CN106241805A - A kind of method that black liquid crude extract lignosulfonates prepare activated carbon - Google Patents
A kind of method that black liquid crude extract lignosulfonates prepare activated carbon Download PDFInfo
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- CN106241805A CN106241805A CN201610700903.XA CN201610700903A CN106241805A CN 106241805 A CN106241805 A CN 106241805A CN 201610700903 A CN201610700903 A CN 201610700903A CN 106241805 A CN106241805 A CN 106241805A
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- Prior art keywords
- lignosulfonates
- activated carbon
- black liquid
- crude extract
- activation
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000007788 liquid Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 38
- 229920001732 Lignosulfonate Polymers 0.000 title claims abstract description 36
- 239000000287 crude extract Substances 0.000 title claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 230000004913 activation Effects 0.000 claims abstract description 38
- 238000002386 leaching Methods 0.000 claims abstract description 24
- 238000002604 ultrasonography Methods 0.000 claims abstract description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000000047 product Substances 0.000 claims abstract description 14
- 239000000706 filtrate Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000001291 vacuum drying Methods 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 230000003213 activating effect Effects 0.000 claims description 6
- 238000006277 sulfonation reaction Methods 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 5
- 239000000284 extract Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 abstract description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011630 iodine Substances 0.000 abstract description 4
- 229910052740 iodine Inorganic materials 0.000 abstract description 4
- 238000001994 activation Methods 0.000 description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- 229960004424 carbon dioxide Drugs 0.000 description 7
- 239000003610 charcoal Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 4
- 229920001342 Bakelite® Polymers 0.000 description 3
- 239000004637 bakelite Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- -1 pottery Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- 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
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The present invention relates to a kind of method that black liquid crude extract lignosulfonates prepare activated carbon, belong to technical field of resource comprehensive utilization.First black liquid crude extract lignosulfonates addition hydrochloric acid solution is obtained one section of acidleach thing；One section of acidleach thing adds the leaching of phosphoric acid solution ultrasound wave and obtains sulphuric leaching thing；It is passed through 0.1m3After the nitrogen air-out of/h, the sulphuric leaching thing microwave heating activation that will obtain, when activation was to last ten minutes, it is passed through carbon dioxide from bottom until activation terminates, is finally cooled to room temperature and obtains activation products；The activation products obtained repeatedly are washed until cleaning mixture pH value is neutrality, be filtrated to get filtrate and filtering residue, from filtrate, reclaim residual phosphoric acid, filtering residue is dried in vacuum drying oven and obtains activated carbon.The Properties of Activated Carbon that this method prepares is preferable, and specific surface area is 1915m2/ g, its average pore size is 2.60nm, and iodine absorbability reaches 1429mg/g.
Description
Technical field
The present invention relates to the method that a kind of black liquid crude extract-lignosulfonates prepare activated carbon, belong to resource
Technical field of comprehensive utilization.
Background technology
Black liquor be in paper industry with alkaline process as standard (soda processes and sulfate process) slurrying and the waste water that obtains, Qi Zhonghan
There is a substantial amounts of lignin in pitchy shape, therefore referred to as black liquor.Black liquor also contains other substantial amounts of suspended solids simultaneously, has
Organic pollutants, inorganic matter and noxious substance, if being directly discharged in water body to cause serious pollution, therefore, to black liquor
In various materials carry out separation and Extraction respectively, can reach to make the best use of everything, the effect turned waste into wealth.The wherein thick extraction of black liquor
Thing-lignosulfonates by modified, process, the method such as compound can be widely used in cement water reducing agent, coal water slurry dispersing agent,
The aspects such as asphalt emulsifier, pottery, oil mining auxiliary agent, absorption.The present invention is by through concentration, sulfonation, dry slightly carrying of dusting
Take thing-lignosulfonates to be further used for preparing activated carbon.Lignin in this crude extract is utilized to have the character of phenolic hydroxyl group,
Use phosphoric acid-ultrasonic activation microwave heating, can be using obtained activated carbon as noble metal catalyst and dyeing
In the adsorbent of discarded acid stain.
