CN102872808B - 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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- CN102872808B CN102872808B CN201210344767.7A CN201210344767A CN102872808B CN 102872808 B CN102872808 B CN 102872808B CN 201210344767 A CN201210344767 A CN 201210344767A CN 102872808 B CN102872808 B CN 102872808B
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 403
- 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 132
- 239000000463 material Substances 0.000 title claims abstract description 128
- 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 30
- 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
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 88
- 239000007788 liquid Substances 0.000 claims abstract description 83
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000010521 absorption reaction Methods 0.000 claims description 70
- 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 25
- 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
- 238000000746 purification Methods 0.000 claims description 23
- 229910000570 Cupronickel Inorganic materials 0.000 claims description 19
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 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
- 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
- 238000012545 processing 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
- 235000014666 liquid concentrate Nutrition 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
- 230000007547 defect 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
- 230000008569 process Effects 0.000 description 2
- 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
- 238000003672 processing method 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 heavy metal separation technology field, be specifically related to a kind of method that realizes the separation of copper nickel, enrichment, purification by heavy metal adsorption material.
Background technology
Along with the develop rapidly of World Economics and the continuous increase of the size of population, a little less than relative inadequacy of resources and environmental carrying capacity, become the important bottleneck of world development.Resources for construction economizing type and friendly environment society, advance Ecological Civilization Construction, 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 to process it, thereby reduce content of beary metal in water resource, reduce the harm of heavy metal pollution.
But, there is the low and high defect of cost of the removal efficiency of heavy metal ions in wastewater in the processing method of all kinds of heavy metal wastewater therebies that adopt at present.
Summary of the invention
The defect existing for prior art, the invention provides a kind of method that realizes the separation of copper nickel, enrichment, purification by heavy metal adsorption material, has advantages of the selective absorption of copper ion strong.
The technical solution used in the present invention is as follows:
The invention provides a kind of method that realizes the separation of copper nickel, enrichment, purification by heavy metal adsorption material, comprise the following steps:
S1 fills respectively 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, injects the described continuous adsorption switching equipment after S1 operation by described pickle liquor;
S4, described continuous adsorption switching equipment carries out separation and concentration purification at 25-40 ℃ to described pickle liquor, specifically comprise: the described pickle liquor that is 0.5-5.0 by pH pumps into the inlet of described continuous adsorption switching equipment; Copper ion described in described the first adsorption column adsorption and enrichment in pickle liquor; The liquid flowing out from described the first adsorption column liquid outlet adjusts pH 1.0-5.5, to pump into the inlet of described the second adsorption column, the nickel ion described in described the second adsorption column adsorption and enrichment in pickle liquor;
S5, the sulfuric acid that is 5-30% by mass fraction rinses respectively described the first adsorption column and described the second adsorption column; Described heavy metal adsorption material in described the first adsorption column carries out desorb operation, the described heavy metal adsorption material that obtains copper ions stripping liquid and be desorbed after desorb operation; Described heavy metal adsorption material in described the second adsorption column carries out desorb operation, obtains containing nickel ion stripping liquid and the described heavy metal adsorption material being desorbed after desorb operation;
S6, the described copper ions stripping liquid that S5 is obtained carries out electrodeposition operation by direct electrowinning equipment, obtains copper metallic plate or copper metal powder; Meanwhile, the described heavy metal adsorption material being desorbed in the first adsorption column recovers absorption property after rinsing processing;
Carry out electrodeposition operation by direct electrowinning equipment described the containing after nickel ion stripping liquid concentrates that S5 is obtained, and obtains nickel metallic plate or nickel metal powder; Meanwhile, the described heavy metal adsorption material being desorbed in the second adsorption column recovers absorption property after rinsing processing.
