CN103480351A - Regeneration method for active carbon contaminated by metal or/and cleaning agent - Google Patents
Regeneration method for active carbon contaminated by metal or/and cleaning agent Download PDFInfo
- Publication number
- CN103480351A CN103480351A CN201210194313.6A CN201210194313A CN103480351A CN 103480351 A CN103480351 A CN 103480351A CN 201210194313 A CN201210194313 A CN 201210194313A CN 103480351 A CN103480351 A CN 103480351A
- Authority
- CN
- China
- Prior art keywords
- called
- short
- activated carbon
- metal
- cleaning agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention relates to a regeneration method for active carbon contaminated by metal or/and a cleaning agent. The regeneration method comprises: a fluid washing step, wherein contaminated active carbon is placed into an accommodation chamber, a removing agent is introduced into the accommodation chamber to carry out fluid washing on the active carbon, a pressure in the accommodation chamber is more than 74 bar, a temperature in the accommodation chamber is higher than 32 DEG C, and the removing agent contains a supercritical carbon dioxide fluid, an auxiliary solvent and a metal compounding agent; and a replacement separation step, wherein a replacement fluid is introduced into the accommodation chamber to replace the removing agent in the accommodation chamber, and then the replacement fluid and the active carbon are separated so as to achieve an active carbon regeneration purpose.
Description
Technical field
The present invention is about a kind of activated carbon renovation process, especially in regard to a kind of, can process linear alkylbenzene sulfonate (LAS) in activated carbon and the method for cobalt metal simultaneously, reduces the content of linear alkylbenzene sulfonate (LAS) and cobalt metal in activated carbon, and activated carbon can be recycled.
Background technology
Along with the progress of domestic industry, science and technology is constantly flourishing, and the mankind grow with each passing day for the demand of electric power.Although the consumption of the energy be take oil, coal, these fossil fuels of natural gas as main in the world now, because fossil fuel is discharged a large amount of refuse waste gas, contaminated environment, discharge great amount of carbon dioxide, cause global greenhouse effect, so various countries start Nuclear Power Development, with in response to electricity needs.Because the gas produced in nuclear power plant or waste water may contain the radioactivity nuclear species, such as cobalt etc., can first use active carbon filtration as gas or waste water discharge nuclear power plant are last, just remaining clean gas or waste water can be discharged, and in processing procedure with the activated carbon of crossing owing to containing the radioactivity nuclear species, therefore activated carbon must be incinerated again, after Pintsch process, then is cured, and therefore final radioactive waste generation is large.If activated carbon regeneration can be used, not only can reduce the output of radioactive waste, also can reduce the operation running cost of nuclear power plant.
For the resource of this recyclable recycling of activated carbon, incinerating and solidifying is processing method not good and waste in fact, and best mode reclaims activated carbon and the use of regenerating exactly effectively, to reach the purpose of recycling.Yet, except the radioactivity nuclear species, nuclear power plant cleans greasy dirt or cleans the cleaning agent that the anti-clothing of spoke is used, also can be adsorbed in activated carbon, the main component of these cleaning agents, be generally linear alkylbenzene sulfonate (LAS) (LAS), in order to reach the purpose of activated carbon regeneration, need a kind of activated carbon renovation process that can simultaneously remove radioactivity nuclear species and cleaning agent of exploitation.
The renovation process of existing activated carbon is mainly to use concentrated hydrochloric acid to be cleaned metal wherein, remove and wash rear residual hydrochloric acid with a large amount of water again, but the acid waste liquid amount produced is large and have a radioactivity, therefore the radioactivity problem caused with regeneration of hydrochloric acid is larger, the use so the activated carbon of nuclear power plant generally can not regenerated, the discarded activated carbon amount of piling up after running for years is large, causes the puzzlement in power plant's operation.
Although prior art provides regeneration techniques and the method for metal processing of activated carbon, do not reach yet the target of simple, low-cost, the few waste liquid of processing procedure and low power consuming.Accordingly, be necessary to provide a kind of cleaning agent and the metal radioactivity nuclear species that can simultaneously process in activated carbon, and can reduce the activated carbon renovation process of the energy and water resources consumption.
Reference:
1. Guo Ya is glad, the difficult problem that can not escape-nuclear waste disposal, science man's magazine number the 76th phase in June, 2008.
2. father-in-law's Golconda, Taiwan radioactive waste historical narrative.
Summary of the invention
Main purpose of the present invention is to provide a kind of activated carbon renovation process that polluted by metal or/and cleaning agent, and it can effectively remove cleaning agent and metal nuclear species in activated carbon.
Of the present invention time a purpose is to provide a kind of activated carbon renovation process that polluted by metal or/and cleaning agent, and it can reduce the consumption of organic solvent and water resource.
Another purpose of the present invention is to provide a kind of activated carbon renovation process that polluted by metal or/and cleaning agent, and it can remove linear alkylbenzene sulfonate (LAS) and cobalt metal in activated carbon with remover simultaneously.
For reaching aforementioned goal of the invention, the activated carbon renovation process that polluted by metal or/and cleaning agent of the present invention comprises: the first-class step of washing, that activated carbon is placed in a room, one remover passes into this room to carry out stream to activated carbon and washes, wherein, pressure in this room is more than 74bar, and the temperature in this room is more than 32 ℃, and this remover comprises supercritical carbon dioxide fluid, a secondary solvent and a metal composite agent; Reaching a displacement separating step, is that a displacement fluid is passed into to this room, to replace the remover in this room, then by this displacement fluid and activity carbon separation.
