CN107337207A - A kind of preparation method of low arsenic coal mass active carbon - Google Patents
A kind of preparation method of low arsenic coal mass active carbon Download PDFInfo
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- CN107337207A CN107337207A CN201710767496.9A CN201710767496A CN107337207A CN 107337207 A CN107337207 A CN 107337207A CN 201710767496 A CN201710767496 A CN 201710767496A CN 107337207 A CN107337207 A CN 107337207A
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- 239000003245 coal Substances 0.000 title claims abstract description 265
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 87
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 86
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 230000004913 activation Effects 0.000 claims abstract description 61
- 238000005406 washing Methods 0.000 claims abstract description 24
- 238000005188 flotation Methods 0.000 claims abstract description 14
- 239000012530 fluid Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 15
- 239000003546 flue gas Substances 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000008246 gaseous mixture Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 238000001994 activation Methods 0.000 description 50
- 239000000463 material Substances 0.000 description 33
- 239000002956 ash Substances 0.000 description 27
- 238000001035 drying Methods 0.000 description 12
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 239000005539 carbonized material Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000004575 stone Substances 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 7
- 229910052740 iodine Inorganic materials 0.000 description 7
- 239000011630 iodine Substances 0.000 description 7
- 238000003801 milling Methods 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000994 depressogenic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000004678 hydrides Chemical class 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000012271 agricultural production Methods 0.000 description 2
- -1 carbon Hydrogen compound Chemical class 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 208000008316 Arsenic Poisoning Diseases 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- JFMOYHBEGWPXBI-UHFFFAOYSA-N [C].[As] Chemical compound [C].[As] JFMOYHBEGWPXBI-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a kind of preparation method of low arsenic coal mass active carbon, the first coal and the second coal are subjected to flotation respectively, obtain the first coal float coal and the second coal float coal；The ash content ＜ 3.5wt.% of first coal, the content of volatile matter is 31~36wt.%, and caking index is 0.5~2.5；The ash content ＜ 2.5wt.% of second coal, the content of volatile matter are 27~30wt.%, and caking index≤1；The density of heavy-fluid independently is 1.40gcm used in first coal and the second coal flotation‑3；Gained the first coal float coal and the second coal float coal are mixed, obtain mixed coal；After the mixed coal is milled, briquetting, charing, activation and washing are carried out successively, obtains low arsenic coal mass active carbon.The arsenic content of the coal mass active carbon prepared by the above method is low, strong to the adsorption capacity of arsenic, will not produce secondary pollution.
Description
Technical field
The present invention relates to solid adsorption material technical field, and in particular to a kind of preparation method of low arsenic coal mass active carbon.
Background technology
In recent years, occur Dushan, guizhou county, Hunan Chenxi County, Guangxi Hechi, Yunnan Yang Zonghai, Henan Dasha River and
The arsenic pollution event of the floodway of Shandong and Jiangxi intersection, crisis of drinking water, harm are caused to contaminated area periphery and the downstream masses
Public health simultaneously causes part population arsenic poisoning, while is had serious consequences to industrial and agricultural production, causes extremely bad social shadow
Ring.Arsenic and its compound are widely used in metal smelt and industrial and agricultural production, are produced in process of manufacture substantial amounts of
Arsenic-containing waste water, waste residue and the unprocessed violation discharge of waste gas, seriously pollute environment；The arsenic of human body excess intake, it can cause to count
It is dead in it or a few hours.At present, arsenic pollution is classified as first place by the World Health Organization.
Coal mass active carbon is usually as the solid absorbent of water process, food, medical treatment processing etc., but arsenic element in coal
Content is in 876.3~8300g/t, mainly with silicate reference state (ash forms), sulfide reference state and complicated difficult dissolved with machine
Reference state is present in coal.Arsenogen cellulose content is high in the coal mass active carbon of in the market, about 2.0~7.55g/t, in application process
In can not effectively adsorb arsenic element, and when arsenogen cellulose content is more than 5g/t, the secondary pollution of arsenic element can be caused.
The content of the invention
It is an object of the invention to provide a kind of preparation method of low arsenic coal mass active carbon, using method provided by the invention
The coal mass active carbon arsenic content being prepared can be down to 1.03mg/kg, can effectively adsorb arsenic element, avoid secondary pollution.