Preferably, described heavy metal adsorption material is prepared by the following method:
Pretreatment: under ultrasonic field, soak raw material silica gel 20-30 hour with the hydrochloric acid solution of 5-7mol/L, wherein, the mass ratio of raw material silica gel and hydrochloric acid solution is 5-8: 1; Then filter, elimination acid solution, Washing of Filter Cake is to neutral, and vacuum drying 5-8 hour at 50-150 ℃, obtains activated silica gel;
Silica gel bonded reaction: add anhydrous dimethyl benzole soln and silylating reagent in reaction vessel, stir silylating reagent is dissolved in anhydrous dimethyl benzole soln, obtain the first solution, wherein, the mass ratio of silylating reagent and xylene solution is 5-8: 1; In activated silica gel, add dry DMF, stir and make to mix, obtain the second solution, 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, after stream adds, continues back flow reaction 10-20 hour; Filtering reacting liquid after being down to 20-30 ℃, filter cake is 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 silica gel bonded reaction specifically comprises following three phases:
First stage: will put into freeze drying box with the filter cake after methyl alcohol and toluene wash, with the be refrigerated to-40--30 ℃ of speed cooling of 10-13 ℃/min, the time of maintain-40--30 ℃ is 7-8 hour;
Second stage, with the be warming up to-10--5 ℃ of speed of 4-5 ℃/min, the time of maintain-10--5 ℃ is 5-6 hour;
Phase III, in putting fast and being the vacuum drying chamber of 160 ℃-170 ℃ to temperature, obtain 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, the pore volume of described heavy metal adsorption material be 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:
First stage: the pickle liquor that is 0.5-5.0 by pH pumps into the inlet of described continuous adsorption switching equipment with the speed of 2-4ml/min, by the first adsorption column while absorbing copper ion and nickel ion, until the first adsorption column is saturated to copper absorption;
Second stage: pickle liquor is pumped into the inlet of 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 completely;
After second stage is processed, it is that after 1.0-5.5, the speed with 1-2ml/min pumps into the second adsorption column that the liquid being flowed out by the first adsorption column liquid outlet is adjusted pH, by the second adsorption column adsorption and enrichment nickel ion.
Preferably, S4 specifically comprises following three phases:
First stage: the pickle liquor that is 3.0-3.5 by pH pumps into the inlet of described continuous adsorption switching equipment with the speed of 3ml/min, by the first adsorption column while absorbing copper ion and nickel ion, until the first adsorption column is saturated to copper absorption;
Second stage: pickle liquor is pumped into the inlet of 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 completely;
After second stage is processed, it is that after 3.5-4.0, the speed with 1.5ml/min pumps into the second adsorption column that the liquid being flowed out by the first adsorption column liquid outlet is adjusted pH, by the second adsorption column adsorption and enrichment nickel ion.
Below the present invention is described further:
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 this feature, for realizing separated to copper ion and nickel ion, inventor has carried out test of many times to the technique of using adsorption column to cross post, unexpected discovery, by the accurate control to the temperature for the treatment of fluid and flow velocity, can realize the separated of good copper ion and nickel ion, therefore, it is provided by the invention that by heavy metal adsorption material, to realize copper nickel separated, enrichment, the method of purifying, can be applied to the separated of trace in liquid or trace copper and mickel and reclaim.
The specific embodiment
Below the method that realizes the separation of copper nickel, enrichment, purification by heavy metal adsorption material provided by the invention is described in detail:
Heavy metal adsorption material preparation method embodiment 1
Pretreatment: under 100 watts of ultrasonic fields, soak 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, elimination acid solution, Washing of Filter Cake is to neutral, and vacuum drying is 8 hours at 50 ℃, obtains activated silica gel;
Silica gel bonded reaction: add anhydrous dimethyl benzole soln and silylating reagent 3-ethylenediamine base propyl trimethoxy silicane in reaction vessel, stirring is dissolved in anhydrous dimethyl benzole soln silylating reagent, obtain the first solution, wherein, the mass ratio of silylating reagent and xylene solution is 8: 1; In activated silica gel, add dry DMF, stir and make to mix, obtain the second solution, 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, after stream adds, continues back flow reaction 10 hours; Filtering reacting liquid after being down to 30 ℃, filter cake is used methyl alcohol and toluene wash successively, and then vacuum drying obtains described heavy metal adsorption material.Described vacuum drying in silica gel bonded reaction specifically comprises following three phases:
First stage: will put into freeze drying box with the filter cake after methyl alcohol and toluene wash, with the be refrigerated to-40--30 ℃ of speed cooling of 12 ℃/min, the time that maintains-38 ℃ is 7.6 hours;
Second stage, is warming up to-10 ℃ with the speed of 4 ℃/min, and the time that maintains-10 ℃ is 5 hours;
Phase III, in putting fast and being the vacuum drying chamber of 165 ℃ to temperature, obtain described heavy metal adsorption material 22 hours drying times.
Making 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
Pretreatment: under 200 watts of ultrasonic fields, soak 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, elimination acid solution, Washing of Filter Cake is to neutral, and vacuum drying is 5 hours at 150 ℃, obtains activated silica gel;
Silica gel bonded reaction: add anhydrous dimethyl benzole soln and silylating reagent 3-Diethylenetriamine base propyl trimethoxy silicane in reaction vessel, stirring is dissolved in anhydrous dimethyl benzole soln silylating reagent, obtain the first solution, wherein, the mass ratio of silylating reagent and xylene solution is 5: 1; In activated silica gel, add dry DMF, stir and make to mix, obtain the second solution, 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, after stream adds, continues back flow reaction 20 hours; Filtering reacting liquid after being down to 20 ℃, filter cake is used methyl alcohol and toluene wash successively, and then vacuum drying obtains described heavy metal adsorption material.Described vacuum drying in silica gel bonded reaction specifically comprises following three phases:
First stage: will put into freeze drying box with the filter cake after methyl alcohol and toluene wash, lower the temperature and be refrigerated to-40 ℃ with the speed of 10 ℃/min, the time that maintains-40 ℃ is 7 hours;
Second stage, is warming up to-5 ℃ with the speed of 5 ℃/min, and the time that maintains-5 ℃ is 6 hours;
Phase III, in putting fast and being the vacuum drying chamber of 167 ℃ to temperature, obtain described heavy metal adsorption material 22 hours drying times.
