Composite peptizing preparation for catalyzing degradation of resin as well as preparation method and application of composite peptizing preparation

Abstract

The invention discloses a composite dispergation preparation for catalyzing resin degradation and a preparation method and application thereof, the composite dispergation preparation for catalyzing resin degradation comprises a composite bio-enzyme preparation and an auxiliary agent; the composite biological enzyme preparation comprises 3-phosphoglycerol dehydrogenase and high-temperature citric acid synthetase. According to the process method for degrading the waste glass steel slag by using the composite peptizing preparation, a catalytic reaction process is adopted, and low-temperature, low-pressure and normal-temperature reaction conditions are adopted, so that the energy consumption is reduced; the reaction time is short, three wastes (waste gas, wastewater and waste residue) are avoided, and water in the whole system is completely recycled; the harmless and resource utilization of the treated waste residues is ensured; and various resins (epoxy resin, phenolic resin, polyacrylamide formaldehyde resin and the like) can be degraded.

Description

Technical Field

[0001] The invention belongs to the technical field of waste glass fiber reinforced plastic slag treatment, and particularly relates to a composite debonding preparation for catalyzing resin degradation, and a preparation method and application thereof. Background Art

[0002] With the rapid development of my country's wind power industry, windmill blades made of FRP are produced in large quantities, and the amount of scraps produced during the processing of windmill blades is huge. In addition, the life of windmill blades is limited, and a large number of wind turbines are retired, resulting in a large amount of waste FRP slag being piled up and placed randomly. Moreover, the waste FRP products are basically not treated at all, and most of them are buried on the spot or incinerated in the natural environment, causing great pollution to the environment. FRP products such as circuit boards also have similar situations.

[0003] The main raw materials of most waste FRP are unsaturated polyester and styrene. Styrene has a stable chemical structure and is not biodegradable. It has a high environmental retention rate and becomes a persistent organic pollutant. Whether in the air, water, or soil, it can be strongly adsorbed on particles and continuously enriched with the help of aquatic and terrestrial food chains, causing serious harm to the ecological environment. Therefore, the recycling of waste FRP has become a major problem that the FRP industry needs to solve urgently.

[0004] At present, the main methods for processing and recycling waste unsaturated polyester products are: landfill, chemical recycling, physical recycling, energy recovery, etc.; landfill will waste a lot of land and pollute the environment for a long time; chemical recycling is to decompose the FRP matrix material by chemical methods, separate it from the fiber, and recycle it into usable oil, combustible gas, etc., but the cost of this method is relatively high; physical recycling refers to the use of physical methods such as cutting, crushing, grinding, etc. to make FRP waste into powder as filler for the production of FRP or other plastic products; energy recovery can utilize part of the heat energy, but it produces a large amount of toxic gases and ash, polluting the environment.

[0005] The technology of bio-enzyme decomposition of unsaturated polyester is still in the experimental research stage. Some people have studied a method of using lipase to decompose poly-1,2-propylene glycol maleic anhydride, but it is greatly affected by reaction temperature, enzyme concentration and pH. Summary of the invention

[0006] In view of the deficiencies in the prior art, the present invention provides a composite debonding preparation for catalyzing resin degradation, and a preparation method and application thereof.

[0007] As a first aspect, the present invention provides a composite debonding preparation for catalyzing resin degradation, including a composite bio-enzyme preparation and an auxiliary agent;

[0008] The composite bioenzyme preparation includes the following components by weight: glycerol-3-phosphate dehydrogenase: 1-5 parts; thermostable citrate synthase: 1-5 parts.

[0009] In the present invention, the auxiliary agent is a composite chemical reagent, including an acidic reagent and a solvent.

[0010] The acidic reagent can be an organic acid or an inorganic acid, selected from formic acid, citric acid, oxalic acid or sulfamic acid.

[0011] The solvent is selected from one or a combination of components of xylene, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol butyl ether, ethyl acetate, trichloroethylene, glycerol, toluene, isopropanol or 1,2-propanediol.