Activated carbon is to have highly developed pore structure and the porous carbon materials of very big internal surface area, and it is mainly by carbon
(mass fraction is 87%-97%) forms, and also contains element and some inorganic minerals such as hydrogen, oxygen, sulfur, nitrogen simultaneously, absorption
Performance is strong, stable chemical nature, and mechanics height is strong, convenient regeneration；And because it is acidproof, alkaline-resisting, heat-resisting and water insoluble, have
Machine solvent so that the scope of activated carbon application is more and more extensive, and demand is the most increasing simultaneously so that market is to activated carbon originally
The prescription of body is more and more higher, and this just requires that activated carbon improves to some extent from preparation cost.Many prepares activated carbon at present
Research focus on the raw material of cheapization, diversification, such as utilize various agriculture and forestry organic waste material or industry byproduct to do and prepare
Raw material, all becomes the good approach of development prospect.
The present invention, with the crude extract-lignosulfonates of papermaking wastewater as raw material, uses ultrasound wave-phosphoric acid leaching first
Stain, and drastically increase activation efficiency toward activating the mode blowing carbon dioxide bottom material, the production reducing activated carbon becomes
This, also mitigate water pollution simultaneously, has accomplished the comprehensive utilization of industry byproduct, and has used microwave heating in activation process
Mode, greatly reduce energy resource consumption, there are good environmental resource and economic results in society.The activated carbon produced
Specific surface area high and rich in micropore, high adsorption capacity, simultaneously because the pretreatment of hydrochloric acid so that ash of active carbon is relatively low, this
Just the comprehensive utilization for the crude extract-ligninsulfonate of black liquid provides another practicable method.
Applicant, in the patent of Patent No. 201510057548.4, discloses " a kind of activation discarded bakelite preparation height
The method of specific surface area active carbon ", this method is first to be crushed by discarded bakelite, is then mixed homogeneously with it by KOH and puts into
Microwave high-temperature reacting furnace；In stove, it is passed through nitrogen to empty furnace air, heats under microwave, after being heated to certain time, fast
Speed is blown into the steam of some time by the conduit bottom connection ceramic crucible, and opens supersonic generator heating simultaneously
Obtain activated material, wash, and reclaim remaining KOH activator；Rinse with tap water after carrying out pickling with hydrochloric acid, be dried
Obtain active carbon with high specific surface area.Foregoing invention is compared with the present invention, and one is that the mass ratio of foregoing invention alkali charcoal is relatively big, wastes
Resource, and be passed through steam in the heating process later stage and increase the probability of pyrocarbon reaction, and the present invention activates the later stage and takes to lead to
The mode entering carbon dioxide carries out carbon protection, then avoid the possibility that under high temperature, activated carbon and steam react；Two is hydroxide
Potassium activator through dipping directly under microwave heating, act on waste gas bakelite so that under part potassium ion high temperature reduce and
Escape, and activation of potassium hydroxide agent does not possess the strong associativity the same with phosphoric acid so that efficiency reduces, and the present invention uses phosphoric acid
Dipping, before heating, the mode of logical 1 ~ 2min nitrogen, has saved resource greatly；Three is that the present invention uses ultrasonic assistant to impregnate,
Significantly improving the dynamic conditions of preparation, the specific surface area finally prepared is 1915m2/ g, its average pore size is 2.60nm,
Iodine absorbability reaches 1429mg/g.
Summary of the invention
The problem existed for above-mentioned prior art and deficiency, the present invention provides a kind of black liquid crude extract-wooden
The method that activated carbon prepared by element sulfonate.The Properties of Activated Carbon that this method prepares is preferable, and specific surface area is 1915m2/ g, its
Average pore size is 2.60nm, and iodine absorbability reaches 1429mg/g.The present invention is achieved through the following technical solutions.