The invention provides a kind of preparation method of low arsenic coal mass active carbon, comprise the following steps：
(1) the first coal and the second coal are subjected to flotation respectively, obtain the first coal float coal and the second coal float coal；Institute
The ash content ＜ 3.5wt.% of the first coal are stated, the content of volatile matter is 31~36wt.%, and caking index is 0.5~2.5；Institute
State the ash content ＜ 2.5wt.% of the second coal, the content of volatile matter is 27~30wt.%, and caking index≤1；First coal
The density of heavy-fluid independently is 1.40gcm used in kind and the second coal flotation-3；
(2) the first coal float coal and the second coal float coal are mixed, obtains mixed coal；
(3) after the mixed coal is milled, briquetting, charing, activation and washing are carried out successively, obtain low arsenic ature of coal activity
Charcoal.
Preferably, the mass ratio of the first coal float coal and the second coal float coal is 1.5~9 in the step (2):1.
Preferably, the charing includes preliminary charing and deep charring.
Preferably, the pressure tentatively carbonized is 96~100kPa, and the temperature tentatively carbonized is 200~300 DEG C, tentatively
The time of charing is 0.5~1.5h；The heating rate for being warming up to the temperature tentatively carbonized is 3~5 DEG C/min.
Preferably, the pressure of the deep charring is 96~100kPa, and the temperature of deep charring is 450~550 DEG C, depth
The time of charing is 2.5~4h；The heating rate for being warming up to the temperature of the deep charring is 3~5 DEG C/min.
Preferably, the activation includes primary activation and deep activation.
Preferably, the pressure of the primary activation is preferably 101.375~101.435kPa；The temperature of the primary activation
Preferably 650~850 DEG C；The time of the primary activation is preferably 2~4.5h.
Preferably, the deep activation is carried out in the mixed gas of water vapour and flue gas, and the pressure of deep activation is
101.375~101.435kPa；The temperature of deep activation is 850~950 DEG C, and the time of deep activation is 55~70h.
Preferably, the volume ratio of the water vapour and flue gas is 1~2.5:1.
Preferably, the washing includes alkali cleaning successively and steam heating washs.
The invention provides a kind of preparation method of low arsenic coal mass active carbon, the first coal and the second coal are carried out respectively
Flotation, obtain the first coal float coal and the second coal float coal；The ash content ＜ 3.5wt.% of first coal, the content of volatile matter
For 31~36wt.%, and caking index is 0.5~2.5；The ash content ＜ 2.5wt.% of second coal, the content of volatile matter
For 27~30wt.%, and caking index≤1；The density of heavy-fluid independently is used in first coal and the second coal flotation
1.40g·cm-3；Gained the first coal float coal and the second coal float coal are mixed, obtain mixed coal；The mixed coal is ground
After powder, briquetting, charing, activation and washing are carried out successively, obtains low arsenic coal mass active carbon.The present invention to coal by floating
Choosing, 50~90% silicate reference state arsenic is removed, then lose volatilization by activating to burn the sulfide reference state arsenic of coal, together
When the molten organically combine state arsenic of complicated difficult is converted into ash content, the scrubbed arsenic element for turning to ash content by inside activated carbon removes.
Test result indicates that the arsenic content for the coal mass active carbon that preparation method provided by the present invention obtains is 1.03~1.29mg/kg,
Specific surface area is 1109~1182m2/ g, the weight/mass percentage composition of ash content is 2.31~3.11%, and uses it for adsorbing waste water
In arsenic when, with the extension of adsorption time, downward trend is presented in the arsenic content in waste water all the time, will not produce secondary pollution, and
When normal activated carbon adsorbs to the arsenic in waste water under identical condition, the arsenic content in waste water increases after falling before, and goes out
The phenomenon of secondary pollution is showed.In addition, coal mass active carbon obtained by preparation method provided herein also has excellent mechanics
Performance, mechanical strength is up to more than 96%, and ball disk hardness is up to more than 92%, and wear-resisting value is up to more than 80%.
Embodiment
The invention provides a kind of preparation method of low arsenic coal mass active carbon, comprise the following steps：
(1) the first coal and the second coal are subjected to flotation respectively, obtain the first coal float coal and the second coal float coal；Institute
The ash content ＜ 3.5wt.% of the first coal are stated, the content of volatile matter is 31~36wt.%, and caking index is 0.5~2.5；Institute
State the ash content ＜ 2.5wt.% of the second coal, the content of volatile matter is 27~30wt.%, and caking index≤1；First coal
The density of heavy-fluid independently is 1.40gcm used in kind and the second coal flotation-3；
(2) the first coal float coal and the second coal float coal are mixed, obtains mixed coal；
(3) after the mixed coal is milled, briquetting, charing, activation and washing are carried out successively, obtain low arsenic ature of coal activity
Charcoal.
