CN107686110A - A kind of activated coke and preparation method thereof - Google Patents
A kind of activated coke and preparation method thereof Download PDFInfo
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- CN107686110A CN107686110A CN201610633043.2A CN201610633043A CN107686110A CN 107686110 A CN107686110 A CN 107686110A CN 201610633043 A CN201610633043 A CN 201610633043A CN 107686110 A CN107686110 A CN 107686110A
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/30—Physical properties of adsorbents
- B01D2253/302—Dimensions
- B01D2253/306—Surface area, e.g. BET-specific surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Abstract
The present invention relates to the preparation field of activated coke, discloses a kind of activated coke and preparation method thereof, this method includes：(1) semicoke after pre-oxidation treatment is mixed with the aqueous solution of polymer with nitrogen, then heat to the first temperature, first temperature is not less than the lowest critical solution temperature of the polymer with nitrogen, and obtaining area load has the semicoke of the polymer with nitrogen；(2) in the presence of protective gas, the semicoke that the area load has the polymer with nitrogen is activated；Wherein, the polymer with nitrogen has LCST characteristics.The specific surface area for the activated coke being prepared by method of the present invention is big, activity is high, stability is good and desulfurized effect is good.The method of the present invention also has the advantages of technique is simple, raw material is cheap and easy to get.
Description
Technical field
The present invention relates to the preparation field of activated coke, in particular it relates to a kind of method for preparing activated coke and by the party
The activated coke that method is prepared.
Background technology
The energy and environment are the two big Tough questions for perplexing world today's sustainable development.
China is the big country using coal as main energy sources, rich coal resources and oil and natural gas is short.China natural resources
The characteristics of preservation, determine that the energy problem for solving China must be based on coal, still, in the same of utilization coal resources
When, problem of environmental pollution caused by fire coal has become increasingly conspicuous, and seriously constrains the sustainable development of China's economic society.
It is the most urgent task in the current Air Pollution Control field in China to control sulfur dioxide pollution.To control atmosphere pollution
The discharge of thing, State Environmental Protection Administration and the National Development and Reform Commission take the measure for strengthening sulfur dioxide pollution preventing and treating,
Successively implement《Administrative Regulations on Pollution Discharge Fee Levy》With《Discharge standard of air pollutants》(GB16297-1996), and
Implemented in 1 day July in 2014《Petroleum refining industry pollutant emission standard》.
Which kind of desulfurization technology can cost-effectively control sulfur dioxide (SO2) emissions to turn into influence coal fired power plant project using to build
And if one of an important factor for normal production.Therefore, study and develop the high-efficiency flue gas desulfurization technology of suitable China's national situation, to solution
The sulfur dioxide pollution on the environment problem tool that certainly coal-burning power plant is discharged is of great significance.
At present, conventional flue gas desulfurization technique has much both at home and abroad, and according to the difference of desulfurization method and product form, flue gas takes off
Sulphur technology can be divided into wet method, semidry method, dry method three major types.Activated coke desulfurization technology is a kind of advanced dry desulfurization skill
Art, it both overcame big, secondary pollution of water consumption existing for the wet limestone-gypsum FGD technology being widely used at present etc. and lacked
Fall into, while recyclable Sulphur ressource and remove multiple pollutant again, for rich coal resources in China but western part of water resources shortage
There is good applicability in area.
The principle of activated coke desulfurization technology is：Utilize the characterization of adsorption of activated coke and the catalysis characteristics of Adsorption
Make sulfur dioxide in flue gas, oxygen and water reaction generation sulfuric acid and adsorb in the pore structure of activated coke.Adsorb sulfur dioxide
Activated coke heating after regenerate, discharge high-concentration sulfur dioxide gas, desorb sulfur dioxide activated coke recycle, it is highly concentrated
Degree sulfur dioxide gas can be processed into a variety of chemical products such as sulfuric acid, elemental sulfur.The major advantage of activated coke desulfurization technology
It is：Smoke desulfurization efficiency is high；Dry FGD is carried out at 110~150 DEG C, is not required to Smoke-heating device.Sweetening process is not produced
Unboiled water consumes, and lacks area suitable for water resource；With active Jiaozhuo adsorbent, renewable to recycle, cost is relatively low；Device accounts for
Ground area is small；Can a variety of byproducts such as by-product sulfuric acid, sulphur after desorption；With good environmental-protecting performance, two are not caused to environment
Secondary pollution.
