CN1188776A - Decomposition method and device for discarded material - Google Patents
Decomposition method and device for discarded material Download PDFInfo
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- CN1188776A CN1188776A CN97102903A CN97102903A CN1188776A CN 1188776 A CN1188776 A CN 1188776A CN 97102903 A CN97102903 A CN 97102903A CN 97102903 A CN97102903 A CN 97102903A CN 1188776 A CN1188776 A CN 1188776A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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Abstract
A process for decomposing the wastes containing one or more of hydrolytic bonds such as ether bond, ester bond, amido bond and isocyanate bond features that the wastes in molten or liquid state are continuously supplied to reactor while supercritical water or high-temp, high-pressure water is continuously supplied to it to decompose object compounds and the obtained target compounds can be recovered to use them as raw materials or derivatives.
Description
The invention relates to and use supercritical water or high pressure-temperature water decomposition to handle the waste that contains by product that produces in the chemical plant, the decomposition method and the device of waste in the chemical plant that the starting compound or derivatives thereof of the object in recovery chemical plant also utilizes again from this waste.And then be about using supercritical water or high pressure-temperature water decomposition processing polyethylene terephthalate bottle, urethane foam the like waste, the method and apparatus of the derivative of their starting compound of recovery or its starting compound from waste.
In the chemical plant, during the synthetic various chemical preparations of industry, except generating object, also produce by product or remained unreacted thing.For example in polymerization equipment, must be provided with and make the isolating device of polymkeric substance that generates in unreacted monomer and the reactive tank, the common unreacted monomer that reclaims utilizes as the polyreaction raw material again.Also known under the situation of polyreaction, polymers such as secondary generation oligopolymer, but polymer then can not get the purpose characteristic if remain in the polymkeric substance, or the disadvantage of long-time back characteristic degradation, therefore separate the polymeric process of removing mostly.Only in the future reaction monomers charging feedstock supply line, to utilize be possible again, polymer can not similarly be handled with monomer certainly, therefore carries out special burning disposal and waste treatment.
In addition, not in polymerization equipment, even in the chemical device of synthetic low molecular compound, also generate polymers such as the dimer of side reaction product and purpose compound and tripolymer, for example be necessary to come with these by products such as methods such as distillation and polymer and purpose compound separation.Under the situation of low molecular compound, the separation of by product is easier to, and is still often relatively difficult with the purpose compound separation together with polymer, therefore containing polymer and purpose compound in final distillation residue the like waste more.Also effectively do not utilize at present the method for these wastes, only be burn, waste treatment, thereby, be the problem of significant from the aspect that economizes on resources.
On the other hand, in recent years, people attempt to utilize hydrolysis and the oxidizing reaction in super critical water or high pressure-temperature water to make waste innoxious always, or obtain the resultant that may effectively utilize.For example, show in the flat 3-500264 communique the spy, having disclosed the oxidizing reaction of utilizing under super (or inferior) critical state, to make discharge opeing be the innoxious method of waste, in addition, open in the flat 5-31000 communique the spy, disclosed the method that the water that uses overcritical or subcritical state comes the various macromolecular compounds of hydrolysis, have again, in special fair 3-16328 communique and the flat 5-271328 communique of Te Kai, disclosed the method that obtains pure terephthalic acid (PTA) and ethylene glycol from useless polyethylene terephthalate.
But, the technology of Te Biaoping 3-500264, as detoxification method, importantly follow the practicality of the resulting material of oxidizing reaction to be a problem, in other communique, about the decomposition method that makes the waste effectively in the polymeric chemical devices such as comprising oligopolymer and dimer and device without any mentioning.
Therefore, the present invention is conceived to not utilize so far the interior waste of chemical device of burning and waste treatment method in addition, resolve into the starting material compound or derivatives thereof of the purpose compound in the chemical device with the objectification compound that will be included in by product in these wastes and polymer etc., the continous treatment process that establishment can utilize effectively again discloses as problem.
