CN116536681A - Environment-friendly hydrogen production process by coupling succinic acid prepared by electrochemical oxidation of waste PBT plastic - Google Patents
Environment-friendly hydrogen production process by coupling succinic acid prepared by electrochemical oxidation of waste PBT plastic Download PDFInfo
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- CN116536681A CN116536681A CN202310798305.0A CN202310798305A CN116536681A CN 116536681 A CN116536681 A CN 116536681A CN 202310798305 A CN202310798305 A CN 202310798305A CN 116536681 A CN116536681 A CN 116536681A
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- succinic acid
- hydrogen production
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000004033 plastic Substances 0.000 title claims abstract description 68
- 229920003023 plastic Polymers 0.000 title claims abstract description 68
- 239000001257 hydrogen Substances 0.000 title claims abstract description 49
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 49
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 43
- 239000001384 succinic acid Substances 0.000 title claims abstract description 40
- 239000002699 waste material Substances 0.000 title claims abstract description 32
- 238000006056 electrooxidation reaction Methods 0.000 title claims abstract description 28
- 230000008878 coupling Effects 0.000 title claims abstract description 18
- 238000010168 coupling process Methods 0.000 title claims abstract description 18
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 63
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 52
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000003792 electrolyte Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 239000002440 industrial waste Substances 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 230000002378 acidificating effect Effects 0.000 claims abstract 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 46
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- -1 phosphide Chemical class 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 4
- 238000000909 electrodialysis Methods 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 239000012621 metal-organic framework Substances 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 150000003346 selenoethers Chemical class 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 claims 2
- 230000002238 attenuated effect Effects 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 11
- 238000011084 recovery Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 238000010668 complexation reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 60
- 239000000047 product Substances 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 230000010287 polarization Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical group O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000005691 oxidative coupling reaction Methods 0.000 description 3
- 239000013502 plastic waste Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000007791 dehumidification Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000002255 enzymatic effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000004382 potting Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- BCBHDSLDGBIFIX-UHFFFAOYSA-M 4-[(2-hydroxyethoxy)carbonyl]benzoate Chemical compound OCCOC(=O)C1=CC=C(C([O-])=O)C=C1 BCBHDSLDGBIFIX-UHFFFAOYSA-M 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 101000989724 Ideonella sakaiensis (strain NBRC 110686 / TISTR 2288 / 201-F6) Mono(2-hydroxyethyl) terephthalate hydrolase Proteins 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000012691 depolymerization reaction Methods 0.000 description 1
- LRUDDHYVRFQYCN-UHFFFAOYSA-L dipotassium;terephthalate Chemical compound [K+].[K+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 LRUDDHYVRFQYCN-UHFFFAOYSA-L 0.000 description 1
- VIQSRHWJEKERKR-UHFFFAOYSA-L disodium;terephthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 VIQSRHWJEKERKR-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
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- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- 238000000629 steam reforming Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a coupling green hydrogen production process for preparing succinic acid by electrochemical oxidation of waste PBT plastic, and belongs to the fields of electrochemical synthesis and plastic recovery. Collecting, classifying, removing impurities and grinding the industrial waste PBT plastic into powder, and putting the powder into an alkaline medium for depolymerization; and (3) continuously electrolyzing the depolymerization solution serving as an electrolyte by taking a non-noble metal catalyst as an anode and taking a Pt/C catalyst as a cathode to obtain hydrogen with the purity of more than 99% at the cathode, and oxidizing and upgrading the 1, 4-butanediol into succinic acid at the anode. Adjusting the pH value of the electrolyzed solution to be acidic, and separating out terephthalic acid; and distilling or complexation extracting the residual solution to obtain the high-purity succinic acid product. Compared with the traditional electrolytic hydrogen production process, the process is simple to operate, has obvious energy-saving effect, realizes the green recovery of waste PBT and the conversion to high-added-value products, can greatly improve the market competitiveness and economic benefit of the electrolytic hydrogen production industry, and has wide application prospect.
Description
Technical Field
The invention belongs to the field of electrochemical synthesis and plastic recovery, and particularly relates to a coupling green hydrogen production process for preparing succinic acid by electrochemical oxidation of waste PBT plastic.