The consumption of activated coke accounts for the 50~70% of activated coke desulfurization technology totle drilling cost, is to influence activated coke desulfurization
The key factor of technical and economic performance.The preparation method for studying economic, efficient, durable activated coke is the target that everybody pursues.
Oxygen-containing or nitrogen-containing functional group the quantity for having document report increase activated coke surface can effectively improve activated coke suction
The performance of Annex II sulfur oxide.Zhang Xiang-lan etc. are modified to obtain table to commercial activated coke with hydrogen peroxide or ammoniacal liquor
The oxygen-containing or nitrogenous activated coke in face, the ability of the absorption sulfur dioxide of modified activated coke has larger compared with commercial activated coke
Improve.Although the above method can prepare the activated coke of surface nitrogen-containing functional group, the preparation method of above-mentioned prior art is deposited
In cost height, route is long and pollutes the shortcomings of more serious, still needs to further improve.
The content of the invention
The purpose of the present invention be by provide a kind of method of new preparations activated coke obtain big specific surface area, activity height,
The activated coke that stability is good and desulfurized effect is good.
To achieve these goals, in a first aspect, the present invention provides a kind of method for preparing activated coke, this method include with
Lower step：
(1) semicoke after pre-oxidation treatment is mixed with the aqueous solution of polymer with nitrogen, then heats to the first temperature,
First temperature is not less than the lowest critical solution temperature of the polymer with nitrogen, and obtaining area load has the nitrogenous polymerization
The semicoke of thing；
(2) in the presence of protective gas, the semicoke that the area load has the polymer with nitrogen is activated；
Wherein, the polymer with nitrogen has LCST characteristics.
Second aspect, the present invention provide the activated coke being prepared by preceding method.
The specific surface area for the activated coke being prepared by method of the present invention is big, activity is high, stability is good and desulfurization
Effect is good.
The method of the present invention also has the advantages of technique is simple, raw material is cheap and easy to get.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
In a first aspect, the invention provides a kind of method for preparing activated coke, this method comprises the following steps：
(1) semicoke after pre-oxidation treatment is mixed with the aqueous solution of polymer with nitrogen, then heats to the first temperature,
First temperature is not less than the lowest critical solution temperature of the polymer with nitrogen, and obtaining area load has the nitrogenous polymerization
The semicoke of thing；
(2) in the presence of protective gas, the semicoke that the area load has the polymer with nitrogen is activated；
Wherein, the polymer with nitrogen has LCST characteristics.
The LCST characteristics refer to that polymer with nitrogen of the invention can be dissolved in water at room temperature, are somebody's turn to do when temperature is not less than
During the lowest critical solution temperature of polymer with nitrogen, characteristic that the polymer with nitrogen can separate out from the aqueous solution.
In addition, it is well known by those skilled in the art that some polymer with nitrogen with LCST characteristics it is minimum critical molten
It is generally all a narrow temperature range to solve temperature, and is not the temperature value of a determination.Here, work as with LCST characteristics
When the lowest critical solution temperature of polymer with nitrogen is a narrow temperature range, first temperature is nitrogenous poly- not less than described
In the statement of the lowest critical solution temperature of compound, lowest critical solution temperature is used as generation using the maximum in the temperature range
Table.
Preferably, the semicoke after pre-oxidation treatment is mixed to enter under agitation with the aqueous solution of polymer with nitrogen
OK, the method for stirring is had no particular limits, those skilled in the art can be selected according to the stirring operation of routine.
Preferably, the polymer with nitrogen in PVCL polymer, PNIPAM polymer and PDEAM polymer at least
One kind, have respectively with following formula (1), formula (2) and formula (3) in the PVCL polymer, PNIPAM polymer and PDEAM polymer
Shown construction unit, the molecular weight of the PVCL polymer, PNIPAM polymer and PDEAM polymer are each independently
0.3 ten thousand to 350,000：
Wherein, R1、R2、R3And R4Be each independently H, methyl, ethyl, n-propyl, isopropyl, primary butyl, sec-butyl and
At least one of tert-butyl group, and in formula (2), R1And R2It is asynchronously H；And in formula (3), R3And R4It is asynchronously H.