The present invention be comprise have ehter bond, the decomposition method of waste in the chemical device of the objectification compound of any above water-disintegrable key in the ester bond, amido linkage, isocyanic acid ester bond, have following main points, promptly with waste with molten state or liquid state continuously in the supply response device, supercritical water or high pressure-temperature water are supplied with above-mentioned reactor continuously, make the object compound decomposition by contacting, as the starting compound or derivatives thereof of this objectification compound and reclaim with this waste.
In addition, the present invention also comprises the decomposer of the waste that is equipped with following apparatus and mechanism:
Reactor;
To comprise have ehter bond, the waste of the objectification compound of any the above water-disintegrable key in the ester bond, amido linkage, isocyanic acid ester bond supplies with the device of above-mentioned reactor continuously with molten state or liquid state former state ground;
Supply with the device of supercritical water or high pressure-temperature water to above-mentioned reactor; And
The device of the liquid effluent lead-in separation device of the resolvent that comprises the objectification compound that will discharge from reactor.
In decomposition method of the present invention, so long as comprise the use that the interior waste of chemical device of the objectification compound of possibility hydrolysis just can not add restriction, but when wherein the objectification compound is polymer substance for the purpose compound in the chemical device by product " the above polymer of the dimer of starting compound ", be by product " the above polymer of the dimer of purpose compound " when perhaps the purpose compound is lower-molecular substance, can use especially effectively.Use decomposition method of the present invention, no matter which kind of of " the above polymer of the dimer of starting compound ", " the above polymer of the dimer of purpose compound " can both resolve into " starting compound or its derivative ", can both effectively utilize the resulting decomposition product.The implication of in the present invention " polymer " is represented the compound that dimer is above, and the numerical value level of the polymerization degree because of type of polymer and polymerization process various variations takes place, and therefore is not particularly limited.
In the methods of the invention, the supercritical water of supply response device or high pressure-temperature water reach more than 100 ℃, more than the 5MPa, with respect to the weight of waste in the chemical device of supply response device, supercritical water or the high pressure-temperature water supplied with more than 1 times are best forms of implementation.
The feature of decomposition method of the present invention is that object is the interior waste of the chemical device of molten state or liquid state, and can reclaim useful compound continuously from this waste.Because the waste of chemical device is to discharge continuously, so batch method of treatment needs the storagetank of waste.And the cooling of the reactor when also being useful on the batch of material replacing and the big problem of power loss of intensification.And then because when packing the solid state waste into because making pulpous state has a large amount of water, need be used to the energy that it is reached a high temperature.But the inventive method can be handled waste in the chemical device of intact molten state or liquid state continuously with certain pressure and temperature condition, so there is not shortcoming as described above, is extremely useful in actually operating.
Decomposition among the present invention to as if comprise have ehter bond, waste in the chemical device of the objectification compound of water-disintegrable key in the ester bond, amido linkage, isocyanic acid ester bond more than any.When the objectification compound in the waste is " the above polymer of the dimer of starting compound " of the by product of purpose compound when being polymer substance, perhaps the purpose compound be lower-molecular substance by product " the above polymer of the dimer of purpose compound " time, the inventive method particularly suitable, can utilize waste effectively again, thereby advantage is many.Below will " polymer that dimer is above " abbreviation " polymer ".
In the ideal objectification compound, can enumerate polyester such as polyethylene terephthalate as the polymer that is categorized as starting compound be polyamide-based oligopolymer (amido linkage is arranged) such as oligopolymer (ester bond is arranged), nylon, polycarbonate-based oligopolymer (ehter bond is arranged) etc.At polyester is that cyclic ester oligopolymer and chain oligopolymer are arranged in the oligopolymer, can resolve into the dicarboxylic acid and the glycol of terephthalic acid etc.As nylon is that oligopolymer can be enumerated by raw material ε-Ji Neixianan synthetic ring-type or chain oligopolymer etc., and the open loop derivative that can access 6-caprolactone from these oligopolymer is an epsilon-amino caproic acid.In addition, under the situation of polycarbonate-based oligopolymer, can resolve into is polyvalent alcohol or the polyphenol and the carbonic acid of raw material.
