CN103240128A - Catalyst and preparation method for preparing methyl methacrylate by composite degradation - Google Patents
Catalyst and preparation method for preparing methyl methacrylate by composite degradation Download PDFInfo
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- CN103240128A CN103240128A CN2013101987069A CN201310198706A CN103240128A CN 103240128 A CN103240128 A CN 103240128A CN 2013101987069 A CN2013101987069 A CN 2013101987069A CN 201310198706 A CN201310198706 A CN 201310198706A CN 103240128 A CN103240128 A CN 103240128A
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Abstract
The invention discloses a catalyst and method for preparing methyl methacrylate by composite degradation. The catalyst is prepared from the following components in parts by weight: 1 part of powder and 1-1.5 parts of peroxide; and the powder is prepared from the following components in parts by weight: 100 parts of oxide, 40-85 parts of chloride and 10-20 parts of organic acid. The catalyst obviously enhances the degradation rate, thereby greatly enhancing the specific yield of the degrader and lowering the energy consumption. The catalyst can enhance the product yield and improve the working environment. The degradation residue of PMMA (polymethyl methacrylate) is reduced by half, the purity of the MMA (methyl methacrylate) crude monomer is enhanced by 10-20%, and the total yield is enhanced by more than 30%.
Description
Technical field
The present invention relates to useless acrylic material is raw material, the catalyst of degraded preparation methyl methacrylate.
Background technology
Acrylic is also referred to as PMMA, and its formal name used at school is polymethyl methacrylate.And seldom use pure methyl methacrylate now, and what use all is the same based copolymers of acrylic acid.So it is more reasonable to be referred to as acrylic (ACRYLIC).
PMMA is commonly called as lucite, and it is obtained by radical polymerization by methyl methacrylate (MMA) monomer, molecular chain length and softening.Be a kind of important thermoplastic, it has excellent optical property and surface property, and its light transmittance reaches 90～92%, and mist degree is not more than 2%, is that transparency is the highest in all plastics.Aspect building, lucite is mainly used in the architectural lighting body, aspects such as transparent roofs, ceiling, telephone booth, stair and room wall backplate.In recent years, the application development aspect expressway and first-class road illuminating lamp shade and automobile lamp is also quite fast.Wherein, the market growth of aspects such as architectural lighting body, bathtub, outdoor advertising lamp box and telephone booth is very fast.Development space from now on is bigger, and market prospects are very wide.
In recent years, construction along with each restaurant, big city, hotel and senior house, China's architectural lighting body development rapidly, the light collecting body made from lucite acryl (acrylic) extrusion board, have the overall construction intensity height, from special benefits such as heavy and light, light transmittance height, security performance height, compare according to putting with unorganic glass daylighting, tool has an enormous advantage.The exploitation of PMMA goods, promote and be applied in when promoting economic development, also produce a large amount of discarded objects because of its large-scale production and consumption.These discarded objects are difficult under the natural conditions and degrade, so can think environmentally hazardous substance.The lucite waste material on the one hand from the substandard product in producing (bubble exists as having in transparent injection moulding sheet material and the section bar, prescription problem is arranged) and the part that can not meet customer need, sprue gate in the forming process and the leftover pieces in the machining, smear metal etc., becomes industrial waste; On the other hand, be to use and consume after poly (methyl methacrylate) plate, engineering plastics and the civilian consumer goods, become consumption back waste material.If can not only can economize on resources to its waste recovery utilization effectively, protect environment, and can form good economic benefits to taking full advantage of of regeneration product.
Reclaim methyl methacrylate monomer by degraded, make the acrylic material goods again by chemical synthesis again.After the lucite degraded, the rate of recovery of monomer can be up to 90%, these characteristics have not only found effective way for the processing of its waste material, and the methyl methacrylate monomer that degraded produces can be made lucite again, thereby reduce the production cost of lucite greatly, produce tangible economic benefit.
The degraded of reaction general name that polymer molecular weight diminishes is comprising depolymerization, random scission and low-molecular-weightly reaction such as remove.Promote the factor of depolymerization to have a lot, as light, heat, mechanical force, ultrasonic wave, chemicals and microorganism etc., also have the common influence of several factors sometimes.