That is, the PVCL polymer has the construction unit shown in formula (1), the PNIPAM polymer has formula (2)
Shown construction unit, and the PDEAM polymer have the construction unit shown in formula (3).
Preferably, in above-mentioned formula (2), R1And R2It is each independently in methyl, ethyl, n-propyl and isopropyl extremely
Few one kind；In above-mentioned formula (3), R3And R4Be each independently methyl, ethyl, n-propyl, isopropyl, primary butyl, sec-butyl and
At least one of tert-butyl group.
It is highly preferred that in above-mentioned formula (2), R1And R2At least one be each independently in methyl, ethyl and n-propyl
Kind；In above-mentioned formula (3), R3And R4It is each independently at least one of ethyl, n-propyl, primary butyl and sec-butyl.
The foregoing nitrogenous compounds of the present invention can also can be closed by commercially available by using the method for prior art
Into obtaining.Also, the synthetic method of prior art includes：Using controllable free radical polymerization process (ATRP
(ATRP), reversible-addition fracture chain transfer polymerization (RAFT) etc.) etc. synthesized.Embodiments of the invention exemplary partial
Synthesized using several preferred embodiments of prior art, those skilled in the art should not be construed as to the present invention
Limitation.
According to a kind of specific preferred embodiment, in above-mentioned formula (2), R1And R2It is methyl；In above-mentioned formula (3),
R3And R4It is ethyl.
Preferably, the dosage weight ratio of the polymer with nitrogen and the semicoke after pre-oxidation treatment is 1-50：
100；More preferably 5-25：100.
Preferably, the semicoke after pre-oxidation treatment is included with the condition that the aqueous solution of polymer with nitrogen mixes：Temperature
Low 0.5-50 DEG C, the time 1-30h for the lowest critical solution temperature than the polymer with nitrogen；It is further preferred that will be through pre-oxidation
Semicoke after processing includes with the condition that the aqueous solution of polymer with nitrogen mixes：Temperature is to face than the minimum of the polymer with nitrogen
Boundary's solution temperature is low 1-25 DEG C, time 1-24h.
Preferably, method of the invention further comprises：By the semicoke after pre-oxidation treatment and polymer with nitrogen
The aqueous solution is mixed and is warming up to after the first temperature, and 1-180min is kept at a temperature of described first, then mixes gained solid-liquid
Compound is filtered.And it is highly preferred that the product obtained after filtering is dried under the conditions of 15-65 DEG C (in order to distinguish,
Second is also referred to as in following examples to dry) 8-48h.
Preferably, first temperature is higher than the lowest critical solution temperature of the polymer with nitrogen 0.1-30 DEG C, more excellent
Select high 0.5-20 DEG C.It was found by the inventors of the present invention that control first temperature is minimum critical more molten than the polymer with nitrogen
When solution temperature is high 0.5-20 DEG C, enable to obvious more by the specific surface area and Sulfur capacity of the activated coke of the method acquisition of the present invention
It is excellent.
Preferably, the concentration of the aqueous solution of the polymer with nitrogen is 1-20 weight %, more preferably 5-18 weight %.This
The inventor of invention has found, under the premise of the total dosage identical for controlling polymer with nitrogen, when polymer with nitrogen the aqueous solution it is dense
Spend for 5-18 weight % when, the specific surface area and Sulfur capacity of the activated coke of acquisition are considerably higher.Inventor speculate, this be probably by
In the aqueous solution advantageously being uniformly dispersed on semicoke in polymer with nitrogen for the polymer with nitrogen that, concentration is 5-18 weight %
Property.
Preferably, the step of semicoke that the area load has the polymer with nitrogen being activated includes：First by institute
Stating area load has the semicoke of the polymer with nitrogen to be warming up to 500-600 DEG C with 5-10 DEG C/min the first heating rate, and
0.2-6h is kept at such a temperature；Then 750-850 DEG C is warming up to 3-5 DEG C/min the second heating rate, and in the temperature
Lower holding 1-4h.