In addition, the compound that the compound that contains ring-type ehter bonds such as epoxy chloropropane, ethene or propylene oxide carries out auto-polymerization is the polymer with ehter bond, and they can exist as " polymer of purpose compound " again as " polymer of starting compound ".That is when using the synthetic polymkeric substance of these compounds,,, be exactly the polymer of purpose compound so, if are secondary polymers of giving birth to during synthetic these compounds if secondary polymer of giving birth to is exactly the polymer of starting compound so.
Have again, when compounds such as synthesis of pentaerythritol, the also secondary autohemagglutination compound that generates with ehter bond, therefore such polymer also becomes " polymer of purpose compound ", is suitable objectification compound of the present invention.
As " polymer of purpose compound ", also can enumerate and take place two or the autoreaction of the polymer (amido linkage is arranged) of triisocyanate compound etc., contain the polymer of the functional group's that can form water-disintegrable key compound.As isocyanate compound can enumerate toluene-2,4-diisocyanate (2,4-or 2,6-TDI) and '-diphenylmethane diisocyanate (MDI) etc., these polymers become and decompose the objectification compound.Resulting compound is the intermediate raw material diamine compound when synthesizing these isocyanic ester, for example tolylene diamine and phenylbenzene diamino methane after decomposing.
Not speech face analogy, the present invention also can use and not be polymeric by product, and promptly starting raw material carries out the by product that side reaction generates, and obtains the starting material compound or derivatives thereof after decomposing in the case.In addition, be difficult under the isolating situation at purpose compound and polymer, both mix indissociably in from the waste of chemical device.Prerequisite of the present invention is effective utilization of waste, therefore will also be according to general idea of the present invention because of not separating with other materials that the purpose compound decomposition of having only burning becomes starting compound so that utilize again, from this point, do not negate in the objectification compound, to comprise purpose compound itself.And then in the present invention, among the purpose compound that obtains with chemical device, outside specification, also can be with the outer goods of the such specification of waste treatment as the objectification compound.Have, the purpose compound is a macromolecular compound again, also can be with these moldinies as the objectification compound.
Specifically describe the decomposition method among the present invention below.
An example that is used to use the decomposer system of the inventive method shown in Figure 1.In a single day be stored in the storage tank by chemical device depleted waste, just infeed reactor continuously by supply pump, perhaps directly infeed reactor continuously from chemical device with molten state or liquid state.Directly the supplier does not need storage tank, so be more suitably.Waste has the residue of the still-process in chemical device and the liquid state waste behind isolating polymer after the polyreaction.The temperature of waste is during less than the decomposition reaction temperature, and one side simultaneously imports reactor with heater heats.
On the other hand, supercritical water or high pressure-temperature water are infeeded reactor continuously from other pipeline.The ideal temperature of supercritical water or high pressure-temperature water and pressure condition are more than 100 ℃, more than the 5MPa.In order to carry out the disaggregating treatment of the objectification compound in the waste more efficiently, recommend below 150 ℃, more than the 8MPa.Moreover the upper limit of temperature is that 400 ℃, upper limit of pressure are 40MPa.With respect to waste weight in the chemical device of supply response device, preferably supply with supercritical water or high pressure-temperature water more than 1 times.So method of the present invention is because of the reaction that can be hydrolyzed efficiently to the aqueous waste of reactor supply, so the upper weight limit of supercritical water or high pressure-temperature water, is 10 times with respect to the waste in the reactor, unnecessary supply is more than 10 times.
In Fig. 1 from the underfeed waste of reactor, supply with supercritical water or high pressure-temperature water from the bottom, the both rises to constitute like that in reactor, but these are an example, the importing position of waste and supercritical water or high pressure-temperature water, according to the character of the objectification compound in the waste suitably design alteration be convection current contact etc.In addition, the reaction times is also suitably set according to the amount of the objectification compound in the waste and hydrolytic reactivity etc., can adjust according to the size and the feed rate (speed) of reactor.