The industrial biodegrading process that adopts has: cracking process, overheating steam method, motlten metal or slaine are made heat transfer medium method, shell and tube pyrolysis furnace cracking process, fluidized bed cracking method and extruder cracking process, their reaction temperature is usually 400～500 ℃ (the common control of the column bottom temperature of overheating steam method will be higher than this temperature, is 550～790 ℃).
Dry distillation method cracking polymethyl methacrylate is one of cleavage method of bibliographical information the earliest.Its method is that waste and old polymethyl methacrylate is ground into fragment earlier, place then in the retort, under atmospheric pressure, with naked light or electrical heating to more than the cracking temperature of polymer.Decompose the monomer vapor that obtains two kinds of processing methods are arranged: the one, monomer vapor is concentrated, further distillation obtains high-purity monomer; Another kind be with monomer vapours directly and other monomer reactions form new acrylic acid series polymeric compounds.When destructive distillation operates in temperature and is higher than cracking temperature, also can under the condition of negative pressure, carry out.The characteristics of dry distillation method are to handle the polymethyl methacrylate waste material of different shape, comprise the substandard product that polymerization process produces, but the thermal efficiency of this technology are low.Use flame heat or electrical heating, cause the interior heat distribution of retort inhomogeneous, temperature near still wall polymer is much higher than still center material temperature, consequently produce more serious coking phenomenon at the still wall, the removing of the residue of this coking is very difficult, has influenced carrying out continuously of course of reaction.
Superheated steam cracking polymethyl methacrylate is to use superheated steam as thermal medium in a cleavage column, and the waste and old polymethyl methacrylate material after will pulverizing with nitrogen or inert gas is sent into the process of decomposing continuously in the tower.Nitrogen fluctuation direction is opposite with the steam flow direction, and the result forms the pneumatic jig effect in steam-heated cleavage column, and the PMMA waste material is ground to particle less than 6mm, brings cleavage column into by inert gas.For the PMMA hybrid particles, the initial big acrylic plastics particle that decomposes is positioned at the bottom of the tower, and temperature is higher, is 550～790 ℃; And the little acrylic plastics particle that decomposes is positioned at cat head, and temperature is 400～550 ℃.Be the monomer polymerization again that prevents from reclaiming, monomer gas must add polymerization inhibitor before entering condenser.
Motlten metal or slaine are a kind of highly effective heat transfer mediums that PMMA decomposes.Used metal has lead, bismuth, cadmium, tin etc. in the PMMA decomposable process, and wherein the most frequently used is plumbous.These metals or salt are heated to more than 500 ℃ in the cracking process of polymethyl methacrylate usually, are in molten condition, and this temperature range is enough to make PMMA to decompose.The alloy of above-mentioned metal also can be done heat transfer medium, comprises the alloy that these metals and other metal alloys form.But the defective that this method exists is that metallic vapour is poisonous and contact area is little.
Recently having developed a kind of liquid and made the continuous recovery technology of mass transfer, is that useless acrylic acid series plastics directly are added on the heat transfer medium surface, and the residue that produces in the decomposition swims in molten metal surface, discharges together with medium after residue reaches predetermined altitude.Heat transfer medium is made up of one or more slaines, can not make useless metha crylic plastics become melt, also can not react with useless metha crylic plastics, used slaine has the mixture of nitrate, sodium nitrate, potassium chloride, sodium chloride, lithium chloride or above-mentioned metallic compound.Motlten metal also can be done liquid heat-transfer medium, and the fusing point of medium generally is lower than 450 ℃, and the relative density of motlten metal or slaine is to contact well with scraped surface in 2.0～3.0 o'clock.Because during with bath of molten metal decomposed P MMA, the solid in the medium and decompose residues need constantly cleaning, replace heat transfer medium so people develop with destilling tower again, are provided with a series of " U " shape pipe in the tower, with natural gas, oil or similar fuel heating." U " shape pipe extends to useless acrylic acid series plastics bed bottom, when waste material contacts with " U " shape pipe of heating, decomposes immediately.Decomposing steam cools off with a condenser that directly contacts, the content of MMA monomer is up to 90%～95% in the condensed product, further distillation purity can reach more than 99%, in whole process, adopt " U " shape pipe to strengthen heat transfer area beyond doubt, whole polymer bed is heated evenly, and this is similar to the effect of motlten metal and slaine a little.
