CN102872808A - Method for separating, enriching and purifying copper and nickel by using heavy metal adsorption material - Google Patents
Method for separating, enriching and purifying copper and nickel by using heavy metal adsorption material Download PDFInfo
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- CN102872808A CN102872808A CN2012103447677A CN201210344767A CN102872808A CN 102872808 A CN102872808 A CN 102872808A CN 2012103447677 A CN2012103447677 A CN 2012103447677A CN 201210344767 A CN201210344767 A CN 201210344767A CN 102872808 A CN102872808 A CN 102872808A
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 405
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 134
- 239000000463 material Substances 0.000 title claims abstract description 130
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 41
- 239000010949 copper Substances 0.000 title claims abstract description 41
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 31
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 93
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 93
- 239000007788 liquid Substances 0.000 claims abstract description 91
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 88
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000010521 absorption reaction Methods 0.000 claims description 70
- 239000000243 solution Substances 0.000 claims description 69
- 235000021110 pickles Nutrition 0.000 claims description 68
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 66
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 48
- 239000003153 chemical reaction reagent Substances 0.000 claims description 34
- 239000000741 silica gel Substances 0.000 claims description 34
- 229910002027 silica gel Inorganic materials 0.000 claims description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000001291 vacuum drying Methods 0.000 claims description 32
- 238000000926 separation method Methods 0.000 claims description 29
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 24
- 239000012065 filter cake Substances 0.000 claims description 24
- 229910000570 Cupronickel Inorganic materials 0.000 claims description 21
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims description 21
- 238000000746 purification Methods 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000004070 electrodeposition Methods 0.000 claims description 16
- 238000005363 electrowinning Methods 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000011010 flushing procedure Methods 0.000 claims description 10
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 230000008030 elimination Effects 0.000 claims description 8
- 238000003379 elimination reaction Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000008096 xylene Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000693 micelle Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 abstract description 15
- 238000002386 leaching Methods 0.000 abstract 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a method for separating, enriching and purifying copper and nickel by using a heavy metal adsorption material. The method comprises the following steps of: 1, filling the heavy metal adsorption material in each adsorption column of continuous adsorption exchange equipment, wherein the continuous adsorption exchange equipment is formed by serially connecting a first adsorption column and a second adsorption column; 2, regulating the pH of liquid which contains copper ions and nickel ions and is to be treated to 0.5 to 5.0 so as to obtain acid leaching liquid; 3, injecting the acid leaching liquid into the continuous adsorption exchange equipment operated in the step 1; and 4, separating, enriching and purifying the acid leaching liquid by using the continuous adsorption exchange equipment. Experiments prove that the copper and the nickel can be well separated by accurately controlling the temperature and flow velocity of the liquid to be treated, so the method for separating, enriching and purifying the copper and the nickel by using the heavy metal adsorption material can be widely used for separating and recycling micro or trace copper and nickel in the liquid.
Description
Technical field
The invention belongs to the heavy metal separation technology field, be specifically related to a kind of method that realizes the separation of copper nickel, enrichment, purification by the heavy metal adsorption material.
Background technology
Along with the develop rapidly of World Economics and the continuous increase of the size of population, become the important bottleneck of world development a little less than relative inadequacy of resources and the environmental carrying capacity.Resources for construction economizing type and friendly environment society advance Ecological Civilization Construction, have become the theme that world is paid close attention to.
At present, for the various industrial wastewaters that contain heavy metal ion, sanitary sewage and nuclear industry waste water, generally adopt the methods such as chemical precipitation method, oxidation-reduction method or ion-exchange that it is processed, thereby reduce content of beary metal in the water resource, reduce the harm of heavy metal pollution.
But the processing method of all kinds of heavy metal wastewater therebies that adopt at present exists the removal efficient of heavy metal ions in wastewater to hang down and the high defective of cost.
Summary of the invention
For the defective that prior art exists, the invention provides a kind of method by the separation of heavy metal adsorption material realization copper nickel, enrichment, purification, have the advantage strong to the selective absorption of copper ion.
The technical solution used in the present invention is as follows:
The invention provides a kind of method by the separation of heavy metal adsorption material realization copper nickel, enrichment, purification, may further comprise the steps:
S1 fills respectively the heavy metal adsorption material in each adsorption column of continuous adsorption switching equipment; Wherein, described continuous adsorption switching equipment is composed in series by the first adsorption column and the second adsorption column;
S2, the pH that adjusts the pending liquid that contains copper ion and nickel ion is 0.5-5.0, obtains pickle liquor;
S3 is with the described continuous adsorption switching equipment after the described pickle liquor injection S1 operation;
S4, described continuous adsorption switching equipment carry out separation and concentration to described pickle liquor and purify under 25-40 ℃, specifically comprise: be the inlet that the described pickle liquor of 0.5-5.0 pumps into described continuous adsorption switching equipment with pH; Copper ion in the described pickle liquor of described the first adsorption column adsorption and enrichment; It is the inlet that pumps into described the second adsorption column behind the 1.0-5.5 that the liquid that flows out from described the first adsorption column liquid outlet is transferred pH, the nickel ion in the described pickle liquor of described the second adsorption column adsorption and enrichment;
S5 is that the sulfuric acid of 5-30% washes respectively described the first adsorption column and described the second adsorption column with mass fraction; Described heavy metal adsorption material in described the first adsorption column carries out the desorb operation, the described heavy metal adsorption material that obtains the copper ions stripping liquid and be desorbed after the desorb operation; Described heavy metal adsorption material in described the second adsorption column carries out the desorb operation, obtains the described heavy metal adsorption material that contains the nickel ion stripping liquid and be desorbed after the desorb operation;
S6, the described copper ions stripping liquid that S5 is obtained carries out the electrodeposition operation by direct electrowinning equipment, obtains copper metallic plate or copper metal powder; Simultaneously, the described heavy metal adsorption material that is desorbed in the first adsorption column recovers absorption property after processing through flushing;
The described nickel ion stripping liquid that contains that S5 is obtained carries out the electrodeposition operation by direct electrowinning equipment after concentrated, obtains nickel metallic plate or nickel metal powder; Simultaneously, the described heavy metal adsorption material that is desorbed in the second adsorption column recovers absorption property after processing through flushing.
Preferably, described heavy metal adsorption material is prepared by the following method:
Preliminary treatment: under ultrasonic field, use the hydrochloric acid solution of 5-7mol/L to soak raw material silica gel 20-30 hour, wherein, the mass ratio of raw material silica gel and hydrochloric acid solution is 5-8: 1; Then filter, the elimination acid solution, Washing of Filter Cake is to neutral, 50-150 ℃ lower vacuum drying 5-8 hour, obtain activated silica gel;
Silica gel bonded reaction: add anhydrous dimethyl benzole soln and silylating reagent in reaction vessel, stirring is dissolved in the anhydrous dimethyl benzole soln silylating reagent, obtains the first solution, and wherein, the mass ratio of silylating reagent and xylene solution is 5-8: 1; Add dry DMF in activated silica gel, stirring makes and mixes, and obtains the second solution, and wherein, the mass ratio of activated silica gel and DMF is 2-4: 1; Silylating reagent and activated silica gel mass ratio are 1-2: 1;
The first flow of solution is added in the second solution of reflux state, stream add complete after, continued back flow reaction 10-20 hour; Filtering reacting liquid after being down to 20-30 ℃, filter cake are used methyl alcohol and toluene wash successively, and then 1 vacuum drying obtains described heavy metal adsorption material.
