CN110479223A - A kind of method of the microwave-heating poplar bits preparation simultaneously rich in phenol bio-oil and the biomass carbon for adsorbing heavy metal ion - Google Patents
A kind of method of the microwave-heating poplar bits preparation simultaneously rich in phenol bio-oil and the biomass carbon for adsorbing heavy metal ion Download PDFInfo
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- CN110479223A CN110479223A CN201910676880.7A CN201910676880A CN110479223A CN 110479223 A CN110479223 A CN 110479223A CN 201910676880 A CN201910676880 A CN 201910676880A CN 110479223 A CN110479223 A CN 110479223A
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- 239000002028 Biomass Substances 0.000 title claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000010438 heat treatment Methods 0.000 title claims abstract description 28
- 239000012075 bio-oil Substances 0.000 title claims abstract description 25
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 241000219000 Populus Species 0.000 title claims abstract description 24
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title description 4
- 238000000197 pyrolysis Methods 0.000 claims abstract description 31
- 239000007789 gas Substances 0.000 claims abstract description 21
- 239000000446 fuel Substances 0.000 claims abstract description 13
- 239000003921 oil Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000012530 fluid Substances 0.000 claims abstract description 10
- 238000009833 condensation Methods 0.000 claims abstract description 7
- 230000005494 condensation Effects 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000003610 charcoal Substances 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 229910052793 cadmium Inorganic materials 0.000 abstract description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 11
- 239000000126 substance Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 240000008892 Helianthus tuberosus Species 0.000 description 3
- 235000003230 Helianthus tuberosus Nutrition 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000002390 heteroarenes Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- 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
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The present invention relates to a kind of microwave-heating poplar bits to prepare the method rich in phenol bio-oil and the biomass carbon for adsorbing heavy metal ion simultaneously, belongs to technical field of resource comprehensive utilization.Poplar bits are crushed by the present invention, and being placed in nitrogen atmosphere, temperature is that 30 ~ 60min of microwave-heating obtains pyrolysis gas and pyrolysis solid at 400 ~ 600 DEG C, and pyrolysis solid cooling obtains biomass carbon；It is the isolated liquid bio matter oil of rapid condensation and biogas fluid fuel at -1 ~ -5 DEG C that pyrolysis gas, which is passed through temperature,.Biomass carbon of the present invention contains abundant functional group, has biggish adsorbance to Pb In Exhausted Water and cadmium；This method produces the bio-oil, biogas fluid fuel and biomass carbon of high value added product using microwave-heating using poplar bits as raw material, realizes the purpose of comprehensive utilization He " treatment of wastes with processes of wastes against one another " of waste resource.
Description
Technical field
It is prepared simultaneously rich in phenol bio-oil the present invention relates to a kind of microwave-heating poplar bits and for adsorbing heavy metal
The method of the biomass carbon of ion, belongs to technical field of resource comprehensive utilization.
Background technique
Increasingly exhausted with fossil energy, the mankind have to energy crisis and chemical resource danger in face of getting worse
Machine finds the emphasis for cleaning the reproducible energy and green chemical as various countries' research；Simultaneously with economical quick
Increase, environmental problem becomes increasingly conspicuous the pollution of especially heavy metal wastewater thereby.Biomass resource is cheap and easy to get as one kind, source is wide
General renewable resource has very huge development and application potentiality, utilization of the countries in the world scientific research personnel to biomass resource
Positive exploration and experimental study have been carried out, certain research achievement is achieved.But these researchs are all often to bias toward life
Some aspect that physical resources utilize, belongs to the mode of " fighting separately ", there is no comprehensively utilize biomass resource
Come.
In recent years, biomass pyrolytic technology prepares high additional chemical product and has obtained rapidly developing, and this method can
Convert biomass efficient to chemical products and easily storage, the easily high fuel of transport, energy density with high added value.Biology
Matter pyrolysis refers to biomass heat resolve under conditions of anaerobic or anoxic, ultimately generates bio-oil, biomass gas and life
The process of substance charcoal.However, there are shortcomings for traditional biomass pyrolytic mode, for example it is difficult to direct to raw material inside
It is heated, traditional heating method can only from outward appearance to inner essence heat raw material, and raw material is influenced most due to uneven heating
The yield and quality of final product can improve pyrolytic process if realizing to being uniformly heated up inside and outside raw material significantly, improve
Technical level.Microwave heating is a kind of love knot heating method, can be realized material and quickly and uniformly heats, and had been pyrolyzed
It can be improved the quality of pyrolysis product in journey.
