CN117443345A - Carbon-based adsorption material and preparation method thereof - Google Patents
Carbon-based adsorption material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 67
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000010802 sludge Substances 0.000 claims abstract description 101
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 238000011282 treatment Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000003763 carbonization Methods 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 11
- 238000010000 carbonizing Methods 0.000 claims abstract description 5
- 238000001994 activation Methods 0.000 claims description 20
- 239000012190 activator Substances 0.000 claims description 19
- 230000004913 activation Effects 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 15
- 239000003463 adsorbent Substances 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000009270 solid waste treatment Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910052740 iodine Inorganic materials 0.000 description 9
- 239000011630 iodine Substances 0.000 description 9
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 239000002154 agricultural waste Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 239000007762 w/o emulsion Substances 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 239000002699 waste material Substances 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the field of solid waste treatment and utilization, and discloses a carbon-based adsorption material and a preparation method thereof, wherein the preparation method of the carbon-based adsorption material comprises the following steps: and (3) mixing biochemical sludge and oily sludge, and carbonizing to obtain the carbon-based adsorption material. The method creatively prepares the carbon by combining the biochemical sludge and the oily sludge, solves the problems existing in the independent carbonization process of the biochemical sludge and the oily sludge, provides a new direction for realizing the combined recycling treatment of the biochemical sludge and the oily sludge, and has simple operation and low cost. Compared with a single oily sludge-based carbon-based adsorption material, the prepared carbon-based adsorption material has better water solubility and better mesoporous and microporous adsorption effects.
Description
Technical Field
The invention relates to the field of solid waste treatment and utilization, in particular to a carbon-based adsorption material and a preparation method thereof.
Background
The oily sludge is generated in various stages of petroleum exploitation, transportation, storage, extraction and the like, and occupies a relatively high proportion in petrochemical industry. The oily sludge is an extremely stable water-in-oil emulsion, and the strong carbon-based property determines that the oily sludge has larger resource utilization value, but cannot be ignored, and a large amount of petroleum hydrocarbon, heavy metal and the like in the oily sludge are also high-concentration toxic substances, so that serious toxic effects can be brought to local environments by improper treatment. On one hand, the existing various treatment processes have more environmental defects, such as incineration; on the other hand, the recycling of the oil gas components, such as pyrolysis, is more important, and the utilization range is narrower. Activated carbon is a generic term for carbon-based materials with high specific surface area, abundant pore structures, various oxygen-containing functional groups and the like, and the preparation of activated carbon materials with excellent performance by using low-cost carbon sources is an important challenge facing the activated carbon industry.
The oily sludge has the characteristics of high carbon content and high volatile matter content, is an objective condition that the oily sludge can become a precursor of a carbon-based adsorption material, and can be prepared into the carbon-based material with certain structural characteristics and surface characteristics through a carbonization and activation process.
The raw materials for preparing the activated carbon are single, a certain oxidation treatment is needed to prepare the carbon-based material, but the nitrogen and oxygen contents in the oily sludge are low, and the process of preparing the carbon-based adsorption material by using the carbon-based material as a single raw material is easy to agglomerate and has poor functions, so that two different kinds of raw materials are often mixed, such as agricultural wastes (walnut shells, coconut shells and the like) and the oily sludge are used for preparing the mixed-base activated carbon material in a synergistic manner, the mixed-base activated carbon material is better in terms of yield improvement, pore expansion and functional group enrichment, and the quality of the single oily sludge-based activated carbon is better improved. In CN107285309A, the oily sludge is centrifuged, the upper oil phase is mixed with agricultural waste biomass particles, and then the mixture is carbonized and activated in a tube furnace to prepare the activated carbon with multistage holes, but the oily sludge is used as a relatively stable water-in-oil emulsion, and the centrifugal separation of the oily sludge increases the process difficulty.
Disclosure of Invention
The invention aims to solve the problems of difficult operation, complex process, easy agglomeration and the like in the process of preparing a carbon-based adsorption material by utilizing oily sludge in the prior art, and provides a carbon-based adsorption material and a preparation method thereof.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a carbon-based adsorption material, the method comprising mixing biochemical sludge and oily sludge and carbonizing to obtain the carbon-based adsorption material.