In the activated carbon renovation process that the present invention is polluted by metal or/and cleaning agent, this metal composite agent can be chosen as Bis-trifluoroethyldithiocarbamate(two-tri-and fluoridize dithiocarbamate salt, be called for short FDDC), the Diethyldithiocarbamate(diethyldithiocar bamic acid, be called for short DDC), the Dipropyl-dithiocarbamate(dipropyl disulfide is for carbaminate, be called for short P3DC), Dibutyldithiocarbamate(dibutyl dithiocaarbamate salt, be called for short BDC), Dipentyldithiocarbamate(diamyl dithiocarbamate salt, be called for short P5DC), Dihexyldithiocarbamate(dihexyl dithiocar-bamate, be called for short P6DC), the Pyrrolidine-dithiocarbamate(pyrrolidine dithiocarbamate, be called for short PDC), Acetylacetone(2, the 4-pentanedione, be called for short AA), Trifluoroacetylacetone(1, 1, 1-tri-fluoro-2, the 4-pentanedione, be called for short TFA), the Hexafluoroacetyl-acetone(hexafluoroacetylacetone, be called for short HFA), the Thenoyltrifluoroacetone(2-TTA, be called for short TTA), Heptafluorobutanoyl-pivaroylmethane(2, 2-dimethyl-6, 6, 7, 7, 8, 8, 8,-seven fluoro-3, the 5-acetyl caproyl, be called for short FOD), the Tributylphosphate(tributyl phosphate, be called for short TBP), Tributylphosphine oxide(tributylphosphine oxide, be called for short TBPO), Trioctylphosphine oxide(TOPO, be called for short TOPO), Triphenyl-phosphine oxide(triphenylphosphine oxide, be called for short TPPO), Bis (2, 4, 4,-trimethylpentyl) phosphinic acid(bis-(2, 4, the 4-tri-methyl-amyl) phosphonic acids, be called for short Cyanex 272), Bis (2, 4, 4,-trimethyl-pentyl) dithiophosphinic acid(bis-(2, 4, the 4-tri-methyl-amyl) phosphonodithioic acid, be called for short Cyanex 301), Bis (2, 4, 4,-trimethylpentyl) monothiophosphinic acid(bis-(2, 4, the 4-tri-methyl-amyl) phosphonothiolic acid, be called for short Cyanex 302), Di (2-ethylhexyl) phosphoric acid(di-(2-ethylhexyl)phosphoric acid, be called for short D2EHPA) or Crown ether (crown ether).
In the activated carbon renovation process that the present invention is polluted by metal or/and cleaning agent, this metal composite agent is more preferred from Di (2-ethylhexyl) phosphoric acid.
In the activated carbon renovation process that the present invention is polluted by metal or/and cleaning agent, this secondary solvent is preferably low carbon number alkanes or alcohols, and its carbon number is 1 to 6, and better system is chosen as methyl alcohol or n-hexane.
In the activated carbon renovation process that the present invention is polluted by metal or/and cleaning agent, the pressure in this room is, more than 74bar, to be preferably 100 ~ 350bar.And the temperature in this room is more than 32 ℃, is preferably 35 ~ 120 ℃.
In the activated carbon renovation process that the present invention is polluted by metal or/and cleaning agent, the percentage by weight that this secondary solvent accounts for this remover is preferably 1.0 ~ 20.0%, the percentage by weight that this metal composite agent accounts for this remover is preferably 0.1 ~ 9.0%, and the percentage by weight that this supercritical carbon dioxide fluid accounts for this remover is preferably 79.9 ~ 98.9%.
A kind of in order to remove the remover of linear alkylbenzene sulfonate (LAS) and cobalt metal in activated carbon, comprise: the secondary solvent that a percentage by weight is 1.0 ~ 20.0%; The metal composite agent that one percentage by weight is 0.1 ~ 9.0%; And the percentage by weight supercritical carbon dioxide fluid that is 79.9 ~ 98.9%.
Of the present invention in order in the remover of removing linear alkylbenzene sulfonate (LAS) and cobalt metal in activated carbon, this metal composite agent can be chosen as Bis-trifluoro-ethyldithiocarbamate(two-tri-and fluoridize dithiocarbamate salt, be called for short FDDC), the Diethyldithiocarbamate(diethyldithiocar bamic acid, be called for short DDC), the Dipropyldithiocarbamate(dipropyl disulfide is for carbaminate, be called for short P3DC), Dibutyldithiocarbamate(dibutyl dithiocaarbamate salt, be called for short BDC), Dipentyl-dithiocarbamate(diamyl dithiocarbamate salt, be called for short P5DC), Dihexyldithiocarbamate(dihexyl dithiocar-bamate, be called for short P6DC) or the Pyrrolidinedithiocarbamate(pyrrolidine dithiocarbamate, be called for short PDC), Acetylacetone(2, the 4-pentanedione, be called for short AA), Trifluoroacetylacetone(1, 1, 1-tri-fluoro-2, the 4-pentanedione, be called for short TFA), the Hexafluoroacetylacetone(hexafluoroacetylacetone, be called for short HFA), the Thenoyl-trifluoroacetone(2-TTA, be called for short TTA) or Heptafluorobutanoyl-pivaroylmethane(2, 2-dimethyl-6, 6, 7, 7, 8, 8, 8,-seven fluoro-3, the 5-acetyl caproyl, be called for short FOD), the Tributylphosphate(tributyl phosphate, be called for short TBP), Tributylphosphine oxide(tributylphosphine oxide, be called for short TBPO), Trioctyl-phosphine oxide(TOPO, be called for short TOPO), Triphenylphosphine oxide(triphenylphosphine oxide, be called for short TPPO), Bis (2, 4, 4,-trimethylpentyl) phosphinic acid (two (2, 4, the 4-tri-methyl-amyl) phosphonic acids, be called for short Cyanex 272), Bis (2, 4, 4,-trimethylpentyl) dithio-phosphinic acid(bis-(2, 4, the 4-tri-methyl-amyl) phosphonodithioic acid, be called for short Cyanex301), Bis (2, 4, 4,-trimethyl-pentyl) monothiophosphinic acid(bis-(2, 4, the 4-tri-methyl-amyl) phosphonothiolic acid, be called for short Cyanex 302), Di (2-ethylhexyl) phosphoric acid(di-(2-ethylhexyl)phosphoric acid, be called for short D2EHPA) or Crown ether (crown ether).