Preferably, the power of described ultrasonic field is 100-200 watt;
Described vacuum drying in the silica gel bonded reaction specifically comprises following three phases:
Phase I: will put into freeze drying box with the filter cake after methyl alcohol and the toluene wash, be refrigerated to-40--30 ℃ with the cooling of the speed of 10-13 ℃/min, keep-time of 40--30 ℃ is 7-8 hour;
Second stage is warming up to-10--5 ℃ with the speed of 4-5 ℃/min, keep-time of 10--5 ℃ is 5-6 hour;
Phase III puts fast and is 160 ℃-170 ℃ vacuum drying chamber to temperature, namely obtains described heavy metal adsorption material 20-23 hour drying time.
Preferably, described silylating reagent is 3-ethylenediamine base propyl trimethoxy silicane or 3-Diethylenetriamine base propyl trimethoxy silicane.
Preferably, the aperture of described heavy metal adsorption material is 10.02-11.23nm, and the pore volume of described heavy metal adsorption material is 0.9-1.5 cubic centimetre/gram.
Preferably, described raw silicon micelle degree is 200-300 order silica gel.
Preferably, S4 specifically comprises following three phases:
Phase I: the pickle liquor that with pH is 0.5-5.0 pumps into the inlet of described continuous adsorption switching equipment with the speed of 2-4ml/min, by the first adsorption column simultaneously absorbing copper ion and nickel ion, until the first adsorption column is saturated to copper absorption;
Second stage: the inlet that pickle liquor is pumped into described continuous adsorption switching equipment with the speed of 6-8ml/min, the continuous absorbing copper ion of the first adsorption column, and the copper ion of new absorption replaces the nickel ion of former absorption, until the nickel ion of the first adsorption column absorption is replaced by copper ion fully;
After second stage was processed, it was that the speed with 1-2ml/min pumps into the second adsorption column behind the 1.0-5.5 that the liquid that is flowed out by the first adsorption column liquid outlet is transferred pH, by the second adsorption column adsorption and enrichment nickel ion.
Preferably, S4 specifically comprises following three phases:
Phase I: the pickle liquor that with pH is 3.0-3.5 pumps into the inlet of described continuous adsorption switching equipment with the speed of 3ml/min, by the first adsorption column simultaneously absorbing copper ion and nickel ion, until the first adsorption column is saturated to copper absorption;
Second stage: the inlet that pickle liquor is pumped into described continuous adsorption switching equipment with the speed of 7ml/min, the continuous absorbing copper ion of the first adsorption column, and the copper ion of new absorption replaces the nickel ion of former absorption, until the nickel ion of the first adsorption column absorption is replaced by copper ion fully;
After second stage was processed, it was that the speed with 1.5ml/min pumps into the second adsorption column behind the 3.5-4.0 that the liquid that is flowed out by the first adsorption column liquid outlet is transferred pH, by the second adsorption column adsorption and enrichment nickel ion.
Below the present invention is further introduced:
Novelty of the present invention prepare a kind of heavy metal adsorption material, the experiment proved that, this heavy metal adsorption material all has adsorptivity to copper ion and nickel ion, and, to the adsorption activity of copper ion far above the adsorption activity to nickel ion, for these characteristics, for realizing separating copper ion and nickel ion, the inventor has carried out test of many times to the technique of using adsorption column to cross post, the unexpected discovery, by to the temperature for the treatment of fluid and the accurate control of flow velocity, can realize preferably separating of copper ion and nickel ion, therefore, provided by the invention by the separation of heavy metal adsorption material realization copper nickel, enrichment, the method of purifying can be applied to separation and the recovery of trace in the liquid or trace copper and mickel.
The specific embodiment
Below realize that by the heavy metal adsorption material method of the separation of copper nickel, enrichment, purification describes in detail to provided by the invention:
Heavy metal adsorption material preparation method embodiment 1
Preliminary treatment: under 100 watts of ultrasonic fields, soaked 200 order raw material silica gel 20 hours with the hydrochloric acid solution of 5mol/L, wherein, the mass ratio of raw material silica gel and hydrochloric acid solution is 5: 1; Then filter, the elimination acid solution, Washing of Filter Cake is to neutral, and 50 ℃ of lower vacuum drying 8 hours obtain activated silica gel;
Silica gel bonded reaction: in reaction vessel, add anhydrous dimethyl benzole soln and silylating reagent 3-ethylenediamine base propyl trimethoxy silicane, stirring is dissolved in the anhydrous dimethyl benzole soln silylating reagent, obtain the first solution, wherein, the mass ratio of silylating reagent and xylene solution is 8: 1; Add dry DMF in activated silica gel, stirring makes and mixes, and obtains the second solution, and wherein, the mass ratio of activated silica gel and DMF is 4: 1; Silylating reagent and activated silica gel mass ratio are 2: 1;
The first flow of solution is added in the second solution of reflux state, stream add complete after, continued back flow reaction 10 hours; Filtering reacting liquid after being down to 30 ℃, filter cake are used methyl alcohol and toluene wash successively, and then vacuum drying obtains described heavy metal adsorption material.Described vacuum drying in the silica gel bonded reaction specifically comprises following three phases:
Phase I: will put into freeze drying box with the filter cake after methyl alcohol and the toluene wash, and be refrigerated to-40--30 ℃ with the cooling of the speed of 12 ℃/min, the time of keeping-38 ℃ is 7.6 hours;
Second stage is warming up to-10 ℃ with the speed of 4 ℃/min, and the time of keeping-10 ℃ is 5 hours;
Phase III puts fast and is 165 ℃ vacuum drying chamber to temperature, namely obtains described heavy metal adsorption material 22 hours drying times.
Making the aperture is that 10.02nm, pore volume are the heavy metal adsorption material of 1.5 cubic centimetres/gram.