Preferably, first heating rate it is higher 3-5 DEG C than second heating rate/min.
Preferably, method of the invention further comprises：When the semicoke keeps 1-4h at 750-850 DEG C, in activity
Carried out in the presence of gas.
Preferably, the active gases is at least one of carbon dioxide, vapor and nitrogen.
Further, in described the step of being activated, obtain after 1-4h half will be preferably kept at 750-850 DEG C
Jiao is cooled to room temperature with 10-15 DEG C/min cooldown rate.
The room temperature of the present invention can be 5-36 DEG C.
Preferably, the semicoke after pre-oxidation treatment is by the way that semicoke raw material and hydrogen peroxide and/or nitric acid are carried out
Contact and obtain.And it is highly preferred that the product obtained after contact is dried under the conditions of 5-50 DEG C (in order to distinguish, with
First is also referred to as in lower embodiment to dry) 5-50h.
Preferably, semicoke raw material is included with the condition that hydrogen peroxide and/or nitric acid are contacted：Temperature is 20-50 DEG C,
Time is 5-30h.
The method of the present invention can also include production obtained from semicoke raw material is contacted with hydrogen peroxide and/or nitric acid
Thing is filtered, washed and dried successively.There is no particular limitation for the method that the present invention is filtered, washed and dried to this, can be with
For conventional use of various operating methods in the art.The hydrogen peroxide can be hydrogen peroxide, preferably 10-70 weight %'s
Hydrogen peroxide.
Preferably, the semicoke raw material and the dosage weight ratio of the hydrogen peroxide and/or nitric acid are 100：5-30.
Preferably, the semicoke raw material is to be obtained by least one of coal, biomass and organic polymer after destructive distillation
Product.
Preferably, the average grain diameter of the semicoke raw material is 1-10mm.
The method of the present invention can also include being pre-processed semicoke raw material, and the method for the pretreatment can be：Will
Semicoke raw material dries 2-4 hours at 120-140 DEG C.
In the present invention, the protective gas can be conventional inert gas in the art, such as nitrogen, helium and argon gas
At least one of.
Second aspect, the present invention provide the activated coke being prepared by preceding method.
The method of the present invention also has the advantages of following specific：
(1) polymer with nitrogen used in the present invention has LCST characteristics, i.e., such polymer with nitrogen is dissolved at room temperature
In water, when temperature is higher than the lowest critical solution temperature of the polymer, it will be separated out from solution, and the present invention is contained using such
This characteristic of nitrogen polymer, semicoke is stirred in the aqueous solution of polymer with nitrogen at room temperature, then heating makes to contain
Nitrogen polymer uniformly separates out and is supported on semicoke surface, and filtering, activation energy accesses activated coke；
(2) the nitrogen-atoms distribution on the activated coke surface that method of the invention obtains is more uniform；
(3) introducing of nitrogen functional group, it is possible to increase the alkalescence on activated coke surface, be advantageous to the raising of desulfuration efficiency.
The present invention will be described in detail by way of examples below.
In following examples, in case of no particular description, the various raw materials used are all from commercially available.
PVCL polymer used below has the construction unit shown in formula (1), and the molecular weight of PVCL polymer is
31.5 ten thousand, lowest critical solution temperature is 31-35 DEG C, and specific preparation method is：In a nitrogen atmosphere by 10mmol VCL
(caprolactam), 0.5mmol AIBN (azodiisobutyronitrile) and 50mL deionized waters are added in there-necked flask, in nitrogen
Stirring is opened under gas atmosphere, while makes that VCL fully dissolves and AIBN is uniformly dispersed, is cooled down after being then warming up to 75 DEG C of reaction 5h
To room temperature (25 DEG C), reaction solution is poured into beaker, 3h is placed in 50 DEG C of baking ovens, is poured out while hot after precipitation completely to be precipitated
Layer deionized water, into precipitation add 15mL THF (tetrahydrofuran) cause precipitation dissolving, be then added dropwise again n-hexane until
Untill Precipitation, filter and wash precipitation with a small amount of ether, be placed in after repeating 3 times in vacuum drying chamber, do
It is dry to obtain PVCL polymer to constant weight.