Of the present invention in order in the remover of removing linear alkylbenzene sulfonate (LAS) and cobalt metal in activated carbon, this metal composite agent is more preferred from D2EHPA.
Of the present invention in order in the remover of removing linear alkylbenzene sulfonate (LAS) and cobalt metal in activated carbon, this secondary solvent is preferably low carbon number alkanes or alcohols, and its carbon number is 1 to 6, better methyl alcohol or the n-hexane of being chosen as.
The accompanying drawing explanation
Fig. 1: the step block diagram of the activated carbon renovation process that the present invention is polluted by metal and cleaning agent.
Fig. 2: the present embodiment activated carbon is for the isothermal adsorption curve map of dodecyl benzene sulfonic acid sodium salt.
Fig. 3: the super critical fluid apparatus configuration schematic diagram that the present embodiment provides.
Fig. 4: the present embodiment cobalt metal removal rate curve map.
[main element symbol description]
1 stream is washed step 2 displacement separating step
3 electric hybrid module 31 carbon dioxide grooves
32 secondary solvents and metal composite agent groove 33 rooms
4 pressure assembly 41 first counterbalance valves
42 second counterbalance valve 5 separating tanks
51 first outlet 52 second outlets.
The specific embodiment
For above-mentioned and other purpose of the present invention, feature and advantage can be become apparent, the present invention's cited below particularly preferred embodiment, and coordinate accompanying drawing, be described in detail below:
Please refer to shown in Fig. 1, the activated carbon renovation process that the present invention is polluted by metal and cleaning agent comprises first-class step 1 and the displacement separating step 2 washed.
This stream is washed step 1, will be subject to the activated carbon that pollutes of metal or/and cleaning agent be placed in a room, a remover passes into this room to carry out stream to activated carbon and washes, this remover comprises supercritical carbon dioxide fluid, a secondary solvent and a metal composite agent.Wherein, operating pressure and temperature that pressure in this room and temperature are defined as this supercritical carbon dioxide fluid, usually know that for having in this field the knowledgeable can understand, especially as shown in this embodiment, pressure in this room is more than 74bar, and it is good making especially the interior pressure of room maintain approximately 100 ~ 350bar; Temperature in this room is more than 32 ℃, makes especially temperature in room maintain approximately 35 ~ 120 ℃ for good.In more detail, the pressure of this room and temperature conditions contribute to maintain polarity (Polarity) characteristic of the contained supercritical carbon dioxide fluid of this remover, with the cleaning agent in lytic activity carbon, the contained secondary solvent of this remover contributes to dissolve this metal composite agent, and by the temperature in this room, pressure condition, help this metal composite agent that the radioactivity nuclear species in activated carbon is dissolved in this remover, make whereby cleaning agent and radioactivity nuclear species desorption in activated carbon, the cleaning agent and the radioactivity nuclear species content that make to be adsorbed on activated carbon reduce.
For example, this secondary solvent is as the dilute solution of this metal composite agent, this secondary solvent is preferably alkanes or the alcohols of low carbon number (C1 ~ C6), particularly methyl alcohol or n-hexane are as the dilute solution of metal composite agent, not only contribute to improve the adsorptivity of metal composite agent, can help to change again the polar character of this supercritical carbon dioxide fluid; This metal composite agent can be chosen as the organic compound of metal-chelating or coordination, and the metal composite agent can be divided into four classes haply: the agent of (1) dithiocarbamates (dithiocarbamate) metal composite, the agent of (2) diketone class (diketone) metal composite, the agent of (3) organic phosphates metal composite and (4) large lopps metal composite agent.
The agent of dithiocarbamates metal composite comprise as:
Bis-trifluoroethyldithiocarbamate(two-tri-fluoridizes dithiocarbamate salt, be called for short FDDC), the Diethyl-dithiocarbamate(diethyldithiocar bamic acid, be called for short DDC), the Dipropyldithiocarbamate(dipropyl disulfide is for carbaminate, be called for short P3DC), Dibutyldithiocarbamate(dibutyl dithiocaarbamate salt, be called for short BDC), Dipentyl-dithiocarbamate(diamyl dithiocarbamate salt, be called for short P5DC), Dihexyldithiocarbamate(dihexyl dithiocar-bamate, be called for short P6DC) or the Pyrrolidinedithiocarbamate(pyrrolidine dithiocarbamate, be called for short PDC).
Diketone metalloid complexing agent comprises as Acetylacetone(2, the 4-pentanedione, be called for short AA), Trifluoroacetylacetone(1,1,1-tri-fluoro-2, the 4-pentanedione, be called for short TFA), the Hexafluoroacetylacetone(hexafluoroacetylacetone, be called for short HFA), the Thenoyltrifluoroacetone(2-TTA, be called for short TTA) or Heptafluorobutanoyl-pivaroylmethane(2,2-dimethyl-6,6,7,7,8,8,8 ,-seven fluoro-3, the 5-acetyl caproyl, be called for short FOD).