In the prior art, the method for biomass pyrolytic preparation bio oil pre-processes biomass progress crushing and screening,
The particle obtained after processing enters fast pyrolysis reactor, and in the at a temperature of progress fast pyrogenation reaction of setting, reaction product is straight
Capable condensation is tapped into, bio oil and solidification charcoal are obtained, this method realizes the separation and utilization of heavy oil, and the bio-oil components of preparation are few,
The characteristics such as high level content height.But the reaction requires height to consersion unit, and energy consumption is high, has ignored the utilization of gaseous product.Using micro-
Wave is pyrolyzed the method that jerusalem artichoke slag generates substance gas, includes the following steps: that jerusalem artichoke slag is dried in (1)；It (2) will be dry
Jerusalem artichoke slag and catalyst are mixed to get reaction mixture, and the catalyst is the mixture of tin oxide, sodium carbonate, potassium carbonate；
(3) it by reflection mixture that step (2) obtains and is transported in microwave reaction kettle, is warming up to the speed of 200~300 DEG C/min
550~680 DEG C, it is pyrolyzed 0.5~15min；(4) the separating biomass charcoal from solid product, the isolated life from gas-phase product
Substance gas.But only considered the utilization of biomass gas product, and the comprehensive utilization of bio-oil and biomass carbon is had ignored,
Resource utilization greatly reduces.
Therefore, how to carry out biomass pyrolytic to realize maximally utilizing for resource is urgent problem.
Summary of the invention
In view of the problems of the existing technology the present invention, provides a kind of microwave-heating poplar bits while preparation is raw rich in phenol
The method of substance oil and the biomass carbon for adsorbing heavy metal ion, the present invention carry out anaerobic microwave thermal by raw material of poplar bits
Solution, by strict control pyrolysis temperature and pyrolysis time, production is rich in the bio-oil of phenol, is rich in CO and H2Biogas
Body and surface are smooth, functional group is abundant and have the biomass carbon of biggish adsorbance to heavy metal ion Pb In Exhausted Water and cadmium,
Realize that the poplar bits of low value are converted to high value added product；
A kind of microwave-heating poplar bits prepare be rich in phenol bio-oil and the biomass carbon for adsorbing heavy metal ion simultaneously
Method, the specific steps are as follows:
(1) poplar bits are crushed, are placed in nitrogen atmosphere, temperature is that 30 ~ 60min of microwave-heating obtains pyrolysis gas at 400 ~ 600 DEG C
Body and pyrolysis solid, pyrolysis solid cooling obtain biomass carbon；
(2) step (1) pyrolysis gas is passed through temperature is the isolated liquid bio matter oil of rapid condensation and life at -1 ~ -5 DEG C
Material gases fuel.
Step (1) microwave power is 1000-2000W.
Step (1) nitrogen flow rate is 200 ~ 400mL/min.
The specific surface area of step (1) biomass carbon is 86.59 ~ 265.12m2/g。
Phenol quality content is 33.16% ~ 49.05% in step (2) the liquid bio matter oil.
CO and H in step (2) the biogas fluid fuel2Total volume content be 45.90% ~ 65.64%.
The beneficial effects of the present invention are:
(1) present invention can be used as the industrial chemicals for extracting phenol by the phenol bio-oil of pyrolysis production high-content, reduce
The production cost of phenol；It can obtain being rich in CO and H simultaneously in pyrolytic process2Biomass gas, can be used as synthesis gas
The raw material of body or as energy substitution product；Obtained biomass carbon surface can be used as processing heavy metal ion rich in functional group
The adsorbent of waste water；
(2) present invention not only realizes the comprehensive utilization of three kinds of thermal decomposition products of solid-liquid-gas, produces high value-added product, realizes
Recycling for waste is conducive to the pressure for alleviating resource and environment, is really achieved the purpose of " treatment of wastes with processes of wastes against one another ".