[0012] Further, the auxiliary agent also includes hydrogen peroxide, which is used as an initiator.

[0013] In the embodiment of the present invention, the composite degumming preparation includes: oxalic acid: 5-10 parts; propylene glycol methyl acetate: 3-10 parts; sulfamic acid: 5-10 parts; glycerol: 2-5 parts; hydrogen peroxide: 10-20 parts; glycerol-3-phosphate dehydrogenase: 1-5 parts; thermostable citrate synthase: 1-5 parts, and the weight percentages of the above biochemical components are 100%.

[0014] In the embodiment of the present invention, the composite degumming preparation includes: citric acid: 3-10 parts; xylene: 5-15 parts; ethyl acetate: 2-5 parts; propylene glycol methyl ether: 3-10 parts; isopropanol: 2-5 parts; glycerol-3-phosphate dehydrogenase: 1-5 parts; thermostable citrate synthase: 1-5 parts, and the weight percentages of the above biochemical components are 100%.

[0015] In the embodiment of the present invention, the composite degumming preparation includes: formic acid: 5-10 parts; propylene glycol butyl ether: 2-8 parts; trichloroethylene: 2-10 parts; toluene: 5-10 parts; 1,2-propanediol: 5-10 parts; glycerol-3-phosphate dehydrogenase: 1-5 parts; thermostable citrate synthase: 1-5 parts, and the weight percentages of the above biochemical components are 100%.

[0016] Among them, the main components of the composite bioenzyme preparation are composed of glycerol 3-phosphate dehydrogenase and thermostable citrate synthase. By the synergistic interaction of glycerol 3-phosphate dehydrogenase and composite chemical reagents, complex macromolecules in fiberglass slag can be degraded into small molecules, including pyruvic acid. Pyruvic acid dissolves the resin. The principle is as follows: through electrostatic interaction with the resin, the carboxyl group of pyruvic acid carries a negative charge and can undergo electrostatic attraction with the positively charged resin group, thus promoting the adsorption of pyruvic acid on the resin. The hydroxyl group of pyruvic acid can form hydrogen bonds with the hydroxyl group (OH) in the resin, thereby enhancing the adsorption capacity of pyruvic acid on the resin. The surface of the resin may have hydrophobic groups, and the polar part of the pyruvic acid molecule can interact with these hydrophobic groups to promote adsorption, thereby achieving the purpose of resin separation and purification. The intermediate product of acetyl CoA is finally degraded into CO2, H2O, NH3, etc. After being activated by catalysis or external heating to 80°C - 93°C, through disproportionation reaction electron transfer self-heating, it can quickly break high-polymer hydrogen bonds and disulfide bonds. Thermostable citrate synthase, under the catalysis of high temperature, can quickly break the C bond of high-polymer molecules and the ions between the amino acid residues at the N-terminus and can regulate fat metabolism, oxidize fatty acids, and hydrolyze acetyl CoA in the tricarboxylic acid cycle into CO2 and H2O, thus realizing the harmless degradation of waste fiberglass slag by biological methods. The composite degumming preparation provided by the present invention has high stability and has the advantages of high efficiency, energy saving, low carbon, cleanliness, environmental protection, etc., and has an inestimable application market prospect.

[0017] In the composite chemical reagent, the effects of each component are as follows:

[0018] 1. Formic acid: Used as a catalyst and solvent, it has unique dissolving and relaxing abilities. As an organic acid, the polar bonds in the molecule can form strong hydrogen bond interactions with the carbonyl bonds of the polyester. These two interaction forces promote the dissociation of the polyester molecular bonds and their dispersion in formic acid, not only promoting the reaction process but also optimizing the processing performance and product quality.

[0019] 2. Citric acid: Its role in dissociating the resin is mainly reflected in its being a component of ion exchange resin. By the ion exchange process, it changes the charge state of the resin, thereby affecting its adsorption property and the ability to release ions.

[0020] 3. Oxalic acid: A strong acid with strong corrosiveness, it can react with the epoxy group in epoxy resin to form oxalate ester, thereby destroying the structure of epoxy resin and achieving the dissociation effect.

