CN101234238A - Method for using carbon monoxide to detoxicate chromium residue - Google Patents
Method for using carbon monoxide to detoxicate chromium residue Download PDFInfo
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- CN101234238A CN101234238A CNA2008100453379A CN200810045337A CN101234238A CN 101234238 A CN101234238 A CN 101234238A CN A2008100453379 A CNA2008100453379 A CN A2008100453379A CN 200810045337 A CN200810045337 A CN 200810045337A CN 101234238 A CN101234238 A CN 101234238A
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- chromium
- slag
- coal
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- dross
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Abstract
The invention relates to a method by using carbon monoxide to detoxify chromium slag which belongs to the technical field in which hexavalent chromium ion Cr<6+> producing sodium bichromate chromium slag is reduced into trivalent chromium ion Cr<3+>. In order to ensure the mixture of chromium slag and coal to produce more CO in high temperature to reduce the hexavalent chromium ion Cr<6+> in the chromium slag into chromium ion Cr<3+>, the chromium slag and the coal are squeezed into chromium slag coal compact with density of 1.5*10<3> to 5.5*10<3>Kg/m<3>, and thickness of 5 to 50mm to calcinate, and ethanol solution is used for water quenching after calcinations. The method includes the following steps: grinding materials, drying, mixing chromium slag powder and coal powder to get a mixture with 91 percent to 98 percent of chromium slag powder and 2 percent to 9 percent of coal powder, squeezing the chromium slag and the coal into chromium slag coal compact, calcinating and water quenching by ethanol solution. The leaching solution of the chromium slag coal compact after being water quenched according to national standards has Cr<6+> with the content of 0.01 to 0.30mg/L, and is in accordance with the requirement of HJ/T301-2007 issued by national environmental protection headquarter.
Description
Technical field
The invention belongs to the hexavalent chromium (Cr in the chromium slag
6+) be reduced into trivalent chromic ion (Cr
3+) technical field, particularly relate to the harmful hexavalent chromium (Cr that produces in the sodium dichromate waste residue
6+) be reduced into nuisanceless trivalent chromic ion (Cr with CO
3+) technology.
Background technology
Chromic salts is a kind of broad-spectrum raw material of industry, but produces one ton of sodium dichromate (Na
2Cr
2O
72H
2O) will efflux 2～3 tons and have harmful hexavalent chromium (Cr
6+) the chromium slag, therefore pile up like a mountain for some domestic chromium salt factory chromium residue discharged, taken large stretch of soil.Even more serious problem is to contain noxious material in the chromium slag---hexavalent chromium (Cr
6+) cause environmental pollution.Learn hexavalent chromium (Cr in the chromium slag through assay
6+) content is up to 1.5%, this chromium slag stacking meeting for a long time causes severe contamination to ecological environment.According to " chromium slag contaminated improvement environmental protection technology standard " (HJ/T301-2007) requirement of State Environmental Protection Administration's promulgation in 2007, chromium slag leachate hexavalent chromium (Cr
6+) content is strict controlled in below the 0.50mg/L, so chromium salt factory faces and is forced to stop production or changes the line of production.(national standard is: 30g chromium slag adds in the 300ml water, vibrates 16 hours, static 8 hours, detects the hexavalent chromium (Cr in the solution
6+) content.) if directly the chromium ground-slag being added coal carries out dry detoxifiedly, the coal content of adding is between 35.00%～10.00%, coal consumption is big, detoxifcation cost height, and the chromium slag leachate hexavalent chromium (Cr after the detoxifcation
6+) content is up to more than the 100.00mg/L, can't reach " chromium slag contaminated improvement environmental protection technology standard " (HJ/T301-2007) requirement of State Environmental Protection Administration's promulgation at all.If adopt wet method detoxifcation, the insoluble hexavalent chromium (CaCrO in the chromium slag
4) can't thoroughly be reduced into trivalent chromic ion (Cr
3+), store up 1 year after, the chromium slag leachate hexavalent chromium (Cr after the detoxifcation
6+) content can rise to more than the 20.00mg/L, can't reach " chromium slag contaminated improvement environmental protection technology standard " (HJ/T301-2007) requirement of State Environmental Protection Administration's promulgation equally.