First coal and the second coal are carried out flotation by the present invention respectively, obtain the first coal float coal and the second coal is floated
Coal；The ash content ＜ 3.5wt.% of first coal, the content of volatile matter are 31~36wt.%, and caking index be 0.5~
2.5；The ash content ＜ 2.5wt.% of second coal, the content of volatile matter are 27~30wt.%, and caking index≤1；It is described
The density of heavy-fluid independently is 1.40gcm used in first coal and the second coal flotation-3.In the present invention, the flotation can
The arsenic of 50~90% silicate reference state is removed.
The present invention does not have particular/special requirement to the species of the heavy-fluid, can be that organic solution or zinc chloride are water-soluble
Liquid, for the present invention preferably using solder(ing)acid as heavy-fluid, the mass concentration of the solder(ing)acid is preferably 39%.
Before the first coal and the second coal are carried out into flotation respectively, the present invention is preferably by the first coal and/or the second coal
Crushed, obtain the first seed coal and/or the second seed coal, the granularity of the first seed coal and the second seed coal is preferably independently 3
~10mm, more preferably 7~9mm.The present invention does not have special requirement to the broken mode, ripe using those skilled in the art
The crumbling method known.Present invention preferably employs simon, this gyratory crusher is crushed.
Complete it is described it is broken after, the broken product is preferably carried out stone by the present invention, obtains the first seed coal and/or the
Two seed coals.In the present invention, the proportion of the first seed coal and/or the second seed coal independently is 0.8~1g/cm3.The present invention is right
The mode for removing stone does not have particular/special requirement, and cubic meter of stone formula is gone using well known to those skilled in the art.The present invention preferably adopts
Stone is carried out with TQSF stone removing machine by use of principle.
After the completion of flotation, the product of the flotation is preferably washed, dried by the present invention successively respectively, obtains the first coal
Kind float coal and the second coal float coal.The present invention does not have particular/special requirement to the mode of the washing, can remove heavy-fluid.
In the present invention, the water content of the first coal float coal and the second coal float coal independently be preferably 5~
10wt.%, more preferably 6~8wt.%.In the present invention, the water content is advantageous to follow-up milling and briquetting.The present invention
There is no particular/special requirement to the mode of the drying, can be by the first coal float coal and the second coal float coal drying to required aqueous
Amount, present invention preferably employs φ 1.0m, long 12m converter, and the product of the washing to be dried.In the present invention, institute
It is preferably 96~100kPa to state dry pressure.In the present invention, the temperature of the drying is preferably 200~450 DEG C, more preferably
300~400 DEG C.
After obtaining the first coal float coal and the second coal float coal, the present invention floats the first coal float coal and the second coal
Coal mixes, and obtains mixed coal.In the present invention, the mixing of the first coal float coal and the second coal float coal can ensure product
With good intensity and wearability.In the present invention, the mass ratio of the first coal float coal and the second coal float coal is preferred
For 1.5~9:1, more preferably 4~6:1.The present invention does not have particular/special requirement to the mode of mixing, can mix both,
It is specific to be mixed by the way of autofeed control proportioning in the embodiment of the present invention.
After obtaining mixed coal, the mixed coal is milled by the present invention.In the present invention, it is described to be milled what is obtained
Powder particle size is preferably≤75 μm.The present invention does not have particular/special requirement to the concrete mode of milling, can obtain particle diameter≤75 μm
Powder.In the present invention, it is preferred to using YGM high-pressure overhang rolls milling machine milling.
After completing the milling, the powder that the milling obtains is carried out briquetting by the present invention, obtains briquetting material.In the present invention
In, the briquetting recombinates the connection between carbon atom, is advantageous to follow-up charing and activation process is carried out.In the present invention
In, the intensity of the briquetting material is preferably greater than 96%, more preferably greater than 97.5%.The present invention does not have to the shape of the briquetting material
Particular/special requirement, using shape commonly used in the art.In an embodiment of the present invention, the briquetting material is preferably that major semiaxis is
7~9mm, semi-minor axis are 5~6mm spheroid shape briquetting material.