Background
Polybutylene terephthalate (PBT) is a polyester prepared by polycondensation of terephthalic acid and 1, 4-butanediol, and after modification by various additives, the polybutylene terephthalate is blended with other resins to obtain good heat resistance, flame retardance, electric insulation and other comprehensive properties and good processability, so that the polybutylene terephthalate is widely used in industries such as electric appliances, automobiles, aircraft manufacturing, communication, household appliances, transportation and the like, such as sockets of integrated circuits, printed circuit boards, computer keyboards, electric appliance switches, protectors, automobile bumpers, carburettors, spark plugs and the like, and has gradually become one of five engineering plastics. With the gradual expansion of the application of PBT plastics, the pollution of waste plastics to the environment is also remarkable, more than 80 hundred million tons of plastics are produced worldwide since the 50 th century according to data statistics, and the national environmental planning agency (UNEP) predicts that the yield of the global primary plastics will reach 340 hundred million tons in 2050. However, only 9% of the billions of tons of plastic waste produced worldwide have been recycled, with only 12% of the remaining plastic being burned, the others mostly wandering in natural environments, or degrading at a slow rate of hundreds of years in landfills. The data in the united nations show that at least 85% of beach waste is plastic waste worldwide. These waste plastics will cause irreversible damage to soil, human bodies and marine ecosystems, and therefore, it is urgent how to properly depolymerize the plastic crisis and realize the recycling of the waste plastics.
In addition, with the advent of fossil energy problems and the increasing environmental pressure, how to find alternative new energy sources has become a viable way to advance global sustainable development. As an emerging energy source for green cleaning, hydrogen energy has become a vital energy source in the world energy stage in the 21 st century. Along with the high-speed development of renewable energy sources such as solar energy, wind energy, nuclear energy and the like, the direct electric energy cost is expected to be further reduced in the future, and compared with the existing processes of coal hydrogen production, methane steam reforming, industrial tail gas hydrogen production and the like commonly used in industry, the water electrolysis hydrogen production also gradually shows own advantages and market competitiveness. However, the whole cost and scale of the existing water electrolysis hydrogen production are still different from those of the coal hydrogen production and other processes, and how to solve the problems of expensive catalyst, high electricity consumption cost and the like becomes a key for the development of the water electrolysis hydrogen production industry.
In order to solve the problems, the Chinese patent application ZL201910941831.1 discloses a method for preparing a usable PET composite material by recycling, chopping, steaming, heating, stirring and separating PET plastic waste, soaking and washing with sodium hydroxide and hydrochloric acid solution, melting, adding a modified elastomer, adding a coupling agent, a lubricant and an antioxidant, and heating and mixing. In addition, the Chinese patent application ZL202210400007.7 discloses a preparation method of an engineering enzyme compound for efficiently degrading PET plastics, wherein MHETase in the engineering enzyme compound can degrade MHET which leads to IsPETase substrate inhibition, and hydrohopbin 4 pulls the compound to the surface of the PET plastics, so that the degradation environment of the IsPETase is obviously improved, and the degradation efficiency is about 5 times higher than that of the IsPETase with highest degradation rate through directional evolution at present. However, current enzymatic plastic conversions remain largely in the laboratory stage, electrochemical recovery processes appear to be more application potential and economically competitive than physical recovery and enzymatic catalysis, and recovery and green upgrades of valuable chemicals can be achieved. The Chinese patent ZL202010499309.5 discloses a plastic recovery method for preparing succinic acid by electrochemical oxidation of PET plastic and coupling green hydrogen production, and obtains good energy-saving effect and economic value. However, recycling and upgrading of PBT plastic are not reported at present.
Disclosure of Invention
In view of the above, the invention discloses a coupling green hydrogen production process for preparing succinic acid by electrochemical oxidation of waste PBT plastic, which has the advantages of low energy consumption, controllable device, small investment, high economic value, green environment protection and the like, and is expected to provide a new feasible path for alleviating plastic crisis and industrial development of hydrogen production by water electrolysis.
In order to achieve the above object, the present invention provides the following technical solutions:
the technology for preparing succinic acid by electrochemical oxidation of waste PBT plastic is coupled with green hydrogen production and specifically comprises the following steps:
step 1, carrying out classified collection on industrial waste PBT plastic, removing other impurities which can affect the purity of subsequent products, such as labels, surface pigments and the like, putting into a ball mill, grinding and crushing into powder, wherein the mesh number is determined according to the actual situation, and the finer the powder, the more thorough the subsequent depolymerization.
And 2, placing the treated powder PBT into a reaction device, and simultaneously adding an excessive alkaline potassium hydroxide/sodium hydroxide aqueous solution, wherein the concentration of the solution ranges from 0.1 mol/L to 10 mol/L, and the depolymerization reaction is easier to occur when the concentration of the alkali solution is higher, and the corrosion of the electrolytic device is accelerated when the excess alkali solution is higher. Heating the device to the temperature of 70-140 ℃ and continuously stirring at a rotating speed of more than 400 turns for more than 2-48 hours so as to fully depolymerize and convert the PBT plastic powder into 1, 4-butanediol and terephthalic acid.
