CN106631759B - A kind of system and method producing methacrylic acid coproducing methyl methacrylaldehyde - Google Patents
A kind of system and method producing methacrylic acid coproducing methyl methacrylaldehyde Download PDFInfo
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- CN106631759B CN106631759B CN201611128699.5A CN201611128699A CN106631759B CN 106631759 B CN106631759 B CN 106631759B CN 201611128699 A CN201611128699 A CN 201611128699A CN 106631759 B CN106631759 B CN 106631759B
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- methacrolein
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- methacrylic acid
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 76
- ACWQBUSCFPJUPN-UHFFFAOYSA-N 2-methylbut-2-enal Chemical compound CC=C(C)C=O ACWQBUSCFPJUPN-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 13
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims abstract description 228
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 62
- 239000002253 acid Substances 0.000 claims abstract description 61
- 230000003647 oxidation Effects 0.000 claims abstract description 60
- 238000010521 absorption reaction Methods 0.000 claims abstract description 55
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000010828 elution Methods 0.000 claims abstract description 50
- 238000011084 recovery Methods 0.000 claims abstract description 28
- 238000009834 vaporization Methods 0.000 claims abstract description 23
- 230000008016 vaporization Effects 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 45
- 239000000047 product Substances 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 25
- 230000003197 catalytic effect Effects 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 23
- 238000000605 extraction Methods 0.000 claims description 20
- 239000012071 phase Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 239000012530 fluid Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 238000004064 recycling Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000012856 packing Methods 0.000 claims description 9
- 150000001299 aldehydes Chemical class 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 7
- 239000007792 gaseous phase Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000011964 heteropoly acid Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 239000010808 liquid waste Substances 0.000 claims 1
- 238000004056 waste incineration Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 208000012839 conversion disease Diseases 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- -1 feedstock preheater Chemical compound 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- 230000000694 effects Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000002745 absorbent Effects 0.000 description 6
- 239000002250 absorbent Substances 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
-
- 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
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
Abstract
The invention discloses a kind of method and systems for producing methacrylic acid coproducing methyl methacrylaldehyde, including feedstock preheater, feed vaporization tower, first oxidation reactor, second oxidation reactor, chilling acid elution coupled, methacrolein stripper, methacrolein absorption tower, methacrolein recovery tower, methacrolein lightness-removing column and methacrolein weight-removing column, by the raw material tert-butyl alcohol or isobutene preheating vaporization, then with air, equipped with the fixed bed reactors of catalyst oxidation reaction generation methacrylic acid and methacrolein occur for the warp let-off after water mixing, and through effective chilling, absorption and rectifying, the crude methacrylic acid of the final methacrolein for obtaining 99%wt and 30%wt；Its advantage is that reaction conversion ratio is high, can effectively recycle unreacted raw material, removes impurity and solid particle, the methacrylic acid and methacrolein of high-purity are produced.
Description
Technical field
The present invention relates to a kind of system and method for producing methacrylic acid coproducing methyl methacrylaldehyde.
Background technique
Methacrylic acid is a kind of important Organic Chemicals, mainly for the production of methyl methacrylate, and the latter
It can be used for producing the chemical products such as coating, auxiliary agent, or as raw material for producing organic glass.
Methacrolein is not only the important intermediate of synthesizing methyl acrylic acid and methyl methacrylate, and synthesis doctor
The intermediate of the important fine chemical product such as medicine, pesticide, dyestuff.
Using the tert-butyl alcohol or isobutene catalysis oxidation production methacrolein and methacrylic acid be very cleaning and it is important
Method.How to effectively improve reaction conversion ratio is to improve reaction efficiency, improve product quality, reduces the key of process energy consumption.
There are the impurity such as unreacted raw material, by-product in the tert-butyl alcohol or isobutene catalytic oxidation process simultaneously, how effectively to recycle original
Material, removal impurity also directly influence production cost and product quality.Further, since will form terephthaldehyde in reaction process
Acid, it can be in the form of solid particle there are in liquid-phase reaction product, and how easy occluding device and pipeline effectively remove to benzene two
Formic acid is also particularly important to improve the device cycle of operation.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of reaction conversion ratio height, impurity and solid can be effectively removed
Grain, and maximumlly reduce the method and system of the production methacrylic acid coproducing methyl methacrylaldehyde of system capacity consumption, the life
The method and system for producing methacrylic acid coproducing methyl methacrylaldehyde can effectively recycle unreacted raw material.