The present invention does not have particular/special requirement to the concrete mode of briquetting, can obtain the briquetting material of required intensity.At this
In invention, it is preferred to use WZ-500 type dry method roll-type cubers.In the present invention, the pressure of the briquetting be preferably 22~
30MPa, more preferably 25~28MPa.In the present invention, the rotating speed that the briquetting uses is preferably 15~50Hz, more preferably
25~35Hz.
After the completion of briquetting, the present invention is carbonized obtained briquetting material, obtains carbonized material.In the present invention, the charcoal
Change the sulphides burn in briquetting material, and play a part of preliminary pore-creating, be that the reaming of activated carbon in subsequent activation process carries
For passage.In the present invention, the charing preferably includes preliminary charing and deep charring.
In the present invention, the pressure tentatively carbonized is preferably 96~100kPa, more preferably 98~99kPa；It is described
The temperature tentatively carbonized is preferably 200~300 DEG C, more preferably 240~260 DEG C；The time tentatively carbonized is preferably 0.5
~1.5h, more preferably 1~1.2h；The heating rate for being warming up to the temperature tentatively carbonized is preferably 3~5 DEG C/min.
In the present invention, the temperature of deep charring is preferably directly warming up to after the completion of the preliminary charing.In the present invention,
The pressure of the deep charring is preferably 96~100kPa, more preferably 98~99kPa；The temperature of the deep charring is preferably
400~550 DEG C, more preferably 450~500 DEG C；The time of the deep charring is preferably 2.5~4h, more preferably 3~
3.5h；It is 3~5 DEG C that the heating rate for being warming up to the temperature of the deep charring, which is preferably,.
After obtaining carbonized material, the present invention is activated the carbonized material, obtains activated material.In the present invention, the work
The sulfide reference state arsenogen biscuiting of coal is lost volatilization by change process, and ashing is lost in the molten organically combine state arsenogen biscuiting of complicated difficult, together
Shi Jinhang pore-creating.In the present invention, the content of ashes of the activated material is preferably 6.5~9.25wt.%, more preferably 8~
9wt.%.The present invention does not have particular/special requirement to activating equipment used, is using activation equipment well known to those skilled in the art
Can.In an embodiment of the present invention, the activation is specifically carried out using Si Lipu activation furnaces.In the present invention, the activation is excellent
Choosing includes primary activation and deep activation.
In the present invention, the primary activation is preferably carried out in water vapour atmosphere；The pressure of the primary activation is preferred
For 101.375kPa~101.435kPa, more preferably 101.385~101.425kPa；The temperature of the primary activation is preferably
650~850 DEG C, more preferably 700~750 DEG C；The time of the primary activation is preferably 2~4.5h, more preferably 3~4h.
In the present invention, after the completion of the primary activation, depth work is carried out after preferably directly atmosphere is replaced
Change.In the present invention, the pressure of the deep activation is preferably 101.375kPa~101.435kPa, more preferably
101.385~101.425kPa；The temperature of the deep activation is preferably 850~950 DEG C, more preferably 900~940 DEG C；Institute
The time for stating deep activation is preferably 55~70h, more preferably 60~65h.
In the present invention, the deep activation is preferably carried out in the mixed gas of water vapour and flue gas；The water vapour
Volume ratio with flue gas is preferably 1~2.5:1, more preferably 1.5~2:1.Species no spy of the present invention for the flue gas
It is different to require, using the flue gas well known to those skilled in the art for being activated to activated carbon.In the implementation of the present invention
In example, the flue gas specifically includes the SO that volume fraction is 2%2, 15% N2, 2% O2, 13% CO, 28% CO2And
Hydrocarbon and 40% oxynitrides.
After the completion of activation, the product of the activation is preferably crushed and sieved successively by the present invention, obtains activated material.
In the present invention, the particle diameter of the activated material is preferably 0.5~2.5mm.The present invention does not have special want to the broken mode
Ask, using crumbling method well known to those skilled in the art.Present invention preferably employs simon, this gyratory crusher is broken
It is broken.The present invention does not have particular/special requirement to the mode of the screening, using screening mode well known to those skilled in the art.
In the embodiment of the present invention, the mode of the screening is vibratory sieve.
After obtaining activated material, the present invention is washed the activated material, obtains low arsenic coal mass active carbon.In the present invention
In, the washing can remove the ash content containing arsenic in activated carbon and impurity.In the present invention, the washing preferably includes alkali successively
Wash and washed with steam heating.