Heavy metal adsorption material preparation method embodiment 2
Preliminary treatment: under 200 watts of ultrasonic fields, soaked 300 order raw material silica gel 30 hours with the hydrochloric acid solution of 7mol/L, wherein, the mass ratio of raw material silica gel and hydrochloric acid solution is 8: 1; Then filter, the elimination acid solution, Washing of Filter Cake is to neutral, and 150 ℃ of lower vacuum drying 5 hours obtain activated silica gel;
Silica gel bonded reaction: in reaction vessel, add anhydrous dimethyl benzole soln and silylating reagent 3-Diethylenetriamine base propyl trimethoxy silicane, stirring is dissolved in the anhydrous dimethyl benzole soln silylating reagent, obtain the first solution, wherein, the mass ratio of silylating reagent and xylene solution is 5: 1; Add dry DMF in activated silica gel, stirring makes and mixes, and obtains the second solution, and wherein, the mass ratio of activated silica gel and DMF is 2: 1; Silylating reagent and activated silica gel mass ratio are 1: 1;
The first flow of solution is added in the second solution of reflux state, stream add complete after, continued back flow reaction 20 hours; Filtering reacting liquid after being down to 20 ℃, filter cake are used methyl alcohol and toluene wash successively, and then vacuum drying obtains described heavy metal adsorption material.Described vacuum drying in the silica gel bonded reaction specifically comprises following three phases:
Phase I: will put into freeze drying box with the filter cake after methyl alcohol and the toluene wash, lowering the temperature with the speed of 10 ℃/min is refrigerated to-40 ℃, and the time of keeping-40 ℃ is 7 hours;
Second stage is warming up to-5 ℃ with the speed of 5 ℃/min, and the time of keeping-5 ℃ is 6 hours;
Phase III puts fast and is 167 ℃ vacuum drying chamber to temperature, namely obtains described heavy metal adsorption material 22 hours drying times.
Making the aperture is that 11.23nm, pore volume are the heavy metal adsorption material of 0.9 cubic centimetre/gram.
Heavy metal adsorption material preparation method embodiment 3
Preliminary treatment: under 150 watts of ultrasonic fields, soaked 250 order raw material silica gel 25 hours with the hydrochloric acid solution of 6mol/L, wherein, the mass ratio of raw material silica gel and hydrochloric acid solution is 6: 1; Then filter, the elimination acid solution, Washing of Filter Cake is to neutral, and 100 ℃ of lower vacuum drying 6 hours obtain activated silica gel;
Silica gel bonded reaction: in reaction vessel, add anhydrous dimethyl benzole soln and silylating reagent 3-ethylenediamine base propyl trimethoxy silicane, stirring is dissolved in the anhydrous dimethyl benzole soln silylating reagent, obtain the first solution, wherein, the mass ratio of silylating reagent and xylene solution is 7: 1; Add dry DMF in activated silica gel, stirring makes and mixes, and obtains the second solution, and wherein, the mass ratio of activated silica gel and DMF is 3: 1; Silylating reagent and activated silica gel mass ratio are 1.5: 1;
The first flow of solution is added in the second solution of reflux state, stream add complete after, continued back flow reaction 15 hours; Filtering reacting liquid after being down to 25 ℃, filter cake are used methyl alcohol and toluene wash successively, and then vacuum drying obtains described heavy metal adsorption material.Described vacuum drying in the silica gel bonded reaction specifically comprises following three phases:
Phase I: will put into freeze drying box with the filter cake after methyl alcohol and the toluene wash, lowering the temperature with the speed of 13 ℃/min is refrigerated to-0 ℃, and the time of keeping-30 ℃ is 7 hours;
Second stage is warming up to-7 ℃ with the speed of 4.5 ℃/min, and the time of keeping-7 ℃ is 5.5 hours;
Phase III puts fast and is 163 ℃ vacuum drying chamber to temperature, namely obtains described heavy metal adsorption material 22 hours drying times.
Making the aperture is that 10.25nm, pore volume are the heavy metal adsorption material of 1.2 cubic centimetres/gram.
Heavy metal adsorption material preparation method embodiment 4
Preliminary treatment: under 120 watts of ultrasonic fields, soaked 220 order raw material silica gel 24 hours with the hydrochloric acid solution of 6.5mol/L, wherein, the mass ratio of raw material silica gel and hydrochloric acid solution is 7: 1; Then filter, the elimination acid solution, Washing of Filter Cake is to neutral, and 80 ℃ of lower vacuum drying 6 hours obtain activated silica gel;
Silica gel bonded reaction: in reaction vessel, add anhydrous dimethyl benzole soln and silylating reagent 3-Diethylenetriamine base propyl trimethoxy silicane, stirring is dissolved in the anhydrous dimethyl benzole soln silylating reagent, obtain the first solution, wherein, the mass ratio of silylating reagent and xylene solution is 7: 1; Add dry DMF in activated silica gel, stirring makes and mixes, and obtains the second solution, and wherein, the mass ratio of activated silica gel and DMF is 2.5: 1; Silylating reagent and activated silica gel mass ratio are 1.2: 1;
The first flow of solution is added in the second solution of reflux state, stream add complete after, continued back flow reaction 16 hours; Filtering reacting liquid after being down to 21 ℃, filter cake are used methyl alcohol and toluene wash successively, and then vacuum drying obtains described heavy metal adsorption material.Described vacuum drying in the silica gel bonded reaction specifically comprises following three phases:
Phase I: will put into freeze drying box with the filter cake after methyl alcohol and the toluene wash, lowering the temperature with the speed of 11 ℃/min is refrigerated to-35 ℃, and the time of keeping-35 ℃ is 7.5 hours;
Second stage is warming up to-7 ℃ with the speed of 4.3 ℃/min, and the time of keeping-7 ℃ is 5.8 hours;
Phase III puts fast and is 165 ℃ vacuum drying chamber to temperature, namely obtains described heavy metal adsorption material 21 hours drying times.
Making the aperture is that 11.10nm, pore volume are the heavy metal adsorption material of 1.0 cubic centimetres/gram.
Heavy metal adsorption material preparation method embodiment 5
Preliminary treatment: under 180 watts of ultrasonic fields, soaked 300 order raw material silica gel 27 hours with the hydrochloric acid solution of 6.5mol/L, wherein, the mass ratio of raw material silica gel and hydrochloric acid solution is 7.2: 1; Then filter, the elimination acid solution, Washing of Filter Cake is to neutral, and 140 ℃ of lower vacuum drying 7 hours obtain activated silica gel;
Silica gel bonded reaction: in reaction vessel, add anhydrous dimethyl benzole soln and silylating reagent 3-ethylenediamine base propyl trimethoxy silicane, stirring is dissolved in the anhydrous dimethyl benzole soln silylating reagent, obtain the first solution, wherein, the mass ratio of silylating reagent and xylene solution is 7: 1; Add dry DMF in activated silica gel, stirring makes and mixes, and obtains the second solution, and wherein, the mass ratio of activated silica gel and DMF is 2.2: 1; Silylating reagent and activated silica gel mass ratio are 1.8: 1;
The first flow of solution is added in the second solution of reflux state, stream add complete after, continued back flow reaction 19 hours; Filtering reacting liquid after being down to 27 ℃, filter cake are used methyl alcohol and toluene wash successively, and then vacuum drying obtains described heavy metal adsorption material.Described vacuum drying in the silica gel bonded reaction specifically comprises following three phases:
Phase I: will put into freeze drying box with the filter cake after methyl alcohol and the toluene wash, lowering the temperature with the speed of 12 ℃/min is refrigerated to-32 ℃, and the time of keeping-32 ℃ is 7.5 hours;
Second stage is warming up to-9 ℃ with the speed of 4.8 ℃/min, and the time of keeping-9 ℃ is 5.8 hours;
Phase III puts fast and is 160 ℃ vacuum drying chamber to temperature, namely obtains described heavy metal adsorption material 20 hours drying times.
