CN103240128B - 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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- CN103240128B CN103240128B CN201310198706.9A CN201310198706A CN103240128B CN 103240128 B CN103240128 B CN 103240128B CN 201310198706 A CN201310198706 A CN 201310198706A CN 103240128 B CN103240128 B CN 103240128B
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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 acrylic material that the present invention relates to give up is raw material, and the catalyst of methyl methacrylate is prepared in degraded.
Background technology
Acrylic is also referred to as PMMA, and its formal name used at school is polymethyl methacrylate.And seldom use now pure methyl methacrylate, and what use is all 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 soft.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 in all plastics, transparency is the highest.Aspect building, lucite is mainly used in architectural lighting body, the 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 the aspect such as architectural lighting body, bathtub, outdoor advertising lamp box and telephone booth is very fast.Development space is from now on larger, and market prospects are very wide.
In recent years, along with the construction of each big city restaurant, hotel and senior house, China's architectural lighting body development rapidly, the light collecting body made from lucite acryl (acrylic) extrusion board, have overall construction intensity high, from heavy and light, the special benefits such as light transmittance is high, security performance is high, compare according to putting with unorganic glass daylighting, tool has an enormous advantage.The exploitation of PMMA goods, propagation and employment, in promoting economic development, also produce a large amount of discarded objects because of its large-scale production and consumption.These discarded objects are difficult to degraded under field conditions (factors), therefore can think environmentally hazardous substance.Lucite waste material on the one hand, from the sprue gate in the substandard product in producing (bubble exists as having in transparent injection moulding sheet material and section bar, formula have problem) and part, the forming process that can not meet customer need and the leftover pieces in machining, smear metal etc., becomes industrial waste; On the other hand, be use and consume after poly (methyl methacrylate) plate, engineering plastics and the civilian consumer goods, become consumption after waste material.If can effectively not only can economize on resources to its waste reclamation, protection of the environment, and can form good economic benefit to making full use of of regeneration product.
Reclaim methyl methacrylate monomer by degraded, more again make acrylic material goods by chemical synthesis.After lucite degraded, the rate of recovery of monomer can be up to 90%, this feature is not only for effective way has been found in the processing of its waste material, and the methyl methacrylate monomer that degraded produces can be made lucite again, thereby greatly reduce the production cost of lucite, produce obvious economic benefit.
The degraded of reaction general name that polymer molecular weight diminishes, comprising depolymerization, random scission and low-molecular-weightly the reaction such as remove.Promote a lot of because have of depolymerization, as light, heat, mechanical force, ultrasonic wave, chemicals and microorganism etc., sometimes also have the joint effect of several factors.
Industrial adopted biodegrading process 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 conventionally 400～500 DEG C (the common control of column bottom temperature of overheating steam method will be higher than these temperature, are 550～790 DEG C).
Dry distillation method cracking polymethyl methacrylate is one of cleavage method of earliest documents report.Its method is that waste and old polymethyl methacrylate is first ground into fragment, be then placed in a retort, under atmospheric pressure, with naked light or electrical heating to more than the cracking temperature of polymer.Decompose the monomer vapor obtaining and have two kinds of processing methods: the one, monomer vapor is concentrated, and further distillation, obtains high-purity monomer; Another kind is that direct monomer vapours and other monomer reactions are formed to new acrylic acid series polymeric compounds.When destructive distillation operates in temperature higher than cracking temperature, also can under the condition of negative pressure, carry out.The feature of dry distillation method is to process the polymethyl methacrylate waste material of various shapes, comprise the substandard product that polymerization process produces, but the thermal efficiency of this technology is low.Use flame heating or electrical heating, cause the interior heat distribution of retort inhomogeneous, be much higher than the temperature of still center material near the temperature of still wall polymer, consequently produce more serious coking phenomenon at still wall, the removing of the residue of this coking is very difficult, has affected carrying out continuously of course of reaction.
Superheated steam cracking polymethyl methacrylate be in a cleavage column with superheated steam as thermal medium, the waste and old polymethyl methacrylate material after pulverizing is sent into the process of carrying out continuous decomposition in tower with nitrogen or inert gas.Nitrogen fluctuation direction and vapor flow opposite direction, result forms pneumatic jig effect in steam-heated cleavage column, PMMA waste material is ground to the particle that is less than 6mm, brings cleavage column into by inert gas.For PMMA hybrid particles, at the bottom of the initial large acrylic plastics particle decomposing is positioned at tower, temperature is higher, is 550～790 DEG C; And the little acrylic plastics particle decomposing is positioned at tower top, temperature is 400～550 DEG C.For the monomer polymerization again that prevents from reclaiming, monomer gas must add polymerization inhibitor before entering condenser.