And 3, directly using the hydrolyzed potassium hydroxide/sodium hydroxide solution as an electrolyte, and continuously electrolyzing the electrolyte in a two-electrode electrolytic cell similar to a water electrolysis device at the running temperature of 30-85 ℃ and the operating pressure of 1-3 MPa by adopting a non-noble metal anode catalyst (Ni-based or Co-based metal oxide, sulfide, phosphide, selenide, or other catalysts such as double-metal layered hydroxide, metal organic frameworks and the like) and a Pt/C catalyst (or other non-noble metal-based catalysts).
And 4, considering the instantaneous fluctuation of the concentration of a reaction substrate in the electrolyte, in order to keep the continuous operation of the device and the stability of the electrolysis rate, a sectional type electrolysis device design can be adopted, wherein the first section is the electrolysis of the electrolyte containing high-concentration 1, 4-butanediol, when the current density is influenced by the concentration, the electrolyte is transferred to a second electrolysis device to be carried out in a stepped manner, so that the energy utilization efficiency of the electrolysis device is ensured, meanwhile, the conversion of 1, 4-butanediol into succinic acid is realized as much as possible, hydrogen with the purity of more than 99% is obtained at a cathode through electrolysis, and the depolymerized 1, 4-butanediol can be oxidized and upgraded to succinic acid at an anode.
Step 5, the electrolyte from the electrolysis system is required to be subjected to subsequent product separation and purification, wherein cathode hydrogen enters a hydrogen/water separator to remove water vapor carried by the gas, and then the gas is subjected to further dehumidification by a dryer, is regulated to rated pressure output by a pressure stabilizing valve and a regulating valve, and is transferred to a required place; transferring the fully reacted electrolyte into a sedimentation tank, adding hydrochloric acid to adjust the pH value to 3-4, crystallizing and separating out terephthalic acid, filtering, washing and drying to obtain a terephthalic acid product with the purity reaching the standard, wherein the main component of the supernatant of the upper electrolyte is succinic acid, and obtaining the high-purity succinic acid product with industrial requirements in various modes such as distillation, complexation extraction, electrodialysis or membrane separation.
Compared with the prior art, the technology for preparing succinic acid by electrochemical oxidation of waste PBT plastic provided by the invention has the following excellent effects:
compared with the traditional landfill and incineration processes, the invention has the advantages of lower carbon, environmental protection and no extra damage to the environment; compared with the physical recovery mode adopted at present, the electrochemical oxidation method circularly upgrades the plastics into succinic acid and terephthalic acid products with high added values, and has higher economic benefit and environmental benefit. From the application point of view, the device is small in scale, low in investment and higher in benefit, and the device scale and the treatment capacity can be flexibly designed according to the requirements. Most importantly, the electrochemical oxidation of the PBT can be used as a substitute for the anodic oxygen evolution reaction and is coupled with the cathodic electrolysis of water to produce hydrogen, and from the aspect of energy utilization, the lower initial potential and the operating potential enable the energy consumption required at the same hydrogen production rate to be lower, and the electric energy cost can be further reduced; in addition to the low value compared to oxygen, terephthalic acid and succinic acid, which range from waste plastics to high added values, are clearly more economically valuable. In general, the technology for preparing succinic acid by electrochemical oxidation of waste PBT plastic, disclosed by the invention, is not only expected to realize recovery and upgrading of waste plastic, but also can be matched with electrolytic water to prepare hydrogen, has lower power consumption and remarkably reduced operation cost, and provides a new feasible scheme for industrialization of commercial electrolytic water, and has wide application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of the process for preparing succinic acid by electrochemical oxidation of waste PBT plastic in example 1, which is coupled with green hydrogen production.
FIG. 2 is a graph comparing the polarization curves of PBT oxidative coupling green hydrogen production with overall water electrolysis in example 3.
Detailed Description
The following description of embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The embodiment of the invention discloses a coupling green hydrogen production process for preparing succinic acid by electrochemical oxidation of waste PBT plastic.
The present invention will be further specifically illustrated by the following examples, which are not to be construed as limiting the invention, but rather as falling within the scope of the present invention, for some non-essential modifications and adaptations of the invention that are apparent to those skilled in the art based on the foregoing disclosure.
The technical scheme of the invention will be further described below with reference to specific embodiments.