(3) biomass carbon of the present invention has that biggish specific surface area and surface functional group are abundant, to containing lead and a cadmium huge sum of money
The adsorbance for belonging to ion waste water is respectively 38.08 ~ 54.13 mg/g and 30.51 ~ 44.73mg/g；
(4) present invention carries out microwave-heating, and low energy consumption, and pyrolytic reaction rate is fast, and pyrolysis product cleans and performance is higher and prepares
The environmental-friendly outstanding advantage of process, while having many advantages, such as that comprehensive utilization of resourcesization is high, added value of product is high.
Detailed description of the invention
Fig. 1 is the GC-MS map of 1 bio-oil ingredient of embodiment；
Fig. 2 is the infrared spectrogram of 1 biomass carbon of embodiment；
Fig. 3 is the scanning electron microscope (SEM) photograph of 3 biomass carbon of embodiment；
Fig. 4 is nitrogen adsorption-desorption curve of 3 biomass carbon of embodiment.
Specific embodiment
Invention is further described in detail With reference to embodiment, but protection scope of the present invention and unlimited
In the content.
Embodiment 1: a kind of microwave-heating poplar bits prepare simultaneously rich in phenol bio-oil and for adsorb heavy metal from
The method of the biomass carbon of son, the specific steps are as follows:
(1) poplar bits are crushed, are placed in nitrogen atmosphere, temperature is that microwave-heating 30min obtains pyrolysis gas and pyrolysis at 400 DEG C
Solid, pyrolysis solid cooling obtain biomass carbon；Wherein microwave power is 1500W, and nitrogen flow rate is 300 mL/min；
(2) step (1) pyrolysis gas rapid condensation in the condenser pipe that temperature is -5 DEG C of connection circulating condensing pumps is passed through to separate
To liquid bio matter oil and biogas fluid fuel；
The GC-MS map of the present embodiment bio-oil ingredient is shown in Fig. 1, from fig. 1, it can be seen that bio-oil peak value is less, it is meant that at
It is point less, highlight the advantage of microwave-heating；Fig. 2 is biomass carbon infrared spectroscopy, as can be seen from Figure 2, in 3400 cm-1Nearby deposit
In the functional group of a large amount of free and association hydroxyl structure (COH), in 1640 and 1390cm-1Nearby there are two peak values,
It is wherein 1640cm in peak value-1Corresponding nearby is-COOH functional group, and is 1390cm in peak value-1It is neighbouring then be CH2Function
Group, in 800cm-1Nearby there is the C-H rocking vibration in aromatic series and heteroaromatic compound；Therefore biomass carbon surface contains
There is functional group abundant, is conducive to the processing to heavy metal ions in wastewater；
Phenol content is 42.71% in the present embodiment liquid bio matter oil, measures CO in biogas fluid fuel using gas-chromatography
And H2Total volume content be 45.90%, use nitrogen adsorption instrument to measure the specific surface area of biomass carbon as 86.59m2/g；
Using Atomic absorption measure biomass carbon to the adsorbance of heavy metal ion Pb In Exhausted Water and cadmium be respectively 38.08mg/g and
30.51mg/g。
Embodiment 2: a kind of microwave-heating poplar bits prepare simultaneously rich in phenol bio-oil and for adsorb heavy metal from
The method of the biomass carbon of son, the specific steps are as follows:
(1) poplar bits are crushed, are placed in nitrogen atmosphere, temperature is that microwave-heating 45min obtains pyrolysis gas and pyrolysis at 500 DEG C
Solid, pyrolysis solid cooling obtain biomass carbon；Wherein microwave power is 1000W, nitrogen flow rate 200mL/min；
(2) step (1) pyrolysis gas rapid condensation in the condenser pipe that temperature is -1 DEG C of connection circulating condensing pump is passed through to separate
To liquid bio matter oil and biogas fluid fuel；
Phenol content is 49.05% in the present embodiment liquid bio matter oil, measures CO in biogas fluid fuel using gas-chromatography
And H2Total volume content be 57.19%, use nitrogen adsorption instrument to measure the specific surface area of biomass carbon as 215.79m2/g；
Using Atomic absorption measure biomass carbon to the adsorbance of heavy metal ion Pb In Exhausted Water and cadmium be respectively 49.27mg/g and
41.56mg/g。