Summary of the invention
The objective of the invention is harmful hexavalent chromium (Cr in the chromium slag
6+) be reduced to harmless trivalent chromic ion (Cr
3+), make the chromium slag meet " chromium slag contaminated improvement environmental protection technology standard " emission request of State Environmental Protection Administration's promulgation.
The problem that the present invention solves is: with the chromium slag be pressed into chromium dross coal briquet after coal mixes, in kiln, form good dark burn condition in 600 ℃～1200 ℃ environment, it is produced than diffusing chromium slag and the more CO of diffusing coal mixtures with a certain amount of coal, and effectively make CO reduction of hexavalent chromium ion (Cr
6+), reach hexavalent chromium (Cr in the harmless treatment chromium slag
6+) purpose, detoxifcation back chromium slag is by standard detection, the hexavalent chromium (Cr of its leachate
6+) content is: below the 0.50mg/L; Reduce the consumption of coal simultaneously, reduce cost.
Technical solution of the present invention is:
Method with carbon monoxide to detoxicate chromium residue: comprise wet ball grinding chromium slag, filter slurry, add in dry chromium slag, the dried chromium slag behind the suction filtration coal, chromium dross coal briquet is put into the high temperature kiln step such as calcine, it is characterized in that: chromium slag and coal are squeezed into chromium dross coal briquet, in the chromium dross coal briquet, dry chromium ground-slag accounts for gross weight 91%～98% behind the suction filtration, coal dust accounts for gross weight 2%～9%, the preferred chromium ground-slag accounts for gross weight 95%, and coal dust accounts for gross weight 5%.The density of chromium dross coal briquet is 1.5 * 10
3Kg/m
3～5.5 * 10
3Kg/m
3The thickness of chromium dross coal briquet is 5mm～50mm.Experiment showed, the chromium dross coal briquet of this density and thickness, form good dark burn condition in 600 ℃～1200 ℃ environment in kiln, the effect that produces CO is the highest, and reduction effect is best.Under 200 ℃～1500 ℃ conditions, the explosion limit of CO concentration is 12.5% in the kiln, and chromium dross coal briquet surface C O concentration can only be lower than 12.0%, so chromium dross coal briquet surface C O reduction of hexavalent chromium ion (Cr
6+) efficient low, in order to make chromium dross coal briquet surface hexavalent chromium ion (Cr
6+) also be reduced into trivalent chromic ion (Cr
3+), after chromium dross coal briquet has been calcined in the high temperature kiln, when chromium dross coal briquet drops to 900 ℃～1000 ℃ in kiln, drop to below 300 ℃ with ethanolic solution shrend high temperature chromium dross coal briquet in 2 minutes.
Method with the CO detoxification chromium slag: may further comprise the steps:
(1) abrasive material: after the chromium slag added water, the wet-milling pulping; Dry coal is worn into coal dust; By weight the chromium slag: the ratio metering of water=1: 1～1: 5 mixes the back and adopts ball mill to carry out wet ball grinding, the slurry fineness is controlled between 80～150 orders, directly adopt vacuum band-type filter machine that slurry is carried out suction filtration, reclaim chromium slag in the slurry and dissolve the part hexavalent chromium (Cr that
6+), recovery contain hexavalent chromium (Cr
6+) filtrate to turn back to the sodium dichromate production process recycling; Filter the chromium slag in also contain a large amount of hexavalent chromium (Cr
6+), following steps be to filter the chromium slag in contained hexavalent chromium (Cr
6+) detoxifcation handle;
(2) drying: suction filtration chromium slag and water, make its chromium slag and moisture from, then slag partly is dried to the chromium ground-slag; Adopt flash distillation dryer that the moisture of chromium slag filter cake is dried below 12%; Preferably 6～10%.