A kind of method that black liquid crude extract-lignosulfonates prepare activated carbon, it includes step in detail below:
(1) first by black liquid crude extract-lignosulfonates according to solid-to-liquid ratio be 10～30:50～90 g/ml add
Concentration is 1mol/l hydrochloric acid solution, and under the conditions of temperature is 20～40 DEG C, ultrasound wave leaching 30～50min obtains one section of acidleach thing；
(2) one section of acidleach thing that step (1) is obtained according to solid-to-liquid ratio be 10～30:50～90 g/ml add concentration be 5～15
Mol/l phosphoric acid solution, under the conditions of temperature is 20～40 DEG C, ultrasound wave leaching 40～80 min obtain sulphuric leaching thing；
(3) it is passed through 0.1m3After the nitrogen air-out of/h, sulphuric leaching thing microwave heating step (2) obtained to temperature is
Activating 30～90min under the conditions of 300～500 DEG C, when activation was to last ten minutes, being passed through flow from bottom is 0.05m3The two of/h
Carbonoxide, until activation terminates, is finally cooled to room temperature and obtains activation products；
(4) activation products that step (3) obtains repeatedly are washed until cleaning mixture pH value is neutrality, be filtrated to get filtrate and
Filtering residue, reclaims residual phosphoric acid from filtrate, is dried by filtering residue and obtains activated carbon in vacuum drying oven.
Described lignosulfonates from black liquid extract process be: black liquid is the most concentrated, sulfonation, dust dry
After the crude extract that obtains be lignosulfonates.
Described step (1) and step (2) ultrasound wave leach power 100～300W.
Described step (4) vacuum drying oven vacuum is 0.005～0.01MPa.
Raw material of the present invention is papermaking wastewater crude extract-lignosulfonates, belongs to macromolecule organic material,
Belonging to nature of glass carbon after charcoal activation, quality is more brittle and hard, and its activated carbon product belongs to cellular porous material.Additionally due to it is wooden
The element organic difference of sulfonate itself, its molecular weight span is the biggest so that active carbon with high specific surface area table prepared by this method
Mainly contain the functional groups such as substantial amounts of phenolic hydroxyl group, ester group, carbonyl on face, be primarily adapted for use in catalyst and the printing and dyeing row doing noble metal
The adsorbent of discarded acid stain in industry.
The invention has the beneficial effects as follows:
(1) this method chooses black liquid crude extract-lignosulfonates to prepare activated carbon, not only achieves industrial by-product
Effective utilization of product, and reduce the production cost of activated carbon.
(2) traditional carbonization, activation preparation process amelioration are that microwave heating charcoal activation integral is efficiently prepared by this method
Activated carbon, not only make use of the dynamical advantage of microwave heating and is ensureing that preparation result has saved preparation on the basis of excellent
The required time, and technical process is become the most simple and convenient.
(3) this method takes ultrasonic assistant phosphate impregnation, utilizes ultrasound wave good directionality accurately, and penetration capacity is strong,
The advantages such as the acoustic energy relatively concentrated so that phosphoric acid is greatly promoted with the strong associativity efficiency of hydrone, organic macromolecule.
(4) present invention takes the method that activation is combined in ultrasound wave-phosphoric acid activation agent, not only shortens dip time, reduces
Activation temperature, and take full advantage of strong absorptive and the organic strong associativity advantage of phosphate anion of phosphoric acid so that
In lignosulfonates raw material, Organic substance and phosphoric acid fully react, and have had young hole to be formed before non-charcoal activates.Charcoal activation rank
Section phosphoric acid self is a small amount of H during at high temperature volatilizing or being combined with Organic substance3The effusion of P gas, at charcoal activated material table
Face diffusion forms a large amount of holes further so that carbonized material has possessed abundant microcellular structure
(5) this method mode of logical nitrogen before taking heating, it is to avoid the oxygen loss of microwave charcoal in high-temperature heating process.
(6) this method phase after activation takes the mode of logical carbon dioxide, serves the effect of carbon protection.
(7) this method is taked to activate the mode colded and heat succeed each other after material has heated, the generation extension of further hole.
(8) this method takes the principle recycled, and reclaims phosphoric acid activation agent, and the response rate can reach 76%.
Accompanying drawing explanation
Fig. 1 is the activated carbon for preparing of the embodiment of the present invention 1 adsorption isotherm line chart at 77K；
Fig. 2 is the activated carbon pore size scattergram that the embodiment of the present invention 1 prepares；
Fig. 3 is the activated carbon scanning electron microscope (SEM) photograph that the embodiment of the present invention 1 prepares.