The technical scheme of the invention to solve the technical problem is: a kind of production methacrylic acid coproducing methyl third
The system of olefine aldehydr, including feedstock preheater, feed vaporization tower, air compressor, the first oxidation reactor, the second oxidation are instead
Answer device, chilling acid elution coupled, methacrolein stripper, methacrolein absorption tower, methacrolein recovery tower, methyl
Methacrylaldehyde lightness-removing column and methacrolein weight-removing column；
The feedstock preheater is connect with the upper feed inlet of the feed vaporization tower, the feed vaporization
The top discharge mouth of tower and air compressor outlet pass through the first mixer and first oxidation reactor
The bottom discharge port of the connection of top feed mouth, first oxidation reactor passes through the second mixer and second oxidation
The bottom feed inlet of reactor connects, the air compressor pass sequentially through third mixer and second mixer with
The bottom feed inlet of second oxidation reactor connects；
The top discharge mouth of second oxidation reactor is coupled by First Heat Exchanger with the chilling acid elution
The tower reactor of tower connects, and the bottom discharge port of the chilling acid elution coupled passes through the second heat exchanger and the metering system
The upper feed inlet of aldehyde stripper connects, the upper part discharge port of the chilling acid elution coupled and the methacrolein
The lower part feed inlet on absorption tower connects, and the bottom discharge port of the methacrolein stripper passes through second heat exchanger
It is connect with the methacrolein absorption tower, crude methacrylic acid discharge port is provided on second heat exchanger, it is described
The top discharge mouth of methacrolein stripper, the bottom discharge port on the methacrolein absorption tower pass through third respectively
Heat exchanger is connect with the middle part feed inlet of the methacrolein recovery tower, and the top on the methacrolein absorption tower goes out
Material mouth is connected with catalytic burning unit, the middle part discharge port on the methacrolein absorption tower and the chilling acid elution coupling
The top feed mouth connection of tower is closed, the top discharge mouth of the methacrolein recovery tower and the methacrolein are de- light
The middle part feed inlet of tower connects, and the bottom discharge port of the methacrolein recovery tower passes through the third heat exchanger and institute
The middle part feed inlet on the methacrolein absorption tower stated is connected, the bottom discharge port of the methacrolein recovery tower also with
The tower reactor of the chilling acid elution coupled connects, the bottom discharge port of the methacrolein lightness-removing column and the first
The middle part feed inlet of base methacrylaldehyde weight-removing column connects, the top discharge mouth of the methacrolein lightness-removing column and described second
Mixer connects, and is provided with methacrolein discharge port, the metering system at the top of the methacrolein weight-removing column
The bottom of aldehyde weight-removing column is provided with discard solution discharge port.
The catalytic burning unit is connected with the tail-gas compressor for pressure-raising part incineration tail gas, the tail gas pressure
The discharge port of contracting machine is connect with first mixer and second mixer respectively, on the catalytic burning unit
It is provided with the exhaust port for discharging remaining incineration tail gas.
First oxidation reactor and second oxidation reactor are calandria type fixed bed isothermal reactor,
First oxidation reactor is equipped with the composite oxide catalysts containing molybdenum, and second oxidation reactor is equipped with containing molybdenum
Heteropolyacid salt catalyst.
3~6 layers are longitudinally evenly equipped in the chilling acid elution coupled for separating the methacrylic acid and institute
The packing layer for the methacrolein stated, the side wall of the chilling acid elution coupled and position corresponding with the packing layer
It is separately provided for the 4th heat exchanger of cooling circulation liquid.
The tower top of the chilling acid elution coupled is provided with for separating the methacrolein and pair
The washing orifice plate of terephthalic acid particles, is provided with multiple sorting holes on the washing orifice plate, the washing orifice plate with it is described
Packing layer between be provided with connecting pipe for conveying gaseous phase materials, taper protection is provided with above the connecting pipe
It covers, the seedpod of the lotus of the methacrylic acid solution returned for Sprayer Circulation is provided with right above the taper shield
Head.
A method of producing methacrylic acid coproducing methyl methacrylaldehyde, comprising the following steps:
1) the raw material tert-butyl alcohol or isobutene are sent into feedstock preheater, feed vaporization tower are sent into after being preheating to 100 DEG C,
In feed vaporization tower, the raw material tert-butyl alcohol or isobutene heating vaporization with impurity separating-purifying and are further superheated to 140 DEG C,
By the tert-butyl alcohol or isobutene after vaporization and the part from methacrolein absorption tower tower top after catalytic burning through tail gas pressure
Tail gas after contracting machine pressure-raising and the fresh air after air compressor pressure-raising are sent into the first oxygen after the mixing of the first mixer
Change reactor；
It 2) is 150~400 DEG C by the temperature control of the first oxidation reactor, pressure control is 0.05~0.15MPaG, uncle
Butanol or isobutene and oxygen react and generate methacrolein, by the reaction product of the first oxidation reactor bottom discharge port
Second is sent into after mixing with humidifying air and from the methacrolein that methacrolein lightness-removing column is recycled back to through the second mixer
Oxidation reactor；Wherein the molar ratio of the first oxidation reactor inlet tert-butyl alcohol and oxygen or isobutene and oxygen is 1:1.5
~3, the tert-butyl alcohol is 1:10~12 with the molar ratio of nitrogen or isobutene and nitrogen；Humidifying air is for steam and through air compressor
Fresh air after pressure-raising is sent into third mixer mixing gained；
It 3) is 150~400 DEG C by the temperature control of the second oxidation reactor, pressure control is 0.05~0.15MPaG, first
Base methacrylaldehyde and oxygen reaction generate methacrylic acid, and the reaction product of the second oxidation reactor top discharge mouth is changed through first
Hot device and boiler water heat exchange recycling heat, are then fed into the lower part feed inlet of chilling acid elution coupled；