[0021] 4. Sulfamic acid: Its main role is to adjust the acidic environment and promote the dissociation of the resin. Sulfamic acid can dissociate into H + and sulfamate ions in water, thereby providing an acidic environment and cooperating with other reagents to achieve the purpose of dissociating fiberglass.

[0022] 5. Xylene: In the dissociation resin, it dissociates the polymer chains and detaches them from the solid skeleton structure through the mechanisms of permeability and hydrogen bond formation, thereby dissociating the resin.

[0023] 6. Propylene glycol methyl ether: It mainly realizes the dissolution and dispersion of the resin through hydrogen bonding and its polar characteristics.

[0024] 7. Ethyl acetate: It mainly includes dissolving the resin, adjusting the viscosity, and reducing the surface tension.

[0025] 8. Propylene glycol butyl ether: It mainly interacts with the resin through the hydrophilic and lipophilic parts in its molecular structure, thereby effectively dispersing the resin particles in the solution.

[0026] 9. Trichloroethylene: It is an organic solvent with strong dissolution properties, and it can dissolve epoxy resin glue.

[0027] 10. Glycerol: It can adjust the reaction rate and viscosity, making the reaction more uniform, and can be used as a solvent for the resin.

[0028] 11. Hydrogen peroxide: Hydrogen peroxide can be used as an initiator in high-polymer molecular resins.

[0029] 12. Toluene: In the dissociation resin, it dissociates the polymer chains and detaches them from the solid skeleton structure through the mechanisms of permeability and hydrogen bond formation, thereby dissociating the resin.

[0030] 13. Isopropyl alcohol: As a solvent with relatively low polarity, in the resin dissociation, it can increase the solubility of the resin and reduce the viscosity, making the resin easier to dissociate.

[0031] 14. 1,2 - Propylene glycol: In the dissociation resin, its main role is as a solvent and diluent, which can dilute epoxy resin and reduce its viscosity.

[0032] 15. Propylene glycol methyl ether acetate (pMA): It is mainly used as a solvent to help dissolve and disperse the resin, and to break the intermolecular attraction of the resin, thereby dispersing it in pMA.

[0033] As the second aspect of the present invention, it lies in providing a preparation method of a composite degumming agent for catalyzing resin degradation, including the following steps:

[0034] First, add the acidic reagent into the reactor, turn on the stirrer, then add the solvent, after stirring, successively add 3 - phosphoglycerol dehydrogenase and thermotolerant citrate synthase into the reactor according to the required ratio, and continue stirring to obtain it.

[0035] As the third aspect of the present invention, it lies in providing the application of the composite degumming preparation for catalyzing resin degradation in treating waste glass fiber reinforced plastics.

[0036] As the fourth aspect of the present invention, it lies in providing a process method for degrading waste glass fiber reinforced plastics residues, comprising the following steps:

[0037] S1, grinding the glass fiber reinforced plastic material;

[0038] S2, placing the ground glass fiber reinforced plastic material in the diluted composite degumming agent for dissociation treatment;

[0039] S3, transferring the slurry added with the composite degumming agent obtained in step S2 to a fermentation tank for catalytic reaction;

[0040] S4, screening the material processed in step S3 through a vibrating screen to remove particles larger than 0.5 mm, and then aging and dehydrating to obtain the finished product.

[0041] Preferably, in step S1, before grinding, the glass fiber reinforced plastic material is first processed into a size of 0.1 - 1 cm; after grinding by a water mill, it is dehydrated.

[0042] Preferably, in step S2, the composite degumming agent is diluted with water, and the dilution ratio is 1:15.

[0043] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0044] (1) The present invention provides a composite biochemical degumming preparation, which exerts the synergistic promotion effect of the enzyme preparation and the chemical reagent, and can effectively degrade the resin in the waste steel slag; in this preparation, the chemical reagent is used as an auxiliary agent, providing a stable pH environment for the biological enzyme, and the biological enzyme has high stability and is not easily inactivated.