Preferably, the oily sludge is used in an amount of 1 to 20 parts by weight, based on dry weight, compared to 1 part by weight of biochemical sludge.
In a second aspect, the present invention provides a carbon-based adsorbent material prepared according to the method described above.
In the prior art, the method focuses on the mixing of oily sludge and agricultural wastes in the carbon conversion of the oily sludge, the invention opens up ideas, tries to couple the oily sludge and biochemical sludge to prepare a novel carbon-based adsorption material, and unexpectedly discovers that the mixing of the biochemical sludge can improve the problems of caking and the like in the carbon conversion of the oily sludge, also overcomes the problems of lower conversion rate, poor adsorption effect and the like caused by more ash when the biochemical sludge is used as a single raw material, and the prepared carbon-based adsorption material has mesoporous and microporous adsorption performance.
The invention converts the sludge substances from low-value wastes into the carbon-based adsorption material with high use value, solves the treatment problem of the sludge substances on one hand, greatly reduces the production cost of the activated carbon on the other hand, and directly provides a new way for realizing the synergic value-added recycling of the oily sludge and the biochemical sludge.
The carbon-based adsorption material obtained by the invention has a certain mesoporous and microporous structure, and the structure endows the carbon-based adsorption material with adsorption capacity on small molecules and neutral size molecules, and can be used for simple physical adsorption of partial pollutants.
Drawings
FIG. 1 shows a graph of the yield of raw char and activated products at various blending ratios for biochemical sludge and oily sludge.
FIG. 2 shows graphs of iodine adsorption capacity of raw carbon and activated products at different blending ratios of biochemical sludge and oily sludge.
FIG. 3 shows a graph of methylene blue adsorption capacity of raw carbon and activated products at various blending ratios for biochemical sludge and oily sludge.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a preparation method of a carbon-based adsorption material, which comprises the steps of mixing biochemical sludge and oily sludge and carbonizing to obtain the carbon-based adsorption material.
In the invention, the biochemical sludge refers to sludge discharged in the secondary treatment process of biochemical treatment process and the like, and has the characteristics of high water content, large production amount and the like, and the C/H is generally about 4-6.
The biochemical sludge can be directly mixed with the oily sludge and carbonized, or can be mixed with the oily sludge and carbonized after treatment, and preferably, the method further comprises drying the biochemical sludge before mixing the biochemical sludge with the oily sludge to obtain the dried biochemical sludge.
Preferably, the water content in the biochemical sludge after the drying treatment is 5% by weight or less.
The conditions of the drying treatment are not particularly limited as long as the biochemical sludge can be dried, and preferably include: the temperature is 50-120 ℃ and the time is 0.5-6h.
In the invention, the biochemical sludge after the drying treatment can also be subjected to crushing treatment, and the crushed material is screened, and the obtained undersize is used for being mixed with the oily sludge for carbonization. The mesh number of the screen used in the sieving treatment may be selected in a wide range, for example, may be 10 mesh or more, and specifically may be any range of 10 mesh, 20 mesh, 40 mesh, 60 mesh, 80 mesh, 100 mesh, and any range between any two values.
In the present invention, the term "oily sludge" refers to a mixture of crude oil or finished oil mixed with soil or other medium, and the oily sludge may be contaminated by environmental pollution because the oily component cannot be recovered directly, and the C/H content in the oily sludge is generally 6 or more.
Preferably, the oily sludge is used in an amount of 1 to 20 parts by weight, such as 1, 2, 3, 4, 5, 8, 10, 15, 20 and any range between any two values, more preferably 1 to 10 parts by weight, still more preferably 1 to 3 parts by weight, per 1 part by weight of biochemical sludge.
In the present invention, biochemical sludge may be mixed with oily sludge by means conventional in the art, for example, by stirring or the like.
Preferably, the carbonization conditions include: the temperature is 500-700 ℃ and the time is 1-3h.