Making 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
Pretreatment: under 150 watts of ultrasonic fields, soak 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, elimination acid solution, Washing of Filter Cake is to neutral, and vacuum drying is 6 hours at 100 ℃, obtains activated silica gel;
Silica gel bonded reaction: add anhydrous dimethyl benzole soln and silylating reagent 3-ethylenediamine base propyl trimethoxy silicane in reaction vessel, stirring is dissolved in anhydrous dimethyl benzole soln silylating reagent, obtain the first solution, wherein, the mass ratio of silylating reagent and xylene solution is 7: 1; In activated silica gel, add dry DMF, stir and make to mix, obtain the second solution, 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, after stream adds, continues back flow reaction 15 hours; Filtering reacting liquid after being down to 25 ℃, filter cake is used methyl alcohol and toluene wash successively, and then vacuum drying obtains described heavy metal adsorption material.Described vacuum drying in silica gel bonded reaction specifically comprises following three phases:
First stage: will put into freeze drying box with the filter cake after methyl alcohol and toluene wash, lower the temperature and be refrigerated to-0 ℃ with the speed of 13 ℃/min, the time that maintains-30 ℃ is 7 hours;
Second stage, is warming up to-7 ℃ with the speed of 4.5 ℃/min, and the time that maintains-7 ℃ is 5.5 hours;
Phase III, in putting fast and being the vacuum drying chamber of 163 ℃ to temperature, obtain described heavy metal adsorption material 22 hours drying times.
Making 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
Pretreatment: under 120 watts of ultrasonic fields, soak 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, elimination acid solution, Washing of Filter Cake is to neutral, and vacuum drying is 6 hours at 80 ℃, obtains activated silica gel;
Silica gel bonded reaction: add anhydrous dimethyl benzole soln and silylating reagent 3-Diethylenetriamine base propyl trimethoxy silicane in reaction vessel, stirring is dissolved in anhydrous dimethyl benzole soln silylating reagent, obtain the first solution, wherein, the mass ratio of silylating reagent and xylene solution is 7: 1; In activated silica gel, add dry DMF, stir and make to mix, obtain the second solution, 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, after stream adds, continues back flow reaction 16 hours; Filtering reacting liquid after being down to 21 ℃, filter cake is used methyl alcohol and toluene wash successively, and then vacuum drying obtains described heavy metal adsorption material.Described vacuum drying in silica gel bonded reaction specifically comprises following three phases:
First stage: will put into freeze drying box with the filter cake after methyl alcohol and toluene wash, lower the temperature and be refrigerated to-35 ℃ with the speed of 11 ℃/min, the time that maintains-35 ℃ is 7.5 hours;
Second stage, is warming up to-7 ℃ with the speed of 4.3 ℃/min, and the time that maintains-7 ℃ is 5.8 hours;
Phase III, in putting fast and being the vacuum drying chamber of 165 ℃ to temperature, obtain described heavy metal adsorption material 21 hours drying times.
Making 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
Pretreatment: under 180 watts of ultrasonic fields, soak 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, elimination acid solution, Washing of Filter Cake is to neutral, and vacuum drying is 7 hours at 140 ℃, obtains activated silica gel;
Silica gel bonded reaction: add anhydrous dimethyl benzole soln and silylating reagent 3-ethylenediamine base propyl trimethoxy silicane in reaction vessel, stirring is dissolved in anhydrous dimethyl benzole soln silylating reagent, obtain the first solution, wherein, the mass ratio of silylating reagent and xylene solution is 7: 1; In activated silica gel, add dry DMF, stir and make to mix, obtain the second solution, 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, after stream adds, continues back flow reaction 19 hours; Filtering reacting liquid after being down to 27 ℃, filter cake is used methyl alcohol and toluene wash successively, and then vacuum drying obtains described heavy metal adsorption material.Described vacuum drying in silica gel bonded reaction specifically comprises following three phases:
First stage: will put into freeze drying box with the filter cake after methyl alcohol and toluene wash, lower the temperature and be refrigerated to-32 ℃ with the speed of 12 ℃/min, the time that maintains-32 ℃ is 7.5 hours;
Second stage, is warming up to-9 ℃ with the speed of 4.8 ℃/min, and the time that maintains-9 ℃ is 5.8 hours;
Phase III, in putting fast and being the vacuum drying chamber of 160 ℃ to temperature, obtain described heavy metal adsorption material 20 hours drying times.