(3) batch mixing: chromium ground-slag and coal dust are mixed, and by weight, the chromium ground-slag accounts for gross weight 91%～98%, and coal dust accounts for gross weight 2%～9%;
(4) moulding: chromium ground-slag and coal dust intermixture are squeezed into chromium dross coal briquet, and the density of chromium dross coal briquet is: 1.5 * 10
3Kg/m
3～5.5 * 10
3Kg/m
3, the thickness of chromium dross coal briquet is 5mm～50mm; When extruding chromium ground-slag and coal dust intermixture, the content of water is 4～8% to be advisable in chromium ground-slag and the coal dust intermixture.
(5) calcining: chromium dross coal briquet is put in the kiln, is that dry zone below 300 ℃ is dried to moisture≤2.0% in temperature earlier, then 600 ℃～1200 ℃ calcinings 5 minutes～30 minutes down; Chromium dross coal briquet produces a large amount of CO, and the reproducibility of CO and simple substance carbon (C) is with virose hexavalent chromium (Cr in the chromium slag
6+) be reduced into non-harmful trivalent chromic ion (Cr
3+); Generally be that handle is with CaCrO
4And Na
2CrO
4Hexavalent chromium (the Cr of form
6+), be reduced into Cr
2O
3Trivalent chromic ion (the Cr of form
3+) and simple substance chromium be crome metal.
(6) shrend: under 200 ℃～1500 ℃ conditions, the explosion limit of CO concentration is 12.5% in the kiln, and chromium dross coal briquet surface C O concentration can only be lower than 12.0%, so chromium dross coal briquet surface C O reduction of hexavalent chromium ion (Cr
6+) efficient low, in order to make chromium dross coal briquet surface hexavalent chromium ion (Cr
6+) also be reduced into trivalent chromic ion (Cr
3+), after chromium dross coal briquet has been calcined in the high temperature kiln, when chromium dross coal briquet drops to 900 ℃～1000 ℃ in kiln, drop to below 300 ℃ with ethanolic solution shrend high temperature chromium dross coal briquet in 2 minutes.
By the following examples present technique is further described,, make the public better grasp the implementation condition of present technique, but present technique is not limited by described embodiment so that further confirm the above-mentioned advantage and the effect of present technique.
Advantage of the present invention: the present invention is only at chromium slag and the coal mixtures coal dust with 2%～9% weight, just can make the only surplus Cr of having in the leachate after the calcining of chromium dross coal briquet
6+Content is: 0.01--0.30mg/L.Meet the requirement of the HJ/T301-2007 of State Environmental Protection Administration's promulgation.Reach hexavalent chromium (Cr in the chromium slag after the harmless treatment
6+) purpose.Reduce the consumption of coal, reduce cost, harmless treatment is higher than the treatment effect of loose chromium slag and diffusing coal.And make the only surplus Cr of having in the leachate with ethanolic solution shrend high temperature chromium dross coal briquet
6+Content is: 0.01mg/L.
Description of drawings
Fig. 1 is a process sequence diagram of the present invention;
The specific embodiment
Embodiment 1
Method with the CO detoxification chromium slag: may further comprise the steps:
(1) abrasive material: (solid contains hexavalent chromium (Cr with the chromium slag
6+) be about more than 1.0%) and add water after, the wet-milling pulping; Coal is dry grinded into coal dust; By weight the chromium slag: the ratio metering of water=1: 5 mixes the back and adopts ball mill to carry out wet ball grinding, the slurry fineness is controlled at about 150 orders, directly adopt vacuum band-type filter machine that slurry is carried out suction filtration, reclaim chromium slag in the slurry and dissolve the part hexavalent chromium (Cr that
6+), recovery contain hexavalent chromium (Cr
6+) filtrate to turn back to the sodium dichromate production process recycling; Filter the chromium slag in also contain a large amount of hexavalent chromium (Cr
6+), following steps be to filter the chromium slag in contained hexavalent chromium (Cr
6+) detoxifcation handle;
(2) drying: suction filtration chromium slag and water, make its chromium slag and moisture from, then slag partly is dried to the chromium ground-slag; Adopt flash distillation dryer that the moisture of chromium slag filter cake is dried 8～10%.