The agent of organic phosphates metal composite comprises the tributyl phosphate as Tributylphosphate(, be called for short TBP), Tributylphosphine oxide(tributylphosphine oxide, be called for short TBPO), Trioctylphosphine oxide(TOPO, be called for short TOPO), Triphenylphosphine oxide(triphenylphosphine oxide, be called for short TPPO), Bis (2, 4, 4,-trimethylpentyl) phosphinic acid(bis-(2, 4, the 4-tri-methyl-amyl) phosphonic acids, be called for short Cyanex 272), Bis (2, 4, 4,-trimethylpentyl) dithio-phosphinic acid(bis-(2, 4, the 4-tri-methyl-amyl) phosphonodithioic acid, be called for short Cyanex 301), Bis (2, 4, 4,-trimethyl-pentyl) monothiophosphinic acid(bis-(2, 4, the 4-tri-methyl-amyl) phosphonothiolic acid, be called for short Cyanex 302) or Di (2-ethylhexyl) phosphoric acid(abbreviation D
2eHPA).
Large lopps metal composite agent, as Crown ether (crown ether).
The metal composite agent of the present embodiment is chosen as D
2eHPA, can be with supercritical carbon dioxide fluid and this secondary solvent mating reaction the cobalt metal on activated carbon, and can not reduce the effect that originally supercritical carbon dioxide fluid dissolves cleaning agent, especially the effect of linear alkylbenzene sulfonate (LAS) in lytic activity carbon, can maintain again the efficiency of the composite metal ion of metal composite agent own.The present invention selects the carbon dioxide that the above-critical state maintenance condition is lower (31.1 ℃ of critical pressure 72bar and critical-temperatures), especially dissolve the primary solvent of alkylbenzenesulfonate as the dissolving cleaning agent, can reduce the energy consumption for preparing supercritical fluid, and (pressure is more than 74bar for the pressure by controlling this supercritical carbon dioxide fluid and temperature, 100 ~ 350bar particularly, temperature is more than 32 ℃, particularly 35 ~ 120 ℃), adjust the polar character of this supercritical carbon dioxide fluid, and can be effectively and tool optionally dissolve cleaning agent, especially alkylbenzenesulfonate, in addition, because carbon dioxide is obtained easily, and it is colourless, tasteless, avirulent, explosive, the nonflammable also non-corrosiveness of tool not, therefore safe.
In addition, this supercritical carbon dioxide fluid contributes to activated carbon, to contact equably, and, by the polarity of supercritical carbon dioxide fluid, the radioactivity nuclear species is discharged, and the radioactivity nuclear species that this metal composite agent captures in activated carbon also is dissolved in this remover.So, the activated carbon renovation process that the present invention is polluted by metal or/and cleaning agent is the cleaning agent in lytic activity carbon effectively, especially alkylbenzenesulfonate, also can, by the effect of this metal composite agent and this supercritical carbon dioxide fluid, improve the effect to the combined efficiency of cobalt metal ion in activated carbon.
This replaces separating step 2, and a displacement fluid is passed into to this room, to replace the remover in this room, by this displacement fluid and activity carbon separation.In more detail, this displacement fluid can be chosen as supercritical fluid, the present embodiment is selected to replace the remover in this room with supercritical carbon dioxide fluid, again by reducing the pressure in this room, make this supercritical carbon dioxide fluid become gas phase, recycle after can selecting directly to drain in external environment by carbon dioxide or reclaiming this carbon dioxide; It is identical that the present embodiment is reduced to the temperature, pressure outer with room by this volume pressure, and carbon dioxide is directly discharged outside room, and the activated carbon in this room has completed the removal of cleaning agent and radioactivity nuclear species.
So, the activated carbon renovation process that the present invention is polluted by metal or/and cleaning agent, can reduce the use of organic solvent, and not needing to expend excessive power is heated activated carbon and this remover, do not need to utilize a large amount of aqueous cleaning activated carbon yet, in addition, this can't residual organic solvent in the activated carbon of resource, and can really reduce cleaning agent and the radioactivity nuclear species content in activated carbon.
For proved is invented the activated carbon renovation process that polluted by metal or/and cleaning agent, really can process cleaning agent and radioactivity nuclear species in activated carbon simultaneously, and effectively reduce the content of cleaning agent in activated carbon, and the radioactivity nuclear species in the reduction activated carbon, the present embodiment is soaked in 48hr in the dodecyl benzene sulfonic acid sodium salt of 5 liters and the aqueous solution of cobalt nitrate (wherein the concentration of the aqueous solution of dodecyl benzene sulfonic acid sodium salt and cobalt nitrate is 30g/L) by 1 kilogram of activated carbon, form the activated carbon sample that simulation is polluted by metal and cleaning agent after drying, and carry out following test: (A) the linear alkylbenzene sulfonate (LAS) content analysis of activated carbon sample, (B) the cobalt metal content analysis of activated carbon sample, (D) linear alkylbenzene sulfonate (LAS) that uses the different auxiliary cosolvent to remove in the activated carbon sample is tested and (E) uses the different auxiliary cosolvent to remove the cobalt metallographictest in the activated carbon sample.
(A) the linear alkylbenzene sulfonate (LAS) content analysis of activated carbon sample
The detection method of the described linear alkylbenzene sulfonate (LAS) content of the present embodiment is analyzed with ultraviolet light/visible spectrometry (UV/VIS), and analytical method is as follows:
1, prepare respectively 100,250,400,600,800 and the linear alkylbenzene sulfonate (LAS) aqueous solution of the variable concentrations such as 1000mg/L, the concentration of above-mentioned each linear alkylbenzene sulfonate (LAS) aqueous solution is defined as initial concentration C
i;
2, fresh activated carbon is soaked in above-mentioned each concentration linear alkylbenzene sulfonate (LAS) aqueous solution after 48hr, by the activated carbon filtering, obtains a soak;
3, measure the trap of each soak with ultraviolet light/visible spectrometry under wavelength 230nm, and calculate its concentration, be defined as equilibrium concentration C
f;
4, utilize formula Q=V * (C
i-C
f)/M
1calculate in each soak, the adsorbance Q of activated carbon, and with C
ffor abscissa, Q is ordinate, draws isothermal adsorption curve as shown in Figure 2, and wherein: the volume that V is the linear alkylbenzene sulfonate (LAS) aqueous solution, unit is mL, M
1for the weight of fresh activated carbon, unit is g;
The activated carbon that 5, polluted by metal and cleaning agent is soaked in deionized water after 48hr, by the activated carbon filtering, and, after utilizing ultraviolet light/visible spectrometry to measure the trap of filtrate, calculates its equilibrium concentration C
f, then according to its adsorbance of isothermal adsorption line computation Q, and then use W
lAS=Q * M
2relational expression calculated activity carbon in the content (W of linear alkylbenzene sulfonate (LAS)
lAS), M
2weight for contaminated activated carbon.