Making 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
Pretreatment: under 191 watts of ultrasonic fields, soak 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, elimination acid solution, Washing of Filter Cake is to neutral, and vacuum drying is 6.9 hours at 80 ℃, obtains activated silica gel;
Silica gel bonded reaction: add anhydrous dimethyl benzole soln and silylating reagent 3-Diethylenetriamine base propyl trimethoxy silicane in reaction vessel, stirring is dissolved in anhydrous dimethyl benzole soln silylating reagent, obtain the first solution, wherein, the mass ratio of silylating reagent and xylene solution is 6.8: 1; In activated silica gel, add dry DMF, stir and make to mix, obtain the second solution, 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, after stream adds, continues back flow reaction 13 hours; Filtering reacting liquid after being down to 24 ℃, filter cake is used methyl alcohol and toluene wash successively, and then vacuum drying obtains described heavy metal adsorption material.Described vacuum drying in silica gel bonded reaction specifically comprises following three phases:
First stage: will put into freeze drying box with the filter cake after methyl alcohol and toluene wash, lower the temperature and be refrigerated to-35 ℃ with the speed of 11 ℃/min, the time that maintains-35 ℃ is 7.6 hours;
Second stage, is warming up to-6 ℃ with the speed of 4.7 ℃/min, and the time that maintains-6 ℃ is 5.7 hours;
Phase III, puts fast to the temperature vacuum drying chamber that is 160 ℃ ℃, obtains described heavy metal adsorption material 23 hours drying times.
Making 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 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, injects the described continuous adsorption switching equipment after S1 operation by described pickle liquor;
S4, described continuous adsorption switching equipment carries out separation and concentration purification at 25 ℃ to described pickle liquor, specifically comprise: the described pickle liquor that is 2.5 by pH pumps into the inlet of described continuous adsorption switching equipment; Copper ion described in described the first adsorption column adsorption and enrichment in pickle liquor; It is the inlet that pumps into described the second adsorption column 3.5 that the liquid flowing out from described the first adsorption column liquid outlet is adjusted pH, the nickel ion described in described the second adsorption column adsorption and enrichment in pickle liquor;
Wherein, specifically comprise following three phases:
First stage: the pickle liquor that is 2.5 by pH pumps into the inlet of described continuous adsorption switching equipment with the speed of 3ml/min, by the first adsorption column while absorbing copper ion and nickel ion, until the first adsorption column is saturated to copper absorption;
Second stage: pickle liquor is pumped into the inlet of 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 is processed, it is that the speed with 1.2ml/min pumps into the second adsorption column after 3.5 that the liquid being flowed out by the first adsorption column liquid outlet is adjusted pH, by the second adsorption column adsorption and enrichment nickel ion.
S5, the sulfuric acid that is 18% by mass fraction rinses respectively described the first adsorption column and described the second adsorption column; Described heavy metal adsorption material in described the first adsorption column carries out desorb operation, the described heavy metal adsorption material that obtains copper ions stripping liquid and be desorbed after desorb operation; Described heavy metal adsorption material in described the second adsorption column carries out desorb operation, obtains containing nickel ion stripping liquid and the described heavy metal adsorption material being desorbed after desorb operation;
S6, carries out 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; Meanwhile, the described heavy metal adsorption material being desorbed in the first adsorption column recovers absorption property after pure water rinsing is processed;
Carry out electrodeposition operation by direct electrowinning equipment described the containing after nickel ion stripping liquid concentrates that S5 is obtained, and obtains nickel metallic plate or nickel metal powder; Meanwhile, the described heavy metal adsorption material being desorbed in the second adsorption column recovers absorption property after rinsing processing.