4) it is 5~35 DEG C by the tower top temperature control of chilling acid elution coupled, is absorbed through circulation fluid chilling, tower top obtains
Gas-phase product is sent into the lower part on methacrolein absorption tower by the gas-phase product containing partial size less than 20 μm of particles；Tower bottom extraction temperature
Crude methacrylic acid is sent into methacrolein stripper after the preheating of the second heat exchanger by the crude methacrylic acid that degree is 70 DEG C；
5) gas-phase product is absorbed in methacrolein absorption tower through the methacrylic acid solution that concentration is 5%-30%wt
Afterwards, the top gaseous phase production on methacrolein absorption tower send to catalytic burning unit and carries out burning disposal；By methacrolein
Absorbing tower kettle liquid is by being sent into methacrolein recovery tower after the heat exchange heating of third heat exchanger；
6) methacrolein pressure of stripping tower is controlled in 20~80KPaA, temperature is controlled at 60~100 DEG C, will be through stripping
The crude methacrylic acid solution that the concentration that tower bottom obtains afterwards is 30%wt transmitting system after the heat exchange cooling of the second heat exchanger；Tower top
It produces methacrolein and methacrolein recovery tower is sent by third heat exchanger；
7) by methacrolein recycling pressure tower control in 100~120KPaA, temperature control is at 50~120 DEG C, methyl-prop
Olefine aldehydr recovery tower overhead extraction contains the gas-phase product of methacrolein, and the gas-phase product containing methacrolein is sent into methyl
The methacrylic acid solution of methacrolein recycling tower bottom extraction is sent into first through third heat exchanger by the processing of methacrylaldehyde lightness-removing column
Absorbing liquid of the base Acrolein absorption tower as methacrolein, and according to methacrolein recycle tower bottoms amount situation of change,
The methacrylic acid solution interval of methacrolein recycling tower bottom extraction is branched into chilling acid elution coupled；
8), methacrolein lightness-removing column pressure is controlled in 50~90KPaA, temperature is controlled at 40~100 DEG C, by toluene,
Polymerization inhibitor is sent into methacrolein lightness-removing column, handles through extracting rectifying, the tower top of final methacrolein lightness-removing column obtains light group
Divide product, light component product is sent into the second mixer entrance, the tower bottom extraction of methacrolein lightness-removing column contains metering system
Material containing methacrolein is sent into the processing of methacrolein weight-removing column by the material of aldehyde；
9), methacrolein weight-removing column pressure is controlled in 50~90KPaA, temperature controls at 40~120 DEG C, will contain
The material refining spearation of methacrolein, tower top obtain the methacrolein and output system of high-purity, and tower bottom discharge waste liquid is burnt
Burning processing.
It will divide after gas warp let-off tail-gas compressor pressure-raising after a portion catalytic burning in step (4) as inert gas
It does not send to the entrance of the first mixer and the second mixer, gas discharge system after another part catalytic burning.
The variation that metering system acid concentration in tower bottoms is absorbed according to methacrolein, by methacrolein stripper tower reactor
Liquid interval extraction a part is sent to methacrolein absorption tower, so that methacrolein is absorbed metering system acid concentration in tower bottoms and is protected
It holds in 5%-30%wt.
The crude methacrylic acid that temperature is 70 DEG C in step (4) is by flowing through the output production concentration of the second heat exchanger
The crude methacrylic acid solution of 30%wt preheats；Absorbing liquid in step (7) is inhaled by flowing through the methacrolein of third heat exchanger
Receive the cooling of tower tower bottoms.
For gas by tower reactor circulation fluid spray-absorption in chilling acid elution coupled, circulation fluid passes through the 4th in step (3)
Heat exchanger is cooled down；Lower section gas after chilling is upwardly into the middle section of chilling acid elution coupled, is sprayed by middle section circulation fluid
Leaching absorbs；Middle section gas is upwardly into the upper section of chilling acid elution coupled further by upper section circulation fluid spray-absorption.
Compared with the prior art, the advantages of the present invention are as follows: the invention discloses a kind of production methacrylic acid coproduction first
The method and system of base methacrylaldehyde, by the raw material tert-butyl alcohol or isobutene preheating vaporization, the warp let-off is equipped with after then mixing with empty gas and water
The calandria type fixed bed isothermal reactor of catalyst occurs oxidation reaction and generates methacrylic acid and methacrolein, and through effective
Chilling, absorption and filtering, the crude methacrylic acid of the final methacrolein for obtaining 99%wt and 30%wt, advantage are as follows:
1, at 150~400 DEG C, pressure is controlled between 0.05~0.15MPaG for the temperature control of the first oxidation reactor,
Feed composition control: the molar ratio of the tert-butyl alcohol or isobutene and oxygen is 1:1.5~3, the tert-butyl alcohol or isobutene and nitrogen 1:10
~12.To guarantee that the tert-butyl alcohol or isobutene conversion in > 99%, selectively guarantee between 70~85%, to guarantee second
The temperature, pressure and compositing range of oxidation reactor ensure that the safety of system not within the scope of explosion limit.
2, using chilling acid elution coupled, multiple absorption towers and a scrubbing tower are realized by chilling acid elution coupled
The separating effect that can be realized.
Tower top setting turns to gas and liquid flowing and washs orifice plate, and the terephthalic acid (TPA) carried secretly in overhead extraction gas phase can be effectively controlled
Grain diameter is maintained within 20 μm, and terephthalic acid (TPA) in gas phase is effectively avoided to be set in tower inner member and inner wall of the pipe, with
The blocking of equipment and pipeline during reduction, while product yield can be improved, and then the production efficiency of whole device is improved.
Methacrolein and methacrylic acid are separated by the way of absorbing by water, in the way of gas-liquid counter current,
Methacrylic acid in gas phase can be absorbed as to liquid phase, enhance assimilation effect.By adjusting the dosage of recirculated water, tower top temperature is controlled
It is 5~35 DEG C, to guarantee that metering system acid concentration is not too high in top gaseous phase, can reduce the energy of later separation methacrylic acid
Amount consumption.