(3) batch mixing: chromium ground-slag and coal dust are mixed, and by weight, the chromium ground-slag accounts for gross weight 91.00%, and coal dust accounts for gross weight 9.00%;
(4) moulding: use pressure 150kg/cm
2Above press is pressed into length and width thick to be the chromium dross coal briquet of 50 * 50 * 5mm, chromium ground-slag and coal dust intermixture are squeezed into chromium dross coal briquet that the density of chromium dross coal briquet is: 1.5 * 10 respectively
3Kg/m
3, the thickness of chromium dross coal briquet is 5mm; When extruding chromium ground-slag and coal dust intermixture, the content of water is 4～8% to be advisable in chromium ground-slag and the coal dust intermixture.
(5) calcining: chromium dross coal briquet is put in the kiln, is that dry zone below 300 ℃ is dried to moisture≤2.0% in temperature earlier, then 600 ℃～1200 ℃ calcinings 5 minutes～10 minutes down; Chromium dross coal briquet produces a large amount of CO, and the reproducibility of CO and simple substance carbon (C) is with virose hexavalent chromium (Cr in the chromium slag
6+) be reduced into non-harmful trivalent chromic ion (Cr
3+); Generally be that handle is with CaCrO
4And Na
2CrO
4Hexavalent chromium (the Cr of form
6+), be reduced into Cr
2O
3Trivalent chromic ion (the Cr of form
3+) and simple substance chromium be crome metal.
(6) shrend: in order to make chromium dross coal briquet surface hexavalent chromium ion (Cr
6+) also be reduced into trivalent chromic ion (Cr
3+), after chromium dross coal briquet has been calcined in the high temperature kiln, when chromium dross coal briquet drops to 900 ℃～1000 ℃ in kiln, with ethanolic solution shrend high temperature chromium dross coal briquet in 2 minutes drop to 100 ℃～below 300 ℃.
By the chromium slag of above-mentioned technology detoxifcation, by hexavalent chromium (Cr in the leachate of chromium dross coal briquet after the GB check shrend
6+) content is: 0.01mg/L.Meet " chromium slag contaminated improvement environmental protection technology standard " requirement (HJ/T301-2007) of State Environmental Protection Administration's promulgation.
Embodiment 2
Method with carbon monoxide to detoxicate chromium residue: may further comprise the steps:
(1) abrasive material: (solid contains hexavalent chromium (Cr with the chromium slag
6+) be about more than 1.0%) and add water after, the wet-milling pulping; Coal is dry grinded into coal dust; By weight the chromium slag: the ratio metering of water=1: 3 mixes the back and adopts ball mill to carry out wet ball grinding, the slurry fineness is controlled at about 100 orders, directly adopt vacuum band-type filter machine that slurry is carried out suction filtration, reclaim chromium slag in the slurry and dissolve the part hexavalent chromium (Cr that
6+), recovery contain hexavalent chromium (Cr
6+) filtrate to turn back to the sodium dichromate production process recycling; Filter the chromium slag in also contain a large amount of hexavalent chromium (Cr
6+), following steps be to filter the chromium slag in contained hexavalent chromium (Cr
6+) detoxifcation handle;
(2) drying: suction filtration chromium slag and water, make its chromium slag and moisture from, then slag partly is dried to the chromium ground-slag; Adopt flash distillation dryer that the moisture of chromium slag filter cake is dried 8～10%.