Making the aperture is that 10.89nm, pore volume are the heavy metal adsorption material of 1.1 cubic centimetres/gram.
Heavy metal adsorption material preparation method embodiment 6
Preliminary treatment: under 191 watts of ultrasonic fields, soaked 250 order raw material silica gel 27 hours with the hydrochloric acid solution of 6.5mol/L, wherein, the mass ratio of raw material silica gel and hydrochloric acid solution is 7.3: 1; Then filter, the elimination acid solution, Washing of Filter Cake is to neutral, and 80 ℃ of lower vacuum drying 6.9 hours obtain activated silica gel;
Silica gel bonded reaction: in reaction vessel, add anhydrous dimethyl benzole soln and silylating reagent 3-Diethylenetriamine base propyl trimethoxy silicane, stirring is dissolved in the anhydrous dimethyl benzole soln silylating reagent, obtain the first solution, wherein, the mass ratio of silylating reagent and xylene solution is 6.8: 1; Add dry DMF in activated silica gel, stirring makes and mixes, and obtains the second solution, and wherein, the mass ratio of activated silica gel and DMF is 3.5: 1; Silylating reagent and activated silica gel mass ratio are 1.8: 1;
The first flow of solution is added in the second solution of reflux state, stream add complete after, continued back flow reaction 13 hours; Filtering reacting liquid after being down to 24 ℃, filter cake are used methyl alcohol and toluene wash successively, and then vacuum drying obtains described heavy metal adsorption material.Described vacuum drying in the silica gel bonded reaction specifically comprises following three phases:
Phase I: will put into freeze drying box with the filter cake after methyl alcohol and the toluene wash, lowering the temperature with the speed of 11 ℃/min is refrigerated to-35 ℃, and the time of keeping-35 ℃ is 7.6 hours;
Second stage is warming up to-6 ℃ with the speed of 4.7 ℃/min, and the time of keeping-6 ℃ is 5.7 hours;
Phase III puts fast and is 160 ℃ ℃ vacuum drying chamber to temperature, namely obtains described heavy metal adsorption material 23 hours drying times.
Making the aperture is that 10.65nm, pore volume are the heavy metal adsorption material of 1.2 cubic centimetres/gram.
The separation of copper nickel, enrichment, method of purification experimental example 1
The heavy metal adsorption material that this experimental example adopts heavy metal adsorption material preparation method embodiment 6 to prepare.
S1 fills respectively the heavy metal adsorption material in each adsorption column of continuous adsorption switching equipment; Wherein, described continuous adsorption switching equipment is composed in series by the first adsorption column and the second adsorption column;
S2, the pH that adjusts the pending liquid that contains copper ion and nickel ion is 2.5, obtains pickle liquor;
S3 is with the described continuous adsorption switching equipment after the described pickle liquor injection S1 operation;
S4, described continuous adsorption switching equipment carry out separation and concentration to described pickle liquor and purify under 25 ℃, specifically comprise: be the inlet that 2.5 described pickle liquor pumps into described continuous adsorption switching equipment with pH; Copper ion in the described pickle liquor of described the first adsorption column adsorption and enrichment; It is the inlet that pumps into described the second adsorption column after 3.5 that the liquid that flows out from described the first adsorption column liquid outlet is transferred pH, the nickel ion in the described pickle liquor of described the second adsorption column adsorption and enrichment;
Wherein, specifically comprise following three phases:
Phase I: being 2.5 pickle liquor with pH pumps into the inlet of described continuous adsorption switching equipment with the speed of 3ml/min, by the first adsorption column simultaneously absorbing copper ion and nickel ion, until the first adsorption column is saturated to copper absorption;
Second stage: the inlet that pickle liquor is pumped into described continuous adsorption switching equipment with the speed of 7ml/min, the continuous absorbing copper ion of the first adsorption column, and the copper ion of new absorption replaces the nickel ion of former absorption, until the copper ion amount of the first adsorption column absorption is much larger than the nickel ion amount of absorption;
After second stage was processed, the liquid accent pH that is flowed out by the first adsorption column liquid outlet was that 3.5 rear speed with 1.2ml/min pump into the second adsorption column, by the second adsorption column adsorption and enrichment nickel ion.
S5 is that 18% sulfuric acid washes respectively described the first adsorption column and described the second adsorption column with mass fraction; Described heavy metal adsorption material in described the first adsorption column carries out the desorb operation, the described heavy metal adsorption material that obtains the copper ions stripping liquid and be desorbed after the desorb operation; Described heavy metal adsorption material in described the second adsorption column carries out the desorb operation, obtains the described heavy metal adsorption material that contains the nickel ion stripping liquid and be desorbed after the desorb operation;
S6 carries out the electrodeposition operation by direct electrowinning equipment after the described copper ions stripping liquid that S5 is obtained is concentrated, obtains copper metallic plate or copper metal powder; Simultaneously, the described heavy metal adsorption material that is desorbed in the first adsorption column recovers absorption property after processing through pure water rinsing;
The described nickel ion stripping liquid that contains that S5 is obtained carries out the electrodeposition operation by direct electrowinning equipment after concentrated, obtains nickel metallic plate or nickel metal powder; Simultaneously, the described heavy metal adsorption material that is desorbed in the second adsorption column recovers absorption property after processing through flushing.
The nickel mass fraction is 99.997% in the nickel powder for preparing, and Copper mass fraction is 0.003%;
Copper mass fraction is 99.999% in the copper powder for preparing, and the nickel mass fraction is 0.001%.
The separation of copper nickel, enrichment, method of purification experimental example 2
The heavy metal adsorption material that this experimental example adopts heavy metal adsorption material preparation method embodiment 5 to prepare.