4th heat exchanger of multistage cooling circulation liquid is set, using self-circulation mode absorption condensation, reduces absorbent dosage,
Separating effect is improved, and tower inner member is effectively washed away, column plate blocking is reduced, improves the runing time of device.
3, for the gas that methacrolein absorption tower top row goes out after catalytic burning removes organic matter, a part passes through tail gas pressure
It is respectively fed to the first mixer and the second mixer after contracting machine pressure-raising, remaining gas drains into atmosphere.Tail gas is burnt through catalysis after absorption
20~40%wt after burning is recycled, first is that the utilities such as the vapor in recycled offgas can be recycled, can be reduced anti-
It answers the supply amount of required vapor and reduces the discharge amount of system waste water；Second is that high heat (about 100 DEG C) after being burned using tail gas,
To reduce supply outside reaction institute's calorific requirement；Third is that can remove objectionable impurities after catalytic burning, avoid recycled offgas into
After entering reactor, makes to react used catalyst poisoning and deactivation, reduce reaction effect.
4, concentration is used to absorb methacrolein as absorbent for the methacrylic acid solution of 5%~30%wt.Using molten
The similar principle that mixes of liquid selects certain density methacrylic acid solution to make there are two absorbent has compared with water makees absorbent
Advantage: first is that methacrylic acid solution is bigger to the solubility of methacrolein, it is more preferable to the assimilation effect of methacrolein；Two
It is that can reduce the production cost of product there is no the Desorption separation to absorbent.
5, a certain amount of metering system aqueous acid is recycled back into such a way that interval flows back.It is absorbed according to methacrolein
The variation of metering system acid concentration in tower bottoms send methacrolein stripper tower bottoms interval extraction a part to methyl-prop
The situation of change of tower bottoms amount is recycled on olefine aldehydr absorption tower according to methacrolein, by methacrolein recycling tower bottom extraction
Methacrylic acid solution interval branches to chilling acid elution coupled, in the absorbent that can effectively ensure that methacrolein absorption tower
The concentration of methacrylic acid maintains 5%~30%wt always, it is ensured that will not be with methyl-prop to the assimilation effect of methacrolein
Olefin(e) acid is reduced and is reduced.
6, the second heat exchanger is set between methacrolein stripper and chilling acid elution coupled, utilizes metering system
The high-temperature material of aldehyde stripper tower reactor extraction can make the steam consumption of the tower with into the crude methacrylic acid aqueous solution heat exchange before tower
10%~20% is reduced, and the Srteam Stripping effect of methacrolein can be improved, is effectively reduced in tower reactor crude methacrylic acid solution
The content of methacrolein.
7, higher boiling additive is done using toluene, and polymerization inhibitor is added in methacrolein lightness-removing column, change metering system
Relative volatility between aldehyde and light component separates light component easily from methacrolein solution, and utilizes extracting rectifying
Mode separate light component with methacrolein.Containing for light component in tower reactor methacrolein solution can be reduced in this way
Amount, and the thermic load of methacrolein lightness-removing column can be reduced, while preventing material from polymerizeing.
Detailed description of the invention
Fig. 1 reacts for the tert-butyl alcohol/isobutene of the present invention with dioxygen oxidation produces methacrylic acid and methacrolein simultaneously
System structural schematic diagram；
Fig. 2 is chilling acid elution coupled structural schematic diagram of the invention.
Specific embodiment
Make below in conjunction with system of the figure embodiment to production methacrylic acid coproducing methyl methacrylaldehyde of the invention into one
Step detailed description.
Embodiment: as depicted in figs. 1 and 2, a kind of system producing methacrylic acid coproducing methyl methacrylaldehyde, including raw material
Feed preheater 1, feed vaporization tower 2, air compressor 3, the first oxidation reactor 4, the second oxidation reactor 5, chilling pickling
It is de- to wash coupled 6, methacrolein stripper 7, methacrolein absorption tower 8, methacrolein recovery tower 9, methacrolein
Light tower 10 and methacrolein weight-removing column 11；
Feedstock preheater 1 is connect with the upper feed inlet of feed vaporization tower 2, the top discharge mouth of feed vaporization tower 2
It is connect by the first mixer 12 with the top feed mouth of the first oxidation reactor 4 with the outlet of air compressor 3, the first oxidation
The bottom discharge port of reactor 4 is connect by the second mixer 13 with the bottom feed inlet of the second oxidation reactor 5, air compression
Machine 3 passes sequentially through third mixer 14 and the second mixer 13 is connect with the bottom feed inlet of the second oxidation reactor 5；
The top discharge mouth of second oxidation reactor 5 passes through the tower reactor of First Heat Exchanger 15 and chilling acid elution coupled 6
Connection, the bottom discharge port of chilling acid elution coupled 6 by the top of the second heat exchanger 16 and methacrolein stripper 7 into
Material mouth connection, the upper part discharge port of chilling acid elution coupled 6 are connect with the lower part feed inlet on methacrolein absorption tower 8, first
The bottom discharge port of base methacrylaldehyde stripper 7 is connect by the second heat exchanger 16 with methacrolein absorption tower 8, the second heat exchanger
Crude methacrylic acid discharge port, the top discharge mouth of methacrolein stripper 7, methacrolein absorption tower 8 are provided on 16
Bottom discharge port pass through third heat exchanger 17 respectively and connect with the middle part feed inlet of methacrolein recovery tower 9, metering system
The top discharge mouth on aldehyde absorption tower 8 is connected with catalytic burning unit 18, the middle part discharge port and chilling on methacrolein absorption tower 8
The top feed mouth of acid elution coupled 6 connects, the top discharge mouth and methacrolein lightness-removing column of methacrolein recovery tower 9
10 middle part feed inlet connection, the bottom discharge port of methacrolein recovery tower 9 pass through third heat exchanger 17 and methacrolein
The middle part feed inlet on absorption tower 8 is connected, the bottom discharge port of methacrolein recovery tower 9 also with chilling acid elution coupled 6
Tower reactor connection, the middle part feed inlet of the bottom discharge port of methacrolein lightness-removing column 10 and methacrolein weight-removing column 11 connects
It connects, the top discharge mouth of methacrolein lightness-removing column 10 is connect with the second mixer 13, the top of methacrolein weight-removing column 11
It is provided with methacrolein discharge port 19, the bottom of methacrolein weight-removing column 11 is provided with discard solution discharge port 20.