(3) batch mixing: chromium ground-slag and coal dust are mixed, and by weight, the chromium ground-slag accounts for gross weight 95.00%, and coal dust accounts for gross weight 5.00%;
(4) moulding: use pressure 150kg/cm
2Above press is pressed into length and width thick to be the chromium dross coal briquet of 150 * 150 * 20mm, chromium ground-slag and coal dust intermixture are squeezed into chromium dross coal briquet that the density of chromium dross coal briquet is: 2.0 * 10 respectively
3Kg/m
3, the thickness of chromium dross coal briquet is 10mm; When extruding chromium ground-slag and coal dust intermixture, the content of water is 4～8% to be advisable in chromium ground-slag and the coal dust intermixture.
(5) calcining: chromium dross coal briquet is put in the kiln, is that dry zone below 300 ℃ is dried to moisture≤2.0% in temperature earlier, then 600 ℃～1200 ℃ calcinings 5 minutes～10 minutes down; Chromium dross coal briquet produces a large amount of CO, and the reproducibility of CO and simple substance carbon (C) is with virose hexavalent chromium (Cr in the chromium slag
6+) be reduced into non-harmful trivalent chromic ion (Cr
3+); Generally be that handle is with CaCrO
4And Na
2CrO
4Hexavalent chromium (the Cr of form
6+), be reduced into Cr
2O
3Trivalent chromic ion (the Cr of form
3+) and simple substance chromium be crome metal.
(6) shrend: in order to make chromium dross coal briquet surface hexavalent chromium ion (Cr
6+) also be reduced into trivalent chromic ion (Cr
3+), after chromium dross coal briquet has been calcined in the high temperature kiln, when chromium dross coal briquet drops to 900 ℃～1000 ℃ in kiln, with ethanolic solution shrend high temperature chromium dross coal briquet in 2 minutes drop to 100 ℃～below 300 ℃.
By the chromium slag of above-mentioned technology detoxifcation, by hexavalent chromium (Cr in the leachate of chromium dross coal briquet after the GB check shrend
6+) content is: 0.02mg/L.Meet " chromium slag contaminated improvement environmental protection technology standard " requirement (HJ/T301-2007) of State Environmental Protection Administration's promulgation.
Embodiment 3
Method with carbon monoxide to detoxicate chromium residue: may further comprise the steps:
(1) abrasive material: (solid contains hexavalent chromium (Cr with the chromium slag
6+) be about more than 1.0%) and add water after, the wet-milling pulping; Coal is dry grinded into coal dust; By weight the chromium slag: the ratio metering of water=1: 1 mixes the back and adopts ball mill to carry out wet ball grinding, the slurry fineness is controlled at about 120 orders, directly adopt vacuum band-type filter machine that slurry is carried out suction filtration, reclaim chromium slag in the slurry and dissolve the part hexavalent chromium (Cr that
6+), recovery contain hexavalent chromium (Cr
6+) filtrate to turn back to the sodium dichromate production process recycling; Filter the chromium slag in also contain a large amount of hexavalent chromium (Cr
6+), following steps be to filter the chromium slag in contained hexavalent chromium (Cr
6+) detoxifcation handle;
(2) drying: suction filtration chromium slag and water, make its chromium slag and moisture from, then slag partly is dried to the chromium ground-slag; Adopt flash distillation dryer that the moisture of chromium slag filter cake is dried 8～10%.
(3) batch mixing: chromium ground-slag and coal dust are mixed, and by weight, the chromium ground-slag accounts for gross weight 98.00%, and coal dust accounts for gross weight 2.00%;
(4) moulding: use pressure 150kg/cm
2Above press is pressed into length and width thick to be the chromium dross coal briquet of 250 * 250 * 40mm, chromium ground-slag and coal dust intermixture are squeezed into chromium dross coal briquet that the density of chromium dross coal briquet is: 4.1 * 10 respectively
3Kg/m
3, the thickness of chromium dross coal briquet is 45mm; When extruding chromium ground-slag and coal dust intermixture, the content of water is 4～8% to be advisable in chromium ground-slag and the coal dust intermixture.