[0045] (2) The process method for degrading waste glass fiber reinforced plastics residues provided by the present invention adopts a catalytic reaction process, and adopts reaction conditions of low temperature, low pressure and normal temperature, reducing energy consumption; the reaction time is short, there are no three wastes (waste gas, waste water, waste residue), and all the water in the whole system is recycled; it ensures that the quality of the treated waste residue reaches harmless and resource utilization; it can degrade various resins (such as epoxy resin, phenolic resin, polyacrylamide formaldehyde resin, etc.).

[0046] (3) The process method for degrading waste glass fiber reinforced plastics residues provided by the present invention can directly degrade resin - type and styrene - type substances in the glass fiber reinforced plastics into CO2 and water, and the remaining solid wastes, calcium powder and glass fibers, can be directly used as cement raw materials and other building materials, such as non - fired bricks, blocks, etc. Description of the Drawings

[0047] The accompanying drawings of the specification, which form a part of the present invention, are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention.

[0048] Figure 1 Process flow diagram for treating waste circuit board slag with the composite catalytic degumming preparation provided for the present invention.

[0049] Figure 2 Appearance of the treated resin powder in Example 2. Detailed Description of the Invention

[0050] It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present invention belongs.

[0051] According to the characteristics of the raw material composition of fiberglass, most fiberglass (FRP), also known as (GRP), that is, fiber-reinforced plastic, generally refers to the reinforced plastic using glass fiber to reinforce unsaturated polyester, epoxy resin and phenolic resin matrix, as well as glass fiber or its products as the reinforcing material. Additionally, styrene is added. It is an organic compound formed by replacing one hydrogen atom of ethylene with a benzene ring. Industrially, it is an important monomer for synthetic resins, ion exchange resins and synthetic rubbers, etc. Its strength is mainly formed by the resin, and the resin type is composed of hydrocarbons. In view of the formation principle of fiberglass, the present invention has developed a preparation of a composite degumming preparation for catalyzing resin degradation and a process method for degrading waste fiberglass slag. This process method mainly uses the composite chemical reagents in the composite degumming preparation and is assisted by a composite biological enzyme preparation, which can efficiently degrade fiberglass slag, directly degrade the resin and styrene substances in fiberglass into CO2 and water, and the remaining solid waste calcium powder and glass fiber can be directly used as cement raw materials and other building materials, such as non-fired bricks, blocks, etc.

[0052] Material source:

[0053] The two biological enzymes are respectively: glycerol 3-phosphate dehydrogenase produced by Shanghai Yuanye Bio-Technology Co., Ltd., which is an oxidoreductase and is specifically classified as an allosteric enzyme. Citrate synthase (high temperature) produced by Shanghai Keshun Bio-Technology Co., Ltd., which is an oxidoreductase and is specifically classified as a transferase.

[0054] Example 1, a composite degumming preparation for catalyzing resin degradation and its preparation method

[0055] (I) Preferred composite degumming preparation formula 1:

[0056] Oxalic acid: 5 - 10 parts; Propylene glycol methyl ether acetate: 3 - 10 parts; Sulfamic acid: 5 - 10 parts; Glycerol: 2 - 5 parts; Hydrogen peroxide: 10 - 20 parts; 3 - Phosphoglyceraldehyde dehydrogenase: 1 - 5 parts; Thermostable citrate synthase: 1 - 5 parts. Note: The weight percentages of the above biochemical reagents are 100%.

[0057] The specific operation method is as follows:

[0058] 1. First, prepare a 2 - cubic reactor with a stirrer (made of 304 stainless steel) and the tools used for backup.

[0059] 2. First, according to the uses and characteristics of the above biological and chemical reagents, add them to the reactor in the required weight ratio and in the order of priority.

[0060] 3. First, add oxalic acid to the reactor and start the stirrer, then add sulfamic acid, hydrogen peroxide, glycerol, and propylene glycol methyl ether acetate in sequence. After stirring for 15 - 30 minutes, then add 3 - phosphoglyceraldehyde dehydrogenase and thermostable citrate synthase to the reactor in the required ratio, continue stirring for 30 minutes, and then pump it into the storage tank, seal it, keep it away from light, and store it for backup.