PNIPAM polymer used below has the construction unit shown in formula (2), and R in formula (2)1And R2It is methyl,
The molecular weight of PNIPAM polymer is 1.65 ten thousand, and lowest critical solution temperature is 32 DEG C, and specific preparation method is：Weigh 10g
NIPA monomer be placed in 100mL three-necked bottle, add 1% initiator of the amount equivalent to monomeric substance
AIBN and 50mL benzene, flow back 10h in 65 DEG C of waters bath with thermostatic control under nitrogen protection, and it is molten with a small amount of acetone that reflux product removes benzo
Solution, then instills and precipitation is separated out in n-hexane dropwise, and being dried in vacuo 48h at 30 DEG C after suction filtration obtains soluble in water and ethanol isopolarity
The poly-N-isopropyl acrylamide white solid of solvent.
PDEAM polymer used below has the construction unit shown in formula (3), and R3And R4It is ethyl, PDEAM gathers
The molecular weight of compound is 9990, and lowest critical solution temperature is 32-34 DEG C, and specific preparation method is：At room temperature to 50mL tri-
2,2 '-bipyridine (1mmol), CuBr (0.5mmol), methanol (7mL), ethyl-alpha-bromopropionate are sequentially added in neck flask
(64 μ L) and DEAM (N, N- acrylamide) (25mmol).Stirring is allowed to be sufficiently mixed, and nitrogen is passed through, in 40 DEG C of constant temperature
Lower reaction 12h, taking-up three-neck flask, which is put it into ice-water bath, to be cooled down, while adds a small amount of tetrahydrofuran dissolving.With tetrahydrochysene furan
Mutter as eluent, reaction solution is passed through neutral alumina column, remove copper catalyst.Rotary evaporation of solvent, then using tetrahydrofuran as
Solvent, n-hexane are precipitating reagent, and circulation dissolving, deposition and purification three times, are dried under vacuum to constant weight, it is white powder to obtain product.
The average grain diameter of semicoke raw material used below is 8mm, is obtained by the dry distillation of coal.
The specific surface area of following activated coke is measured using BET methods, and Sulfur capacity is using country of People's Republic of China (PRC) mark
Quasi- GB/T7702.14-2008 methods are measured.
Embodiment 1
(1) pre-process：100g semicokes raw material is dried into 3h at 130 DEG C；
(2) pre-oxidation treatment：With semicokes of the hydrogen peroxide 50g that concentration is 30 weight % at 25 DEG C with being obtained after pretreatment
Raw material contacts 14h, then carries out filtering and first successively and dries, and the first time dried was 24h, and temperature is 25 DEG C；
(3) preparing area load has the semicoke of the polymer with nitrogen：It is with concentration by the semicoke after pre-oxidation treatment
The 10 weight % common 100g of PVCL aqueous solutions of polymers mixes 4h at 25 DEG C；40 DEG C (first temperature) are then heated to,
And 1h is kept at such a temperature, and then obtained solidliquid mixture is carried out to filtering and second successively dried, described second
The dry time is 12h, and temperature is 50 DEG C；
(4) activation process；In the presence of nitrogen, the area load is had the semicoke of the polymer with nitrogen with 7 DEG C/
Min speed is warming up to 550 DEG C, keeps 1h at this temperature；Then 800 DEG C are warming up to 3 DEG C/min speed, in this temperature
Lower holding 2.5h, also, carbon dioxide is passed through into system during this period；Finally carried out with 12 DEG C/min cooldown rate
Cooling processing obtains the activated coke A1 of property shown in table 1 to room temperature (25 DEG C).