(5) calcining: chromium dross coal briquet is put in the kiln, is that dry zone below 300 ℃ is dried to moisture≤2.0% in temperature earlier, then 600 ℃～1200 ℃ calcinings 5 minutes～10 minutes down; Chromium dross coal briquet produces a large amount of CO, and the reproducibility of CO and simple substance carbon (C) is with virose hexavalent chromium (Cr in the chromium slag
6+) be reduced into non-harmful trivalent chromic ion (Cr
3+); Generally be that handle is with CaCrO
4And Na
2CrO
4Hexavalent chromium (the Cr of form
6+), be reduced into Cr
2O
3Trivalent chromic ion (the Cr of form
3+) and simple substance chromium be crome metal.
(6) shrend: in order to make chromium dross coal briquet surface hexavalent chromium ion (Cr
6+) also be reduced into trivalent chromic ion (Cr
3+), after chromium dross coal briquet has been calcined in the high temperature kiln, when chromium dross coal briquet drops to 900 ℃～1000 ℃ in kiln, with ethanolic solution shrend high temperature chromium dross coal briquet in 2 minutes drop to 100 ℃～below 300 ℃.
By the chromium slag of above-mentioned technology detoxifcation, by hexavalent chromium (Cr in the leachate of chromium dross coal briquet after the GB check shrend
6+) content is: 0.02mg/L.Meet " chromium slag contaminated improvement environmental protection technology standard " requirement (HJ/T301-2007) of State Environmental Protection Administration's promulgation.
Embodiment 4
Method with carbon monoxide to detoxicate chromium residue: may further comprise the steps:
(1) abrasive material: (solid contains hexavalent chromium (Cr with the chromium slag
6+) be about more than 1.0%) and add water after, the wet-milling pulping; Coal is dry grinded into coal dust; By weight the chromium slag: the ratio metering of water=1: 5 mixes the back and adopts ball mill to carry out wet ball grinding, the slurry fineness is controlled at about 80 orders, directly adopt vacuum band-type filter machine that slurry is carried out suction filtration, reclaim chromium slag in the slurry and dissolve the part hexavalent chromium (Cr that
6+), recovery contain hexavalent chromium (Cr
6+) filtrate to turn back to the sodium dichromate production process recycling; Filter the chromium slag in also contain a large amount of hexavalent chromium (Cr
6+), following steps be to filter the chromium slag in contained hexavalent chromium (Cr
6+) detoxifcation handle;
(2) drying: suction filtration chromium slag and water, make its chromium slag and moisture from, then slag partly is dried to the chromium ground-slag; Adopt flash distillation dryer that the moisture of chromium slag filter cake is dried 8～10%.
(3) batch mixing: chromium ground-slag and coal dust are mixed, and by weight, the chromium ground-slag accounts for gross weight 93.00%, and coal dust accounts for gross weight 7.00%;
(4) moulding: use pressure 150kg/cm
2Above press is pressed into length and width thick to be the chromium dross coal briquet of 250 * 250 * 50mm, chromium ground-slag and coal dust intermixture are squeezed into chromium dross coal briquet that the density of chromium dross coal briquet is: 5.1 * 10 respectively
3Kg/m
3, the thickness of chromium dross coal briquet is 50mm; When extruding chromium ground-slag and coal dust intermixture, the content of water is 4～8% to be advisable in chromium ground-slag and the coal dust intermixture.
(5) calcining: chromium dross coal briquet is put in the kiln, is that dry zone below 300 ℃ is dried to moisture≤2.0% in temperature earlier, then 600 ℃～1200 ℃ calcinings 5 minutes～10 minutes down; Chromium dross coal briquet produces a large amount of CO, and the reproducibility of CO and simple substance carbon (C) is with virose hexavalent chromium (Cr in the chromium slag
6+) be reduced into non-harmful trivalent chromic ion (Cr
3+); Generally be that handle is with CaCrO
4And Na
2CrO
4Hexavalent chromium (the Cr of form
6+), be reduced into Cr
2O
3Trivalent chromic ion (the Cr of form
3+) and simple substance chromium be crome metal.