In the present invention, the alkali cleaning is preferably to soak the activated material using alkaline rinse.In the present invention, the alkali
Property washing lotion is preferably sodium hydrate aqueous solution；The concentration of the sodium hydrate aqueous solution is preferably 5~15wt.%, and more preferably 8
~12wt.%.The present invention does not have particular/special requirement to the dosage of the alkaline rinse, can submerge activated material.In this hair
In bright, the soak time of the alkali cleaning is preferably 20~36h, more preferably 28~30h.In the present invention, the alkali cleaning preferably exists
Normal temperature is carried out.
In the present invention, the temperature of the steam heating washing is preferably 60~120 DEG C, more preferably 80~100 DEG C.
In the present invention, the time of the steam heating washing is preferably 5~10h, more preferably 7~8h.
After completing washing, product of the present invention preferably by the washing is dried, and obtains low arsenic coal mass active carbon.At this
In invention, the water content of the low arsenic coal mass active carbon is preferably less than 3wt.%, more preferably less than 2wt.%.The present invention is right
The mode of the drying does not have particular/special requirement, the water content of the activated carbon can be down into necessary requirement.The present invention is excellent
The product after the washing is dried using φ 1.0m, long 12m converter for choosing.In the present invention, the pressure of the drying
Preferably 96~100kPa, more preferably 98~99kPa；The temperature of the drying is preferably 300~500 DEG C, more preferably 400
~450 DEG C.
Below in conjunction with the embodiment in the present invention, the technical scheme in the present invention is clearly and completely described.It is aobvious
So, described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.Based on the reality in the present invention
Example is applied, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, is all belonged to
In the scope of protection of the invention.
Embodiment 1
(1) by the first coal (content of ashes 3.3wt.%, volatile matter content 34wt.%, caking index 1.7) and
Second coal (content of ashes 2.4wt.%, volatile matter content 29wt.%, caking index 0.7) is broken for particle diameter respectively
It is respectively 0.87g/cm through going stone to obtain bulk density for 6~10mm seed coal3And 0.96g/cm3The first coal seed coal and second
Coal seed coal；Then the use of density is 1.4gcm-3Zinc chloride heavy-fluid respectively to the first coal seed coal and the second coal
Seed coal carries out flotation, washing and drying successively, obtains the first coal float coal and the second coal float coal；Gained the first coal float coal and
The moisture of second coal float coal is 5.8wt.%；The drying diameter 1.0m, long 12m converter in carry out, it is described dry
Dry pressure is 96kPa, temperature is 380 DEG C；
(2) take the first coal float coal 73kg, the second coal float coal 27kg to mix, obtain mixed coal；
(3) mixed coal is milled, obtains the powder of particle diameter≤75 μm, by powder with domestic WZ-500 dry method roll-type
Cuber is depressed into the briquetting material of bulk, and the pressure used in briquetting is 27MPa, and rotating speed 28Hz, the machinery of gained briquetting material is by force
Spend for 98%；
(4) gained briquetting material is put into retort, briquetting material is warming up to 250 with 3.5 DEG C/min heating rate first
DEG C temperature, tentatively carbonized 1.2 hours in 96kPa, be then warming up to 510 DEG C again with 3.5 DEG C/min heating rate,
98kPa deep charrings 3 hours, obtain the carbonized material that volatile content is 18.5wt.%；
(5) carbonized material is subjected to primary activation in water vapour atmosphere at 785 DEG C, the time of primary activation is
2.5 hours, the pressure of the primary activation was 101.39kPa；Then it is 11 in water vapour and flue gas volume ratio:In 9 atmosphere
Deep activation is carried out at 950 DEG C, the pressure of the deep activation is 101.39kPa, obtains activated material, the deep activation
Time is 65h, the flue gas by volume fraction be 2% SO2, 15% N2, 2% O2, 13% CO, 28% CO2And carbon
Hydrogen compound and 40% oxynitrides composition；
(6) activated material is subjected to alkali cleaning, alkali cleaning in the sodium hydrate aqueous solution that concentration is 11wt.% after crushing
Time be 32h；Then 7h is washed with 100 DEG C of steam heating；
(7) activated carbon obtained after washing is put into diameter 1.0m, long 12m converter, is 96kPa, temperature in pressure
To be dried under conditions of 450 DEG C, the low arsenic coal mass active carbon that water content is 1.5wt.% is obtained.