Embodiment 2
(1) pre-process：100g semicokes raw material is dried into 4h at 120 DEG C；
(2) pre-oxidation treatment：With semicokes of the hydrogen peroxide 50g that concentration is 25 weight % at 25 DEG C with being obtained after pretreatment
Raw material contacts 16h, then carries out filtering and first successively and dries, and the first time dried was 20h, and temperature is 30 DEG C；
(3) preparing area load has the semicoke of the polymer with nitrogen：It is with concentration by the semicoke after pre-oxidation treatment
The 12 weight % common 100g of PNIPAM aqueous solutions of polymers mixes 6h at 28 DEG C；Then heat to 38 DEG C of (first temperature
Degree), and 1.5h is kept at such a temperature, then obtained solidliquid mixture is carried out to filtering and second successively dried, institute
The time for stating the second drying is 24h, and temperature is 40 DEG C；
(4) activation process；In the presence of nitrogen, the area load is had the semicoke of the polymer with nitrogen with 8 DEG C/
Min speed is warming up to 580 DEG C, keeps 1.5h at this temperature；Then 820 DEG C are warming up to 4 DEG C/min speed, it is warm herein
Degree is lower to keep 3h, also, is passed through carbon dioxide into system during this period；Finally carried out with 10 DEG C/min cooldown rate
Cooling processing obtains the activated coke A2 of property shown in table 1 to room temperature (25 DEG C).
Embodiment 3
(1) pre-process：100g semicokes raw material is dried into 2h at 140 DEG C；
(2) pre-oxidation treatment：With concentration be 30 weight % the common 70g of hydrogen peroxide at 30 DEG C with obtained after pretreatment partly
Burnt raw material contacts 18h, then carries out filtering and first successively and dries, and the first time dried was 28h, and temperature is 22 DEG C；
(3) preparing area load has the semicoke of the polymer with nitrogen：It is with concentration by the semicoke after pre-oxidation treatment
The 15 weight % common 120g of PDEAM aqueous solutions of polymers mixes 8h at 28 DEG C；40 DEG C (first temperature) are then heated to,
And 2h is kept at such a temperature, and then obtained solidliquid mixture is carried out to filtering and second successively dried, described second
The dry time is 20h, and temperature is 45 DEG C；
(4) activation process；In the presence of nitrogen, the area load is had the semicoke of the polymer with nitrogen with 10 DEG C/
Min speed is warming up to 600 DEG C, keeps 2h at this temperature；Then 850 DEG C are warming up to 5 DEG C/min speed, in this temperature
Lower holding 2h, also, carbon dioxide is passed through into system during this period；Finally dropped with 14 DEG C/min cooldown rate
Temperature processing obtains the activated coke A3 of property shown in table 1 to room temperature (25 DEG C).
Table 1
| Activated coke | Specific surface area (m2/g) | Sulfur capacity (mg/g) |
| A1 | 400 | 39 |
| A2 | 350 | 40 |
| A3 | 370 | 39 |
| A4 | 320 | 34 |
| A5 | 330 | 35 |
| A6 | 340 | 34 |
| A7 | 330 | 32 |
| A8 | 330 | 34 |
| DA1 | 230 | 20 |
| DA2 | 290 | 30 |
Embodiment 4
The present embodiment is carried out using method similar to Example 2, except that, the PNIPAM used in the present embodiment
The concentration of aqueous solutions of polymers is 3 weight %, dosage 400g.That is, the present embodiment polymerize with the PNIPAM that embodiment 2 uses
The concentration of the thing aqueous solution is different, but the total amount of PNIPAM polymer is identical.
Remaining is in the same manner as in Example 2.
Obtain the activated coke A4 of property shown in table 1.
Embodiment 5
The present embodiment is carried out using method similar to Example 2, except that, the PNIPAM used in the present embodiment
The concentration of aqueous solutions of polymers is 20 weight %, dosage 60g.That is, the present embodiment polymerize with the PNIPAM that embodiment 2 uses
The concentration of the thing aqueous solution is different, but the total amount of PNIPAM polymer is identical.
Remaining is in the same manner as in Example 2.
Obtain the activated coke A5 of property shown in table 1.
Embodiment 6
The present embodiment is carried out using method similar to Example 1, except that, the PVCL used in the present embodiment gathers
The dosage of the compound aqueous solution is 300g.That is, the concentration phase for the PVCL aqueous solutions of polymers that the present embodiment uses with embodiment 1
Together, but the total amount of PVCL polymer is different.
Remaining is in the same manner as in Example 1.