In this particular embodiment, catalytic burning unit 18 is connected with the tail-gas compressor for pressure-raising part incineration tail gas
21, the discharge port of tail-gas compressor 21 is connect with the first mixer 12 and the second mixer 13 respectively, on catalytic burning unit 18
It is provided with the exhaust port 22 for discharging remaining incineration tail gas.
In this particular embodiment, the first oxidation reactor 4 and the second oxidation reactor 5 are calandria type fixed bed isothermal
Reactor, the first oxidation reactor 4 are equipped with the composite oxide catalysts containing molybdenum, and the second oxidation reactor 5 is equipped with containing the miscellaneous of molybdenum
Polyacid salt catalyst.
In this particular embodiment, 3~6 layers are longitudinally evenly equipped in chilling acid elution coupled 6 for separating metering system
The packing layer 23 of acid and methacrolein, the side wall of chilling acid elution coupled 6 and position corresponding with packing layer 23 is set respectively
It is equipped with the 4th heat exchanger 24 for cooling circulation liquid.
In this particular embodiment, the tower top of chilling acid elution coupled 6 is provided with for separating methacrylic acid and first
The washing orifice plate 25 of base methacrylaldehyde washs and is provided with multiple sorting holes on orifice plate 25, washs and sets between orifice plate 25 and packing layer 23
It is equipped with the connecting pipe 26 for conveying gaseous phase materials, taper shield 27, taper shield are provided with above connecting pipe 26
27 surface is provided with the shower nozzle 28 of the methacrylic acid solution returned for Sprayer Circulation.
The present invention also provides a kind of lifes corresponding with the system of above-mentioned production methacrylic acid coproducing methyl methacrylaldehyde
Production method is with reference to embodiments described in further detail production method of the invention.
Embodiment: a method of producing methacrylic acid coproducing methyl methacrylaldehyde, comprising the following steps:
1) the raw material tert-butyl alcohol or isobutene are sent into feedstock preheater 1, feed vaporization tower is sent into after being preheating to 100 DEG C
2, in feed vaporization tower 2, the raw material tert-butyl alcohol or isobutene are heated into vaporization and impurity separating-purifying and are further superheated to 140
DEG C, by the tert-butyl alcohol or isobutene after vaporization and the part from 8 tower top of methacrolein absorption tower after catalytic burning through tail
Tail gas after 21 pressure-raising of air compressor and the fresh air after 3 pressure-raising of air compressor are sent after the mixing of the first mixer 12
Enter the first oxidation reactor 4；
It 2) is 150~400 DEG C by the temperature control of the first oxidation reactor 4, pressure control is 0.05~0.15MPaG, uncle
Butanol or isobutene and oxygen react and generate methacrolein, and the reaction of 4 bottom discharge port of the first oxidation reactor is produced
Object is sent after mixing with humidifying air and from the methacrolein that methacrolein lightness-removing column 10 is recycled back to through the second mixer 13
Enter the second oxidation reactor 5；The wherein molar ratio of the 4 inlet tert-butyl alcohol of the first oxidation reactor and oxygen or isobutene and oxygen
For 1:1.5~3, the tert-butyl alcohol is 1:10~12 with the molar ratio of nitrogen or isobutene and nitrogen；Humidifying air is for steam and through sky
Fresh air after 3 pressure-raising of air compressor is sent into the mixing gained of third mixer 14；
It 3) is 150~400 DEG C by the temperature control of the second oxidation reactor 5, pressure control is 0.05~0.15MPaG, first
Base methacrylaldehyde and oxygen reaction generate methacrylic acid, by the reaction product of 5 top discharge mouth of the second oxidation reactor through first
Heat exchanger 15 and boiler water heat exchange recycling heat, are then fed into the lower part feed inlet of chilling acid elution coupled 6；
4) it is 5~35 DEG C by the tower top temperature control of chilling acid elution coupled 6, is absorbed through circulation fluid chilling, tower top obtains
To the gas-phase product containing partial size less than 20 μm of particles, gas-phase product is sent into the lower part on methacrolein absorption tower 8；Tower bottom extraction
Crude methacrylic acid is sent into methacrolein stripping by the crude methacrylic acid that temperature is 70 DEG C after the preheating of the second heat exchanger 16
Tower 7；
5) gas-phase product is absorbed in methacrolein absorption tower 8 through the methacrylic acid solution that concentration is 5%-30%wt
Afterwards, the top gaseous phase production on methacrolein absorption tower 8 send to catalytic burning unit 18 and carries out burning disposal；By metering system
Aldehyde absorbing tower kettle liquid is by being sent into methacrolein recovery tower 9 after the heat exchange heating of third heat exchanger 17；
6) 7 pressure of methacrolein stripper is controlled in 20~80KPaA, temperature is controlled at 60~100 DEG C, will be through vapour
Mention crude methacrylic acid solution that concentration that rear tower bottom obtains is 30%wt transmitting system, tower top after the preheating of the second heat exchanger 16
It produces methacrolein and methacrolein recovery tower 9 is sent by third heat exchanger 17；
7) 9 pressure of methacrolein recovery tower is controlled in 100~120KPaA, temperature control is at 50~120 DEG C, methyl
9 overhead extraction of methacrylaldehyde recovery tower contains the gas-phase product of methacrolein, and the gas-phase product containing methacrolein is sent into
The processing of methacrolein lightness-removing column 10, the methacrylic acid solution that 9 bottom of methacrolein recovery tower produces is exchanged heat through third
Device 17 is sent into absorbing liquid of the methacrolein absorption tower 8 as methacrolein, and recycles tower bottoms amount according to methacrolein
Situation of change, the methacrylic acid solution interval of 9 bottom of methacrolein recovery tower extraction is branched into chilling acid elution coupling
Close tower 6；
8) 10 pressure of methacrolein lightness-removing column is controlled in 50~90KPaA, temperature is controlled at 40~100 DEG C, by first