Example 1
As shown in FIG. 1, the implementation steps of the process for preparing succinic acid by electrochemical oxidation of waste PBT plastic and coupling green hydrogen production are as follows:
step 1, carrying out classified collection on industrial waste PBT plastic, removing other impurities which can affect the purity of subsequent products, such as labels, surface pigments and the like, crushing by adopting a crusher, and further grinding into powder at a high rotating speed in a ball mill, wherein the mesh number of the PBT powder reaches 200 meshes.
Step 2, performing a test on a small scale in a laboratory, placing 100 parts of processed powder PBT g into a round-bottomed flask, adding a prepared 2 mol/L aqueous solution of potassium hydroxide, placing into an oil bath, heating to 110 ℃, setting the rotating speed to 600 revolutions, continuously stirring for 12 hours, and fully depolymerizing the PBT plastic powder into 1, 4-butanediol and terephthalic acid.
And 3, the fully depolymerized solution is directly used as electrolyte, and a commercial foam nickel is adopted as an anode catalyst of an electrolysis system, and the pretreatment mode is as follows: commercially available nickel foam was placed in a 2 mol/L hydrochloric acid solution for 30 minutes, then rinsed with ethanol, water, and dried to remove surface oxide layers. For the cathode catalyst, a commercially available 20% Pt/C catalyst was used, which was immobilized on carbon fiber paper via a Nifion dispersion to be used as the cathode catalyst.
And 4, carrying out continuous electrolysis in a two-electrode electrolytic cell similar to the water electrolysis device, wherein the operation temperature of the electrolysis device is 30 ℃, and the operation pressure is 1 MPa. In a three-electrode system, voltage is applied by an electrochemical workstation, a cathode catalyst and an anode catalyst are activated by CV scanning, then voltage of 1.6V is applied to the two-electrode system in a summarizing way, a transverse potential test method is adopted for continuous electrolysis test, the current density is reduced along with the reduction of the concentration of 1, 4-butanediol in the electrolyte, and the electrolysis is carried out continuously for 20 h until the complete oxidation of the 1, 4-butanediol in the electrolyte to succinic acid is finished. For simplicity, the cascade design of the electrolysis device is not performed, and the device can be designed separately in consideration of the operational stability and efficiency of the device in the practical industry.
And 5, conveying electrolyte from the electrolysis system to a separation system through a pump, firstly adding 1 mol/L hydrochloric acid into a sedimentation tank until the pH value of the solution is regulated to 3-4, rapidly crystallizing and separating terephthalic acid in the electrolyte due to acid insolubility, filtering, washing and drying a lower layer of precipitate to obtain a terephthalic acid product with the purity reaching the standard, wherein the main component of supernatant of the upper layer of electrolyte is succinic acid, and obtaining the high-purity succinic acid product required by industry by adopting a reduced pressure distillation device. And the cathode gas-phase product-hydrogen is conveyed to a hydrogen/water separator to remove water vapor carried by the gas, and then is subjected to further dehumidification by a dryer, and is regulated to rated pressure output by a pressure stabilizing valve and a regulating valve.
Example 2
The core of the invention is the oxidation and cathodic hydrogen evolution reaction of the PBT in the electrolysis system, so in order to better embody the remarkable energy-saving effect of the invention in the practical industry, the non-noble metal-based catalyst with higher catalytic performance and lower cost is redesigned and synthesized, and the specific contents are as follows:
and 1, collecting, classifying, preprocessing and grinding the industrial waste PBT plastic into powder.
And 2, adding the powder PBT into a reaction device, adding an excessive alkaline potassium hydroxide aqueous solution, heating the device to above 110 ℃ and continuously stirring at a rotating speed of 600 turns for more than 12 hours to fully depolymerize the PBT plastic powder into 1, 4-butanediol and terephthalic acid.
Step 3, designing and synthesizing a cathode catalyst and an anode catalyst, wherein a non-noble metal-based NiCo-LDH/NF double-function catalyst is directly used as the cathode catalyst and the anode catalyst, and the synthesis method comprises the following steps: commercial nickel foam (2 x 4 cm) -2 ) Putting the mixture into a hydrochloric acid solution with the concentration of 2 mol/L for ultrasonic treatment for 30 minutes, and then sequentially flushing with ethanol and water and drying to remove a surface oxide layer; 0.291 g of Ni (NO) 3 ) 2 ·6H 2 O、0.290 g Co(NO 3 ) 2 ·6H 2 O and 0.3. 0.3 g urea were dissolved in 30 mL water and stirred for 30 minutes to complete dissolution, the solution was transferred to a 50 mL polytetrafluoroethylene-lined stainless steel autoclave with treated foamed nickel and held at 12 h in an oven at 120 ℃. And (3) cooling, sequentially cleaning with deionized water and ethanol, and drying overnight to obtain the NiCo-LDH/NF catalyst, and then directly using the NiCo-LDH/NF catalyst as an anode catalyst and a cathode catalyst.