The carbonization may be performed in a tube furnace. It should be understood that the heating and cooling program can be set to reach the carbonization temperature and to reduce the carbonization temperature to the room temperature, the heating program can be set to heat 8-12 ℃/min to the carbonization temperature, the cooling program can naturally cool down, and the cooling program can also be set to cool down to the room temperature at 1-5 ℃/min.
Preferably, the carbonization is performed in an inert atmosphere. The inert atmosphere may be an inert atmosphere commonly used in the art, preferably, the inert atmosphere is a nitrogen atmosphere.
Preferably, the method further comprises subjecting the carbon-based adsorbent material to an activation treatment.
Preferably, the conditions of the activation treatment include: the temperature is 700-900 ℃ and the time is 1-3h.
Preferably, the activation treatment is by physical activation and/or chemical activation.
In general, physical activation refers to gas activation, and chemical activation refers to activation using a chemical agent.
Preferably, the activator used in the physical activation is selected from at least one of carbon dioxide, water vapor and air.
Preferably, the activator used in the chemical activation is at least one selected from the group consisting of an acidic activator, a basic activator and an inorganic salt activator.
Preferably, the acidic activator is sulfuric acid and/or phosphoric acid.
Preferably, the alkaline activator is selected from at least one of sodium hydroxide, potassium hydroxide and potassium carbonate.
Preferably, the inorganic salt activator is selected from ZnCl 2 、K 2 SO 4 And K 2 At least one of S.
More preferably, the activator is ZnCl 2 。
The methods of use of the various activators may be found in methods conventional in the art and are not described herein.
For example, znCl 2 The addition may be in the form of a solution, preferably at a concentration of 3-5mo/L.
Preferably, the activator is used in an amount of 0.5 to 1.5 parts by weight, relative to 1 part by weight of the carbon-based adsorption material.
In the invention, the activated carbon-based adsorption material can be subjected to multiple washing treatments for removing residual reagents, ash and the like, washing until the pH value of supernatant is close to neutral, and drying in an oven.
In a second aspect, the present invention provides a carbon-based adsorbent material prepared according to the method described above.
The carbon-based adsorption material provided by the invention has micropore and mesopore adsorption performance.
The present invention will be described in detail by examples.
In the following examples, biochemical sludge is derived from sludge which is simply dehydrated after being treated by a sewage treatment process in a sewage plant area of a petrochemical plant, and the water content is about 67%; wherein the C, H, O content is 15-17 wt%, 3-5 wt% and 24-26 wt%, respectively, on a dry weight basis, and the C/H is about 5.1;
the oily sludge is derived from clear tank sludge of a petrochemical plant, and has a water content of about 65% by weight, wherein the content of C, H, O is 55-57% by weight, 8-10% by weight and 4-6% by weight respectively, and the C/H is about 6.7.
Example 1
This example is intended to illustrate the preparation process and product yield of carbon-based adsorbent materials.
(1) The weight ratio of the oily sludge to the biochemical sludge is 1:0 and 9 respectively by wet weight: 1. 8: 2. 7: 3. 6: 4. 5: 5. the oily sludge and biochemical sludge were weighed in a ratio of 0:1.
And (3) drying the biochemical sludge at 105 ℃ for 2-3 hours to remove excessive water, and then carrying out simple grinding and sieving with 60 meshes to obtain biochemical sludge powder. Then placing the biochemical sludge powder and the oily sludge into a quartz boat (accurately weighing the quartz boat weight, recording as m) a1 、m a2 、m a3 、m a4 、m a5 、m a6 、m a7 ) In the process, the mixture is fully stirred and evenly mixed until the mixture is homogeneous, and the total weight of the sample and the boat before combustion is weighed and recorded as m b1 、m b2 、m b3 、m b4 、m b5 、m b6 、m b7 。
(2) Carbonizing: the tube furnace is pre-aerated with large flow of nitrogen to form nitrogen inert atmosphere, a uniformly mixed sample is placed in the tube furnace, the nitrogen flow is regulated, a heating program is set, the temperature is raised to 600 ℃ at 10 ℃/min, the tube furnace enters a program cooling section after stable operation is carried out for 2 hours, the tube furnace is closed after the program is finished, and nitrogen air inlet is closed after the tube furnace is naturally cooled to room temperatureThe obtained sample is unactivated raw carbon, and is numbered A1, A2, A3, A4, A5, A6, A7, and is weighed and recorded as m c1 、m c2 、m c3 、m c4 、m c5 、m c6 、m c7 . The nitrogen flow rate in the program operation section is about 50mL/min, and the same applies below.