The arsenic content of above-mentioned low arsenic coal mass active carbon is determined using hydride generation-atomic spectrophotometer absorption process, is obtained
Its arsenic content is 1.21mg/kg；
The content of ashes of above-mentioned low arsenic coal mass active carbon is measured using standard GB/T7702.15-2008, obtains its ash
It is 2.45wt.% to divide content；
The iodine number of above-mentioned low arsenic coal mass active carbon is measured using standard GB/T7702.7-2008, obtaining its iodine number is
1121mg/g；
The mechanical strength of above-mentioned low arsenic coal mass active carbon is measured using standard GB/T7702.3-2008, obtains its machine
Tool intensity 97.6%；
The ball disk hardness of above-mentioned low arsenic coal mass active carbon is measured using standard ASTM, obtaining its ball disk hardness is
92.9%；
The wearability of above-mentioned low arsenic coal mass active carbon is measured using standard ASTM, obtains its wear-resisting value as 85.5%；
The specific surface area of above-mentioned low arsenic coal mass active carbon is measured using standard GB/T7702.20-2008, obtains its ratio
Surface area is 1146m2/g。
Embodiment 2
(1) by the first coal (content of ashes 3.1wt.%, volatile matter content 34.8wt.%, caking index 1.8)
It is broken for respectively with the second coal (content of ashes 2.2wt.%, volatile matter content 29.7wt.%, caking index 0.8)
Particle diameter is 6~10mm seed coal, is respectively 0.83g/cm through going stone to obtain proportion3And 0.91g/cm3The first coal seed coal and
Two coal seed coals；Then the use of density is 1.4gcm-3Zinc chloride heavy-fluid respectively to the first coal seed coal and the second coal
Seed coal carries out flotation, washing and drying successively, obtains the first coal float coal and the second coal float coal；Gained the first coal float coal
Moisture with the second coal float coal is 5.5wt.%；The drying diameter 1.0m, long 12m converter in carry out, it is described
Dry pressure is 98kPa, temperature is 369 DEG C.
(2) take the first coal float coal 80kg, the second coal float coal 20kg to mix, obtain mixed coal；
(3) mixed coal is milled, obtains the powder of particle diameter≤75 μm, by powder with domestic WZ-500 dry method roll-type
Cuber is depressed into the briquetting material of bulk, and the pressure used in briquetting is 28MPa, rotating speed 30Hz, and the intensity of gained briquetting is
98.3%；
(4) gained briquetting material is put into retort, briquetting material is warming up to 280 DEG C with 4 DEG C/min heating rate first
Temperature, tentatively carbonized 1 hour in 99kPa, be then warming up to 500 DEG C again with 4.5 DEG C/min heating rate, it is deep in 99kPa
Degree charing 3.5 hours, obtain the carbonized material that volatile content is 18.1wt.%；
(5) carbonized material is subjected to primary activation, the time of primary activation in water vapour atmosphere at a temperature of 800 DEG C
For 2 hours, the pressure of the primary activation was 101.43kPa；Then it is 13 in water vapour and flue gas volume ratio:In 7 atmosphere
Deep activation is carried out at 950 DEG C, the pressure of the deep activation is 101.43kPa, obtains activated material, the deep activation
Time is 60h, the flue gas by volume fraction be 2% SO2, 15% N2, 2% O2, 13% CO, 28% CO2And carbon
Hydrogen compound and 40% oxynitrides composition；
(6) activated material is subjected to alkali cleaning, alkali in the sodium hydrate aqueous solution that concentration is 10.8wt.% after crushing
The time washed is 33h；Then 8.5h is washed with 95 DEG C of steam heating；
(7) activated carbon obtained after washing is put into diameter 1.0m, long 12m converter, is 98kPa, temperature in pressure
To be dried under conditions of 420 DEG C, the low arsenic coal mass active carbon that water content is 1.9wt.% is obtained.