And 4, constructing a two-electrode system electrolysis device, which is similar to the water electrolysis device, and is free from separating a cathode and an anode by an ion exchange membrane, wherein the operation temperature of the electrolysis device is 30 ℃ and the operation pressure is 1 MPa. In a three-electrode system, a Chenhua 760E electrochemical workstation is used for carrying out CV scanning to activate the catalyst, then the catalyst is changed into a two-electrode system, a transverse potential test method is adopted for carrying out continuous electrolysis test under the voltage of 1.6V, the current density is reduced along with the concentration reduction of 1, 4-butanediol in the electrolyte, and the continuous electrolysis of 15 h is carried out until the complete oxidation of 1, 4-butanediol in the electrolyte to succinic acid is finished.
Compared with the foam nickel and Pt/C catalyst adopted in the example 1, the synthesized NiCo-LDH/NF catalyst has more excellent catalytic activity on anodic oxidation, and the cathode can be compared with the Pt/C catalyst, but the cost is lower. The overall results therefore show that at a voltage of 1.6V, which is higher in current density than example 1, the time for complete oxidation of 1, 4-butanediol to succinic acid is also reduced.
And 5, conveying electrolyte from the electrolysis system to a separation system through a pump, firstly adjusting the pH value to 3-4 in a sedimentation tank, crystallizing and separating terephthalic acid, filtering, washing and drying to obtain a product with the purity reaching the standard, and obtaining a high-purity succinic acid product with industrial requirements from supernatant electrolyte by adopting a reduced pressure distillation device. The cathode hydrogen was purified by the same procedure as in example 1.
Example 3
In order to fully feed back the energy-saving advantage of the electrochemical oxidative coupling green hydrogen production process of the waste PBT plastic disclosed by the invention, the distinction between a polarization curve in an electrolysis device and the water electrolysis hydrogen production device is mainly studied.
The solution in which 1, 4-butanediol and terephthalic acid are dissolved is obtained as electrolyte in the manner provided in example 1, a non-noble metal-based NiCo-LDH/NF double-function catalyst is directly used as a cathode catalyst and an anode catalyst, CV scanning is carried out by using a Chen Hua 760E electrochemical workstation to pre-activate the catalyst, then a two-electrode system is changed, polarization curve LSV scanning is carried out, the scanning speed is 10 mV/s, the scanning interval is 0-1.8V, the iR compensation is set to 85%, and the scanning is carried out continuously for a plurality of times until the catalyst tends to be stable.
In order to compare commercial electrolyzed water, the same NiCo-LDH/NF bifunctional catalyst is directly used as a cathode catalyst and an anode catalyst, 2 mol/L potassium hydroxide is adopted as electrolyte, CV scanning activation is firstly carried out in the same mode, then a two-electrode system is replaced, polarization curve LSV scanning is carried out, the scanning speed is 10 mV/s, the scanning interval is 0-2.0V, iR compensation is set to 85%, and continuous scanning is carried out for a plurality of times.
By comparing the two LSV curves (FIG. 2), it can be clearly observed that the same current density is achieved, and the energy consumption input required by the PBT plastic oxidation coupling green hydrogen production system is significantly smaller than that of the water electrolysis device, especially at 200 mA cm -2 And 400 mA cm -2 The energy consumption can be saved by 250 mV and 300 mV, respectively, which is clearly more energy efficient and surpasses most of the reported electrolyzed water systems.
Example 4
In fact, unlike traditional commercial electrolyzed water systems, which are dominated by electricity consumption costs, the cost of the separation system of the waste PBT plastic electrochemical oxidation coupling green hydrogen production process cannot be ignored, and particularly the separation of liquid phase products is proposed, and the separation process is explored.
The steps of example 1 are adopted to carry out electrochemical oxidation and cathodic hydrogen evolution reaction on PBT depolymerization solution, after the reaction is completed, electrolyte is conveyed to a separation system, firstly hydrochloric acid solution is added into a sedimentation tank, the pH is regulated to 3-4, terephthalic acid is rapidly crystallized and separated out, and then products with the purity reaching the standard are obtained through filtration, washing and drying, wherein the space which can be optimally designed is not too much, and the supernatant electrolyte is subjected to calcium salt method, namely calcium ions are added to calcifie the supernatant, and then acidolysis, ion exchange purification and crystallization are carried out.