[0061] (2) Preferred formulation two of the composite degumming agent:

[0062] Citric acid: 3 - 10 parts; Xylene: 5 - 15 parts; Ethyl acetate: 2 - 5 parts; Propylene glycol methyl ether: 3 - 5 parts; Isopropanol: 2 - 5 parts; 3 - Phosphoglyceraldehyde dehydrogenase: 1 - 5 parts; Thermostable citrate synthase: 1 - 5 parts. Note: The weight percentages of the above biochemical reagents are 100%.

[0063] The specific operation method is as follows:

[0064] 1. First, prepare a 2 - cubic reactor with a stirrer (made of 304 stainless steel) and the tools used.

[0065] 2. First, according to the uses and characteristics of the above biochemical reagents, add them to the reactor in the required ratio and in the order of priority.

[0066] 3. After starting the stirrer of the reactor, add citric acid, ethyl acetate, propylene glycol methyl ether, isopropanol, and xylene in sequence in the required ratio and in the order of priority. After stirring for 15 - 30 minutes, then add 3 - phosphoglyceraldehyde dehydrogenase and thermostable citrate synthase preparation. After continuing to stir for 30 minutes, pump the generated composite degumming agent into the storage tank, seal it, and keep it away from light for backup.

[0067] (3) Preferred formulation three of the composite degumming agent:

[0068] Formic acid: 5 - 10 parts; Propylene glycol butyl ether: 2 - 8 parts; Trichloroethylene: 2 - 10 parts; Toluene: 5 - 10 parts; 1,2 - Propylene glycol: 5 - 10 parts; 3 - Phosphoglyceraldehyde dehydrogenase: 1 - 5 parts; Thermostable citrate synthase: 1 - 5 parts. Note: The weight percentages of the above biological and chemical reagents are 100%. The specific operation method is as follows:

[0069] 1. First, prepare a 2 - cubic reactor with a stirrer (made of 304 stainless steel) and the tools used for backup.

[0070] 2. First, based on the uses and characteristics of the above biochemical reagents. Then, in accordance with the required proportions and the order, add them to the reactor in turn.

[0071] 3. First, start the stirrer of the reactor, and then add the biochemical reagents. In accordance with the required proportions and the order, add formic acid, propylene glycol butyl ether, 1,2 - propylene glycol, toluene, and trichloroethylene to the reactor in turn. After continuing to stir for 15 - 30 minutes, then, add 3 - phosphoglyceraldehyde dehydrogenase and thermostable citrate synthase preparations to the reactor in accordance with the required proportions, continue to stir for 30 minutes, then pump it into the storage tank, seal it, keep it away from light, and store it for backup.

[0072] The composite degumming preparation provided by the present invention reacts under normal temperature, normal pressure, acidic conditions and in an aqueous environment for the above two kinds of biological enzyme preparations. Since the mixture of various substances will release energy, the present invention adopts a method of gradually releasing energy in batches, so that the energy can be fully stored and utilized. Most of the energy is stored in the form of ATP. During the process of electrons from reduced coenzyme → O2, the released energy accounts for most of the total oxidative energy production. The oxidation of carbon and the oxidation of hydrogen are non - synchronous oxidation processes. The hydrogen protons and electrons removed are usually transferred by various carriers. The role of water is to provide an environment to participate in the reaction process, and dehydrogenation by adding water can generate energy. For the two kinds of biological enzymes, the present invention provides the most suitable enzyme activity acidity and reaction temperature, with good thermal stability and fast reaction speed.

[0073] The composite degumming preparation provided by the present invention can be compounded with various biological and chemical components in an ideal proportion, maximizing the synergistic promotion effect between the enzyme preparation and the chemical reagent. Under high - temperature catalytic conditions, it can significantly reduce the reaction viscosity and reduce the power consumption cost during the production process. The composite catalytic preparation developed by the present invention has clear components and known action points, and can effectively prevent the generation of by - products and the occurrence of unwanted reactions. In the present invention, under high - temperature conditions, it can also increase the solubility of the reaction substrate, reduce the reaction volume, and simplify the process operation conditions. At the same time, it has good pushing performance and a long half - life, and can significantly save the usage amount of biochemical preparations. The composite degumming preparation provided by the present invention is colorless, non - toxic, easy to prepare, convenient for storage, transportation and use.