Raw carbon yield (a%) at different ratios was calculated, referring to formula (1):
according to calculation, the raw carbon yield (A%) is 18.39%, 16.94%, 17.54%, 17.79%, 17.97%, 18.64% and 19.72% respectively under different blending ratios, and it is intuitively obtained that the raw carbon yield is reduced when biochemical sludge is blended to a certain degree, but the raw carbon yield starts to be gradually increased along with the increase of the blending ratio of the biochemical sludge.
(3) Activating: grinding and sieving a raw carbon sample, taking a certain amount of raw carbon sample, fully soaking the raw carbon sample with a zinc chloride solution with the concentration of 4mol/L at room temperature, and drying the raw carbon sample in a drying oven at 105 ℃ after 20 hours. Wherein, the addition amount of the zinc chloride solution is 1.5mL compared with 1g of raw carbon.
Placing the dried sample in a tube furnace with nitrogen atmosphere, setting a heating program, heating to 800 ℃ at 10 ℃/min, stabilizing for 2.5 hours, then entering a cooling program, cooling the sample to room temperature after the program is ended, closing nitrogen inlet after the sample is cooled to room temperature, obtaining an activated product, and respectively numbering B1, B2, B3, B4, B5, B6 and B7, accurately weighing and recording as m d1 、m d2 、m d3 、m d4 、m d5 、m d6 、m d7 。
The yields (B%) of the activated products at the different ratios were calculated, referring to formula (2):
calculated, the yields (B%) of the activated products at different blending ratios were 16.79%, 15.12%, 15.83%, respectively,16.65%, 16.62%, 16.50%, 14.87%, it being noted that the yield calculation was assumed to be ZnCl 2 All pyrolysis escapes.
As is readily apparent from the yields of activated products, as biochemical sludge blending increases, the yields of activated products show a tendency to change from rising to falling over a small range, i.e., there is a better blending ratio. The yields of raw carbon and activated products as a function of biochemical sludge incorporation are shown in figure 1.
In addition, the prepared activated products are respectively put into water, the activated products prepared by taking the oil-containing sludge as a single raw material are found to have obvious floatability and are difficult to mix with water phase uniformly, the activated products prepared by doping biochemical sludge are easier to form suspension liquid with uniform dispersion in the water phase, and the hydrophilicity of the activated products is relatively enhanced along with the increase of the mixing proportion of the biochemical sludge, so that the activated products are particularly easier to combine with the water phase, and the activated products have better practical significance for the subsequent application of the activated products to the removal of pollutants in the water phase.
(4) Washing: and (3) alternately washing the activated product sample with 5wt% of diluted hydrochloric acid and ultrapure water for multiple times to remove redundant medicament residues and residual ash, washing until the pH value of supernatant is close to neutral, and drying and grinding in an oven to obtain a novel carbon-based adsorption material final product obtained by coupling the oily sludge and the biochemical sludge.
Example 2
This example is used to illustrate the microporous adsorption characterization of carbon-based adsorbent materials—iodine adsorption values.
Grinding and sieving the raw carbon and the activated product under each mixing proportion, drying to constant weight in a drying oven, cooling to room temperature in a drying dish, weighing 0.5g of A (1-7) and B (1-7) samples respectively in 14 conical flasks with plugs, sequentially adding 10mL of 5wt% dilute hydrochloric acid, micro-boiling for 30 seconds on a closed electric furnace, cooling to room temperature, sequentially adding 50mL of 0.05mol/L iodine standard solution respectively, sufficiently shaking for 15min on a shaking table, rapidly filtering to a conical flask, transferring 10mL of filtrate into the conical flask containing 100mL of ultrapure water, and respectively titrating the residual iodine concentration after the raw carbon and the activated product sample are adsorbed under each mixing proportion by using the sodium thiosulfate standard solution.