In the nickel powder preparing, nickel mass fraction is 99.997%, and Copper mass fraction is 0.003%;
In the copper powder preparing, Copper mass fraction is 99.999%, and 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 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, injects the described continuous adsorption switching equipment after S1 operation by described pickle liquor;
S4, described continuous adsorption switching equipment is purified at 40 ℃ to described pickle liquor, specifically comprises: the described pickle liquor that is 5.0 by pH pumps into the inlet of described continuous adsorption switching equipment; Copper ion described in described the first adsorption column adsorption and enrichment in pickle liquor; It is the inlet that pumps into described the second adsorption column 3.5 that the liquid flowing out from described the first adsorption column liquid outlet is adjusted pH, the nickel ion described in described the second adsorption column adsorption and enrichment in pickle liquor;
Wherein, specifically comprise following three phases:
First stage: the pickle liquor that is 5.0 by pH pumps into the inlet of described continuous adsorption switching equipment with the speed of 2ml/min, by the first adsorption column while absorbing copper ion and nickel ion, until the first adsorption column is saturated to copper absorption;
Second stage: pickle liquor is pumped into the inlet of 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 is processed, it is that the speed with 2ml/min pumps into the second adsorption column after 3.5 that the liquid being flowed out by the first adsorption column liquid outlet is adjusted pH, by the second adsorption column adsorption and enrichment nickel ion.
S5, the sulfuric acid that is 26% by mass fraction rinses respectively described the first adsorption column and described the second adsorption column; Described heavy metal adsorption material in described the first adsorption column carries out desorb operation, the described heavy metal adsorption material that obtains copper ions stripping liquid and be desorbed after desorb operation; Described heavy metal adsorption material in described the second adsorption column carries out desorb operation, obtains containing nickel ion stripping liquid and the described heavy metal adsorption material being desorbed after desorb operation;
S6, carries out 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; Meanwhile, the described heavy metal adsorption material being desorbed in the first adsorption column recovers absorption property after pure water rinsing is processed;
Carry out electrodeposition operation by direct electrowinning equipment described the containing after nickel ion stripping liquid concentrates that S5 is obtained, and obtains nickel metallic plate or nickel metal powder; Meanwhile, the described heavy metal adsorption material being desorbed in the second adsorption column recovers absorption property after rinsing processing.
In the nickel powder preparing, nickel mass fraction is 99.998%, and Copper mass fraction is 0.002%;
In the copper powder preparing, Copper mass fraction is 99.999%, and 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 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, injects the described continuous adsorption switching equipment after S1 operation by described pickle liquor;
S4, described continuous adsorption switching equipment is purified at 28 ℃ to described pickle liquor, specifically comprises: the described pickle liquor that is 2.0 by pH pumps into the inlet of described continuous adsorption switching equipment; Copper ion described in described the first adsorption column adsorption and enrichment in pickle liquor; It is the inlet that pumps into described the second adsorption column 4.5 that the liquid flowing out from described the first adsorption column liquid outlet is adjusted pH, the nickel ion described in described the second adsorption column adsorption and enrichment in pickle liquor;
Wherein, specifically comprise following three phases:
First stage: the pickle liquor that is 2.0 by pH pumps into the inlet of described continuous adsorption switching equipment with the speed of 3ml/min, by the first adsorption column while absorbing copper ion and nickel ion, until the first adsorption column is saturated to copper absorption;
Second stage: pickle liquor is pumped into the inlet of 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 is processed, it is that the speed with 2ml/min pumps into the second adsorption column after 4.5 that the liquid being flowed out by the first adsorption column liquid outlet is adjusted pH, by the second adsorption column adsorption and enrichment nickel ion.
S5, the sulfuric acid that is 30% by mass fraction rinses respectively described the first adsorption column and described the second adsorption column; Described heavy metal adsorption material in described the first adsorption column carries out desorb operation, the described heavy metal adsorption material that obtains copper ions stripping liquid and be desorbed after desorb operation; Described heavy metal adsorption material in described the second adsorption column carries out desorb operation, obtains containing nickel ion stripping liquid and the described heavy metal adsorption material being desorbed after desorb operation;
S6, carries out 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; Meanwhile, the described heavy metal adsorption material being desorbed in the first adsorption column recovers absorption property after pure water rinsing is processed;
Carry out electrodeposition operation by direct electrowinning equipment described the containing after nickel ion stripping liquid concentrates that S5 is obtained, and obtains nickel metallic plate or nickel metal powder; Meanwhile, the described heavy metal adsorption material being desorbed in the second adsorption column recovers absorption property after rinsing processing.
In the nickel powder preparing, nickel mass fraction is 99.996%, and Copper mass fraction is 0.004%;
In the copper powder preparing, Copper mass fraction is 99.999%, and 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 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, injects the described continuous adsorption switching equipment after S1 operation by described pickle liquor;
S4, described continuous adsorption switching equipment carries out separation and concentration purification at 32 ℃ to described pickle liquor, specifically comprise: the described pickle liquor that is 1.0 by pH pumps into the inlet of described continuous adsorption switching equipment; Copper ion described in described the first adsorption column adsorption and enrichment in pickle liquor; It is the inlet that pumps into described the second adsorption column 2.0 that the liquid flowing out from described the first adsorption column liquid outlet is adjusted pH, the nickel ion described in described the second adsorption column adsorption and enrichment in pickle liquor;
Wherein, specifically comprise following three phases:
First stage: the pickle liquor that is 1.0 by pH pumps into the inlet of described continuous adsorption switching equipment with the speed of 2.5ml/min, by the first adsorption column while absorbing copper ion and nickel ion, until the first adsorption column is saturated to copper absorption;
Second stage: pickle liquor is pumped into the inlet of 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 is processed, it is that the speed with 1.4ml/min pumps into the second adsorption column after 2.0 that the liquid being flowed out by the first adsorption column liquid outlet is adjusted pH, by the second adsorption column adsorption and enrichment nickel ion.