But in the decomposable process, residues such as organic decomposition product and inorganic filler, pigment and other auxiliary agents are deposited on the inwall of pipe and reactor, therefore need cessation reaction after reflecting certain hour, with air and steam flush reactor wall, make residue become the graininess ashes, then vacuum sucking-off or blow out reactor with air.For carrying out continuously of guaranteeing to produce, package unit adopts two destilling towers usually, and such one when cleaning, another still can turn round, and reaches the purpose of continuous decomposition.
The fluidised bed decomposition plastic product is quite general in industrial application, comprises that the multiple plastic product of polyethylene, polypropylene, terylene resin, polyvinyl chloride can carry out resolution process with fluid bed.In recent years, also obtained successful experience with fluidized-bed reactor cracking polymethyl methacrylate.
The waste and old polymethyl methacrylate of fluidized bed cracking is as fluidized solid with bauxite or sandstone, go into fluid bed with nitrogen or other inert blowing gas and make that solid is in fluidized state in the bed, fluidized-bed reactor electricity consumption simultaneously is heated to 510 ℃, useless poly methyl methacrylate plastic enters fluidized-bed layer top after crushed, with decompose immediately after bauxite contacts, collect the steam that decomposes with condenser.Organic equally and inorganic residue in fluid bed, but because the shape that generates is graininess, and be evenly distributed in around the fluidized solid, can be used as a kind of heat transfer medium circulation in fluid bed equally, can't influence the carrying out of cracking process.But the amount of this granular residue will be changed whole fluidized solids after surpassing License Value.
In PMMA decomposes, organic and the inorganic residue that filler in the waste material, pigment, auxiliary agent produce is the difficult problem that many decomposers are difficult to overcome, and in the process of extruder method cracking polymethyl methacrylate, screw rod constantly advances in inner chamber, the pyrolysis solid accessory substance is pushed a residue feeder continuously, and wherein screw flight can prevent that through special design residue is in the internal chamber wall adhesion.The air of introducing trace in cracking zone can further prevent at internal chamber wall coking, in case residue causes deadlock, air enters the cracking zone the coking carbon dioxide that changes into is removed.It is similar to single screw extrusion machine that double screw extruder decomposes useless metha crylic plastics, but extruder need be done the heater heating with the copper of cast.Because two screw threads of double screw extruder intermesh, can more effective elimination dead band and the back-mixing of material, it is more even with the time of staying that handled polymer is heated at the extruder inner chamber, can improve lysis efficiency effectively, and prevent that the lysate degree of depth from transforming.The monomer purity that the purity of the monomer that the employing double screw extruder obtains and the decomposition of liquid heat-transfer medium method obtain is suitable.
Summary of the invention
The objective of the invention is to disclose and a kind ofly prepare the Catalysts and its preparation method of methyl methacrylate for composite degradation, to overcome the above-mentioned defective that prior art exists.
Catalyst of the present invention, formed by the component of following weight portion:
1 part of powder
1～1.5 part of peroxide
Described powder comprises the component of following weight portion:
100 parts of oxides
40～85 parts of chlorides
10～20 parts of organic acids
Wherein:
Described oxide is selected from MnO
2, Fe
2O
3, Co
2O
3, V
2O
5, Al
2O
3Or among the PbO etc. more than one, particle diameter is 400～800 orders;
Described chloride is selected from FeCl
3, ZnCl
2, CaCl
2Or AlCl
3Deng in more than one, particle diameter is 400～800 orders;
Described organic acid is selected from the aliphatic acid of 4～16 carbonic acid, preferred n-butyric acie, isooctyl acid, oleic acid, aphthenic acids or formic acid etc.;
Described peroxide is selected from cumyl peroxide, two " 25 " [2,5-dimethyl-2,5-two (tert-butyl peroxide) hexin-3] or dual-tert-butyl peroxidating diisopropyl benzene etc.;
Described Preparation of catalysts method comprises the steps:
With oxide, chloride and organic acid, added the ball mill ball milling 4～16 hours, become dough, 105～130 ℃ of oven dry 4～6 hours, pulverize then, obtain powder;
Or oxide, chloride and organic acid and water added the sand mill sand milling 0.5～4 hour, and become dough, 105～130 ℃ of oven dry 4～6 hours, pulverize then, obtain powder; The consumption of water is 15～50% of oxide, chloride and organic acid gross weight.