In each gram sample of activated carbon that polluted by metal and cleaning agent of the present embodiment, the content of linear alkylbenzene sulfonate (LAS) is approximately 31.00mg.
(B) the cobalt metal content analysis of activated carbon sample
The detection method of the described activated carbon sample of the present embodiment cobalt tenor is analyzed by induction coupled plasma Anlysis of Emission spectrometry (ICP-OES), and analytical method is as follows:
1, by about 0.1g (W
a) be placed in microwave digesting tank through the activated carbon of immersion;
2, sequentially add 4.5mL nitric acid and 4.5mL hydrogen peroxide;
3, place the 20min question response and finish, digester is put into to the microwave digestion device;
4, microwave digestion device operating temperature is set as 220 ℃, and the heating-up time is set as 20min, and holding the temperature time is 50min;
5, digester is placed in water-bath to 20min after lowering the temperature, by digestive juice with deionized water quantitatively to 25mL;
6, after above-mentioned digestive juice is filtered, be placed in the sky test tube, and prepare against and analyze with the sealed membrane sealing.
7, will analyze the heavy metal cobalt obtained and contain concentration C
a, be multiplied by volume 0.025L and be multiplied by again 150g and be written into cleaning active carbon in room, then divided by the activated carbon weight W that is placed in digester
a, the remaining heavy metal weight of cobalt W that fails to wash out on known activated carbon
aCo.As following relational expression W
aCo=C
a* 0.025 * 150/W
a.
In each gram sample of activated carbon that polluted by metal and cleaning agent of the present embodiment, the content of linear alkylbenzene sulfonate (LAS) is approximately 14.33mg.
(C) the cobalt metal content analysis of secondary solvent and metal composite agent
The detection method of the cobalt tenor of the described secondary solvent of the present embodiment and metal composite agent is analyzed by induction coupled plasma Anlysis of Emission spectrometry (ICP-OES), and analytical method is as follows:
1. by about 1mL (V
e) secondary solvent and metal composite agent sample be placed in microwave digesting tank;
2. microwave digesting tank is placed in to 60 ℃ of lower baking oven 4hr, to remove methyl alcohol or n-hexane;
3. sequentially add 4mL nitric acid and 3mL hydrogen peroxide;
4. the microwave digestion actuator temperature is set 200 ℃, and the heating-up time is set 3min, holds temperature time 35min;
5. digester is placed in water-bath to 20min after lowering the temperature, by digestive juice with deionized water quantitatively to 25mL;
6., after above-mentioned digestive juice being filtered, be placed in the sky test tube, and prepare against and analyze with the sealed membrane sealing;
7. heavy metal cobalt icp analysis obtained is containing concentration C
e, be multiplied by quantitative volume 0.025L and secondary solvent and metal composite agent cumulative volume V
eT, then divided by the secondary solvent that is placed in digester and metal composite agent volume V
e, can learn the content W of heavy metal cobalt in original auxiliary cosolvent and metal composite agent
eCo.As following relational expression W
eCo=C
e* 0.025 * V
eT/ V
e.
(D) use the different auxiliary cosolvent to remove the linear alkylbenzene sulfonate (LAS) test in the activated carbon sample
The present embodiment provides a super critical fluid apparatus as shown in Figure 3, it comprises an electric hybrid module 3, a pressure assembly 4 and a separating tank 5, and this electric hybrid module 3 and this separating tank 5 are interconnected, and control the internal pressure of these electric hybrid modules 3 and this separating tank 5 with this pressure assembly 4.
This electric hybrid module 3 is provided with a carbon dioxide groove 31, secondary solvent and metal composite agent groove 32 and a room 33, this carbon dioxide groove 31 and this secondary solvent are communicated with this room 33 with metal composite agent groove 32, this carbon dioxide groove 31 is in order to accommodating carbon dioxide, this secondary solvent and metal composite agent groove 32 in order to accommodating this secondary solvent (as methyl alcohol or n-hexane) and this metal composite agent (as D
2eHPA), this room 33 is processed sample in order to an accommodating wish, this carbon dioxide groove 31 and this secondary solvent and metal composite agent groove 32 have the function (as heater H or the cooler C of accompanying drawing sign) of regulating tank internal temperature and pressure, all be connected with separately infusion pump P and flow regulator F internal solution is delivered in this room 33.
This pressure assembly 4 comprises one first counterbalance valve 41 and one second counterbalance valve 42, and wherein this first counterbalance valve 41 is controlled the internal pressure of this room 33, and this second counterbalance valve 42 is controlled the internal pressure of this separating tank 5.
This separating tank 5 includes one first outlet 51 and 1 second outlet 52, these the first outlet 51 supplied gas loss are to environment or a collecting vessel groove (figure do not illustrate), and this second 52 of outlet can make this secondary solvent mixed with cobalt metal and linear alkylbenzene sulfonate (LAS) and metal composite agent outflow.