Embodiment 3: a kind of microwave-heating poplar bits prepare simultaneously rich in phenol bio-oil and for adsorb heavy metal from
The method of the biomass carbon of son, the specific steps are as follows:
(1) poplar bits are crushed, are placed in nitrogen atmosphere, temperature is that microwave-heating 60min obtains pyrolysis gas and pyrolysis at 600 DEG C
Solid, pyrolysis solid cooling obtain biomass carbon；Wherein microwave power is 2000W, nitrogen flow rate 400mL/min；
(2) step (1) pyrolysis gas rapid condensation in the condenser pipe that temperature is -3 DEG C of connection circulating condensing pumps is passed through to separate
To liquid bio matter oil and biogas fluid fuel；
The scanning electron microscope (SEM) photograph of the present embodiment biomass carbon is shown in Fig. 3, as can be seen from Figure 3, the biomass carbon surface light under this pyrolytical condition
It is sliding, there is the generation of uniform bore；
The present embodiment biomass carbon is shown in Fig. 4 using nitrogen adsorption-desorption curve that nitrogen adsorption instrument measures, as can be seen from Figure 4, biology
Matter charcoal has biggish surface area；
Phenol content is 33.16% in the present embodiment liquid bio matter oil, measures CO in biogas fluid fuel using gas-chromatography
And H2Total volume content be 65.64%, use nitrogen adsorption instrument to measure the specific surface area of biomass carbon as 265.12m2/g；
Using Atomic absorption measure biomass carbon to the adsorbance of heavy metal ion Pb In Exhausted Water and cadmium be respectively 54.13mg/g and
44.73mg/g。
Above the embodiment of the present invention is explained in detail, but the present invention is not limited to above-mentioned embodiment party
Formula can also be made without departing from the purpose of the present invention within the knowledge of a person skilled in the art
Various change out.
Claims (6)
1. a kind of microwave-heating poplar bits prepare be rich in phenol bio-oil and the biomass for adsorbing heavy metal ion simultaneously
The method of charcoal, which is characterized in that specific step is as follows:
(1) poplar bits are crushed, are placed in nitrogen atmosphere, temperature is that 30 ~ 60min of microwave-heating obtains pyrolysis gas at 400 ~ 600 DEG C
Body and pyrolysis solid, pyrolysis solid cooling obtain biomass carbon；
(2) step (1) pyrolysis gas is passed through temperature is the isolated liquid bio matter oil of rapid condensation and life at -1 ~ -5 DEG C
Material gases fuel.
2. microwave-heating poplar bits prepare rich in phenol bio-oil simultaneously and for adsorbing heavy metal according to claim 1
The method of the biomass carbon of ion, it is characterised in that: step (1) microwave power is 1000-2000W.
3. microwave-heating poplar bits prepare rich in phenol bio-oil simultaneously and for adsorbing heavy metal according to claim 1
The method of the biomass carbon of ion, it is characterised in that: step (1) nitrogen flow rate is 200 ~ 400mL/min.
4. microwave-heating poplar bits prepare rich in phenol bio-oil simultaneously and for adsorbing heavy metal according to claim 1
The method of the biomass carbon of ion, it is characterised in that: the specific surface area of step (1) biomass carbon is 86.59 ~ 265.12m2/g。
5. microwave-heating poplar bits prepare rich in phenol bio-oil simultaneously and for adsorbing heavy metal according to claim 1
The method of the biomass carbon of ion, it is characterised in that: step (2) liquid bio matter oil in phenol quality content be 33.16% ~
49.05%。
6. microwave-heating poplar bits prepare rich in phenol bio-oil simultaneously and for adsorbing heavy metal according to claim 1
The method of the biomass carbon of ion, it is characterised in that: CO and H in step (2) biogas fluid fuel2Total volume content be
45.90%~65.64%。
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| CN110342580B (en) * | 2019-06-20 | 2022-04-05 | 昆明理工大学 | Microwave-assisted method for preparing activated carbon-manganese dioxide nanocomposite |
| CN113025355A (en) * | 2021-03-22 | 2021-06-25 | 上海交通大学 | Method for recycling livestock and poultry manure and straw |
| CN113800746A (en) * | 2021-09-18 | 2021-12-17 | 常州大学 | Crude oil refining scum microwave ultrasonic separation method based on wood chip carrier |
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Application publication date: 20191122 |