Through calculation, the iodine adsorption value change under different conditions is shown as figure 2, and the activation process improves the micropore adsorption capacity of the carbon-based adsorption material as can be seen from the iodine adsorption value change; meanwhile, whether the raw carbon or the activated product is the raw carbon, along with the continuous increase of the mixing proportion of the biochemical sludge, the iodine adsorption value is increased and then reduced (the iodine adsorption value is highest when the weight ratio of the oily sludge to the biochemical sludge is 7:3 and 6:4 respectively), and when the single biochemical sludge is taken as a raw material, the iodine adsorption value is lower and the micropore adsorption capacity is minimum.
Example 3
This example is used to illustrate the mesoporous adsorption characterization evaluation of carbon-based adsorbent materials-methylene blue adsorption values.
Grinding and sieving the raw carbon and activated product samples in the blending proportion, drying the raw carbon and activated product samples in an oven to constant weight, cooling the raw carbon and activated product samples in a drying dish to room temperature, weighing 0.2g of the raw carbon and activated product samples A (1-7) and B (1-7) in 14 250mL conical flasks with plugs respectively, sequentially adding 20mL of methylene blue with the concentration of 0.75g/L into the conical flasks respectively, sufficiently oscillating the conical flasks for 30min, rapidly filtering the mixture into the conical flasks, diluting the mixture for a certain proportion, measuring the absorbance, comparing the absorbance with a standard line to calculate the methylene blue adsorption value change of the novel carbon-based adsorption material of each mixed base, wherein the methylene blue adsorption value change is shown as figure 3, the highest mesoporous adsorption capacity is obtained when the weight ratio of the oily sludge to the biochemical sludge is 6:4, and the mesoporous adsorption capacity of the carbon-based adsorption material is improved in the activation process, and the mesoporous adsorption performance of the adsorption material obtained by the single biochemical sludge is the same and shows the worst.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (11)
1. A preparation method of a carbon-based adsorption material is characterized by comprising the steps of mixing biochemical sludge and oily sludge and carbonizing to obtain the carbon-based adsorption material.
2. The method according to claim 1, wherein the oily sludge is used in an amount of 1-20 parts by weight, preferably 1-10 parts by weight, more preferably 1-3 parts by weight, relative to 1 part by weight of biochemical sludge on a dry weight basis.
3. The method according to claim 1 or 2, wherein the method further comprises drying the biochemical sludge before mixing the biochemical sludge with the oily sludge to obtain the dried biochemical sludge.
4. A method according to any one of claims 1-3, wherein the carbonization conditions comprise: the temperature is 500-700 ℃ and the time is 1-3h.
5. The process according to any one of claims 1 to 4, wherein the carbonization is carried out in an inert atmosphere,
preferably, the inert atmosphere is a nitrogen atmosphere.
6. The method of any one of claims 1-5, further comprising activating the carbon-based adsorbent material.
7. The method of claim 6, wherein the conditions of the activation treatment comprise: the temperature is 700-900 ℃ and the time is 1-3h.
8. The method according to claim 6 or 7, wherein the activation treatment is by physical activation and/or chemical activation.
9. The method of claim 8, wherein the activator used in the physical activation is selected from at least one of carbon dioxide, water vapor, and air;
the activator used in the chemical activation is at least one selected from an acidic activator, a basic activator and an inorganic salt activator;
preferably, the acidic activator is sulfuric acid and/or phosphoric acid;
preferably, the alkaline activator is selected from at least one of sodium hydroxide, potassium hydroxide and potassium carbonate;
preferably, the inorganic salt activator is selected from ZnCl 2 、K 2 SO 4 And K 2 At least one of S.
10. The method of claim 9, wherein the ZnCl is compared to 1 part by weight of a carbon-based adsorbing material 2 The amount of (C) is 0.5-1.5 parts by weight.
11. A carbon-based adsorption material prepared by the method according to any one of claims 1 to 10.
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