(6) shrend: in order to make chromium dross coal briquet surface hexavalent chromium ion (Cr
6+) also be reduced into trivalent chromic ion (Cr
3+), after chromium dross coal briquet has been calcined in the high temperature kiln, when chromium dross coal briquet drops to 900 ℃～1000 ℃ in kiln, with ethanolic solution shrend high temperature chromium dross coal briquet in 2 minutes drop to 100 ℃～below 300 ℃.
By the chromium slag of above-mentioned technology detoxifcation, by hexavalent chromium (Cr in the leachate of chromium dross coal briquet after the GB check shrend
6+) content is: 0.00mg/L.Meet " chromium slag contaminated improvement environmental protection technology standard " requirement (HJ/T301-2007) of State Environmental Protection Administration's promulgation.
Embodiment 5
Method with carbon monoxide to detoxicate chromium residue: may further comprise the steps:
(1) abrasive material: (solid contains hexavalent chromium (Cr with the chromium slag
6+) be about more than 1.0%) and add water after, the wet-milling pulping; Coal is dry grinded into coal dust; By weight the chromium slag: the ratio metering of water=1: 1 mixes the back and adopts ball mill to carry out wet ball grinding, the slurry fineness is controlled at about 60 orders, directly adopt vacuum band-type filter machine that slurry is carried out suction filtration, reclaim chromium slag in the slurry and dissolve the part hexavalent chromium (Cr that
6+), recovery contain hexavalent chromium (Cr
6+) filtrate to turn back to the sodium dichromate production process recycling; Filter the chromium slag in also contain a large amount of hexavalent chromium (Cr
6+), following steps be to filter the chromium slag in contained hexavalent chromium (Cr
6+) detoxifcation handle;
(2) drying: suction filtration chromium slag and water, make its chromium slag and moisture from, then slag partly is dried to the chromium ground-slag; Adopt flash distillation dryer that the moisture of chromium slag filter cake is dried 8～10%.
(3) batch mixing: chromium ground-slag and coal dust are mixed, and by weight, the chromium ground-slag accounts for gross weight 98.00%, and it is 2.00% that coal dust accounts for gross weight;
(4) moulding: use pressure 150kg/cm
2Above press is pressed into length and width thick to be the chromium dross coal briquet of 50 * 50 * 5mm, chromium ground-slag and coal dust intermixture are squeezed into chromium dross coal briquet that the density of chromium dross coal briquet is: 2.0 * 10 respectively
3Kg/m
3, the thickness of chromium dross coal briquet is 5mm; When extruding chromium ground-slag and coal dust intermixture, the content of water is 4～8% to be advisable in chromium ground-slag and the coal dust intermixture.
(5) calcining: chromium dross coal briquet is put in the kiln, is that dry zone below 300 ℃ is dried to moisture≤2.0% in temperature earlier, then 600 ℃～1200 ℃ calcinings 5 minutes～10 minutes down; Chromium dross coal briquet produces a large amount of CO, and the reproducibility of CO and simple substance carbon (C) is with virose hexavalent chromium (Cr in the chromium slag
6+) be reduced into non-harmful trivalent chromic ion (Cr
3+); Generally be that handle is with CaCrO
4And Na
2CrO
4Hexavalent chromium (the Cr of form
6+), be reduced into Cr
2O
3Trivalent chromic ion (the Cr of form
3+) and simple substance chromium be crome metal.
(6) shrend: in order to make chromium dross coal briquet surface hexavalent chromium ion (Cr
6+) also be reduced into trivalent chromic ion (Cr
3+), after chromium dross coal briquet has been calcined in the high temperature kiln, when chromium dross coal briquet drops to 900 ℃～1000 ℃ in kiln, water shrend high temperature chromium dross coal briquet in 2 minutes drop to 100 ℃～below 300 ℃.
By the chromium slag of above-mentioned technology detoxifcation, by hexavalent chromium (Cr in the leachate of chromium dross coal briquet after the GB check shrend
6+) content is: 0.30mg/L.Meet " chromium slag contaminated improvement environmental protection technology standard " requirement (HJ/T301-2007) of State Environmental Protection Administration's promulgation.