The method can also adopt a bipolar membrane electrodialysis method, a sugar separation extraction combined with crystallization separation and purification method, a complexation extraction method and the like, which are reported in various documents, but different modes are adopted according to different product concentration requirements, and the electrodialysis method has high product purity but high cost, and the complexation extraction is a relatively common mode.
The final succinic acid product and terephthalic acid product were obtained in the above manner.
Example 5
The hydrolysis condition of the PBT plastic in the process of preparing succinic acid by using the waste PBT electrochemical oxidation is explored.
Step 1, placing 100 parts of processed powder PBT g into a round-bottom flask, adding prepared 0.5 mol/L, 1 mol/L, 2 mol/L, 5 mol/L and 10 mol/L aqueous potassium hydroxide solution, placing into an oil bath pot, heating to 110 ℃, setting the rotating speed to 600 revolutions, and continuously stirring for 12 hours, wherein the PBT plastic powder is fully depolymerized into 1, 4-butanediol and terephthalic acid.
The research shows that the increase of the concentration of potassium hydroxide can promote the depolymerization of the PBT plastic, but the depolymerization of the PBT plastic can be realized under the condition of low concentration, the required stirring time is longer, the concentration of the monomer in the solution is relatively low, and the concentration of the potassium hydroxide solution can be adjusted according to the actual requirement of a subsequent electrolysis system.
Example 6
The hydrolysis temperature of the PBT plastic in the process of preparing succinic acid by using the waste PBT electrochemical oxidation is explored.
Step 1, placing 100 g of the processed powder PBT into a round bottom flask, adding a prepared 2 mol/L potassium hydroxide aqueous solution, placing into an oil bath pot and heating, wherein the temperature of the oil bath is controlled to be 70 ℃, 90 ℃, 110 ℃, 130 ℃ and 140 ℃ by adjusting variables, the rotating speed is set to be 600 revolutions, and continuously stirring for 12 hours, so that the PBT plastic powder is fully depolymerized into 1, 4-butanediol and terephthalic acid.
As a result, it was found that the increase in the oil bath temperature promoted depolymerization of the PBT plastic, and as the temperature increased, the depolymerization rate increased, and the depolymerization of the PBT plastic was also more sufficient, but the temperature was too high, which increased the cost of the heat utility on the one hand and reduced the stability of the depolymerized monomer on the other hand.
Example 7
The hydrolysis speed and the stirring time of the PBT plastic in the process of preparing succinic acid by the electrochemical oxidation of the waste PBT are explored.
Step 1, placing 100 parts g of the processed powder PBT into a round bottom flask, adding a prepared 2 mol/L potassium hydroxide aqueous solution, placing into an oil bath pot and heating to 100 ℃, wherein the stirring speed is controlled to 400, 500, 600, 700 and 800 revolutions by adjusting a variable, and continuously stirring for 12 hours, so that the PBT plastic powder is fully depolymerized into 1, 4-butanediol and terephthalic acid.
As a result, it was found that depolymerization of PBT plastic was promoted with increasing rotational speed, but too high rotational speed also increased cost and affected device stability, typically set at 500 and 600 revolutions. In addition, the depolymerization of PBT has already occurred at a stirring time of 2 h, but the concentration of depolymerized monomer in the solution is relatively low, and as the stirring time increases, the concentration of depolymerized monomer gradually increases, the higher the concentration thereof increases, the longer the time it takes for the subsequent electrolysis apparatus to operate, and the higher the current density for stable operation, so that it is generally set to 12 hours.
Example 8
The type of the PBT plastic depolymerization solution in the process of preparing succinic acid by using the waste PBT electrochemical oxidation and coupling green hydrogen production is researched.
Step 1, taking 100 parts of processed powder PBT g, placing the powder PBT into a round-bottom flask, simultaneously adding prepared 2 mol/L potassium hydroxide and sodium hydroxide aqueous solution respectively, placing the mixture into an oil bath pot, heating the mixture to 100 ℃, controlling the stirring speed to 600 revolutions, and continuously stirring the mixture for 12 hours, wherein the PBT plastic powder is fully depolymerized into 1, 4-butanediol and terephthalic acid.
As a result, it was found that the effect of the two alkaline solutions on the depolymerization effect was substantially the same, except that in the process of implementation, terephthalic acid was reacted with alkali liquor to produce sodium terephthalate or potassium terephthalate, but since the pH was adjusted in the subsequent separation process, terephthalic acid could be directly precipitated, and the separation of the product was not affected.