Detailed description of the invention
Below in conjunction with the accompanying drawings and detailed description of the invention, the invention will be further described.
In experiment, specific surface area uses Full-automatic physical chemical adsorption instrument (Autosorb-1-C, Kang Ta company) to measure, iodine
Adsorptive value measures according to standard GB/T/T 12496.10-1999, and experimental water is distilled water.
Embodiment 1
The method that these black liquid crude extract-lignosulfonates prepare activated carbon, it includes step in detail below:
(1) first by 20g black liquid crude extract-lignosulfonates according to solid-to-liquid ratio be 20:80g/ml add concentration be
1mol/l hydrochloric acid solution, under the conditions of temperature is 30 DEG C, ultrasound wave leaching 40min obtains one section of acidleach thing, and wherein ultrasound wave leaches
Power 100W；
(2) one section of acidleach thing that step (1) is obtained according to solid-to-liquid ratio be 20:80g/ml add concentration be that 10mol/l phosphoric acid is molten
Liquid, under the conditions of temperature is 30 DEG C, ultrasound wave leaching 60min obtains sulphuric leaching thing, and wherein ultrasound wave leaches power 100W；
(3) it is passed through 0.1m3After the nitrogen air-out of/h, sulphuric leaching thing microwave heating step (2) obtained to temperature is
Activating 60min under the conditions of 400 DEG C, when activation was to last ten minutes, being passed through flow from bottom is 0.05m3The carbon dioxide of/h is straight
Terminate to activation, be finally cooled to room temperature and obtain activation products；
(4) activation products that step (3) obtains repeatedly are washed until cleaning mixture pH value is neutrality, be filtrated to get filtrate and
Filtering residue, reclaims residual phosphoric acid from filtrate, is entered by filtering residue in vacuum drying oven (vacuum drying oven vacuum is 0.005MPa)
Row is dried to obtain activated carbon.
Above-mentioned lignosulfonates from black liquid extract process be: black liquid is the most concentrated, sulfonation, dust dry
After the crude extract that obtains be lignosulfonates.
The activated carbon that the present embodiment prepares at the adsorption isotherm line chart of 77K as it is shown in figure 1, activated carbon pore size scattergram
As in figure 2 it is shown, activated carbon scanning electron microscope (SEM) photograph is as shown in Figure 3.Data from figure can calculate the BET of lignosulfonates and compare table
Area is 1915m2/ g, its average pore size is 2.60nm.
Embodiment 2
The method that these black liquid crude extract-lignosulfonates prepare activated carbon, it includes step in detail below:
(1) first by 10g black liquid crude extract-lignosulfonates according to solid-to-liquid ratio be 10:50g/ml add concentration be
1mol/l hydrochloric acid solution, under the conditions of temperature is 20 DEG C, ultrasound wave leaching 30min obtains one section of acidleach thing, and wherein ultrasound wave leaches
Power 300W；
(2) one section of acidleach thing that step (1) is obtained according to solid-to-liquid ratio be 10:50g/ml add concentration be that 5mol/l phosphoric acid is molten
Liquid, under the conditions of temperature is 20 DEG C, ultrasound wave leaching 40min obtains sulphuric leaching thing, and wherein ultrasound wave leaches power 300W；
(3) it is passed through 0.1m3After the nitrogen air-out of/h, sulphuric leaching thing microwave heating step (2) obtained to temperature is
Activating 30min under the conditions of 300 DEG C, when activation was to last ten minutes, being passed through flow from bottom is 0.05m3The carbon dioxide of/h is straight
Terminate to activation, be finally cooled to room temperature and obtain activation products；
(4) activation products that step (3) obtains repeatedly are washed until cleaning mixture pH value is neutrality, be filtrated to get filtrate and
Filtering residue, reclaims residual phosphoric acid from filtrate, is carried out by filtering residue in vacuum drying oven (vacuum drying oven vacuum is 0.01MPa)
It is dried to obtain activated carbon.