The liquid effluent that decomposition reaction finishes to discharge from reactor the back is imported into tripping device.Tripping device can be the device that adopts according to the known separation method of gained resolvent, is not particularly limited.Be recommended between tripping device and the reactor and be equipped with heat exchanger, utilize this heat exchanger, supercritical water or water that is used to form high pressure-temperature and the liquid effluent of discharging with high temperature carry out heat exchange, thereby energy efficiency is used energy well.
Decomposition method of the present invention and device, because decompose continuously, thus when packing waste into, do not need to be used to form the water of pulpous state, and when step batch of material is changed, be not used for the power loss of the cooling and the intensification of reactor.In addition, can handle waste in the chemical device of intact molten state or liquid state continuously with certain condition, so be extremely useful in actually operating.
Below illustrate in greater detail the present invention according to embodiment, but following embodiment is not a limitation of the present invention, implements change and all is included in the technical scope of the present invention not breaking away from foregoing purport scope.
Embodiment 1
Use device shown in Figure 1 to press the secondary PET oligopolymer of giving birth in the chemical device of making polyethylene terephthalate (PET) of the condition disaggregating treatment shown in the table 1.The resultant that is produced by decomposition is terephthalic acid and ethylene glycol.The rate of recovery of the terephthalic acid in each experiment is shown among table 1 and Fig. 2.Moreover the rate of recovery is the weight % with respect to the terephthalic acid of the recovery of the generation terephthalic acid weight of being passed through Theoretical Calculation by the PET oligopolymer weight of packing into.As Fig. 2 shows, under any pressure of 10MPa, 30MPa, in the rate of recovery that all obtains 100% more than 250 ℃.
Table 1
* " water addition ratio " is the high pressure-temperature water weight/waste weight in the reactor.
| Experiment No. | ????1 | ????2 | ????3 | ????4 | ????5 | ????6 |
| Temperature of reaction (℃) | ????200 | ????250 | ????300 | ????200 | ????250 | ????300 |
| Reaction pressure (MPa) | ????30 | ????30 | ????30 | ????10 | ????10 | ????10 |
| Water addition ratio * | ????5 | ????5 | ????5 | ????5 | ????5 | ????5 |
| Reaction times (branch) | ????30 | ????30 | ????30 | ????30 | ????30 | ????30 |
| The rate of recovery (%) | ????94.8 | ????100 | ????100 | ????93.9 | ????99.6 | ????100 |
Embodiment 2
Use the chemical device depleted distillation residue of synthetic toluene-2,4-diisocyanate (TDI), the experiment of reclaiming the intermediate raw material tolylene diamine of TDI.Experiment condition is shown in Table 2.The composition of distillation residue is the dimer 20% (weight) of TDI40% (weight), TDI, the tripolymer 40% (weight) of TDI.Contain a large amount of purpose compound TDI in the distillation residue of this moment, this is because polymer is difficult to separate with distillation with TDI.But, because TDI also resolves into tolylene diamine, so resulting decomposition handled thing (diamine compound) can be re-used as the intermediate raw material in the isocyanic ester building-up process fully.
The rate of recovery of the tolylene diamine in each experiment is shown among table 2 and Fig. 3.The rate of recovery is the weight % with respect to the tolylene diamine of the recovery of the generation tolylene diamine weight of being calculated through theory by the distillation residue weight of packing into.As Fig. 3 shows, in the rate of recovery that obtains 100% more than 180 ℃.
Table 2
* " water addition ratio " is the high pressure-temperature water weight/waste weight in the reactor.
| Experiment No. | ????1 | ????2 | ????3 | ????4 |
| Temperature of reaction (℃) | ????150 | ????180 | ????250 | ????300 |
| Reaction pressure (MPa) | ????10 | ????10 | ????10 | ????10 |
| Water addition ratio * | ????5 | ????5 | ????5 | ????5 |
| Reaction times (branch) | ????10 | ????10 | ????10 | ????10 |
| The rate of recovery (%) | ????92.8 | ????99.6 | ????100 | ????100 |
The effect of invention
With the inventive method and device, can effectively recycle the discarded object of except burning and waste treatment, having no idea to utilize up to now. The inventive method is the resolution process discarded object continuously, when packing waste material into, do not need water to form pulpous state, and be used for the cooling of reactor and the energy loss of intensification when not having step batch of material to change, can process continuously the molten condition that remains untouched or the discarded object of liquid state with certain condition, be method and apparatus extremely useful in the practical operation.