Example 9
In order to research the general applicability of the catalyst in the electrochemical oxidative coupling green hydrogen production process of the waste PBT plastic disclosed by the invention, the influence of different catalysts on the energy-saving effect of the whole process and the selectivity of the product is mainly researched.
A solution in which 1, 4-butanediol and terephthalic acid were dissolved was obtained as an electrolyte in the manner provided in example 1, and non-noble metal-based NiS x /NF、NiP x The dual-function catalyst such as/NF and NiSe/NF is directly used as a cathode catalyst and an anode catalyst, a Chenhua 760E electrochemical workstation is adopted to perform CV scanning to pre-activate the catalyst, then a two-electrode system is used to perform LSV scanning of a polarization curve, the scanning speed is 10 mV/s, the scanning interval is 0-1.8V, the iR compensation is set to 85%, and the scanning is performed continuously for multiple times until the catalyst tends to be stable.
To compare commercial electrolyzed water, niS was treated with the same non-noble metal base x /NF、NiP x The dual-function catalysts of/NF and NiSe/NF are directly used as cathode and anode catalysts, electrolyte adopts 2 mol/L potassium hydroxide, CV scanning activation is firstly carried out in the same mode, then a two-electrode system is changed, polarization curve LSV scanning is carried out, the scanning speed is 10 mV/s, the scanning interval is 0-2.0V, iR compensation is set to 85%, and continuous scanning is carried out for multiple times.
The research shows that all three catalysts can realize the oxidation upgrading of PBT plastic into succinic acid, and the catalyst performance is excellent, especially in 200 mA cm -2 And 400 mA cm -2 The required electrode voltage is significantly less than the anodic oxygen evolution reaction of commercial electrolyzed water at commercial current densities.
Example 10
The influence of different catalysts on the energy-saving effect and the product selectivity of the whole process is continuously researched.
The solution in which 1, 4-butanediol and terephthalic acid are dissolved is obtained as an electrolyte in the manner provided in example 1, and the non-noble metal-based NiCo-MOF/NF catalyst and the NiCo-LDH/NF bifunctional catalyst are directly used as a cathode and anode catalyst, and the synthesis method is obtained from the literature, and the prepared catalyst is usually in a nano array structure. The Chenhua 760E electrochemical workstation is adopted to perform CV scanning to pre-activate the catalyst, then a two-electrode system is adopted to perform LSV scanning of a polarization curve, the scanning speed is 10 mV/s, the scanning interval is 0-1.8V, the iR compensation is set to be 85%, and the scanning is performed continuously for multiple times until the catalyst tends to be stable.
Through the test of LSV curve and the test research of the product, both catalysts can realize the oxidation upgrading of PBT plastic into succinic acid, and have higher Faraday efficiency and excellent catalytic performance, and especially under the industrial current density, the required electrode voltage is obviously smaller than the anodic oxygen evolution reaction of commercial electrolyzed water.
Example 11
The influence of the reaction condition of an electrolysis system on the oxidation upgrading of PBT plastic is researched.
The solution in which 1, 4-butanediol and terephthalic acid are dissolved is obtained as an electrolyte in the manner provided in example 1, and the non-noble metal-based NiCo-LDH/NF bifunctional catalyst is directly used as a cathode and anode catalyst, and the synthesis method is obtained from the literature, and the prepared catalyst is usually in a nano array structure. The Chenhua 760E electrochemical workstation is adopted to perform CV scanning to pre-activate the catalyst, then a two-electrode system is adopted to perform LSV scanning of a polarization curve, the scanning speed is 10 mV/s, the scanning interval is 0-1.8V, the iR compensation is set to be 85%, and the scanning is performed continuously for multiple times until the catalyst tends to be stable. The electrolyzer simulates a commercial water electrolyzer, and the reaction temperature control variable is 25 ℃, 50 ℃, 65 ℃ and 85 ℃. The pressure is set to be 1 MPa, 2MPa and 3 MPa through the regulation and control variable.
Electrochemical tests are carried out under different running conditions of the electrolysis device, and the LSV curve test and quantitative analysis of products show that the reaction temperature has obvious influence on the catalytic activity and the catalytic rate, the transfer speed of electrons and ions is increased along with the increase of the temperature, and the catalytic reaction rate is also obviously improved, but the reaction temperature can be usually set to 65 ℃ in consideration of the energy consumption required by high temperature and the evaporation rate of water vapor. The influence of the pressure on the electrolysis device is not obvious, and the pressure can be set to be 1 MPa under no special requirement.