[0074] Example 2, a process method for treating various resins and fiberglass waste residues using the composite peptizing agent provided in Example 1

[0075] It can be used to treat resin and fiberglass waste residues, including circuit board waste residues, waste fan blades, etc.

[0076] (1) The main equipment process flow chart for treating circuit board waste residues is as follows Figure 1 shown as

[0077] Bin 1 → Belt conveyor 2 → Electronic metering feeder 3 → Water ball mill 4 (water is added to the water ball mill through an intelligent metering water pump) → Slurry pump 5 → Ultrasonic crusher 6 → No. 1 slurry storage tank 7 → Belt filter press 8 → Belt conveyor → No. 2 slurry storage tank 9 → Slurry pump → Rotary drum fermenter 10 → No. 1 aging tank 12 → Vibrating screen 12 → No. 2 aging tank 13 → Slurry pump → No. 2 belt filter press 14 → Belt conveyor → Finished product bin 15.

[0078] (2) The peptizing agent selected for this test is the preferred No. 2 formulation for the test.

[0079] Citric acid: 3 - 10 parts; Xylene: 5 - 15 parts; Ethyl acetate: 2 - 5 parts; Propylene glycol methyl ether: 3 - 10 parts; Isopropyl alcohol: 2 - 5 parts; 3 - Phosphoglyceraldehyde dehydrogenase: 1 - 5 parts; High - temperature citrate synthase: 1 - 5 parts. Note: The weight percentage of the above biochemical reagents is 100%.

[0080] (3) Select the preferred composite catalytic peptizing agent standby preparation that has been compounded and set aside.

[0081] (4) The specific operation method steps are as follows:

[0082] (1) First, put the pre - cut (0.1 - 1.0 cm) and processed waste circuit board waste residues into the raw material bin with a loader for standby.

[0083] (2) Then, sequentially start the application equipment on the production line, start the feeder to enter the ball mill (water mill), and require the fineness of the milled product to be (80 mesh - 120 mesh). Then, use ultrasonic waves at (25 Hz - 35 Hz) to vibrate for 10 minutes, and then pump it to the No. 1 slurry storage tank 7 for standby with a slurry pump 5; in this example, the No. 1 slurry storage tank 7 is a 30m 3 Aeration stirring tank, connected to a high - pressure air pump to supply air source.

[0084] (3) Then, it is pumped from the No. 1 slurry storage tank 7 into the belt filter press 8 by a slurry pump for dehydration. In this embodiment, the dehydration is carried out until the water content is less than 65 - 70%. The water discharged is returned to the ball mill for recycling through a sedimentation tank and a filtrate pump. The discharged material is conveyed to the No. 2 slurry storage tank 9 by a belt conveyor for standby. In this embodiment, the No. 2 slurry storage tank 9 has a volume of 30 m 3 Weighing storage tank.

[0085] (4) Then, from the No. 2 slurry storage tank 9, through a metering belt conveyor, before conveying, it is put into a 5 - cubic - meter dilution tank and the mixer is started. A diluted composite peptizer (including a compounded composite bio - enzyme preparation and a composite chemical reagent) is added, and the liquid - to - ratio of the diluent is water at 1:15 (peptizer: water = 1:15). After continuous stirring for 30 - 40 minutes, it is for standby.

[0086] In this embodiment, a medicine storage tank 901, a dispensing tank 902 and a stirring tank 903 are also provided. Pipes and metering pumps are respectively arranged between the medicine storage tank and the dispensing tank 902, and between the dispensing tank 902 and the stirring tank 903. The medicine supplied by the medicine storage tank 901 is dispensed with water (1:15) in the dispensing tank and then pumped into the stirring tank 903 for use during production. A mixer is added to the stirring tank to make the medicine uniform..