Preferably, oxide, chloride and organic acid and water are added the ball mill ball milling 4～16 hours, become dough, 105～130 ℃ of oven dry 4～6 hours, pulverize then, obtain powder; The consumption of water is 3～6% of oxide, chloride and organic acid gross weight;
The powder that obtains with after peroxide mixes, is crushed to particle diameter 1～10 μ m, can obtains described catalyst;
Catalyst of the present invention can be used for composite degradation and prepare methyl methacrylate, and application process comprises the steps:
The adding screw extruder that particle or pulverous acrylic material and described catalyst is continuous, rotation and shearing at screw rod are rubbed down, push ahead, be introduced into melting zone 240～280 ℃ of following fusions, enter cracking zone again, 300～400 ℃ of following cracking, degraded gas is discharged by outlet, collects methyl methacrylate then from degraded gas;
Particle or the time of staying of pulverous acrylic material in screw extruder are 1～10 minute;
The weight consumption of catalyst is 0.01～2% of acrylic material, preferably 0.1～0.5%;
Described collection method is conventional, comprises the steps:
Degraded gas with outlet is discharged is cooled to 20～50 ℃, collects condensate liquid, is the MMA crude monomer, and purity is 92～96%, and yield is about 90～96%, can obtain smart MMA monomer through steps such as rectifying then, and its purity can surpass 99.5%;
Acrylic material comprises: 1) from the sprue gate in the substandard product in producing (bubble exists as having in transparent injection moulding sheet material and the section bar, the prescription problem is arranged) forming process and the leftover pieces in the machining, smear metal etc.; 2) be to use and consume after poly (methyl methacrylate) plate, engineering plastics and the civilian consumer goods, become consumption back waste material; 3) waste product that produces in the polymerization process and accessory substance.
The present invention has the following advantages: because the existence of catalyst has obviously improved degradation speed, make the specific yield of Degradator improve greatly, can cut down the consumption of energy again.The yield of product can either be improved, also working environment can be improved greatly.The residue that in degradation process, produces, can be used for the tackify of rubber and the preparation of waterproof material owing to contain various polarity group and higher softening point, the residue that in degradation process, produces, can be used for the tackify of rubber and the preparation of waterproof material owing to contain various polarity group and higher softening point, the degraded residue of PMMA reduces half, MMA crude monomer purity improves 10～20%, and overall yield improves more than 30%.
The specific embodiment
Embodiment 1
With oxide, chloride and organic acid and water, added the ball mill ball milling 10 hours, become dough, 120 ℃ of oven dry 5 hours, air-flow was pulverized then, obtained powder; The consumption of water is 6% of oxide, chloride and organic acid gross weight;
The powder that obtains with after peroxide mixes, is crushed to particle diameter 5 μ m, can obtains catalyst;
The parts by weight of component are:
1 part of powder, DCP(cumyl peroxide) 1 part
The weight portion of powder:
V
2O
5100 parts, particle diameter 400 orders;
FeCl
340 parts, particle diameter 400 orders;
20 parts of n-butyric acies
The adding screw extruder that granular acrylic material and above-mentioned catalyst is continuous carries out cracking, the temperature of melting zone is 280 ℃ of fusions, and the temperature of cracking zone is 400 ℃, and degraded gas is discharged by outlet, be cooled to 40 ℃, collect condensate liquid, be the MMA crude monomer, purity is 96%, yield is about 96%, pass through rectification step then, obtain smart MMA monomer, its purity is 99.5%;
The time of staying of acrylic material in screw extruder is 2 minutes; The weight consumption of catalyst is 0.5% of acrylic material.
Embodiment 2
With oxide, chloride and organic acid and water, added the sand mill sand milling 1 hour, become dough, 130 ℃ of oven dry 6 hours, air-flow was pulverized then, obtained powder; The consumption of water is 15% of oxide, chloride and organic acid gross weight.