S1 fills respectively the heavy metal adsorption material in each adsorption column of continuous adsorption switching equipment; Wherein, described continuous adsorption switching equipment is composed in series by the first adsorption column and the second adsorption column;
S2, the pH that adjusts the pending liquid that contains copper ion and nickel ion is 5.0, obtains pickle liquor;
S3 is with the described continuous adsorption switching equipment after the described pickle liquor injection S1 operation;
S4, described continuous adsorption switching equipment is purified under 40 ℃ to described pickle liquor, specifically comprises: be the inlet that 5.0 described pickle liquor pumps into described continuous adsorption switching equipment with pH; Copper ion in the described pickle liquor of described the first adsorption column adsorption and enrichment; It is the inlet that pumps into described the second adsorption column after 3.5 that the liquid that flows out from described the first adsorption column liquid outlet is transferred pH, the nickel ion in the described pickle liquor of described the second adsorption column adsorption and enrichment;
Wherein, specifically comprise following three phases:
Phase I: being 5.0 pickle liquor with pH pumps into the inlet of described continuous adsorption switching equipment with the speed of 2ml/min, by the first adsorption column simultaneously absorbing copper ion and nickel ion, until the first adsorption column is saturated to copper absorption;
Second stage: the inlet that pickle liquor is pumped into described continuous adsorption switching equipment with the speed of 6ml/min, the continuous absorbing copper ion of the first adsorption column, and the copper ion of new absorption replaces the nickel ion of former absorption, until the copper ion amount of the first adsorption column absorption is much larger than the nickel ion amount of absorption;
After second stage was processed, the liquid accent pH that is flowed out by the first adsorption column liquid outlet was that 3.5 rear speed with 2ml/min pump into the second adsorption column, by the second adsorption column adsorption and enrichment nickel ion.
S5 is that 26% sulfuric acid washes respectively described the first adsorption column and described the second adsorption column with mass fraction; Described heavy metal adsorption material in described the first adsorption column carries out the desorb operation, the described heavy metal adsorption material that obtains the copper ions stripping liquid and be desorbed after the desorb operation; Described heavy metal adsorption material in described the second adsorption column carries out the desorb operation, obtains the described heavy metal adsorption material that contains the nickel ion stripping liquid and be desorbed after the desorb operation;
S6 carries out the electrodeposition operation by direct electrowinning equipment after the described copper ions stripping liquid that S5 is obtained is concentrated, obtains copper metallic plate or copper metal powder; Simultaneously, the described heavy metal adsorption material that is desorbed in the first adsorption column recovers absorption property after processing through pure water rinsing;
The described nickel ion stripping liquid that contains that S5 is obtained carries out the electrodeposition operation by direct electrowinning equipment after concentrated, obtains nickel metallic plate or nickel metal powder; Simultaneously, the described heavy metal adsorption material that is desorbed in the second adsorption column recovers absorption property after processing through flushing.
The nickel mass fraction is 99.998% in the nickel powder for preparing, and Copper mass fraction is 0.002%;
Copper mass fraction is 99.999% in the copper powder for preparing, and the nickel mass fraction is 0.001%.
The separation of copper nickel, enrichment, method of purification experimental example 3
The heavy metal adsorption material that this experimental example adopts heavy metal adsorption material preparation method embodiment 1 to prepare.
S1 fills respectively the heavy metal adsorption material in each adsorption column of continuous adsorption switching equipment; Wherein, described continuous adsorption switching equipment is composed in series by the first adsorption column and the second adsorption column;
S2, the pH that adjusts the pending liquid that contains copper ion and nickel ion is 2.0, obtains pickle liquor;
S3 is with the described continuous adsorption switching equipment after the described pickle liquor injection S1 operation;
S4, described continuous adsorption switching equipment is purified under 28 ℃ to described pickle liquor, specifically comprises: be the inlet that 2.0 described pickle liquor pumps into described continuous adsorption switching equipment with pH; Copper ion in the described pickle liquor of described the first adsorption column adsorption and enrichment; It is the inlet that pumps into described the second adsorption column after 4.5 that the liquid that flows out from described the first adsorption column liquid outlet is transferred pH, the nickel ion in the described pickle liquor of described the second adsorption column adsorption and enrichment;
Wherein, specifically comprise following three phases:
Phase I: being 2.0 pickle liquor with pH pumps into the inlet of described continuous adsorption switching equipment with the speed of 3ml/min, by the first adsorption column simultaneously absorbing copper ion and nickel ion, until the first adsorption column is saturated to copper absorption;
Second stage: the inlet that pickle liquor is pumped into described continuous adsorption switching equipment with the speed of 7ml/min, the continuous absorbing copper ion of the first adsorption column, and the copper ion of new absorption replaces the nickel ion of former absorption, until the copper ion amount of the first adsorption column absorption is much larger than the nickel ion amount of absorption;
After second stage was processed, the liquid accent pH that is flowed out by the first adsorption column liquid outlet was that 4.5 rear speed with 2ml/min pump into the second adsorption column, by the second adsorption column adsorption and enrichment nickel ion.
S5 is that 30% sulfuric acid washes respectively described the first adsorption column and described the second adsorption column with mass fraction; Described heavy metal adsorption material in described the first adsorption column carries out the desorb operation, the described heavy metal adsorption material that obtains the copper ions stripping liquid and be desorbed after the desorb operation; Described heavy metal adsorption material in described the second adsorption column carries out the desorb operation, obtains the described heavy metal adsorption material that contains the nickel ion stripping liquid and be desorbed after the desorb operation;
S6 carries out the electrodeposition operation by direct electrowinning equipment after the described copper ions stripping liquid that S5 is obtained is concentrated, obtains copper metallic plate or copper metal powder; Simultaneously, the described heavy metal adsorption material that is desorbed in the first adsorption column recovers absorption property after processing through pure water rinsing;
The described nickel ion stripping liquid that contains that S5 is obtained carries out the electrodeposition operation by direct electrowinning equipment after concentrated, obtains nickel metallic plate or nickel metal powder; Simultaneously, the described heavy metal adsorption material that is desorbed in the second adsorption column recovers absorption property after processing through flushing.
The nickel mass fraction is 99.996% in the nickel powder for preparing, and Copper mass fraction is 0.004%;
Copper mass fraction is 99.999% in the copper powder for preparing, and the nickel mass fraction is 0.001%.
The separation of copper nickel, enrichment, method of purification experimental example 4
The heavy metal adsorption material that this experimental example adopts heavy metal adsorption material preparation method embodiment 6 to prepare.
S1 fills respectively the heavy metal adsorption material in each adsorption column of continuous adsorption switching equipment; Wherein, described continuous adsorption switching equipment is composed in series by the first adsorption column and the second adsorption column;
S2, the pH that adjusts the pending liquid that contains copper ion and nickel ion is 1.0, obtains pickle liquor;
S3 is with the described continuous adsorption switching equipment after the described pickle liquor injection S1 operation;
S4, described continuous adsorption switching equipment carry out separation and concentration to described pickle liquor and purify under 32 ℃, specifically comprise: be the inlet that 1.0 described pickle liquor pumps into described continuous adsorption switching equipment with pH; Copper ion in the described pickle liquor of described the first adsorption column adsorption and enrichment; It is the inlet that pumps into described the second adsorption column after 2.0 that the liquid that flows out from described the first adsorption column liquid outlet is transferred pH, the nickel ion in the described pickle liquor of described the second adsorption column adsorption and enrichment;
Wherein, specifically comprise following three phases:
Phase I: being 1.0 pickle liquor with pH pumps into the inlet of described continuous adsorption switching equipment with the speed of 2.5ml/min, by the first adsorption column simultaneously absorbing copper ion and nickel ion, until the first adsorption column is saturated to copper absorption;
Second stage: the inlet that pickle liquor is pumped into described continuous adsorption switching equipment with the speed of 7ml/min, the continuous absorbing copper ion of the first adsorption column, and the copper ion of new absorption replaces the nickel ion of former absorption, until the copper ion amount of the first adsorption column absorption is much larger than the nickel ion amount of absorption;
After second stage was processed, the liquid accent pH that is flowed out by the first adsorption column liquid outlet was that 2.0 rear speed with 1.4ml/min pump into the second adsorption column, by the second adsorption column adsorption and enrichment nickel ion.