The arsenic content of above-mentioned low arsenic coal mass active carbon is determined using hydride generation-atomic spectrophotometer absorption process, is obtained
Its arsenic content is 1.03mg/kg；
The content of ashes of above-mentioned low arsenic coal mass active carbon is measured using standard GB/T7702.15-2008, obtains its ash
It is 2.31wt.% to divide content；
The iodine number of above-mentioned low arsenic coal mass active carbon is measured using standard GB/T7702.7-2008, obtaining its iodine number is
1169mg/g；
The mechanical strength of above-mentioned low arsenic coal mass active carbon is measured using standard GB/T7702.3-2008, obtains its machine
Tool intensity 97.8%；
The ball disk hardness of above-mentioned low arsenic coal mass active carbon is measured using standard ASTM, obtaining its ball disk hardness is
93.1%；
The wearability of above-mentioned low arsenic coal mass active carbon is measured using standard ASTM, obtains its wear-resisting value as 86.1%；
The specific surface area of above-mentioned low arsenic coal mass active carbon is measured using standard GB/T7702.20-2008, obtains its ratio
Surface area is 1182m2/g。
Embodiment 3
(1) by the first coal (content of ashes 3.4wt.%, volatile matter content 32.9wt.%, caking index 1.0)
It is broken for respectively with the second coal (content of ashes 2.4wt.%, volatile matter content 28.3wt.%, caking index 0.6)
Particle diameter is 6~10mm seed coal, is respectively 0.89g/cm through going stone to obtain proportion3And 0.99g/cm3The first coal seed coal and
Two coal seed coals；Then the use of density is 1.4gcm-3Zinc chloride heavy-fluid respectively to the first coal seed coal and the second coal
Seed coal carries out flotation, washing and drying successively, obtains the first coal float coal and the second coal float coal；Gained the first coal float coal
Moisture with the second coal float coal is 6.3wt.%；The drying diameter 1.0m, long 12m converter in carry out, it is described
Dry pressure is 100kPa, temperature is 374 DEG C；
(2) take the first coal float coal 88kg, the second coal float coal 12kg to mix, obtain mixed coal；
(3) mixed coal is milled, obtains the powder of particle diameter≤75 μm, by powder with domestic WZ-500 dry method roll-type
Cuber is depressed into the briquetting material of bulk, and the pressure used in briquetting is 29MPa, rotating speed 31Hz, and the intensity of gained briquetting is
97.5%；
(4) gained briquetting material is put into retort, briquetting material is warming up to 260 DEG C with 4 DEG C/min heating rate first
Temperature, tentatively carbonized 1.4 hours in 97kPa, then 530 DEG C be warming up to again with 3.5 DEG C/min heating rate, in 97kPa
Deep charring 3.2 hours, obtain the carbonized material that volatile content is 17.2wt.%；
(5) carbonized material is subjected to primary activation, the time of primary activation in water vapour atmosphere at a temperature of 800 DEG C
For 3 hours, the pressure of the primary activation was 101.4kPa；Then it is 12 in water vapour and flue gas volume ratio：In 8 atmosphere in
Deep activation is carried out at 950 DEG C, the pressure of the deep activation is 101.4kPa, obtains activated material, the deep activation when
Between be 70h, the flue gas is by SO that volume fraction is 2%2, 15% N2, 2% O2, 13% CO, 28% CO2It is and hydrocarbon
Compound and 40% oxynitrides composition；
(6) activated material is subjected to alkali cleaning, alkali in the sodium hydrate aqueous solution that concentration is 11.3wt.% after crushing
The time washed is 36h；Then 8h is washed with 100 DEG C of steam heating；
(7) activated carbon obtained after washing is put into diameter 1.0m, long 12m converter, is 98kPa, temperature in pressure
To be dried under conditions of 445 DEG C, the low arsenic coal mass active carbon that water content is 1.6wt.% is obtained.
The arsenic content of above-mentioned low arsenic coal mass active carbon is determined using hydride generation-atomic spectrophotometer absorption process, is obtained
Its arsenic content is 1.29mg/kg；
The content of ashes of above-mentioned low arsenic coal mass active carbon is measured using standard GB/T7702.15-2008, obtains its ash
It is 3.11wt.% to divide content；
The iodine number of above-mentioned low arsenic coal mass active carbon is measured using standard GB/T7702.7-2008, obtaining its iodine number is
1109mg/g；
The mechanical strength of above-mentioned low arsenic coal mass active carbon is measured using standard GB/T7702.3-2008, obtains its machine
Tool intensity 96.6%；
The ball disk hardness of above-mentioned low arsenic coal mass active carbon is measured using standard ASTM, obtaining its ball disk hardness is
92.5%；
The wearability of above-mentioned low arsenic coal mass active carbon is measured using standard ASTM, obtains its wear-resisting value as 83.7%；
The specific surface area of above-mentioned low arsenic coal mass active carbon is measured using standard GB/T7702.20-2008, obtains its ratio
Surface area is 1119m2/g。
Embodiment 4
(1) compound concentration is 10mg/L arsenic-containing water solution, and the pH value of the arsenic-containing water solution is adjusted to 4.5；
(2) the low arsenic coal mass active carbon (being denoted as activated carbon A) of the gained of 0.2g embodiments 3 is weighed to be put into containing 100mL steps 1 institute
In the arsenic-containing water solution obtained, at 25 DEG C, 400min is shaken in placement on the oscillator, and activity is measured by sampling in point at different moments
The arsenic concentration in arsenic content and arsenic-containing water solution in charcoal A；Commercially available activated carbon (being denoted as activated carbon B) is determined using same method
Arsenic removal performance, the initial arsenic content of the activated carbon B is 2.23mg/kg, content of ashes 3.31wt.%, and iodine number is
1119mg/g, mechanical strength 97.0%, ball disk hardness are 92.8%, wear-resisting value 85.4%, specific surface area 1098m2/g。
Test result is shown in Table 1.