Obtain the activated coke A6 of property shown in table 1.
Embodiment 7
The present embodiment is carried out using method similar to Example 1, except that, the PVCL used in the present embodiment gathers
The dosage of the compound aqueous solution is 30g.That is, the present embodiment is identical with the concentration for the PVCL aqueous solutions of polymers that embodiment 1 uses,
But the total amount of PVCL polymer is different.
Remaining is in the same manner as in Example 1.
Obtain the activated coke A7 of property shown in table 1.
Embodiment 8
The present embodiment is carried out using method similar to Example 3, except that, in the present embodiment, preparing surface
When being loaded with the semicoke of the polymer with nitrogen, the semicoke after pre-oxidation treatment is polymerize with the PVCL that concentration is 10 weight %
Solution after thing aqueous solution mixed processing is warming up to 65 DEG C (first temperature), and keeps 1h at such a temperature.That is, the present embodiment
In the first temperature it is higher than the lowest critical solution temperature of the polymer with nitrogen 30 DEG C.
Remaining is in the same manner as in Example 3.
Obtain the activated coke A8 of property shown in table 1.
Comparative example 1
This comparative example is carried out using method similar to Example 1, except that：
Polymer with nitrogen in this comparative example is PVP (PVP).
Remaining is in the same manner as in Example 1.
Obtain the activated coke DA1 of property shown in table 1.
Comparative example 2
This comparative example is carried out using the method substantially similar to embodiment 3, unlike, this comparative example uses and removes solvent method
Carry out, specifically：
100g semicokes raw material is dried into 2h at 140 DEG C；
18h is contacted with the semicoke raw material obtained after pretreatment at 30 DEG C with the common 70g of hydrogen peroxide that concentration is 30 weight %,
Then carry out filtering and first successively to dry, the first time dried was 28h, and temperature is 22 DEG C；
By the copolymer of vinyl pyrrolidone and vinylacetate (poly- (vinyl pyrrolidone-vinylacetate)
Poly (vinylpyrolidone-co-vinyl acetate), which is dissolved in dichloromethane, is made solution, adds at 100g pre-oxidation
Semicoke after reason, stirs 10min under the conditions of 25 DEG C, is evaporated under reduced pressure and removes organic solvent, obtains solid, 120 DEG C of dry 12h,
Obtaining area load has the semicoke of the polymer with nitrogen.
Then, in the presence of nitrogen, the area load is had to the semicoke of the polymer with nitrogen with 10 DEG C/min speed
Degree is warming up to 600 DEG C, keeps 2h at this temperature；Then 750 DEG C are warming up to 5 DEG C/min speed, kept at this temperature
2h, also, carbon dioxide is passed through into system during this period；Cooling processing is finally carried out with 14 DEG C/min cooldown rate
To room temperature (25 DEG C), activated coke DA2 is obtained.
The specific surface area and Sulfur capacity of the activated coke obtained using the method for the present invention are can be seen that from the result of above-mentioned table 1
It is superior to the activated coke that the method for comparative example is prepared.
More specifically, the result of contrast embodiments of the invention and comparative example 1 can be seen that the embodiment of the present invention using tool
The polymer with nitrogen for having LCST characteristics prepares activated coke relative to comparative example 1 using the polymer with nitrogen without LCST characteristics
In method, under the premise of remaining method identical, the specific surface area and Sulfur capacity of the activated coke of the method acquisition of the present embodiment are obvious
Due to the activated coke obtained in comparative example.
The result of contrast embodiments of the invention and comparative example 2 can be seen that the present invention using containing with LCST characteristics
The activated coke that nitrogen polymer is prepared, the activated coke being prepared except solvent method is used compared to prior art, it is of the invention to obtain
The specific surface area and Sulfur capacity of the activated coke arrived are significantly superior.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (12)
1. a kind of method for preparing activated coke, this method comprise the following steps：
(1) semicoke after pre-oxidation treatment is mixed with the aqueous solution of polymer with nitrogen, then heats to the first temperature, it is described
First temperature is not less than the lowest critical solution temperature of the polymer with nitrogen, and obtaining area load has the polymer with nitrogen
Semicoke；
(2) in the presence of protective gas, the semicoke that the area load has the polymer with nitrogen is activated；
Wherein, the polymer with nitrogen has LCST characteristics.