The powder that obtains with after peroxide mixes, is crushed to particle diameter 5 μ m, can obtains catalyst;
The parts by weight of component are:
1 part of powder
1.5 parts of peroxide
The weight portion of powder:
100 parts of oxides
60 parts of chlorides
10 parts of organic acids
Oxide is iron oxide (Fe
2O
3); Particle diameter is 325 orders;
Chloride is zinc chloride (ZnCl
2), particle diameter is 325 orders;
Organic acid is isooctyl acid;
Peroxide is BIPB(dual-tert-butyl peroxidating diisopropyl benzene);
The adding screw extruder that pulverous acrylic material and above-mentioned catalyst is continuous carries out cracking, the temperature of melting zone is 240 ℃ of fusions, and the temperature of cracking zone is 350 ℃, and degraded gas is discharged by outlet, be cooled to 30 ℃, collect condensate liquid, be the MMA crude monomer, purity is 95%, yield is about 96%, pass through rectification step then, obtain smart MMA monomer, its purity is 99.5%;
The time of staying of acrylic material in screw extruder is 2.5 minutes, and the weight consumption of catalyst is 0.1% of acrylic material.
Embodiment 3
With oxide, chloride and organic acid and water, added the ball mill ball milling 10 hours, become dough, 120 ℃ of oven dry 5 hours, air-flow was pulverized then, obtained powder; The consumption of water is 3% of oxide, chloride and organic acid gross weight;
The powder that obtains with after peroxide mixes, is crushed to particle diameter 5 μ m, can obtains catalyst;
The parts by weight of component are:
1 part of powder
1.3 parts of peroxide
The weight portion of powder:
100 parts of oxides
82 parts of chlorides
15 parts of organic acids
Oxide is cobalt oxide (Co
2O
3), particle diameter is 400 orders;
Chloride is calcium chloride (CaCl
2), particle diameter is 200 orders;
Organic acid is n-butyric acie;
Peroxide is [2,5-dimethyl-2,5-two (tert-butyl peroxide) hexin-3];
The adding screw extruder that granular acrylic material and above-mentioned catalyst is continuous carries out cracking, the temperature of melting zone is 260 ℃ of fusions, and the temperature of cracking zone is 350 ℃, and degraded gas is discharged by outlet, be cooled to 20 ℃, collect condensate liquid, be the MMA crude monomer, purity is 92%, yield is about 96%, pass through rectification step then, obtain smart MMA monomer, its purity is 99.5%;
The time of staying of acrylic material in screw extruder is 1 minute; The weight consumption of catalyst is 0.4% of acrylic material.
Embodiment 4
With oxide, chloride and organic acid and water, added the ball mill ball milling 10 hours, become dough, 120 ℃ of oven dry 5 hours, air-flow was pulverized then, obtained powder; The consumption of water is 4% of oxide, chloride and organic acid gross weight;
The powder that obtains with after peroxide mixes, is crushed to particle diameter 5 μ m, can obtains catalyst;
The parts by weight of component are:
1 part of powder
1 part of peroxide
The weight portion of powder:
100 parts of oxides
45 parts of chlorides
20 parts of organic acids
Oxide is vanadium oxide (V
2O
5), particle diameter is 325 orders;
Chloride is zinc chloride (ZnCl
2), particle diameter is 400 orders;
Organic acid is aphthenic acids;
Peroxide is the DCP(cumyl peroxide);
The adding screw extruder that granular acrylic material and above-mentioned catalyst is continuous carries out cracking, the temperature of melting zone is 270 ℃ of fusions, and the temperature of cracking zone is 380 ℃, and degraded gas is discharged by outlet, be cooled to 30 ℃, collect condensate liquid, be the MMA crude monomer, purity is 95%, yield is about 95%, pass through rectification step then, obtain smart MMA monomer, its purity can surpass 99.8%;
The time of staying of acrylic material in screw extruder is 1.5 minutes, and the weight consumption of catalyst is 0.2% of acrylic material.
Embodiment 5
Oxide, chloride and organic acid and water were added the sand mill sand milling 2 hours, become dough, 120 ℃ of oven dry 5 hours, air-flow was pulverized then, obtained powder; The consumption of water is 30% of oxide, chloride and organic acid gross weight.
The powder that obtains with after peroxide mixes, is crushed to particle diameter 5 μ m, can obtains catalyst;
The parts by weight of component are:
1 part of powder
1 part of peroxide
The weight portion of powder:
100 parts of oxides
80 parts of chlorides
12 parts of organic acids
Oxide is lead oxide (PbO); Particle diameter is 200 orders;
Chloride is iron chloride (Fe
2O
3), particle diameter is 400 orders;
Organic acid is isooctyl acid;
Peroxide is the DCP(cumyl peroxide);
The adding screw extruder that granular acrylic material and above-mentioned catalyst is continuous carries out cracking, the temperature of melting zone is 240 ℃ of fusions, and the temperature of cracking zone is 450 ℃, and degraded gas is discharged by outlet, be cooled to 40 ℃, collect condensate liquid, be the MMA crude monomer, purity is 95%, yield is about 96%, pass through rectification step then, obtain smart MMA monomer, its purity can surpass 99.5%; The time of staying of acrylic material in screw extruder is 2.5 minutes; The weight consumption of catalyst is 0.4% of acrylic material.