Motlten metal or slaine are the highly effective heat transfer mediums of one that PMMA decomposes.In PMMA decomposable process, metal used has lead, bismuth, cadmium, tin etc., and wherein the most frequently used is plumbous.These metals or salt are conventionally heated to more than 500 DEG C in the cracking process of polymethyl methacrylate, and in molten condition, this temperature range is enough to make PMMA to decompose.The alloy of above-mentioned metal also can do heat transfer medium, comprises the alloy that these metals and other metal alloys form.But the defect that the 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 process of mass transfer, is that useless acrylic acid series plastics are directly added on heat transfer medium surface, and the residue producing in decomposition swims in molten metal surface, after residue reaches predetermined altitude, discharges together with medium.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, slaine used has the mixture of nitrate, sodium nitrate, potassium chloride, sodium chloride, lithium chloride or above-mentioned metallic compound.Motlten metal also can do liquid heat-transfer medium, and the fusing point of medium is generally lower than 450 DEG C, and the relative density of motlten metal or slaine is to contact well with scraped surface for 2.0～3.0 o'clock.When with bath of molten metal decomposed P MMA, the solid in medium and decompose residues need constantly cleaning, replace heat transfer medium so people develop again with destilling tower, are provided with a series of " U " shape pipe in tower, heat with natural gas, oil or similar fuel." U " shape pipe extends to useless acrylic acid series plastic bed bottom, in the time that waste material contacts with " U " shape pipe of heating, decomposes immediately.Decompose steam cooling with a condenser directly contacting, in condensed product, the content of MMA monomer is up to 90%～95%, further distillation purity is more than 99%, in whole process, adopt " U " shape pipe to strengthen beyond doubt heat transfer area, whole polymer bed is heated evenly, and this is similar to a little the effect of motlten metal and slaine.
But in decomposable process, the residues such as organic decomposition product and inorganic filler, pigment and other auxiliary agents are deposited on the inwall of pipe and reactor, therefore after reflecting certain hour, need cessation reaction, with air and steam flush reactor wall, make residue become graininess ashes, then vacuum sucking-off or use Air blowing reactor.For carrying out continuously of ensureing to produce, package unit adopts two destilling towers conventionally, and when such cleaning, another still can turn round, and reaches the object of continuous decomposition.
Fluidised bed decomposition plastic product is quite general in industrial application, and the multiple plastic product including 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 using bauxite or sandstone as fluidized solid, entering fluid bed with nitrogen or other inert blowing gas makes in bed solid in fluidized state, fluidized-bed reactor electricity consumption is simultaneously heated to 510 DEG C, useless poly methyl methacrylate plastic enters fluidized-bed layer top after crushed, after contacting with bauxite, decompose immediately, collect the steam decomposing with condenser.Organic equally and inorganic residue in fluid bed, but because the shape generating is graininess, and be evenly distributed in around fluidized solid, can be used as equally a kind of heat transfer medium circulation in fluid bed, can't affect the carrying out of cracking process.But the amount of this granular residue exceedes after License Value, will change whole fluidized solid.
In PMMA decomposes, organic and the inorganic residue that filler in 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, pyrolysis solid accessory substance is pushed to a residue feeder continuously, and wherein screw flight can prevent that through special design residue is in internal chamber wall adhesion.Introduce micro-air in cracking region and can further prevent at internal chamber wall cokingly, once residue causes deadlock, air enters cracking region 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 to be done heater heating with the copper of cast.Because two screw threads of double screw extruder intermesh, can more effective deadband eliminating and the back-mixing of material, handled polymer is heated more even with the time of staying at extruder inner chamber, can effectively improves lysis efficiency, and prevent lysate deep conversion.Adopt the purity of the monomer that obtains of double screw extruder and liquid heat-transfer medium method to decompose the monomer purity obtaining suitable.
Summary of the invention
The object of the invention is to openly a kind of Catalysts and its preparation method of preparing methyl methacrylate for composite degradation, the above-mentioned defect existing to overcome prior art.