2. according to the method for claim 1, wherein, the polymer with nitrogen is selected from PVCL polymer, PNIPAM polymer
At least one of with PDEAM polymer, have respectively in the PVCL polymer, PNIPAM polymer and PDEAM polymer
With the construction unit shown in following formula (1), formula (2) and formula (3), the PVCL polymer, PNIPAM polymer and PDEAM polymer
Molecular weight be each independently 0.3 ten thousand to 350,000：
Wherein, R1、R2、R3And R4It is each independently H, methyl, ethyl, n-propyl, isopropyl, primary butyl, sec-butyl and tertiary fourth
At least one of base, and in formula (2), R1And R2It is asynchronously H；And in formula (3), R3And R4It is asynchronously H；It is preferred that
Ground,
In formula (2), R1And R2It is each independently at least one of methyl, ethyl, n-propyl and isopropyl；In formula (3)
In, R3And R4At least one be each independently in methyl, ethyl, n-propyl, isopropyl, primary butyl, sec-butyl and the tert-butyl group
Kind；It is highly preferred that
In formula (2), R1And R2It is each independently at least one of methyl, ethyl and n-propyl；In formula (3), R3And R4
It is each independently at least one of ethyl, n-propyl, primary butyl and sec-butyl.
3. method according to claim 1 or 2, wherein, the polymer with nitrogen with it is described after pre-oxidation treatment half
Burnt dosage weight ratio is 1-50：100；Preferably 5-25：100.
4. according to the method described in any one in claim 1-3, wherein, the semicoke after pre-oxidation treatment is gathered with nitrogenous
The condition of the aqueous solution mixing of compound includes：Temperature is lower 0.5-50 than the lowest critical solution temperature of the polymer with nitrogen
DEG C, time 1-30h；Preferably,
Semicoke after pre-oxidation treatment is included with the condition that the aqueous solution of polymer with nitrogen mixes：Temperature is more nitrogenous than described
The lowest critical solution temperature of polymer is low 1-25 DEG C, time 1-24h.
5. according to the method for claim 4, wherein, this method further comprises：By the semicoke after pre-oxidation treatment
After being mixed with the aqueous solution of polymer with nitrogen and being warming up to the first temperature, 1-180min is kept at a temperature of described first, so
Gained solidliquid mixture is filtered afterwards；Preferably,
First temperature is higher than the lowest critical solution temperature of the polymer with nitrogen 0.1-30 DEG C, more preferably high 0.5-20
℃。
6. according to the method described in any one in claim 1-5, wherein, the concentration of the aqueous solution of the polymer with nitrogen is
1-20 weight %.
7. according to the method described in any one in claim 1-6, wherein, the area load there is into the polymer with nitrogen
Semicoke the step of being activated include：The area load is first had to the semicoke of the polymer with nitrogen with 5-10 DEG C/min's
First heating rate is warming up to 500-600 DEG C, and keeps 0.2-6h at such a temperature；Then with 3-5 DEG C/min the second heating
Speed is warming up to 750-850 DEG C, and keeps 1-4h at such a temperature.
8. according to the method for claim 7, wherein, first heating rate is higher 3-5 DEG C than second heating rate/
min。
9. the method according to claim 7 or 8, wherein, this method further comprises：The semicoke is at 750-850 DEG C
When keeping 1-4h, carried out in the presence of active gases；Preferably,
The active gases is at least one of carbon dioxide, vapor and nitrogen.
10. according to the method described in any one in claim 1-9, wherein, the semicoke after pre-oxidation treatment passes through
Semicoke raw material is contacted with hydrogen peroxide and/or nitric acid and obtained；Preferably,
The condition of the contact includes：Temperature is 20-50 DEG C, time 5-30h.
11. according to the method for claim 10, wherein, the semicoke raw material is by coal, biomass and organic polymer
At least one product obtained after destructive distillation；Preferably,
The average grain diameter of the semicoke raw material is 1-10mm.
12. the activated coke being prepared as the method described in any one in claim 1-11.
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