Claims (10)
1. be used for the catalyst that composite degradation prepares methyl methacrylate, it is characterized in that, formed by the component of following weight portion:
1 part of powder
1～1.5 part of peroxide
Described powder comprises the component of following weight portion:
100 parts of oxides
40～85 parts of chlorides
10～20 parts of organic acids.
2. according to claim 1ly prepare the catalyst of methyl methacrylate for composite degradation, it is characterized in that described oxide is selected from MnO
2, Fe
2O
3, Co
2O
3, V
2O
5, Al
2O
3Or among the PbO more than one.
3. according to claim 2ly prepare the catalyst of methyl methacrylate for composite degradation, it is characterized in that described oxide diameter sizes is 400～800 orders.
4. according to claim 1ly prepare the catalyst of methyl methacrylate for composite degradation, it is characterized in that described chloride is selected from FeCl
3, ZnCl
2, CaCl
2Or AlCl
3In more than one.
5. according to claim 4ly prepare the catalyst of methyl methacrylate for composite degradation, it is characterized in that described chloride particle diameter is 400～800 orders.
6. according to claim 4ly prepare the catalyst of methyl methacrylate for composite degradation, it is characterized in that described oxide is selected from MnO
2, Fe
2O
3, Co
2O
3, V
2O
5, Al
2O
3Or among the PbO more than one.
7. according to claim 1ly prepare the catalyst of methyl methacrylate for composite degradation, it is characterized in that described organic acid is selected from the aliphatic acid of 4～16 carbonic acid.
8. according to claim 6ly prepare the catalyst of methyl methacrylate for composite degradation, it is characterized in that described organic acid is selected from the aliphatic acid of 4～16 carbonic acid.
9. according to each described catalyst for preparing methyl methacrylate for composite degradation of claim 1～8, it is characterized in that, described peroxide is selected from cumyl peroxide, two " 25 " [2,5-dimethyl-2,5-two (tert-butyl peroxide) hexin-3] or dual-tert-butyl peroxidating diisopropyl benzene.
10. each describedly prepares the catalyst of methyl methacrylate for composite degradation according to claim 1～9, the preparation method, it is characterized in that, comprise the steps:
With oxide, chloride and organic acid, added the ball mill ball milling 4～16 hours, become dough, 105～130 ℃ of oven dry 4～6 hours, pulverize then, obtain powder; The powder that obtains with after peroxide mixes, is crushed to particle diameter 1～10 μ m, can obtains described catalyst;
Or
Oxide, chloride and organic acid and water are added the sand mill sand milling 0.5～4 hour, become dough, 105～130 ℃ of oven dry 4～6 hours, pulverize then, obtain powder; The consumption of water is 3～6% of oxide, chloride and organic acid gross weight;
Perhaps:
Or oxide, chloride and organic acid and water added the sand mill sand milling 0.5～4 hour, and become dough, 105～130 ℃ of oven dry 4～6 hours, pulverize then, obtain powder; The consumption of water is 15～50% of oxide, chloride and organic acid gross weight.
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| CN111362786A (en) * | 2018-12-25 | 2020-07-03 | 万华化学集团股份有限公司 | Method for recycling methyl acrylate heavy component |
| CN113462016A (en) * | 2020-03-30 | 2021-10-01 | 中石油吉林化工工程有限公司 | Pyrolysis recovery equipment for producing polymethyl methacrylate |
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| US20080195223A1 (en) * | 2006-11-03 | 2008-08-14 | Avram Allan Eddin | Materials and Methods and Systems for Delivering Localized Medical Treatments |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111362786A (en) * | 2018-12-25 | 2020-07-03 | 万华化学集团股份有限公司 | Method for recycling methyl acrylate heavy component |
| CN113462016A (en) * | 2020-03-30 | 2021-10-01 | 中石油吉林化工工程有限公司 | Pyrolysis recovery equipment for producing polymethyl methacrylate |
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|---|---|
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