S5 is that 22% sulfuric acid washes respectively described the first adsorption column and described the second adsorption column with mass fraction; Described heavy metal adsorption material in described the first adsorption column carries out the desorb operation, the described heavy metal adsorption material that obtains the copper ions stripping liquid and be desorbed after the desorb operation; Described heavy metal adsorption material in described the second adsorption column carries out the desorb operation, obtains the described heavy metal adsorption material that contains the nickel ion stripping liquid and be desorbed after the desorb operation;
S6 carries out the electrodeposition operation by direct electrowinning equipment after the described copper ions stripping liquid that S5 is obtained is concentrated, obtains copper metallic plate or copper metal powder; Simultaneously, the described heavy metal adsorption material that is desorbed in the first adsorption column recovers absorption property after processing through pure water rinsing;
The described nickel ion stripping liquid that contains that S5 is obtained carries out the electrodeposition operation by direct electrowinning equipment after concentrated, obtains nickel metallic plate or nickel metal powder; Simultaneously, the described heavy metal adsorption material that is desorbed in the second adsorption column recovers absorption property after processing through flushing.
The nickel mass fraction is 99.997% in the nickel powder for preparing, and Copper mass fraction is 0.003%;
Copper mass fraction is 99.998% in the copper powder for preparing, and the nickel mass fraction is 0.002%.
The separation of copper nickel, enrichment, method of purification experimental example 5
The heavy metal adsorption material that this experimental example adopts heavy metal adsorption material preparation method embodiment 3 to prepare.
S1 fills respectively the heavy metal adsorption material in each adsorption column of continuous adsorption switching equipment; Wherein, described continuous adsorption switching equipment is composed in series by the first adsorption column and the second adsorption column;
S2, the pH that adjusts the pending liquid that contains copper ion and nickel ion is 3.0, obtains pickle liquor;
S3 is with the described continuous adsorption switching equipment after the described pickle liquor injection S1 operation;
S4, described continuous adsorption switching equipment carry out separation and concentration to described pickle liquor and purify under 36 ℃, specifically comprise: be the inlet that 3.0 described pickle liquor pumps into described continuous adsorption switching equipment with pH; Copper ion in the described pickle liquor of described the first adsorption column adsorption and enrichment; It is the inlet that pumps into described the second adsorption column after 5.5 that the liquid that flows out from described the first adsorption column liquid outlet is transferred pH, the nickel ion in the described pickle liquor of described the second adsorption column adsorption and enrichment;
Wherein, specifically comprise following three phases:
Phase I: being 3.0 pickle liquor with pH pumps into the inlet of described continuous adsorption switching equipment with the speed of 3.5ml/min, by the first adsorption column simultaneously absorbing copper ion and nickel ion, until the first adsorption column is saturated to copper absorption;
Second stage: the inlet that pickle liquor is pumped into described continuous adsorption switching equipment with the speed of 7.9ml/min, the continuous absorbing copper ion of the first adsorption column, and, the copper ion of new absorption replaces the nickel ion of former absorption, until the copper ion amount of the first adsorption column absorption is much larger than the nickel ion amount of absorption;
After second stage was processed, the liquid accent pH that is flowed out by the first adsorption column liquid outlet was that 5.5 rear speed with 2ml/min pump into the second adsorption column, by the second adsorption column adsorption and enrichment nickel ion.
S5 is that 12% sulfuric acid washes respectively described the first adsorption column and described the second adsorption column with mass fraction; Described heavy metal adsorption material in described the first adsorption column carries out the desorb operation, the described heavy metal adsorption material that obtains the copper ions stripping liquid and be desorbed after the desorb operation; Described heavy metal adsorption material in described the second adsorption column carries out the desorb operation, obtains the described heavy metal adsorption material that contains the nickel ion stripping liquid and be desorbed after the desorb operation;
S6 carries out the electrodeposition operation by direct electrowinning equipment after the described copper ions stripping liquid that S5 is obtained is concentrated, obtains copper metallic plate or copper metal powder; Simultaneously, the described heavy metal adsorption material that is desorbed in the first adsorption column recovers absorption property after processing through pure water rinsing;
The described nickel ion stripping liquid that contains that S5 is obtained carries out the electrodeposition operation by direct electrowinning equipment after concentrated, obtains nickel metallic plate or nickel metal powder; Simultaneously, the described heavy metal adsorption material that is desorbed in the second adsorption column recovers absorption property after processing through flushing.
The nickel mass fraction is 99.999% in the nickel powder for preparing, and Copper mass fraction is 0.001%;
Copper mass fraction is 99.999% in the copper powder for preparing, and the nickel mass fraction is 0.001%.
The separation of copper nickel, enrichment, method of purification experimental example 6
The heavy metal adsorption material that this experimental example adopts heavy metal adsorption material preparation method embodiment 5 to prepare.
S1 fills respectively the heavy metal adsorption material in each adsorption column of continuous adsorption switching equipment; Wherein, described continuous adsorption switching equipment is composed in series by the first adsorption column and the second adsorption column;
S2, the pH that adjusts the pending liquid that contains copper ion and nickel ion is 4.0, obtains pickle liquor;
S3 is with the described continuous adsorption switching equipment after the described pickle liquor injection S1 operation;
S4, described continuous adsorption switching equipment carry out separation and concentration to described pickle liquor and purify under 35 ℃, specifically comprise: be the inlet that 4.0 described pickle liquor pumps into described continuous adsorption switching equipment with pH; Copper ion in the described pickle liquor of described the first adsorption column adsorption and enrichment; It is the inlet that pumps into described the second adsorption column after 1.0 that the liquid that flows out from described the first adsorption column liquid outlet is transferred pH, the nickel ion in the described pickle liquor of described the second adsorption column adsorption and enrichment;
Wherein, specifically comprise following three phases:
Phase I: being 4.0 pickle liquors with pH pumps into the inlet of described continuous adsorption switching equipment with the speed of 4ml/min, by the first adsorption column simultaneously absorbing copper ion and nickel ion, until the first adsorption column is saturated to copper absorption;
Second stage: the inlet that pickle liquor is pumped into described continuous adsorption switching equipment with the speed of 7.5ml/min, the continuous absorbing copper ion of the first adsorption column, and, the copper ion of new absorption replaces the nickel ion of former absorption, until the copper ion amount of the first adsorption column absorption is much larger than the nickel ion amount of absorption;
After second stage was processed, the liquid accent pH that is flowed out by the first adsorption column liquid outlet was that 1.0 rear speed with 1.9ml/min pump into the second adsorption column, by the second adsorption column adsorption and enrichment nickel ion.