[0087] (5) Start the slurry pump, pump the peptizer - added and diluted slurry from the No. 2 slurry storage tank 9 into the (60 - cubic - meter) drum - type fermenter 10, close the feed door of the drum - type fermenter, and at the same time start the heater, and require the temperature to be between (35 - 95 degrees) for catalytic reaction. In this embodiment, the heater uses a steam boiler 101 to heat each drum - type fermenter 10 with steam. After the required reaction time of 60 - 90 minutes, open the discharge door of the drum - type fermenter, and convey the processed material to the No. 1 aging tank 11 by the conveyor below the drum - type fermenter for standby. In this embodiment, multiple drum - type fermenters 10 are connected in parallel, and the material outlet is connected to the No. 1 aging tank 11 through a shaftless screw conveyor. When the material in the drum - type fermenter is processed, it is conveyed to the No. 1 aging tank through the conveyor at the bottom of the fermenter, playing a role in collecting, storing and aging the material.

[0088] (6) Then, use a slurry pump to pump the slurry in aging tank No. 1 (11) to the vibrating screen (12) for screening (the vibrating screen (12) is respectively connected to an intelligent metering water pump). The large particles (larger than 0.5 mm) screened out are returned to the ball mill process section for secondary treatment, and the glass fibers are stored separately for standby. The treated slurry enters aging tank No. 2 (13) for standby. Aging tank No. 2 serves as a storage tank, ensuring a stable feed for the next step of dehydration in the belt filter press. The connection of the two aging tanks is for two purposes. One is to save pipelines and valves. The second, and more important, is to ensure that the materials in the two fermentation tanks can be discharged in a timely manner without affecting production. Third, with a stable feeding system, it ensures that the belt filter press operates at full load and avoids production stoppage caused by unstable feeding.

[0089] (7) Then, pump the slurry in aging tank No. 2 to the belt filter press (14) using a slurry pump for dehydration. The water separated out is recycled back to the rotary drum fermenter and aging tank through the sedimentation tank and a water return pump.

[0090] (8) Convey the dehydrated materials to the finished product bin (15) using a conveyor for standby.

[0091] The appearance of the treated resin powder is as Figure 2 shown. The main by-products include talcum powder, glass fibers, etc. Currently, it is mainly used for non-fired bricks, concrete fillers, roadbeds, cement production, partial recycling of glass fibers, and can also be used as raw materials for glass, etc.

[0092] The process method of the composite deflocculant preparation for degrading waste fiberglass slag provided by the present invention has the following advantages

[0093] 1. In the stock preparation process section, a shredder with low speed and small power is used. The equipment is simply installed, with the maximum recovery rate, and no dust, wastewater, or waste gas is generated, truly achieving zero emissions and zero pollution.

[0094] 2. In the pretreatment process section, a metering system with a high degree of automation and an information system is adopted. A dust-free water ball mill with ultrasonic vibration is used. The entire pretreatment process section uses closed pipelines and is pumped to ensure an advanced production line system with dust-free pretreatment for the entire production line system.

[0095] 3. In the catalytic reaction process section, reaction conditions of low temperature, low pressure, and normal temperature are adopted, reducing energy consumption.

[0096] 4. The reaction time is short, and there are no three wastes (waste gas, wastewater, and waste residue). All the water in the entire system is recycled.

[0097] 5. In the aging and finished product process sections, fully enclosed production is adopted to ensure that the quality of the treated waste residue reaches harmlessness and resource utilization.

[0098] 6. During the production process, no alkali is used, no harmful waste is generated, there is no secondary pollution, production can be reduced in quantity, and the harmful components of the resin are thoroughly treated.

[0099] 7. It can degrade various resins (such as epoxy resin, phenolic resin, polyacrylamide formaldehyde resin, etc.).