Simple declaration to accompanying drawing
Fig. 1 is the diagrammatic illustration figure that expression is used to implement an example of device of the present invention.
Fig. 2 is the rate of recovery of terephthalic acid is reclaimed in expression by the PET oligopolymer a graphic representation.
Fig. 3 represents that the distillation residue that produce reclaim the rate of recovery graphic representation of tolylene diamine from the TDI building-up process.
Claims (6)
1, the decomposition method of waste, it be comprise have ehter bond, the decomposition method of the waste of the objectification compound of any above water-disintegrable key in the ester bond, amido linkage, isocyanic acid ester bond, it is characterized in that, with waste with molten state or liquid state continuously in the supply response device, in above-mentioned reactor, supply with supercritical water or high pressure-temperature water continuously, make it to contact with this waste, with the object compound decomposition, as the starting compound or derivatives thereof of this objectification compound and reclaim.
2, the described decomposition method of claim 1, wherein, the purpose compound is a macromolecular compound, the objectification compound is the above polymer of dimer of starting compound.
3, the described decomposition method of claim 1, wherein, the purpose compound is a low molecular compound, the objectification compound is the above polymer of dimer of purpose compound.
4, each described decomposition method among the claim 1-3, wherein, the supercritical water of supply response device or high pressure-temperature water are more than 100 ℃, more than the 5MPa.
5, each described decomposition method among the claim 1-4 wherein, with respect to the waste weight of supply response device, is supplied with supercritical water or high pressure-temperature water more than 1 times.
6, the decomposer of waste is characterized in that, it is equipped with:
Reactor;
To comprise have ehter bond, in the ester bond, amido linkage, isocyanic acid ester bond in the chemical device of the objectification compound of any above water-disintegrable key waste supply with the feedway of above-mentioned reactor continuously with intact molten state or liquid state;
Supply with the device of supercritical water or high pressure-temperature water continuously to above-mentioned reactor; And
The device of liquid effluent lead-in separation device that will comprise the resolvent of the objectification compound of discharging from reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97102903A CN1101417C (en) | 1997-01-20 | 1997-01-20 | Decomposition method and device for discarded material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97102903A CN1101417C (en) | 1997-01-20 | 1997-01-20 | Decomposition method and device for discarded material |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN02107350A Division CN1434010A (en) | 2002-03-14 | 2002-03-14 | Method and device for decomposing waste material |
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| Publication Number | Publication Date |
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| CN1188776A true CN1188776A (en) | 1998-07-29 |
| CN1101417C CN1101417C (en) | 2003-02-12 |
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| CN97102903A Expired - Lifetime CN1101417C (en) | 1997-01-20 | 1997-01-20 | Decomposition method and device for discarded material |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100432530C (en) * | 2005-12-20 | 2008-11-12 | 山东大学 | Internal combustion circulating energy conversion system for supercritical oxidation |
| US7585930B2 (en) | 2004-02-12 | 2009-09-08 | Teijin Limited | Method of decomposing a polycarbonate |
| US7629419B2 (en) | 2001-10-16 | 2009-12-08 | Sekisui Chemical Co., Ltd. | Process for producing modified polymer, apparatus for producing modified polymer, and modified polymer |