The operating instruction of the present embodiment super critical fluid apparatus is as follows: an activated carbon sample is placed in to this room 33, make temperature and the pressure condition of this room 33 reach preset value, adjusting this operation secondary solvent is 4.5mL/min (wherein secondary solvent mixes with the volume ratio of metal composite agent with 1:1) with the volume flow rate that the fluid of metal composite agent flows into this room 33 again, and sets and wash a period of time (as 3 ~ 6 hours) to start to remove linear alkylbenzene sulfonate (LAS) and the cobalt metal of this sample with the carbon dioxide flow velocity stream of 30g/min; This operating fluid flow in this separating tank 5 from this room 33, and the pressure decreased of this separating tank 5, to 40bar, is made to this supercritical carbon dioxide fluid vaporization, and this carbon dioxide can reclaim and re-use, or directly drains in environment; The extraction fluid of a secondary solvent and metal composite agent is left in these separating tank 5 inside, it includes linear alkylbenzene sulfonate (LAS), metal composite agent and the metal composite agent compound with cobalt, activated carbon in this room 33 has been removed linear alkylbenzene sulfonate (LAS) wherein, and can be recycled.
For example, this first embodiment first is placed in this room 33 by this activated carbon sample (approximately 150 grams), and with this secondary solvent (methyl alcohol), this metal composite agent (D
2eHPA) with this supercritical carbon dioxide fluid according to better percentage by weight be respectively 5.3%, 6.4% and 88.3% mix after, take the carbon dioxide flow velocity as 30g/min, this room 33 and flow velocity that secondary solvent and metal composite agent flow velocity are 4.5mL/min is flowed through, treat that the stream time of washing finishes to take out this activated carbon sample, the linear alkylbenzene sulfonate (LAS) total content of more treated and undressed activated carbon sample is respectively 466.56mg and 4649.58mg, calculates its linear alkylbenzene sulfonate (LAS) clearance and can reach 89.97%.
This second embodiment is placed in this room 33 by another activated carbon sample (approximately 150 grams) subsequently, and with this secondary solvent (n-hexane), this metal composite agent (D2EHPA) is respectively 4.4% with this supercritical carbon dioxide fluid according to better percentage by weight, after 6.5% and 89.1% mixing, take the carbon dioxide flow velocity as 30g/min, this room 33 and flow velocity that secondary solvent and metal composite agent flow velocity are 4.5mL/min is flowed through, treat that the stream time of washing finishes to take out this activated carbon sample, the linear alkylbenzene sulfonate (LAS) content of more treated and undressed activated carbon sample is respectively 290.33mg and 4565.42mg, calculate its linear alkylbenzene sulfonate (LAS) clearance and can reach 93.64%.
The activated carbon sample that this first and second embodiment processes, analyze its linear alkylbenzene sulfonate (LAS) clearance in the mode of test (A); Hence one can see that, uses methyl alcohol and n-hexane all can obtain the approximately linear alkylbenzene sulfonate (LAS) clearance more than 90% as secondary solvent.
(E) use the different auxiliary cosolvent to remove the cobalt metallographictest in the activated carbon sample
This first and second embodiment is when stream is washed step, respectively get two groups of activated carbon samples and 30,60,90,120,150 and extract remainder samples of collecting in this second outlet 52 of 180min carry out the cobalt metal content analysis with the method for test (B) and test (C) respectively, wherein: the methyl alcohol of take is 243.87mg as the cobalt tenor of the handled activated carbon sample of the first embodiment of secondary solvent, and cobalt tenor and clearance of its extraction fluid sample please refer to shown in the first table; The n-hexane of take is 288.25mg as the cobalt tenor of the handled activated carbon of the second embodiment of secondary solvent, and cobalt tenor and clearance of its extraction fluid sample please refer to shown in the second table.
The first table: the first embodiment be take cobalt content and the clearance that methyl alcohol is secondary solvent test
| Time (min) | Cobalt content (mg) | Cobalt cumulative amount (mg) | Clearance (%) |
| 0 | 0 | 0 | 0 |
| 30 | 263.55 | 263.55 | 13.44 |
| 60 | 458.71 | 722.26 | 36.84 |
| 90 | 447.37 | 1169.63 | 59.65 |
| 120 | 281.33 | 1450.96 | 74.00 |
| 150 | 151.07 | 1602.03 | 81.71 |
| 180 | 92.48 | 1694.51 | 86.42 |
The second table: the second embodiment be take cobalt content and the clearance that n-hexane is secondary solvent test
| Time (min) | Cobalt content (mg) | Cobalt cumulative amount (mg) | Clearance (%) |
| 0 | 0 | 0 | 0 |
| 30 | 238.59 | 238.59 | 11.95 |
| 60 | 835.23 | 1073.82 | 53.81 |
| 90 | 349.14 | 1422.96 | 71.30 |
| 120 | 172.61 | 1595.57 | 79.95 |
| 150 | 71.51 | 1667.08 | 83.53 |
| 180 | 31.43 | 1698.51 | 85.11 |
The clearance of extraction fluid sample is to utilize following relational expression to calculate to obtain:
By the above results, the present invention can draw clearance curve map as shown in Figure 4.As seen from the figure, use methyl alcohol or n-hexane as secondary solvent, all can effectively remove the metallic cobalt in activated carbon.For activated carbon regeneration and recycling, after processing via method of the present invention, whole cobalt tenor obviously descends.
From above result, the present invention can reduce linear alkylbenzene sulfonate (LAS) and the cobalt tenor in this activated carbon really simultaneously, and according to contained linear alkylbenzene sulfonate (LAS) in activated carbon and cobalt tenor, selection is usingd methyl alcohol or n-hexane as secondary solvent, all can improve the efficiency of processing linear alkylbenzene sulfonate (LAS) or cobalt metal.From the above, the activated carbon renovation process that the present invention is polluted by metal and cleaning agent can effectively improve the treatment effeciency to linear alkylbenzene sulfonate (LAS) in activated carbon and cobalt metal really.