In addition, succinic acid is used as an important chemical raw material, has wide application and higher value in the fields of food, chemical industry, medicine and the like, which means that the PBT plastic can be recycled by an electrochemical method and fine chemicals with high added value can be obtained, and meanwhile, the cost of hydrogen production by water electrolysis is reduced, so that the method has wide application prospect.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. The technology for preparing succinic acid by electrochemical oxidation of waste PBT plastic is characterized by comprising the following steps:
step 1), collecting, classifying, removing impurities and grinding the industrial waste PBT plastic into powder for later use;
step 2) adding excessive alkaline aqueous solution into the PBT powder treated in the step 1), heating and continuously stirring to fully depolymerize the PBT plastic powder into 1, 4-butanediol and terephthalic acid;
step 3) continuously electrolyzing the depolymerized alkaline aqueous solution serving as electrolyte by taking a non-noble metal catalyst as an anode and a Pt/C catalyst as a cathode to obtain hydrogen at the cathode, wherein the anode oxidatively upgrades the depolymerized 1, 4-butanediol into succinic acid;
and 4) regulating the pH value of the solution subjected to the electrolysis in the step 3) to be acidic so as to crystallize and separate terephthalic acid, and separating and purifying the residual electrolyte to obtain a high-purity succinic acid product.
2. The process for preparing succinic acid by electrochemical oxidation coupling green hydrogen production by using waste PBT plastic according to claim 1, wherein in the step 2), the heating temperature is 70-140 ℃, the stirring time is 2-48 h, and the stirring rotation speed is 400-800 r/min.
3. The process for preparing succinic acid coupling green hydrogen production by electrochemical oxidation of waste PBT plastic according to claim 1 or 2, wherein the alkaline aqueous solution is potassium hydroxide or sodium hydroxide, and the concentration of the alkaline aqueous solution is 0.1 mol/L-10 mol/L.
4. The process for preparing succinic acid coupling green hydrogen by electrochemical oxidation of waste PBT plastic according to claim 1, wherein the electrolysis in the step 3) adopts a sectional type electrolysis device; wherein, the liquid crystal display device comprises a liquid crystal display device,
the first section is the electrolysis of the high-concentration 1, 4-butanediol-containing electrolyte, when the current density is attenuated to 80%, the electrolyte is transferred to a second electrolysis device to be carried out in a gradient manner, so that the energy utilization efficiency of the electrolysis device is ensured, and the conversion of 1, 4-butanediol into succinic acid is realized.
5. The process for preparing succinic acid coupling green hydrogen by electrochemical oxidation of waste PBT plastic according to claim 1 or 4, wherein the non-noble metal catalyst is Ni-based or Co-based metal oxide, sulfide, phosphide, selenide or bi-metal layered hydroxide, or metal organic framework.
6. The process for preparing succinic acid by electrochemical oxidation coupling green hydrogen production from waste PBT plastic according to claim 5, wherein the electrolysis operation temperature in the step 3) is 30-85 ℃ and the operation pressure is 1-3 MPa.
7. The process for preparing succinic acid by electrochemical oxidation coupling green hydrogen production by using waste PBT plastic according to claim 1, wherein hydrogen generated by a cathode in electrolysis is required to pass through a water/gas separation device and a drying device to remove water vapor carried by the gas.
8. The process for preparing succinic acid by electrochemical oxidation coupling green hydrogen production according to claim 1, wherein the separation and purification process in the step 4) comprises complex extraction, aqueous two-phase extraction, calcium salt method, direct crystallization method, ion exchange method, electrodialysis method or distillation method.
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| US20220170167A1 (en) * | 2020-11-30 | 2022-06-02 | The Regents Of The University Of Colorado, A Body Corporate | Methods for chemical degradation of polyester polymers |
| CN115896836A (en) * | 2022-11-29 | 2023-04-04 | 同济大学 | Nickel-based integrated electrocatalyst and preparation method and application thereof |
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| WO2021180432A1 (en) * | 2020-03-10 | 2021-09-16 | Rittec Umwelttechnik Gmbh | Method and device for recycling polycondensate-containing waste |
| CN113774399A (en) * | 2020-06-04 | 2021-12-10 | 清华大学 | Method for co-producing hydrogen, formic acid and terephthalic acid from waste PET (polyethylene terephthalate) plastic through electrocatalysis |
| US20220170167A1 (en) * | 2020-11-30 | 2022-06-02 | The Regents Of The University Of Colorado, A Body Corporate | Methods for chemical degradation of polyester polymers |
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