S5 is that 5% sulfuric acid washes respectively described the first adsorption column and described the second adsorption column with mass fraction; Described heavy metal adsorption material in described the first adsorption column carries out the desorb operation, the described heavy metal adsorption material that obtains the copper ions stripping liquid and be desorbed after the desorb operation; Described heavy metal adsorption material in described the second adsorption column carries out the desorb operation, obtains the described heavy metal adsorption material that contains the nickel ion stripping liquid and be desorbed after the desorb operation;
S6 carries out the electrodeposition operation by direct electrowinning equipment after the described copper ions stripping liquid that S5 is obtained is concentrated, obtains copper metallic plate or copper metal powder; Simultaneously, the described heavy metal adsorption material that is desorbed in the first adsorption column recovers absorption property after processing through pure water rinsing;
The described nickel ion stripping liquid that contains that S5 is obtained carries out the electrodeposition operation by direct electrowinning equipment after concentrated, obtains nickel metallic plate or nickel metal powder; Simultaneously, the described heavy metal adsorption material that is desorbed in the second adsorption column recovers absorption property after processing through flushing.
The nickel mass fraction is 99.997% in the nickel powder for preparing, and Copper mass fraction is 0.003%;
Copper mass fraction is 99.998% in the copper powder for preparing, and the nickel mass fraction is 0.002%.
Test example 1
This test example is used for test heavy metal adsorption material to the absorption property of copper ion and nickel ion, specifically comprises: pH is on the impact on adsorbance of the impact of adsorbance and temperature.
Experimental technique: compound concentration is the copper ion solution of 0.02mol/L, utilizes acidometer to regulate the pH of copper ion solution; The solution 50ml that mixes up pH is placed in the wide-mouth bottle that 1g heavy metal adsorption material is housed, wide-mouth bottle is placed in 25 ℃ the water bath with thermostatic control 36 hours, take out and filter, measure the concentration of copper ion in the filtrate.According to
Formula (one) calculates adsorbance;
Q＝(C
0-C)*V/m
Wherein, Q is adsorbance (mmol/g); C
0For adsorbing front copper ion concentration (mol/L); C is the rear copper ion concentration (mol/L) of absorption; V is the volume (ml) of solution; The attach most importance to quality (g) of metal-adsorbing material of m.
Experimental technique to nickel ion is identical with above-mentioned experimental technique to copper ion.
(1) pH is on the impact experiment of adsorbance
Change the pH of above-mentioned experimental technique, carry out adsorption experiment to copper ion with to nickel ion respectively, experimental result sees Table 1.
Table 1
| Copper adsorbance (mmol/g) | Nickel adsorbance (mmol/g) | |
| pH＝1 | 0.46 | 0.21 |
| pH＝2 | 0.53 | 0.29 |
| pH＝3 | 0.92 | 0.31 |
| pH＝3.5 | 0.94 | 0.43 |
| pH＝4 | 0.85 | 0.45 |
| pH＝4.5 | 0.76 | 0.34 |
| pH＝5 | 0.53 | 0.26 |
As can be seen from Table 1, the heavy metal adsorption material that the present invention prepares all has certain adsorption capacity to copper ion and nickel ion, and the absorption property of copper ion is better than absorption property to nickel ion.So, by the heavy metal adsorption material that adopts the present invention to prepare, after separating technology is optimized, can realize the effect that copper ion is separated with nickel ion.
In addition, for the adsorption experiment to copper ion, along with the increase of pH, the heavy metal adsorption material increases gradually to the adsorbance of copper ion, and when pH reached 3.5, adsorbance reached maximum; Therefore, the best pH of copper absorption is 3.0-3.5.
To the adsorption experiment of nickel ion, along with the increase of pH, the heavy metal adsorption material increases gradually to the adsorbance of nickel ion, and pH is when 3.5-4.0, and adsorbance is larger; Therefore, the best pH of cobalt ions absorption is 3.5-4.0.
(2) temperature is on the impact experiment of adsorbance
PH3.5 is got in the copper absorption experiment, and the nickel ion adsorption experiment is got pH3.8; Change the bath temperature of above-mentioned experimental technique, carry out adsorption experiment to copper ion with to nickel ion respectively, experimental result sees Table 2.
Table 2
| Copper adsorbance (mmol/g) | Nickel adsorbance (mmol/g) | |
| 10 | 0.20 | 0.08 |
| 15 | 0.55 | 0.13 |
| 20 | 0.70 | 0.25 |
| 28 | 0.90 | 0.40 |
| 30 | 0.91 | 0.42 |
| 35 | 0.92 | 0.43 |
| 40 | 0.93 | 0.44 |
| 45 | 0.73 | 0.32 |
| 50 | 0.58 | 0.23 |
As can be seen from Table 2, along with the increase of temperature, the heavy metal adsorption material increases rapidly the adsorbance of copper ion, and when temperature reached 28 ℃, adsorbance was larger; Then the continuation along with temperature increases, and the adsorbance increasing degree is slow.Temperature is approximate with the impact on copper on the adsorbance impact of nickel ion.So, can determine that in the process of carrying out the separation of copper nickel, optimum temperature is 28 ℃.
The above only is preferred embodiment of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be looked protection scope of the present invention.
Claims (8)
1. the method by the separation of heavy metal adsorption material realization copper nickel, enrichment, purification is characterized in that, may further comprise the steps:
S1 fills respectively the heavy metal adsorption material in each adsorption column of continuous adsorption switching equipment; Wherein, described continuous adsorption switching equipment is composed in series by the first adsorption column and the second adsorption column;
S2, the pH that adjusts the pending liquid that contains copper ion and nickel ion is 0.5-5.0, obtains pickle liquor;
S3 is with the described continuous adsorption switching equipment after the described pickle liquor injection S1 operation;
S4, described continuous adsorption switching equipment carry out separation and concentration to described pickle liquor and purify under 25-40 ℃, specifically comprise: be the inlet that the described pickle liquor of 0.5-5.0 pumps into described continuous adsorption switching equipment with pH; Copper ion in the described pickle liquor of described the first adsorption column adsorption and enrichment; It is the inlet that pumps into described the second adsorption column behind the 1.0-5.5 that the liquid that flows out from described the first adsorption column liquid outlet is transferred pH, the nickel ion in the described pickle liquor of described the second adsorption column adsorption and enrichment;
S5 is that the sulfuric acid of 5-30% washes respectively described the first adsorption column and described the second adsorption column with mass fraction; Described heavy metal adsorption material in described the first adsorption column carries out the desorb operation, the described heavy metal adsorption material that obtains the copper ions stripping liquid and be desorbed after the desorb operation; Described heavy metal adsorption material in described the second adsorption column carries out the desorb operation, obtains the described heavy metal adsorption material that contains the nickel ion stripping liquid and be desorbed after the desorb operation;
S6, the described copper ions stripping liquid that S5 is obtained carries out the electrodeposition operation by direct electrowinning equipment, obtains copper metallic plate or copper metal powder; Simultaneously, the described heavy metal adsorption material that is desorbed in the first adsorption column recovers absorption property after processing through flushing;
The described nickel ion stripping liquid that contains that S5 is obtained carries out the electrodeposition operation by direct electrowinning equipment after concentrated, obtains nickel metallic plate or nickel metal powder; Simultaneously, the described heavy metal adsorption material that is desorbed in the second adsorption column recovers absorption property after processing through flushing.