Benzene, polymerization inhibitor are sent into methacrolein lightness-removing column 10, handle through extracting rectifying, the tower top of final methacrolein lightness-removing column 10 obtains
To light component product, light component product is sent into 13 entrance of the second mixer, the tower bottom extraction of methacrolein lightness-removing column 10 contains
There is the material of methacrolein, the material containing methacrolein is sent into methacrolein weight-removing column 11 and is handled；
9) 11 pressure of methacrolein weight-removing column is controlled in 50~90KPaA, temperature controls at 40~120 DEG C, will contain
The material refining spearation of methacrolein, tower top obtain the methacrolein and output system of high-purity, and tower bottom discharge waste liquid is burnt
Burning processing.
In this particular embodiment, by gas warp let-off tail-gas compressor 21 after a portion catalytic burning in step (4)
It is sent respectively as inert gas to the entrance of the first mixer 12 and the second mixer 13 after pressure-raising, gas after another part burns
Discharge system.
It in this particular embodiment, will according to the variation of metering system acid concentration in methacrolein absorbing tower kettle liquid
Methacrolein stripper tower bottoms interval extraction a part is sent to methacrolein absorption tower 6, and methacrolein absorption tower is made
Metering system acid concentration is maintained at 5%-30%wt in kettle liquid.
In this particular embodiment, the crude methacrylic acid that temperature is 70 DEG C in step (4) is by flowing through the second heat exchanger
The crude methacrylic acid solution that 16 output production concentration is 30%wt preheats；Absorbing liquid in step (7) is changed by flowing through third
The methacrolein absorbing tower kettle liquid of hot device 17 cools down.
In this particular embodiment, gas sprays suction by tower reactor circulation fluid in chilling acid elution coupled 6 in step (3)
It receives, circulation fluid is cooled down by the 4th heat exchanger 24；Lower section gas after chilling is upwardly into chilling acid elution coupled 6
Middle section, by middle section circulation fluid spray-absorption；Middle section gas is upwardly into the upper section of chilling acid elution coupled 6 further by upper section
Circulation fluid spray-absorption.
Claims (8)
1. a kind of system for producing methacrylic acid coproducing methyl methacrylaldehyde, it is characterised in that: including feedstock preheater, original
Expect vaporization tower, air compressor, the first oxidation reactor, the second oxidation reactor, chilling acid elution coupled, methacrolein
Stripper, methacrolein absorption tower, methacrolein recovery tower, methacrolein lightness-removing column and methacrolein weight-removing column；
The feedstock preheater is connect with the upper feed inlet of the feed vaporization tower, the feed vaporization tower
The outlet of top discharge mouth and the air compressor passes through the top of the first mixer and first oxidation reactor
The bottom discharge port of the connection of portion's feed inlet, first oxidation reactor is anti-by the second mixer and second oxidation
The bottom feed inlet of device is answered to connect, the air compressor passes sequentially through third mixer and second mixer and institute
The bottom feed inlet for the second oxidation reactor stated connects；
The top discharge mouth of second oxidation reactor passes through First Heat Exchanger and the chilling acid elution coupled
The bottom discharge port of tower reactor connection, the chilling acid elution coupled passes through the second heat exchanger and the methacrolein vapour
The upper feed inlet of stripper connects, and the upper part discharge port of the chilling acid elution coupled and the methacrolein absorb
The lower part feed inlet of tower connects,
3~6 layers are longitudinally evenly equipped in the chilling acid elution coupled for separating the methacrylic acid and described
The packing layer of methacrolein, the side wall and position corresponding with packing layer difference of the chilling acid elution coupled
It is provided with the 4th heat exchanger for cooling circulation liquid, the tower top of the chilling acid elution coupled is provided with for separating
The washing orifice plate of the methacrolein and the terephthalic acid particles stated is provided with multiple separation on the washing orifice plate
Hole is provided with the connecting pipe for conveying gaseous phase materials, the company between washing orifice plate and the packing layer
It is provided with taper shield above adapter tube road, is provided with right above the taper shield for described in Sprayer Circulation time
Methacrylic acid solution shower nozzle；The bottom discharge port of the methacrolein stripper passes through second heat exchange
Device is connect with the methacrolein absorption tower, and crude methacrylic acid discharge port, institute are provided on second heat exchanger
The top discharge mouth for the methacrolein stripper stated, the methacrolein absorption tower bottom discharge port pass through respectively
Three heat exchangers are connect with the middle part feed inlet of the methacrolein recovery tower, the top on the methacrolein absorption tower
Discharge port is connected with catalytic burning unit, the middle part discharge port on the methacrolein absorption tower and the chilling acid elution
The top feed mouth of coupled connects, and the top discharge mouth of the methacrolein recovery tower and the methacrolein are de-
The middle part feed inlet connection of light tower, the bottom discharge port of the methacrolein recovery tower by the third heat exchanger and
The middle part feed inlet on the methacrolein absorption tower is connected, and the bottom discharge port of the methacrolein recovery tower is also
It is connect with the tower reactor of the chilling acid elution coupled, the bottom discharge port of the methacrolein lightness-removing column and described
The middle part feed inlet of methacrolein weight-removing column connects, the top discharge mouth of the methacrolein lightness-removing column and described the
Two mixers connect, and are provided with methacrolein discharge port, the methyl-prop at the top of the methacrolein weight-removing column
The bottom of olefine aldehydr weight-removing column is provided with discard solution discharge port.
