DEG C of operation temperature, 0.1～0.5MPa of operating pressure,
Reaction velocity 2000～5000L Kg-1h-1。
8. one step of propane oxidation prepares acrylic acid system, including the oxidation of raw material premix component, propane selectivity
Reaction component, product separation assembly and vent gas treatment component, it is characterised in that described vent gas treatment component
Connection product separation assembly and raw material premix component, including the tail gas drain sump (V-103) for setting gradually, take off
Except CO reactors (R-102) and compressor (K-101).
9. system according to claim 8, it is characterised in that described removing CO reactors (R-102)
Middle filling load type metal catalyst, its active component selected from Pt, Pd, Ru, nanometer gold, Ni, Fe and
Mn, loading are 1～5%；Carrier is selected from Al2O3、ZrO2、MgO、FeOx、SiO2, activated carbon and
MCM-41 molecular sieves.
10. the system described in claim 8 or 9, including：
Raw material premix component, including entry mixers (M-102), which is used to receive and mixes from battery limit (BL)
Propane, O2、N2, vapor and the recycled offgas from vent gas treatment component, and will be mixed material gas defeated
Deliver to propane selectivity oxidation reaction component；
Propane selectivity oxidation reaction component, for receiving the mixed material from entry mixers (M-102)
Gas is simultaneously catalyzed propane selectivity oxidation reaction and carries out, including the selective oxidation of propane containing cooling section (E-103)
Reactor (R-101)；
Product separation assembly, for receiving the product from propane selectivity oxidation reaction component, separates
Propylene acid crude, and tail gas is exported to vent gas treatment component, including the quencher (V-104) being sequentially connected
With absorption tower (C-110)；
Vent gas treatment component, connection product separation assembly and raw material premix component, for receiving from product point
From the tail gas of component, and the recycled offgas Jing after dehydration and removal of carbon monoxide are processed is input into raw material premix group
Part；Vent gas treatment component include being sequentially connected to absorption tower (C-110) and entry mixers (M-102) it
Between tail gas drain sump (V-103), removing CO reactors (R-102) and compressor (K-101).
11. systems according to claim 10, it is characterised in that described raw material premix component includes
Entry mixers (M-102) and connected propane superheater (E-102) and premixer (M-101)；
The propane superheater (E-102) for receiving and heating the propane of Jing vaporization process, and be transported to into
Material blender (M-102)；Described premixer (M-101) for receive and mix battery limit (BL) input O2、
N2, vapor and from vent gas treatment component recycled offgas, and be transported to entry mixers (M-102).
12. systems according to claim 10, it is characterised in that described selective oxidation of propane reaction
Filling mixed metal oxide catalyst in device (R-101), the catalyst contain Mo, V, Sb, Te,
Any 4 kinds in Nb, Al, W, K, Co or more than 4 kinds elements.
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| CN107935836A (en) * | 2016-10-13 | 2018-04-20 | 中国科学院大连化学物理研究所 | CO selective oxidation removals method, one step oxidation of propane prepare acrylic acid and system |
| CN110835312A (en) * | 2018-08-16 | 2020-02-25 | 中国科学院大连化学物理研究所 | System and process for preparing acrylonitrile by selective ammoxidation of propane |
| CN112439300A (en) * | 2019-09-05 | 2021-03-05 | 中石油吉林化工工程有限公司 | Tail gas treatment system and tail gas treatment method for preparing acrylic acid |
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| CN103193617A (en) * | 2013-03-25 | 2013-07-10 | 中国石油集团东北炼化工程有限公司吉林设计院 | Tail gas circulating process in acrylic acid production by propane one-step method |
| WO2016056851A1 (en) * | 2014-10-07 | 2016-04-14 | 주식회사 엘지화학 | Method and apparatus for manufacturing continuous acrylic acid through propane partial oxidation reaction |
| KR20160041259A (en) * | 2014-10-07 | 2016-04-18 | 주식회사 엘지화학 | Method for continous acrylic acid by partial oxidation of propane and appratus for manufacturing of continous acrylic acid |
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| CN107935836A (en) * | 2016-10-13 | 2018-04-20 | 中国科学院大连化学物理研究所 | CO selective oxidation removals method, one step oxidation of propane prepare acrylic acid and system |
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| CN110835312A (en) * | 2018-08-16 | 2020-02-25 | 中国科学院大连化学物理研究所 | System and process for preparing acrylonitrile by selective ammoxidation of propane |
| CN110835312B (en) * | 2018-08-16 | 2021-03-16 | 中国科学院大连化学物理研究所 | System and process for preparing acrylonitrile by selective ammoxidation of propane |
| CN112439300A (en) * | 2019-09-05 | 2021-03-05 | 中石油吉林化工工程有限公司 | Tail gas treatment system and tail gas treatment method for preparing acrylic acid |
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