Catalyst of the present invention, is made up of 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 more than one in PbO etc., 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, preferably 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-bis-(tert-butyl peroxide) hexin-3] or dual-tert-butyl peroxidating diisopropyl benzene etc.;
The preparation method of described catalyst, comprises the steps:
By oxide, chloride and organic acid, add ball mill ball milling 4～16 hours, become dough, then dry 4～6 hours at 105～130 DEG C, pulverize, obtain powder;
Or oxide, chloride and organic acid and water are added to sand mill sand milling 0.5～4 hour, and become dough, then dry 4～6 hours at 105～130 DEG C, pulverize, 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 to ball mill ball milling 4～16 hours, become dough, then dry 4～6 hours at 105～130 DEG C, pulverize, obtain powder; The consumption of water is 3～6% of oxide, chloride and organic acid gross weight;
After the powder obtaining is mixed with peroxide, be crushed to particle diameter 1～10 μ m, can obtain described catalyst;
Catalyst of the present invention, can prepare methyl methacrylate for composite degradation, and application process comprises the steps:
By particle or pulverous acrylic material and described catalyst continuous add screw extruder, under the rotation of screw rod and shearing are rubbed, push ahead, be introduced into melting zone melting at 240～280 DEG C, enter again cracking zone, cracking at 300～400 DEG C, degraded gas is discharged by outlet, then from degraded gas, collects methyl methacrylate;
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:
The degraded gas that outlet is discharged, is cooled to 20～50 DEG C, collects condensate liquid, is MMA crude monomer, and purity is 92～96%, and yield is about 90～96%, then can obtain smart MMA monomer through steps such as rectifying, and its purity can exceed 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 section bar, formula have a problem) forming process and the leftover pieces in machining, smear metal etc.; 2) be use and consume after poly (methyl methacrylate) plate, engineering plastics and the civilian consumer goods, become consumption after waste material; 3) waste product producing in polymerization process and accessory substance.
The present invention has the following advantages: due to the existence of catalyst, obviously improved degradation speed, the specific yield of Degradator is improved greatly, can reduce again energy consumption.Can either improve the yield of product, also can greatly improve working environment.The residue producing in degradation process, owing to containing various polarity group and higher softening point can be for the preparation of the tackify of rubber and waterproof material, the residue producing in degradation process, owing to containing various polarity group and higher softening point can be for the preparation of the tackify of rubber and waterproof material, the degraded residue of PMMA reduces half, MMA crude monomer purity improves 10～20%, and overall yield improves more than 30%.
Detailed description of the invention
Embodiment 1
By oxide, chloride and organic acid and water, add ball mill ball milling 10 hours, become dough, then to dry 5 hours at 120 DEG C, air-flow crushing, obtains powder; The consumption of water is 6% of oxide, chloride and organic acid gross weight;
After the powder obtaining is mixed with peroxide, be crushed to particle diameter 5 μ m, can obtain 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
Granular acrylic material and the continuous screw extruder that adds of above-mentioned catalyst are carried out to cracking, the temperature of melting zone is 280 DEG C of meltings, and the temperature of cracking zone is 400 DEG C, and degraded gas is discharged by outlet, be cooled to 40 DEG C, collect condensate liquid, be MMA crude monomer, purity is 96%, yield is about 96%, then pass through rectification step, 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
By oxide, chloride and organic acid and water, add sand mill sand milling 1 hour, become dough, then to dry 6 hours at 130 DEG C, air-flow crushing, obtains powder; The consumption of water is 15% of oxide, chloride and organic acid gross weight.
After the powder obtaining is mixed with peroxide, be crushed to particle diameter 5 μ m, can obtain 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);
Pulverous acrylic material and the continuous screw extruder that adds of above-mentioned catalyst are carried out to cracking, the temperature of melting zone is 240 DEG C of meltings, and the temperature of cracking zone is 350 DEG C, and degraded gas is discharged by outlet, be cooled to 30 DEG C, collect condensate liquid, be MMA crude monomer, purity is 95%, yield is about 96%, then pass through rectification step, 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 acrylic material 0.1%.