2. a kind of system for producing methacrylic acid coproducing methyl methacrylaldehyde according to claim 1, it is characterised in that institute
The catalytic burning unit stated is connected with the tail-gas compressor for pressure-raising part incineration tail gas, the discharging of the tail-gas compressor
Mouth is connect with first mixer and second mixer respectively, is provided with and is used on the catalytic burning unit
Discharge the exhaust port of remaining incineration tail gas.
3. a kind of system for producing methacrylic acid coproducing methyl methacrylaldehyde according to claim 1, it is characterised in that institute
The first oxidation reactor and second oxidation reactor stated are calandria type fixed bed isothermal reactor, and described first
Oxidation reactor is equipped with the composite oxide catalysts containing molybdenum, and second oxidation reactor is urged equipped with the heteropolyacid salt containing molybdenum
Agent.
4. a kind of method for producing methacrylic acid coproducing methyl methacrylaldehyde, this method is using described in any one of claim 1-3
A kind of system for producing methacrylic acid coproducing methyl methacrylaldehyde, it is characterised in that the following steps are included:
1) the raw material tert-butyl alcohol or isobutene are sent into feedstock preheater, feed vaporization tower are sent into after being preheating to 100 DEG C, in original
Expect in vaporization tower, the raw material tert-butyl alcohol or isobutene are heated into vaporization and impurity separating-purifying and be further superheated to 140 DEG C, by vapour
The tert-butyl alcohol or isobutene after change and the part from methacrolein absorption tower tower top after catalytic burning are through tail-gas compressor
It is anti-that tail gas after pressure-raising and the fresh air after air compressor pressure-raising are sent into the first oxidation after the mixing of the first mixer
Answer device；
It 2) is 150~400 DEG C by the temperature control of the first oxidation reactor, pressure control is 0.05~0.15MPaG, the tert-butyl alcohol
Or isobutene and oxygen react and generate methacrolein, by the reaction product of the first oxidation reactor bottom discharge port and add
Humid air and the second oxidation of feeding after the mixing of the second mixer from the methacrolein that methacrolein lightness-removing column is recycled back to
Reactor；Wherein the molar ratio of the first oxidation reactor inlet tert-butyl alcohol and oxygen or isobutene and oxygen is 1:1.5~3,
The molar ratio of the tert-butyl alcohol and nitrogen or isobutene and nitrogen is 1:10~12；Humidifying air is for steam and through air compressor pressure-raising
Fresh air afterwards is sent into third mixer mixing gained；
It 3) is 150~400 DEG C by the temperature control of the second oxidation reactor, pressure control is 0.05~0.15MPaG, methyl-prop
Olefine aldehydr and oxygen reaction generate methacrylic acid, by the reaction product of the second oxidation reactor top discharge mouth through First Heat Exchanger
It exchanges heat with boiler water and recycles heat, be then fed into the lower part feed inlet of chilling acid elution coupled；
4) it is 5~35 DEG C by the tower top temperature control of chilling acid elution coupled, is absorbed through circulation fluid chilling, tower top is obtained containing grain
Diameter is the gas-phase product less than 20 μm of particles, and gas-phase product is sent into the lower part on methacrolein absorption tower；Tower bottom produces temperature
For 70 DEG C of crude methacrylic acid, crude methacrylic acid is sent into methacrolein stripper after the preheating of the second heat exchanger；
5), gas-phase product is absorbed in methacrolein absorption tower through the methacrylic acid solution that concentration is 5%-30%wt
Afterwards, the top gaseous phase production on methacrolein absorption tower send to catalytic burning unit and carries out burning disposal；By methacrolein
Absorbing tower kettle liquid is by being sent into methacrolein recovery tower after the heat exchange heating of third heat exchanger；
6) methacrolein pressure of stripping tower is controlled in 20~80KPaA, temperature is controlled at 60~100 DEG C, will after stripping tower
The crude methacrylic acid solution that the concentration that bottom obtains is 30%wt transmitting system after the heat exchange cooling of the second heat exchanger；Overhead extraction
Methacrolein is sent into methacrolein recovery tower by third heat exchanger；
7) by methacrolein recycling pressure tower control in 100~120KPaA, temperature control is at 50~120 DEG C, methacrolein
Recovery tower overhead extraction contains the gas-phase product of methacrolein, and the gas-phase product containing methacrolein is sent into metering system