2. according to claim 1ly realize the method for the separation of copper nickel, enrichment, purification it is characterized in that described heavy metal adsorption material is prepared by the following method by the heavy metal adsorption material:
Preliminary treatment: under ultrasonic field, use the hydrochloric acid solution of 5-7mol/L to soak raw material silica gel 20-30 hour, wherein, the mass ratio of raw material silica gel and hydrochloric acid solution is 5-8: 1; Then filter, the elimination acid solution, Washing of Filter Cake is to neutral, 50-150 ℃ lower vacuum drying 5-8 hour, obtain activated silica gel;
Silica gel bonded reaction: add anhydrous dimethyl benzole soln and silylating reagent in reaction vessel, stirring is dissolved in the anhydrous dimethyl benzole soln silylating reagent, obtains the first solution, and wherein, the mass ratio of silylating reagent and xylene solution is 5-8: 1; Add dry DMF in activated silica gel, stirring makes and mixes, and obtains the second solution, and wherein, the mass ratio of activated silica gel and DMF is 2-4: 1; Silylating reagent and activated silica gel mass ratio are 1-2: 1;
The first flow of solution is added in the second solution of reflux state, stream add complete after, continued back flow reaction 10-20 hour; Filtering reacting liquid after being down to 20-30 ℃, filter cake are used methyl alcohol and toluene wash successively, and then 1 vacuum drying obtains described heavy metal adsorption material.
3. the method by the separation of heavy metal adsorption material realization copper nickel, enrichment, purification according to claim 2 is characterized in that the power of described ultrasonic field is 100-200 watt;
Described vacuum drying in the silica gel bonded reaction specifically comprises following three phases:
Phase I: will put into freeze drying box with the filter cake after methyl alcohol and the toluene wash, be refrigerated to-40--30 ℃ with the cooling of the speed of 10-13 ℃/min, keep-time of 40--30 ℃ is 7-8 hour;
Second stage is warming up to-10--5 ℃ with the speed of 4-5 ℃/min, keep-time of 10--5 ℃ is 5-6 hour;
Phase III puts fast and is 160 ℃-170 ℃ vacuum drying chamber to temperature, namely obtains described heavy metal adsorption material 20-23 hour drying time.
4. the method by the separation of heavy metal adsorption material realization copper nickel, enrichment, purification according to claim 2 is characterized in that described silylating reagent is 3-ethylenediamine base propyl trimethoxy silicane or 3-Diethylenetriamine base propyl trimethoxy silicane.
5. the method that realizes the separation of copper nickel, enrichment, purification by the heavy metal adsorption material according to claim 2, it is characterized in that, the aperture of described heavy metal adsorption material is 10.02-11.23nm, and the pore volume of described heavy metal adsorption material is 0.9-1.5 cubic centimetre/gram.
6. the method by the separation of heavy metal adsorption material realization copper nickel, enrichment, purification according to claim 2 is characterized in that described raw silicon micelle degree is 200-300 order silica gel.
7. according to claim 1ly realize the method for the separation of copper nickel, enrichment, purification it is characterized in that S4 specifically comprises following three phases by the heavy metal adsorption material:
Phase I: the pickle liquor that with pH is 0.5-5.0 pumps into the inlet of described continuous adsorption switching equipment with the speed of 2-4ml/min, by the first adsorption column simultaneously absorbing copper ion and nickel ion, until the first adsorption column is saturated to copper absorption;
Second stage: the inlet that pickle liquor is pumped into described continuous adsorption switching equipment with the speed of 6-8ml/min, the continuous absorbing copper ion of the first adsorption column, and the copper ion of new absorption replaces the nickel ion of former absorption, until the nickel ion of the first adsorption column absorption is replaced by copper ion fully;
After second stage was processed, it was that the speed with 1-2ml/min pumps into the second adsorption column behind the 1.0-5.5 that the liquid that is flowed out by the first adsorption column liquid outlet is transferred pH, by the second adsorption column adsorption and enrichment nickel ion.
8. according to claim 7ly realize the method for the separation of copper nickel, enrichment, purification it is characterized in that S4 specifically comprises following three phases by the heavy metal adsorption material:
Phase I: the pickle liquor that with pH is 3.0-3.5 pumps into the inlet of described continuous adsorption switching equipment with the speed of 3ml/min, by the first adsorption column simultaneously absorbing copper ion and nickel ion, until the first adsorption column is saturated to copper absorption;
Second stage: the inlet that pickle liquor is pumped into described continuous adsorption switching equipment with the speed of 7ml/min, the continuous absorbing copper ion of the first adsorption column, and the copper ion of new absorption replaces the nickel ion of former absorption, until the nickel ion of the first adsorption column absorption is replaced by copper ion fully;
After second stage was processed, it was that the speed with 1.5ml/min pumps into the second adsorption column behind the 3.5-4.0 that the liquid that is flowed out by the first adsorption column liquid outlet is transferred pH, by the second adsorption column adsorption and enrichment nickel ion.
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| CN104178628A (en) * | 2013-05-28 | 2014-12-03 | 工信华鑫科技有限公司 | Novel wet-smelting technology |
| CN114195288A (en) * | 2021-12-10 | 2022-03-18 | 中新联科环境科技(安徽)有限公司 | Method for purifying comprehensive nickel wastewater and copper-containing wastewater |
| CN114210204A (en) * | 2021-12-23 | 2022-03-22 | 中国原子能科学研究院 | Method for separating nickel isotopes |
| CN117222765A (en) * | 2023-07-31 | 2023-12-12 | 青美邦新能源材料有限公司 | Method for extracting nickel and cobalt from laterite-nickel ore in green and low cost manner |
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| CN104178628A (en) * | 2013-05-28 | 2014-12-03 | 工信华鑫科技有限公司 | Novel wet-smelting technology |
| CN114195288A (en) * | 2021-12-10 | 2022-03-18 | 中新联科环境科技(安徽)有限公司 | Method for purifying comprehensive nickel wastewater and copper-containing wastewater |
| CN114210204A (en) * | 2021-12-23 | 2022-03-22 | 中国原子能科学研究院 | Method for separating nickel isotopes |
| CN117222765A (en) * | 2023-07-31 | 2023-12-12 | 青美邦新能源材料有限公司 | Method for extracting nickel and cobalt from laterite-nickel ore in green and low cost manner |
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