S5, the sulfuric acid that is 22% by mass fraction rinses respectively described the first adsorption column and described the second adsorption column; Described heavy metal adsorption material in described the first adsorption column carries out desorb operation, the described heavy metal adsorption material that obtains copper ions stripping liquid and be desorbed after desorb operation; Described heavy metal adsorption material in described the second adsorption column carries out desorb operation, obtains containing nickel ion stripping liquid and the described heavy metal adsorption material being desorbed after desorb operation;
S6, carries out 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; Meanwhile, the described heavy metal adsorption material being desorbed in the first adsorption column recovers absorption property after pure water rinsing is processed;
Carry out electrodeposition operation by direct electrowinning equipment described the containing after nickel ion stripping liquid concentrates that S5 is obtained, and obtains nickel metallic plate or nickel metal powder; Meanwhile, the described heavy metal adsorption material being desorbed in the second adsorption column recovers absorption property after rinsing processing.
In the nickel powder preparing, nickel mass fraction is 99.997%, and Copper mass fraction is 0.003%;
In the copper powder preparing, Copper mass fraction is 99.998%, and 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 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, injects the described continuous adsorption switching equipment after S1 operation by described pickle liquor;
S4, described continuous adsorption switching equipment carries out separation and concentration purification at 36 ℃ to described pickle liquor, specifically comprise: the described pickle liquor that is 3.0 by pH pumps into the inlet of described continuous adsorption switching equipment; Copper ion described in described the first adsorption column adsorption and enrichment in pickle liquor; It is the inlet that pumps into described the second adsorption column 5.5 that the liquid flowing out from described the first adsorption column liquid outlet is adjusted pH, the nickel ion described in described the second adsorption column adsorption and enrichment in pickle liquor;
Wherein, specifically comprise following three phases:
First stage: the pickle liquor that is 3.0 by pH pumps into the inlet of described continuous adsorption switching equipment with the speed of 3.5ml/min, by the first adsorption column while absorbing copper ion and nickel ion, until the first adsorption column is saturated to copper absorption;
Second stage: pickle liquor is pumped into the inlet of 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 is processed, it is that the speed with 2ml/min pumps into the second adsorption column after 5.5 that the liquid being flowed out by the first adsorption column liquid outlet is adjusted pH, by the second adsorption column adsorption and enrichment nickel ion.
S5, the sulfuric acid that is 12% by mass fraction rinses respectively described the first adsorption column and described the second adsorption column; Described heavy metal adsorption material in described the first adsorption column carries out desorb operation, the described heavy metal adsorption material that obtains copper ions stripping liquid and be desorbed after desorb operation; Described heavy metal adsorption material in described the second adsorption column carries out desorb operation, obtains containing nickel ion stripping liquid and the described heavy metal adsorption material being desorbed after desorb operation;
S6, carries out 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; Meanwhile, the described heavy metal adsorption material being desorbed in the first adsorption column recovers absorption property after pure water rinsing is processed;
Carry out electrodeposition operation by direct electrowinning equipment described the containing after nickel ion stripping liquid concentrates that S5 is obtained, and obtains nickel metallic plate or nickel metal powder; Meanwhile, the described heavy metal adsorption material being desorbed in the second adsorption column recovers absorption property after rinsing processing.
In the nickel powder preparing, nickel mass fraction is 99.999%, and Copper mass fraction is 0.001%;
In the copper powder preparing, Copper mass fraction is 99.999%, and 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 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, injects the described continuous adsorption switching equipment after S1 operation by described pickle liquor;
S4, described continuous adsorption switching equipment carries out separation and concentration purification at 35 ℃ to described pickle liquor, specifically comprise: the described pickle liquor that is 4.0 by pH pumps into the inlet of described continuous adsorption switching equipment; Copper ion described in described the first adsorption column adsorption and enrichment in pickle liquor; It is the inlet that pumps into described the second adsorption column 1.0 that the liquid flowing out from described the first adsorption column liquid outlet is adjusted pH, the nickel ion described in described the second adsorption column adsorption and enrichment in pickle liquor;
Wherein, specifically comprise following three phases:
First stage: be that 4.0 pickle liquors pump into the inlet of described continuous adsorption switching equipment with the speed of 4ml/min by pH, by the first adsorption column while absorbing copper ion and nickel ion, until the first adsorption column is saturated to copper absorption;
Second stage: pickle liquor is pumped into the inlet of 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 is processed, it is that the speed with 1.9ml/min pumps into the second adsorption column after 1.0 that the liquid being flowed out by the first adsorption column liquid outlet is adjusted pH, by the second adsorption column adsorption and enrichment nickel ion.