Absorption property measurement results of the activated carbon A and B of table 1 to arsenic
As can be seen from Table 1, when activated carbon A is used to adsorb arsenic in water, the arsenic content in arsenic-containing water solution is declining all the time,
The arsenic concentration of final gained arsenic-containing water solution can be down to 0.5mg/L, disclosure satisfy that the discharge standard of China's arsenic-containing waste water (is less than
1mg/L).Activated carbon B is in adsorption process, and as time went on, the arsenic content in arsenic-containing water solution is in first to reduce what is increased afterwards
Trend, and do not reach discharge standard finally, cause secondary pollution.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of low arsenic coal mass active carbon, comprises the following steps：
(1) the first coal and the second coal are subjected to flotation respectively, obtain the first coal float coal and the second coal float coal；Described
The ash content ＜ 3.5wt.% of one coal, the content of volatile matter is 31~36wt.%, and caking index is 0.5~2.5；Described
The ash content ＜ 2.5wt.% of two coals, the content of volatile matter are 27~30wt.%, and caking index≤1；First coal and
The density of heavy-fluid independently is 1.40gcm used in second coal flotation-3；
(2) the first coal float coal and the second coal float coal are mixed, obtains mixed coal；
(3) after the mixed coal is milled, briquetting, charing, activation and washing are carried out successively, obtains low arsenic coal mass active carbon.
2. preparation method as claimed in claim 1, it is characterised in that the first coal float coal and the second coal in the step (2)
The mass ratio of kind float coal is 1.5~9:1.
3. preparation method as claimed in claim 1, it is characterised in that the charing includes preliminary charing and deep charring.
4. preparation method as claimed in claim 3, it is characterised in that the pressure tentatively carbonized is 96~100kPa, just
The temperature of step charing is 200~300 DEG C, and the time tentatively carbonized is 0.5~1.5h；It is warming up to the temperature tentatively carbonized
Heating rate is 3~5 DEG C/min.
5. preparation method as claimed in claim 3, it is characterised in that the pressure of the deep charring is 96~100kPa, deep
The temperature of degree charing is 400~550 DEG C, and the time of deep charring is 2.5~3h；It is warming up to the liter of the temperature of the deep charring
Warm speed is 3~5 DEG C/min.
6. preparation method as claimed in claim 1, it is characterised in that the activation includes primary activation and deep activation.
7. preparation method as claimed in claim 6, it is characterised in that the primary activation is carried out in water vapour atmosphere, just
The pressure of step activation be 101.375~101.435kPa, and the temperature of primary activation is 650~850 DEG C, and the time of primary activation is
2~4.5h.
8. preparation method as claimed in claim 6, it is characterised in that the deep activation is in water vapour and the gaseous mixture of flue gas
Carried out in body, the pressure of deep activation is 101.375~101.435kPa, and the temperature of deep activation is 850~950 DEG C, depth
The time of activation is 55~70h.
9. preparation method as claimed in claim 8, it is characterised in that the volume ratio of the water vapour and flue gas is 1~2.5:
1。
10. preparation method as claimed in claim 1, it is characterised in that the washing includes alkali cleaning and steam heating successively
Washing.
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Effective date of registration: 20200109 Address after: Dang Liu Zhuang Xiang Dang Liu Zhuang Cun Nan, Yunzhou District, Datong City, Shanxi Province Applicant after: Shanxi Huaqing activated carbon group Limited by Share Ltd Address before: 037000 No. 1, unit 2, building 98, Xiangyang West Street, Datong, Shanxi, 10 Applicant before: He Shouyin |
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