Embodiment 3
By oxide, chloride and organic acid and water, add ball mill ball milling 10 hours, become dough, then to dry 5 hours at 120 DEG C, air-flow crushing, obtains powder; The consumption of water is 3% of oxide, chloride and organic acid gross weight;
After the powder obtaining is mixed with peroxide, be crushed to particle diameter 5 μ m, can obtain 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-bis-(tert-butyl peroxide) hexin-3];
Granular acrylic material and the continuous screw extruder that adds of above-mentioned catalyst are carried out to cracking, the temperature of melting zone is 260 DEG C of meltings, and the temperature of cracking zone is 350 DEG C, and degraded gas is discharged by outlet, be cooled to 20 DEG C, collect condensate liquid, be MMA crude monomer, purity is 92%, yield is about 96%, then pass through rectification step, 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
By oxide, chloride and organic acid and water, add ball mill ball milling 10 hours, become dough, then to dry 5 hours at 120 DEG C, air-flow crushing, obtains powder; The consumption of water is 4% of oxide, chloride and organic acid gross weight;
After the powder obtaining is mixed with peroxide, be crushed to particle diameter 5 μ m, can obtain 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 DCP(cumyl peroxide);
Granular acrylic material and the continuous screw extruder that adds of above-mentioned catalyst are carried out to cracking, the temperature of melting zone is 270 DEG C of meltings, and the temperature of cracking zone is 380 DEG C, and degraded gas is discharged by outlet, be cooled to 30 DEG C, collect condensate liquid, be MMA crude monomer, purity is 95%, yield is about 95%, then pass through rectification step, obtain smart MMA monomer, its purity can exceed 99.8%;
The time of staying of acrylic material in screw extruder is 1.5 minutes, and the weight consumption of catalyst is acrylic material 0.2%.
Embodiment 5
Oxide, chloride and organic acid and water are added to sand mill sand milling 2 hours, become dough, then dry 5 hours at 120 DEG C, air-flow crushing, obtains powder; The consumption of water is 30% of oxide, chloride and organic acid gross weight.
After the powder obtaining is mixed with peroxide, be crushed to particle diameter 5 μ m, can obtain 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 DCP(cumyl peroxide);
Granular acrylic material and the continuous screw extruder that adds of above-mentioned catalyst are carried out to cracking, the temperature of melting zone is 240 DEG C of meltings, and the temperature of cracking zone is 450 DEG C, and degraded gas is discharged by outlet, be cooled to 40 DEG C, collect condensate liquid, be MMA crude monomer, purity is 95%, yield is about 96%, then pass through rectification step, obtain smart MMA monomer, its purity can exceed 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 (4)
1. the catalyst of preparing methyl methacrylate for composite degradation, is characterized in that, is made up of the component of following weight portion:
1 part of powder
1～1.5 part of peroxide
Described powder is made up of the component of following weight portion:
100 parts of oxides
40～85 parts of chlorides
10～20 parts of organic acids
Described oxide is selected from Fe
2o
3, Co
2o
3, V
2o
5or more than one in PbO;
Described chloride is selected from FeCl
3, ZnCl
2or CaCl
2in more than one;
Described organic acid is selected from n-butyric acie, isooctyl acid or aphthenic acids;
Described peroxide is selected from cumyl peroxide, [2,5-dimethyl-2,5-bis-(tert-butyl peroxide) 3-hexin] or dual-tert-butyl peroxidating diisopropyl benzene.
2. the catalyst of preparing methyl methacrylate for composite degradation according to claim 1, is characterized in that, described oxide diameter sizes is 400～800 orders.
3. the catalyst of preparing methyl methacrylate for composite degradation according to claim 1, is characterized in that, described chloride particle diameter is 400～800 orders.
4. according to preparing the catalyst of methyl methacrylate for composite degradation described in claim 1～3 any one, preparation method, it is characterized in that, comprise the steps:
By oxide, chloride and organic acid, add ball mill ball milling 4～16 hours, become dough, then dry 4～6 hours at 105～130 DEG C, pulverize, obtain powder; After the powder obtaining is mixed with peroxide, be crushed to particle diameter 1～10 μ m, can obtain described catalyst;
Or
Oxide, chloride and organic acid and water are added to sand mill sand milling 4～16 hours, become dough, then dry 4～6 hours at 105～130 DEG C, pulverize, obtain powder; The consumption of water is 3～6% of oxide, chloride and organic acid gross weight;
Or
Oxide, chloride and organic acid and water are added to sand mill sand milling 0.5～4 hour, become dough, then dry 4～6 hours at 105～130 DEG C, pulverize, obtain powder; The consumption of water is 15～50% of oxide, chloride and organic acid gross weight.
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| 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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