[0100] This process method also overcomes the deficiencies of traditional chemical recovery methods, physical recovery methods, energy recovery methods, etc., such as large investment, high operating costs, large secondary pollution, and inability to be completely degraded (and some also have secondary pollution residues), avoiding the problems of persistent organic pollutants formed by FRP waste and environmental hazards.

[0101] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A composite disintegrating preparation for catalyzing resin degradation, characterized in that: Including compound biological enzyme preparations and additives; The composite biological enzyme preparation comprises the following components by weight: 1-5 parts of 3-phosphoglycerate dehydrogenase and 1-5 parts of high-temperature citrate synthase.

2. The composite disintegrating preparation for catalyzing resin degradation according to claim 1, characterized in that: The auxiliary agent is a composite chemical reagent, including an acidic reagent and a solvent; The acidic reagent is an organic acid or an inorganic acid; The solvent is selected from a combination of one or more components selected from xylene, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol butyl ether, ethyl acetate, trichloroethylene, glycerol, toluene, isopropanol or 1,2-propylene glycol.

3. The composite disintegrating preparation for catalyzing resin degradation according to claim 2, characterized in that: The acidic agent is selected from formic acid, citric acid, oxalic acid or aminosulfonic acid.

4. The composite disintegrating preparation for catalyzing resin degradation according to claim 2, characterized in that: The auxiliary agent also includes hydrogen peroxide.

5. The composite disintegrating preparation for catalyzing resin degradation according to claim 1, characterized in that: The composite disintegrating preparation comprises: oxalic acid: 5-10 parts; propylene glycol methyl acetate: 3-10 parts; aminosulfonic acid: 5-10 parts; glycerol: 2-5 parts; hydrogen peroxide: 10-20 parts; 3-phosphoglycerate dehydrogenase: 1-5 parts; high temperature citrate synthase: 1-5 parts, and the weight percentage of the above biochemical components is 100%.

6. The composite disintegrating preparation for catalyzing resin degradation according to claim 2, characterized in that: The composite disintegrating preparation comprises: 3-10 parts of citric acid, 5-15 parts of xylene, 2-5 parts of ethyl acetate, 3-10 parts of propylene glycol methyl ether, 2-5 parts of isopropanol, 1-5 parts of 3-phosphoglycerate dehydrogenase and 1-5 parts of high temperature citrate synthase, and the weight percentage of the above biochemical components is 100%.

7. The composite disintegrating preparation for catalyzing resin degradation according to claim 2, characterized in that: The composite disintegrating preparation comprises: formic acid: 5-10 parts; propylene glycol butyl ether: 2-8 parts; trichloroethylene: 2-10 parts; toluene: 5-10 parts; 1,2-propylene glycol: 5-10 parts; 3-phosphoglycerate dehydrogenase: 1-5 parts; high temperature citrate synthase: 1-5 parts, and the weight percentage of the above biochemical components is 100%.

8. The method for preparing the composite disintegration preparation for catalyzing resin degradation according to any one of claims 1 to 7, characterized in that: The steps include: First, add the acidic reagent into the reactor, turn on the stirrer, then add the solvent, stir, then add 3-glycerol phosphate dehydrogenase and high-temperature citrate synthase into the reactor in the required proportion, continue stirring, and obtain.

9. Use of the composite disintegrating agent for catalyzing resin degradation as claimed in any one of claims 1 to 7 in treating glass fiber reinforced plastic waste residue.

10. A process for degrading waste glass fiber reinforced plastic slag, characterized in that: The steps include: S1, grinding the glass fiber reinforced plastic material; S2, the ground FRP material is placed in a diluted composite disintegrator for dissociation treatment; the composite disintegrator comprises a composite bio-enzyme preparation and an auxiliary agent; the composite bio-enzyme preparation comprises the following components by weight: 1-5 parts of 3-phosphoglycerate dehydrogenase; 1-5 parts of high-temperature citrate synthase; S3, transferring the slurry with the composite dissolving agent obtained in step S2 to a fermentation tank for catalytic reaction; S4, the material after processing in step S3 is screened by a vibrating screen to remove particles larger than 0.5 mm, and then precipitated and dehydrated to obtain a finished product.

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