Above-mentioned lignosulfonates from black liquid extract process be: black liquid is the most concentrated, sulfonation, dust dry
After the crude extract that obtains be lignosulfonates.
Embodiment 3
The method that these black liquid crude extract-lignosulfonates prepare activated carbon, it includes step in detail below:
(1) first by black liquid crude extract-lignosulfonates according to solid-to-liquid ratio be 30:90g/ml add concentration be
1mol/l hydrochloric acid solution, under the conditions of temperature is 40 DEG C, ultrasound wave leaching 50min obtains one section of acidleach thing, and wherein ultrasound wave leaches
Power 200W；
(2) one section of acidleach thing that step (1) is obtained according to solid-to-liquid ratio be 30:90g/ml add concentration be that 15mol/l phosphoric acid is molten
Liquid, under the conditions of temperature is 40 DEG C, ultrasound wave leaching 80min obtains sulphuric leaching thing, and wherein ultrasound wave leaches power 200W；
(3) it is passed through 0.1m3After the nitrogen air-out of/h, sulphuric leaching thing microwave heating step (2) obtained to temperature is
Activating 90min under the conditions of 500 DEG C, when activation was to last ten minutes, being passed through flow from bottom is 0.05m3The carbon dioxide of/h is straight
Terminate to activation, be finally cooled to room temperature and obtain activation products；
(4) activation products that step (3) obtains repeatedly are washed until cleaning mixture pH value is neutrality, be filtrated to get filtrate and
Filtering residue, reclaims residual phosphoric acid from filtrate, is entered by filtering residue in vacuum drying oven (vacuum drying oven vacuum is 0.008MPa)
Row is dried to obtain activated carbon.
Above-mentioned lignosulfonates from black liquid extract process be: black liquid is the most concentrated, sulfonation, dust dry
After the crude extract that obtains be lignosulfonates.
Above in association with accompanying drawing, the detailed description of the invention of the present invention is explained in detail, but the present invention is not limited to above-mentioned
Embodiment, in the ken that those of ordinary skill in the art are possessed, it is also possible to before without departing from present inventive concept
Put that various changes can be made.
Claims (4)
1. the method that black liquid crude extract-lignosulfonates prepare activated carbon, it is characterised in that include following tool
Body step:
(1) first by black liquid crude extract-lignosulfonates according to solid-to-liquid ratio be 10～30:50～90 g/ml add
Concentration is 1mol/l hydrochloric acid solution, and under the conditions of temperature is 20～40 DEG C, ultrasound wave leaching 30～50min obtains one section of acidleach thing；
(2) one section of acidleach thing that step (1) is obtained according to solid-to-liquid ratio be 10～30:50～90g/ml add concentration be 5～
15mol/l phosphoric acid solution, under the conditions of temperature is 20～40 DEG C, ultrasound wave leaching 40～80min obtains sulphuric leaching thing；
(3) it is passed through 0.1m3After the nitrogen air-out of/h, sulphuric leaching thing microwave heating step (2) obtained to temperature is
Activating 30～90min under the conditions of 300～500 DEG C, when activation was to last ten minutes, being passed through flow from bottom is 0.05m3/ h unit
Carbon dioxide until activation terminate, be finally cooled to room temperature and obtain activation products；
(4) activation products that step (3) obtains repeatedly are washed until cleaning mixture pH value is neutrality, be filtrated to get filtrate and
Filtering residue, reclaims residual phosphoric acid from filtrate, is dried by filtering residue and obtains activated carbon in vacuum drying oven.
The method that black liquid crude extract-lignosulfonates the most according to claim 1 prepare activated carbon, its feature
Be: described lignosulfonates extract process from black liquid and are: black liquid is the most concentrated, sulfonation, dust dried
The crude extract obtained is lignosulfonates.
The method that black liquid crude extract-lignosulfonates the most according to claim 1 prepare activated carbon, its feature
It is: described step (1) and step (2) ultrasound wave leach power 100～300W.
The method that black liquid crude extract-lignosulfonates the most according to claim 1 prepare activated carbon, its feature
It is: described step (4) vacuum drying oven vacuum is 0.005～0.01MPa.
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