S5, the sulfuric acid that is 5% by mass fraction rinses respectively described the first adsorption column and described the second adsorption column; Described heavy metal adsorption material in described the first adsorption column carries out desorb operation, the described heavy metal adsorption material that obtains copper ions stripping liquid and be desorbed after desorb operation; Described heavy metal adsorption material in described the second adsorption column carries out desorb operation, obtains containing nickel ion stripping liquid and the described heavy metal adsorption material being desorbed after desorb operation;
S6, carries out 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; Meanwhile, the described heavy metal adsorption material being desorbed in the first adsorption column recovers absorption property after pure water rinsing is processed;
Carry out electrodeposition operation by direct electrowinning equipment described the containing after nickel ion stripping liquid concentrates that S5 is obtained, and obtains nickel metallic plate or nickel metal powder; Meanwhile, the described heavy metal adsorption material being desorbed in the second adsorption column recovers absorption property after rinsing processing.
In the nickel powder preparing, nickel mass fraction is 99.997%, and Copper mass fraction is 0.003%;
In the copper powder preparing, Copper mass fraction is 99.998%, and nickel mass fraction is 0.002%.
Test example 1
This test example, for testing the absorption property of heavy metal adsorption material to copper ion and nickel ion, specifically comprises: pH impact on adsorbance on the impact of adsorbance and temperature.
Experimental technique: the copper ion solution that compound concentration is 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 the water bath with thermostatic control of 25 ℃ to 36 hours, take out and filter, measure the concentration of copper ion in 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.
Identical with the above-mentioned experimental technique to copper ion to the experimental technique of nickel ion.
(1) the impact experiment of pH on adsorbance
Change the pH of above-mentioned experimental technique, carry out adsorption experiment respectively to copper ion with to nickel ion, experimental result is in 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 to the 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 separated with nickel ion to copper ion.
In addition, for the adsorption experiment to copper ion, along with the increase of pH, heavy metal adsorption material increases gradually to the adsorbance of copper ion, and when pH reaches 3.5, adsorbance reaches maximum; Therefore, the best pH of copper absorption is 3.0-3.5.
Adsorption experiment to nickel ion, along with the increase of pH, 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) the impact experiment of temperature on adsorbance
PH3.5 is got in copper absorption experiment, and nickel ion adsorption experiment is got pH3.8; Change the bath temperature of above-mentioned experimental technique, carry out adsorption experiment respectively to copper ion with to nickel ion, experimental result is in 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, heavy metal adsorption material increases rapidly the adsorbance of copper ion, and when temperature reaches 28 ℃, adsorbance is larger; Then the continuation along with temperature increases, and adsorbance increasing degree is slow.Temperature is on the adsorbance impact of nickel ion and approximate on the impact of copper.So, can determine, in carrying out the process of copper nickel separation, optimum temperature is 28 ℃.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles 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 (6)
1. by heavy metal adsorption material, realize a method for the separation of copper nickel, enrichment, purification, it is characterized in that, comprise the following steps:
S1 fills respectively 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; Described heavy metal adsorption material is prepared by the following method:
Pretreatment: under ultrasonic field, soak raw material silica gel 20-30 hour with the hydrochloric acid solution of 5-7mol/L, wherein, the mass ratio of raw material silica gel and hydrochloric acid solution is 5-8:1; Then filter, elimination acid solution, Washing of Filter Cake is to neutral, and vacuum drying 5-8 hour at 50-150 ℃, obtains activated silica gel;
Silica gel bonded reaction: add anhydrous dimethyl benzole soln and silylating reagent in reaction vessel, stir silylating reagent is dissolved in anhydrous dimethyl benzole soln, obtain the first solution, wherein, the mass ratio of silylating reagent and xylene solution is 5-8:1; In activated silica gel, add dry DMF, stir and make to mix, obtain the second solution, 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, after stream adds, continues back flow reaction 10-20 hour; Filtering reacting liquid after being down to 20-30 ℃, filter cake is used methyl alcohol and toluene wash successively, and then vacuum drying obtains described heavy metal adsorption material;
S2, the pH that adjusts the pending liquid that contains copper ion and nickel ion is 0.5-5.0, obtains pickle liquor;
S3, injects the described continuous adsorption switching equipment after S1 operation by described pickle liquor;