Accordingly, the activated carbon renovation process that the present invention is polluted by metal or/and cleaning agent, can utilize this supercritical carbon dioxide fluid, secondary solvent and metal composite agent, provide than at the temperature and pressure condition of low power consuming, by the linear alkylbenzene sulfonate (LAS) in activated carbon and cobalt metal, there is the effect of the treatment effeciency that improves linear alkylbenzene sulfonate (LAS) and cobalt metal simultaneously.
The activated carbon renovation process that the present invention is polluted by metal or/and cleaning agent, it can reduce the consumption of organic solvent and water resource, to reach effect friendly to environment and that economize on resources.
Of the present invention in order to remove the remover of linear alkylbenzene sulfonate (LAS) and cobalt metal in activated carbon, to have the effect of removing linear alkylbenzene sulfonate (LAS) and cobalt metal in activated carbon simultaneously.
Claims (10)
1. an activated carbon renovation process that polluted by metal or/and cleaning agent, its feature comprises:
A stream is washed step, and activated carbon is placed in a room, and remover passes into this room to carry out stream to activated carbon and wash, and this remover comprises supercritical carbon dioxide fluid, a kind of secondary solvent and a kind of metal composite agent; And
A displacement separating step, pass into this room by a kind of displacement fluid, to replace the remover in this room, then by this displacement fluid and activity carbon separation.
2. the activated carbon renovation process that polluted by metal or/and cleaning agent as claimed in claim 1, it is characterized in that: this metal composite agent is that Bis-trifluoroethyldithiocarbamate(two-tri-fluoridizes dithiocarbamate salt, be called for short FDDC), the Diethyldithiocarbamate(diethyldithiocar bamic acid, be called for short DDC), Dipropyl-dithiocarbamate(dipropyl disulfide is for carbaminate, be called for short P3DC), Dibutyldithiocarbamate(dibutyl dithiocaarbamate salt, be called for short BDC), Dipentyldithiocarbamate(diamyl dithiocarbamate salt, be called for short P5DC), Dihexyldithiocarbamate(dihexyl dithiocar-bamate, be called for short P6DC), the Pyrrolidine-dithiocarbamate(pyrrolidine dithiocarbamate, be called for short PDC), Acetylacetone(2, the 4-pentanedione, be called for short AA), Trifluoroacetylacetone(1, 1, 1-tri-fluoro-2, the 4-pentanedione, be called for short TFA), Hexafluoroacetyl-acetone(hexafluoroacetylacetone, be called for short HFA), the Thenoyltrifluoroacetone(2-TTA, be called for short TTA), Heptafluorobutanoyl-pivaroylmethane(2, 2-dimethyl-6, 6, 7, 7, 8, 8, 8,-seven fluoro-3, the 5-acetyl caproyl, be called for short FOD), the Tributylphosphate(tributyl phosphate, be called for short TBP), Tributylphosphine oxide(tributylphosphine oxide, be called for short TBPO), Trioctylphosphine oxide(TOPO, be called for short TOPO), Triphenylphosphine oxide(triphenylphosphine oxide, be called for short TPPO), Bis (2, 4, 4,-trimethylpentyl) phosphinic acid(bis-(2, 4, the 4-tri-methyl-amyl) phosphonic acids, be called for short Cyanex 272), Bis (2, 4, 4,-trimethylpentyl) dithiophosphinic acid(bis-(2, 4, the 4-tri-methyl-amyl) phosphonodithioic acid, be called for short Cyanex 301), Bis (2, 4, 4,-trimethylpentyl) monothio-phosphinic acid(bis-(2, 4, the 4-tri-methyl-amyl) phosphonothiolic acid, be called for short Cyanex 302), Di (2-ethylhexyl) phosphoric acid(is called for short D2EHPA) or Crown ether (crown ether).
3. the activated carbon renovation process that polluted by metal or/and cleaning agent as claimed in claim 1, it is characterized in that: this metal composite agent is Di (2-ethylhexyl) phosphoric acid.
4. the activated carbon renovation process that polluted by metal or/and cleaning agent as claimed in claim 1, it is characterized in that: this secondary solvent is low carbon number alkanes or low carbon number alcohols, its carbon number is 1 to 6.
5. the activated carbon renovation process that polluted by metal or/and cleaning agent as claimed in claim 4, it is characterized in that: this secondary solvent is methyl alcohol or n-hexane.
6. as claim 1,2,3, the 4 or 5 described activated carbon renovation process that polluted by metal or/and cleaning agent, it is characterized in that: the pressure in this room is more than 74 bar.
7. as claim 1,2,3, the 4 or 5 described activated carbon renovation process that polluted by metal or/and cleaning agent, it is characterized in that: the pressure in this room is 100 ~ 350 bar.
8. as claim 1,2,3, the 4 or 5 described activated carbon renovation process that polluted by metal or/and cleaning agent, it is characterized in that: the temperature in this room is more than 32 ℃.
9. as claim 1,2,3, the 4 or 5 described activated carbon renovation process that polluted by metal or/and cleaning agent, it is characterized in that: the temperature in this room is 35 ~ 120 ℃.