The methacrylic acid solution of methacrolein recycling tower bottom extraction is sent into methyl-prop through third heat exchanger by the processing of aldehyde lightness-removing column
Absorbing liquid of the olefine aldehydr absorption tower as methacrolein, and according to the situation of change of methacrolein recycling tower bottoms amount, by first
The methacrylic acid solution interval of base methacrylaldehyde recycling tower bottom extraction branches to chilling acid elution coupled；
8), methacrolein lightness-removing column pressure is controlled in 50~90KPaA, temperature is controlled at 40~100 DEG C, by toluene, polymerization inhibitor
Methacrolein lightness-removing column is sent into agent, is handled through extracting rectifying, and the tower top of final methacrolein lightness-removing column obtains light component production
Light component product is sent into the second mixer entrance by object, and the tower bottom extraction of methacrolein lightness-removing column contains methacrolein
Material containing methacrolein is sent into the processing of methacrolein weight-removing column by material；
9), methacrolein weight-removing column pressure is controlled in 50~90KPaA, temperature is controlled at 40~120 DEG C, will contain methyl
The material refining spearation of methacrylaldehyde, tower top obtain methacrolein and output system, and liquid waste incineration processing is discharged in tower bottom.
5. a kind of method for producing methacrylic acid coproducing methyl methacrylaldehyde according to claim 4, it is characterised in that will
It is sent respectively as inert gas to first after gas warp let-off tail-gas compressor pressure-raising after a portion catalytic burning in step (5)
The entrance of mixer and the second mixer, gas discharge system after another part catalytic burning.
6. a kind of method for producing methacrylic acid coproducing methyl methacrylaldehyde according to claim 4, it is characterised in that root
The variation that metering system acid concentration in tower bottoms is absorbed according to methacrolein produces methacrolein stripper tower bottoms interval
A part is sent to methacrolein absorption tower, so that methacrolein is absorbed metering system acid concentration in tower bottoms and is maintained at 5%-
30%wt.
7. a kind of method for producing methacrylic acid coproducing methyl methacrylaldehyde according to claim 4, it is characterised in that step
Suddenly the thick first that the crude methacrylic acid that temperature is 70 DEG C in (4) is 30%wt by the output production concentration for flowing through the second heat exchanger
The preheating of base acrylic acid solution；Absorbing liquid in step (7) is by flowing through the methacrolein absorbing tower kettle liquid of third heat exchanger
Cooling.
8. a kind of method for producing methacrylic acid coproducing methyl methacrylaldehyde according to claim 4, it is characterised in that step
Suddenly by tower reactor circulation fluid spray-absorption in chilling acid elution coupled, circulation fluid is carried out gas by the 4th heat exchanger in (3)
It is cooling；Lower section gas after chilling is upwardly into the middle section of chilling acid elution coupled, by middle section circulation fluid spray-absorption；Middle section
Gas is upwardly into the upper section of chilling acid elution coupled further by upper section circulation fluid spray-absorption.
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| SG11202002053RA (en) * | 2017-09-11 | 2020-04-29 | Dow Global Technologies Llc | Method for recovery of methacrolein and methanol from methacrolein dimethylacetal |
| CN110551008B (en) * | 2018-05-30 | 2022-07-19 | 中石油吉林化工工程有限公司 | Tail gas recycling method in acrolein production process |
| CN110551013A (en) * | 2018-05-30 | 2019-12-10 | 中国石油集团东北炼化工程有限公司吉林设计院 | energy recovery method of acrolein refining process |
| JP6574294B1 (en) * | 2018-09-11 | 2019-09-11 | 住友化学株式会社 | Methacrylic acid production equipment |
| JP6611391B1 (en) * | 2018-11-14 | 2019-11-27 | 住友化学株式会社 | Methacrylic acid production equipment |
| JP6611390B1 (en) * | 2018-11-14 | 2019-11-27 | 住友化学株式会社 | Methacrylic acid production equipment |
| CN109232232B (en) * | 2018-11-19 | 2021-06-22 | 平湖石化有限责任公司 | Refining method of acrylic acid |
| 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 |
| CN111138266B (en) * | 2019-11-18 | 2023-07-14 | 中国寰球工程有限公司 | Method and device for preparing acrylic acid or methacrylic acid |
| CN111116335B (en) * | 2019-11-25 | 2023-05-23 | 中国寰球工程有限公司 | Process for preparing acrolein or methacrolein |
| CN111001359A (en) * | 2019-12-30 | 2020-04-14 | 宁夏荆洪生物科技有限公司 | Acrolein tail gas treatment system |
| CN111217697B (en) * | 2020-01-13 | 2022-08-05 | 万华化学集团股份有限公司 | Method for preparing methacrylic acid by gas phase oxidation of C4 compound |
| CN115368231B (en) * | 2022-09-19 | 2024-04-09 | 万华化学集团股份有限公司 | Continuous production process of methacrylic acid |
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