S4, described continuous adsorption switching equipment carries out separation and concentration purification at 25-40 ℃ to described pickle liquor, specifically comprise: the described pickle liquor that is 0.5-5.0 by pH pumps into the inlet of described continuous adsorption switching equipment; Copper ion described in described the first adsorption column adsorption and enrichment in pickle liquor; The liquid flowing out from described the first adsorption column liquid outlet adjusts pH 1.0-5.5, to pump into the inlet of described the second adsorption column, the nickel ion described in described the second adsorption column adsorption and enrichment in pickle liquor; S4 specifically comprises following three phases:
First stage: the pickle liquor that is 0.5-5.0 by pH pumps into the inlet of described continuous adsorption switching equipment with the speed of 2-4ml/min, by the first adsorption column while absorbing copper ion and nickel ion, until the first adsorption column is saturated to copper absorption;
Second stage: pickle liquor is pumped into the inlet of 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 completely;
After second stage is processed, it is that after 1.0-5.5, the speed with 1-2ml/min pumps into the second adsorption column that the liquid being flowed out by the first adsorption column liquid outlet is adjusted pH, by the second adsorption column adsorption and enrichment nickel ion;
S5, the sulfuric acid that is 5-30% by mass fraction rinses respectively described the first adsorption column and described the second adsorption column; Described heavy metal adsorption material in described the first adsorption column carries out desorb operation, the described heavy metal adsorption material that obtains copper ions stripping liquid and be desorbed after desorb operation; Described heavy metal adsorption material in described the second adsorption column carries out desorb operation, obtains containing nickel ion stripping liquid and the described heavy metal adsorption material being desorbed after desorb operation;
S6, the described copper ions stripping liquid that S5 is obtained carries out electrodeposition operation by direct electrowinning equipment, obtains copper metallic plate or copper metal powder; Meanwhile, the described heavy metal adsorption material being desorbed in the first adsorption column recovers absorption property after rinsing processing;
Carry out electrodeposition operation by direct electrowinning equipment described the containing after nickel ion stripping liquid concentrates that S5 is obtained, and obtains nickel metallic plate or nickel metal powder; Meanwhile, the described heavy metal adsorption material being desorbed in the second adsorption column recovers absorption property after rinsing processing.
2. the method that realizes the separation of copper nickel, enrichment, purification by heavy metal adsorption material according to claim 1, is characterized in that, the power of described ultrasonic field is 100-200 watt;
Described vacuum drying in silica gel bonded reaction specifically comprises following three phases:
First stage: will put into freeze drying box with the filter cake after methyl alcohol and toluene wash, with the be refrigerated to-40--30 ℃ of speed cooling of 10-13 ℃/min, the time of maintain-40--30 ℃ is 7-8 hour;
Second stage, with the be warming up to-10--5 ℃ of speed of 4-5 ℃/min, the time of maintain-10--5 ℃ is 5-6 hour;
Phase III, in putting fast and being the vacuum drying chamber of 160 ℃-170 ℃ to temperature, obtain described heavy metal adsorption material 20-23 hour drying time.
3. the method that realizes the separation of copper nickel, enrichment, purification by heavy metal adsorption material according to claim 1, is characterized in that, described silylating reagent is 3-ethylenediamine base propyl trimethoxy silicane or 3-Diethylenetriamine base propyl trimethoxy silicane.
4. the method that realizes the separation of copper nickel, enrichment, purification by heavy metal adsorption material according to claim 1, it is characterized in that, the aperture of described heavy metal adsorption material is 10.02-11.23nm, the pore volume of described heavy metal adsorption material be 0.9-1.5 cubic centimetre/gram.
5. the method that realizes the separation of copper nickel, enrichment, purification by heavy metal adsorption material according to claim 1, is characterized in that, described raw silicon micelle degree is 200-300 order silica gel.
6. the method that realizes the separation of copper nickel, enrichment, purification by heavy metal adsorption material according to claim 1, is characterized in that, S4 specifically comprises following three phases:
First stage: the pickle liquor that is 3.0-3.5 by pH pumps into the inlet of described continuous adsorption switching equipment with the speed of 3ml/min, by the first adsorption column while absorbing copper ion and nickel ion, until the first adsorption column is saturated to copper absorption;
Second stage: pickle liquor is pumped into the inlet of 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 completely;
After second stage is processed, it is that after 3.5-4.0, the speed with 1.5ml/min pumps into the second adsorption column that the liquid being flowed out by the first adsorption column liquid outlet is adjusted pH, by the second adsorption column adsorption and enrichment nickel ion.
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