| CN101914216A (en) * | 2010-08-03 | 2010-12-15 | 陈东升 | Method for efficiently decomposing macromolecular organic compound |
| CN101979422A (en) * | 2010-10-15 | 2011-02-23 | 济南大学 | Method for preparing environmentally-friendly macromoleclar polymer and application |
| CN103145541A (en) * | 2013-03-26 | 2013-06-12 | 浙江大学 | Hydrolyzing method of acetone polymer |
| CN108423924A (en) * | 2018-03-05 | 2018-08-21 | 苏州科特环保股份有限公司 | A kind of processing method of the waste water of polyethylene glycol containing high concentration |
| CN109848191A (en) * | 2019-04-12 | 2019-06-07 | 南京大学 | A kind of device of continuous treatment high COD chemical industry dangerous waste with high salt |
| CN109943026A (en) * | 2019-02-12 | 2019-06-28 | 武汉博茗低碳产业股份有限公司 | A kind of degradation by supercritical water polyester gradient phase-change heat-storage material and preparation method thereof |
| CN111388934A (en) * | 2020-05-18 | 2020-07-10 | 中国人民警察大学 | TDI macromolecular gel decontaminating agent |
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| CN111494868B (en) * | 2020-05-15 | 2021-03-19 | 中国人民警察大学 | IPDI macromolecular gel decontaminating agent |
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Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5326791A (en) * | 1991-12-20 | 1994-07-05 | Exxon Research And Engineering Company | Process for separation of hydrolyzable from non-hydrolyzable waste plastics for recovery of starting materials and other conversion processes, respectively |
| CA2128788A1 (en) * | 1992-02-20 | 1993-09-02 | Michael Siskin | Process for recycling polymers having repeating ether linkages |
-
1997
- 1997-01-20 CN CN97102903A patent/CN1101417C/en not_active Expired - Lifetime
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7629419B2 (en) | 2001-10-16 | 2009-12-08 | Sekisui Chemical Co., Ltd. | Process for producing modified polymer, apparatus for producing modified polymer, and modified polymer |
| US7585930B2 (en) | 2004-02-12 | 2009-09-08 | Teijin Limited | Method of decomposing a polycarbonate |
| CN100432530C (en) * | 2005-12-20 | 2008-11-12 | 山东大学 | Internal combustion circulating energy conversion system for supercritical oxidation |
| CN101914216A (en) * | 2010-08-03 | 2010-12-15 | 陈东升 | Method for efficiently decomposing macromolecular organic compound |
| CN101979422A (en) * | 2010-10-15 | 2011-02-23 | 济南大学 | Method for preparing environmentally-friendly macromoleclar polymer and application |
| CN101979422B (en) * | 2010-10-15 | 2012-02-22 | 济南大学 | Method for preparing environmentally-friendly macromoleclar polymer and application |
| CN103145541A (en) * | 2013-03-26 | 2013-06-12 | 浙江大学 | Hydrolyzing method of acetone polymer |
| CN108423924A (en) * | 2018-03-05 | 2018-08-21 | 苏州科特环保股份有限公司 | A kind of processing method of the waste water of polyethylene glycol containing high concentration |
| CN109943026A (en) * | 2019-02-12 | 2019-06-28 | 武汉博茗低碳产业股份有限公司 | A kind of degradation by supercritical water polyester gradient phase-change heat-storage material and preparation method thereof |
| CN109943026B (en) * | 2019-02-12 | 2021-06-08 | 武汉博茗低碳产业股份有限公司 | Supercritical water degradation polyester gradient phase change heat storage material and preparation method thereof |
| CN109848191A (en) * | 2019-04-12 | 2019-06-07 | 南京大学 | A kind of device of continuous treatment high COD chemical industry dangerous waste with high salt |
| CN109848191B (en) * | 2019-04-12 | 2021-05-28 | 南京大学 | Device for continuously treating high-salt high-COD (chemical oxygen demand) chemical hazardous waste |
| CN111388934A (en) * | 2020-05-18 | 2020-07-10 | 中国人民警察大学 | TDI macromolecular gel decontaminating agent |
| CN111388934B (en) * | 2020-05-18 | 2020-12-22 | 中国人民警察大学 | TDI macromolecular gel decontaminating agent |
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| CN1101417C (en) | 2003-02-12 |
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