10. as claim 1,2,3, the 4 or 5 described activated carbon renovation process that polluted by metal or/and cleaning agent, it is characterized in that: the percentage by weight that this secondary solvent accounts for this remover is 1.0 ~ 20.0%, the percentage by weight that this metal composite agent accounts for this remover is 0.1 ~ 9.0%, and the percentage by weight that this supercritical carbon dioxide fluid accounts for this remover is 79.9 ~ 98.9%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210194313.6A CN103480351A (en) | 2012-06-13 | 2012-06-13 | Regeneration method for active carbon contaminated by metal or/and cleaning agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210194313.6A CN103480351A (en) | 2012-06-13 | 2012-06-13 | Regeneration method for active carbon contaminated by metal or/and cleaning agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103480351A true CN103480351A (en) | 2014-01-01 |
Family
ID=49821137
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210194313.6A Pending CN103480351A (en) | 2012-06-13 | 2012-06-13 | Regeneration method for active carbon contaminated by metal or/and cleaning agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103480351A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109261125A (en) * | 2018-11-30 | 2019-01-25 | 湖南农业大学 | A kind of Solidago Canadensis stalk charcoal, preparation method and its in removal washes LAS application |
| CN111036667A (en) * | 2019-11-23 | 2020-04-21 | 山东碧泉环境工程技术有限公司 | Method for repairing heavy metal contaminated soil |
| CN115385335A (en) * | 2022-08-23 | 2022-11-25 | 浙江浙能技术研究院有限公司 | Supercritical cleaning method for deeply purifying super-capacitive porous carbon material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4124528A (en) * | 1974-10-04 | 1978-11-07 | Arthur D. Little, Inc. | Process for regenerating adsorbents with supercritical fluids |
| CN1128961A (en) * | 1994-04-21 | 1996-08-14 | 英国核子燃料公司 | Solvent extraction for metalic matter |
| CN1152260A (en) * | 1994-06-02 | 1997-06-18 | 爱达荷研究基础公司 | Fluid extraction of metal and/or metalloid |
| WO2006023779A2 (en) * | 2004-08-20 | 2006-03-02 | Idaho Research Foundation, Inc. | Metal extraction in liquid or supercritical-fluid solvents |
| CN101530677A (en) * | 2009-03-10 | 2009-09-16 | 武汉工程大学 | Technology for extracting heavy metal ions by supercritical carbon dioxide complexation-reverse micelle coupling |
-
2012
- 2012-06-13 CN CN201210194313.6A patent/CN103480351A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4124528A (en) * | 1974-10-04 | 1978-11-07 | Arthur D. Little, Inc. | Process for regenerating adsorbents with supercritical fluids |
| CN1128961A (en) * | 1994-04-21 | 1996-08-14 | 英国核子燃料公司 | Solvent extraction for metalic matter |
| CN1152260A (en) * | 1994-06-02 | 1997-06-18 | 爱达荷研究基础公司 | Fluid extraction of metal and/or metalloid |
| WO2006023779A2 (en) * | 2004-08-20 | 2006-03-02 | Idaho Research Foundation, Inc. | Metal extraction in liquid or supercritical-fluid solvents |
| CN101530677A (en) * | 2009-03-10 | 2009-09-16 | 武汉工程大学 | Technology for extracting heavy metal ions by supercritical carbon dioxide complexation-reverse micelle coupling |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109261125A (en) * | 2018-11-30 | 2019-01-25 | 湖南农业大学 | A kind of Solidago Canadensis stalk charcoal, preparation method and its in removal washes LAS application |
| CN111036667A (en) * | 2019-11-23 | 2020-04-21 | 山东碧泉环境工程技术有限公司 | Method for repairing heavy metal contaminated soil |
| CN115385335A (en) * | 2022-08-23 | 2022-11-25 | 浙江浙能技术研究院有限公司 | Supercritical cleaning method for deeply purifying super-capacitive porous carbon material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106882884B (en) | A kind of method of chloride ion in recycling waste water | |
| CN111574859B (en) | Treatment system and treatment method for waste tire cracking carbon black | |
| CN108862954B (en) | Method for treating oily waste by adopting switch type mixed solvent system | |
| CN106399697B (en) | A kind of soil Compound Heavy Metals are administered and method of resource | |
| CN103480351A (en) | Regeneration method for active carbon contaminated by metal or/and cleaning agent | |
| CN104436946B (en) | A kind of Painting Shop environment-friendly disposal system | |
| CN1119286C (en) | Process for pre-treating waste liquid of p-benzoic acid by complexing and extraction | |
| CN113979568B (en) | Arsenic removal treatment process for high-arsenic strong-acid wastewater | |
| Qing et al. | Deep fluoride removal from the sulfate leaching solution of spent LIBs by complexation extraction with Al3+ loaded solvent | |
| CN204973394U (en) | Oiliness waste gas recovery equipment | |
| TWI466712B (en) | Treatment of fly ash and elimination agent for dioxins and leachable-metals in fly ash | |
| CN211133535U (en) | Chlorinated paraffin tail gas recovery processing system | |
| CN111218288B (en) | Washing liquid for treating light oil product polluted silt and recovering oil content and use method thereof | |
| Gasser et al. | Sustainability of solvent extraction techniques in pollution prevention and control | |
| CN114380435B (en) | Online recovery process for lost organic phase of hydrometallurgical extraction separation system | |
| CN105169846A (en) | Recovery apparatus and recovery method for oil-containing waste gas | |
| CN103388078A (en) | Fly ash utilization method and remover for removing dioxin homologue and soluble heavy metal from fly ash | |
| CN112361211A (en) | Method and device for treating residual ammonia and dirt of liquid ammonia tank car | |
| CN209123363U (en) | A kind of organic purification reclaimer of fully automatic vacuum | |
| CN209872557U (en) | System for separating acid and salt in wastewater | |
| Cheremisina et al. | Sorption purification of acid storage facility water from iron and titanium on organic polymeric materials | |
| CN209322593U (en) | A kind of special equipment of the demineralized water production technology of coal chemical industry | |
| CN104928477A (en) | Method for extracting and separating trivalent actinide and lanthanide ions in high activity liquid waste | |
| CN103395746B (en) | Method for purifying byproduct hydrochloric acid in 3, 4-dichloronitrobenzene production process | |
| CN216513279U (en) | Hydrometallurgy extraction piece-rate system runs off online recovery unit of organic phase |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140101 |