Claims (6)
1, with the method for carbon monoxide to detoxicate chromium residue: comprise wet ball grinding chromium slag, filter in dry chromium slag behind slurry, the suction filtration, the dried chromium slag and add coal, chromium dross coal briquet is put into the high temperature kiln calcine, it is characterized in that: chromium slag and coal are squeezed into chromium dross coal briquet, in the chromium dross coal briquet, dry chromium ground-slag weight is 91%～98% behind the suction filtration, and the weight of coal dust is 2%～9%.
2, the method with carbon monoxide to detoxicate chromium residue according to claim 1, it is characterized in that: the density of chromium dross coal briquet is 1.5 * 10
3Kg/m
3～5.5 * 10
3Kg/m
3
3, the method with carbon monoxide to detoxicate chromium residue according to claim 2, it is characterized in that: the thickness of chromium dross coal briquet is 5mm～50mm.
4, according to claim 1 or 2 or 3 described methods with carbon monoxide to detoxicate chromium residue, it is characterized in that: chromium slag and coal carry out shrend with ethanolic solution after having calcined in the high temperature kiln.
5, with the method for carbon monoxide to detoxicate chromium residue: may further comprise the steps:
(1) abrasive material: after the chromium slag added water, the wet-milling pulping; Coal is dry grinded into coal dust;
(2) drying: suction filtration chromium slag and water, make its chromium slag and moisture from, then slag partly is dried to the chromium ground-slag;
(3) batch mixing: chromium ground-slag and coal dust are mixed, and by weight, chromium ground-slag weight is 91%～98%, and the weight of coal dust is 2%～9%;
(4) moulding: chromium ground-slag and coal dust intermixture are squeezed into chromium dross coal briquet, and the density of chromium dross coal briquet is: 1.5 * 10
3Kg/m
3～5.5 * 10
3Kg/m
3, the thickness of chromium dross coal briquet is 5mm～50mm;
(5) calcining: chromium dross coal briquet is put in the kiln, is that dry zone below 300 ℃ is dried to moisture≤2.0% in temperature earlier, then 600 ℃～1200 ℃ 5 fens kind～30 minute kinds of calcining down;
(6) shrend: when chromium dross coal compact temperature dropped to 900 ℃～1000 ℃ in kiln, water shrend high temperature chromium dross coal briquet in 2 minutes dropped to below 300 ℃.
6, the method with carbon monoxide to detoxicate chromium residue according to claim 5 is characterized in that: drop to below 300 ℃ with ethanolic solution shrend high temperature chromium dross coal briquet in 2 minutes.
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| CN104140185A (en) * | 2014-08-06 | 2014-11-12 | 江西省广德环保科技有限公司 | Harmless recycling method for high-iron-chromium sludge |
| CN104496218A (en) * | 2014-11-26 | 2015-04-08 | 长沙紫宸科技开发有限公司 | Method for preparing active slag powder by utilizing chromium slag and chromium sludge |
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| CN104140185A (en) * | 2014-08-06 | 2014-11-12 | 江西省广德环保科技有限公司 | Harmless recycling method for high-iron-chromium sludge |
| CN104496218A (en) * | 2014-11-26 | 2015-04-08 | 长沙紫宸科技开发有限公司 | Method for preparing active slag powder by utilizing chromium slag and chromium sludge |
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| CN106082973A (en) * | 2016-03-08 | 2016-11-09 | 侯绪华 | A kind of chromium slag brickmaking technology |
| CN108785952A (en) * | 2018-05-21 | 2018-11-13 | 北京高能时代环境技术股份有限公司 | Middle low temperature hydrogen reduced chromium slag and muck mixture equipment and its reduction and detoxication method |
| CN108969957A (en) * | 2018-07-03 | 2018-12-11 | 中国科学院生态环境研究中心 | A kind of method of cellulose hydro-thermal high-efficiency detoxication chromium slag |
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