CN102814159A - Heavy metal adsorption material reparation process - Google Patents
Heavy metal adsorption material reparation process Download PDFInfo
- Publication number
- CN102814159A CN102814159A CN2011101509392A CN201110150939A CN102814159A CN 102814159 A CN102814159 A CN 102814159A CN 2011101509392 A CN2011101509392 A CN 2011101509392A CN 201110150939 A CN201110150939 A CN 201110150939A CN 102814159 A CN102814159 A CN 102814159A
- Authority
- CN
- China
- Prior art keywords
- heavy metal
- mixed liquor
- sorbing material
- value
- methanol solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 112
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000008569 process Effects 0.000 title claims abstract description 18
- 238000001179 sorption measurement Methods 0.000 title abstract description 7
- 239000000243 solution Substances 0.000 claims abstract description 98
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 95
- 238000003756 stirring Methods 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 230000001105 regulatory effect Effects 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 230000007935 neutral effect Effects 0.000 claims abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 8
- 239000003929 acidic solution Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 37
- PSSZUJBGBCPXMS-UHFFFAOYSA-N CO.Cl.ClCC1=NC=CC=C1 Chemical compound CO.Cl.ClCC1=NC=CC=C1 PSSZUJBGBCPXMS-UHFFFAOYSA-N 0.000 claims description 23
- KIDXYAWWICJAFK-UHFFFAOYSA-N O.[Na].OC Chemical compound O.[Na].OC KIDXYAWWICJAFK-UHFFFAOYSA-N 0.000 claims description 23
- 239000010949 copper Substances 0.000 claims description 22
- 230000008439 repair process Effects 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 19
- 238000000967 suction filtration Methods 0.000 claims description 18
- 125000003368 amide group Chemical group 0.000 claims description 16
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000007822 coupling agent Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000000741 silica gel Substances 0.000 claims description 8
- 229910002027 silica gel Inorganic materials 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- JPMRGPPMXHGKRO-UHFFFAOYSA-N 2-(chloromethyl)pyridine hydrochloride Chemical compound Cl.ClCC1=CC=CC=N1 JPMRGPPMXHGKRO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000007769 metal material Substances 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- YWOITFUKFOYODT-UHFFFAOYSA-N methanol;sodium Chemical compound [Na].OC YWOITFUKFOYODT-UHFFFAOYSA-N 0.000 claims description 2
- 238000012360 testing method Methods 0.000 claims description 2
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 abstract description 13
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000706 filtrate Substances 0.000 abstract 2
- 238000001914 filtration Methods 0.000 abstract 2
- 239000011259 mixed solution Substances 0.000 abstract 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 abstract 1
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000004590 computer program Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 241000270666 Testudines Species 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000009418 renovation Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241001411320 Eriogonum inflatum Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
The invention relates to the field of heavy metal adsorption materials, and discloses a heavy metal adsorption material reparation process. According to the invention, metal ions on the surface of a GXA-Cu material requiring reparation are removed by desorbing; the material is washed until a pH value is neutral; the material is dried by baking, and is preserved for later use; an NaOH methanol solution and a 2-PC methanol solution are mixed and stirred, wherein a pH value is regulated within a predetermined range during the mixing procedure, until complete dissolving; the GXA-Cu material is added into the mixed solution, and the mixture is stirred; the mixture is subjected to a reaction under vacuum; the mixture is heated to a predetermined temperature under normal pressure; the mixture is subjected to a reaction, wherein the pH value is maintained within a predetermined range; heating is stopped, and the mixture is naturally cooled until the temperature is below 30 DEG C; stirring is stopped; the mixed solution is pumped into a suction filter; filtrate is collected; the GXA-Cu material is washed by using deionized water, such that inorganic salts are removed; the GXA-Cu material is washed by using a weakly acidic solution, until a filtrate turns weakly acidic; the GXA-Cu material is washed by deionized water; methanol is added to the GXA-Cu material; the mixture is heated and stirred; methanol is removed by pump filtration; and the GXA-Cu material after pump filtration and separation is subjected to standing, and is subjected to vacuum drying, such that the reparation is completed.
Description
Technical field
The present invention relates to a heavy metal species sorbing material renovation technique, relate generally to the repair process of a heavy metal species sorbing material.
Background technology
The heavy metal sorbing material is to be framework material with silica gel, through activation, coupling, and the organic/inorganic composite functional material of the various organo-functional groups of grafting.Be mainly used in metallurgy industry various little (trace) amount heavy metal with organometallic absorption, separate, enrichment, purification and recovery; Be used for cities and towns drinking water and wastewater treatment at environmental protection industry (epi), industry/mining and metallurgy waste water and nuclear industry wastewater treatment, water pollution control; The separation purificant that is used to make active material such as amino acid, peptide, protein, enzyme, various antibiotic etc. in pharmacy/bioengineering industry; Be used to make catalyst, release agent etc. in chemical industry.
The heavy metal sorbing material has and recycles the life-span 3000 times, descends 10% the time when the user uses to the initial absorption property of material, needs to change the heavy metal sorbing material.As it is discarded to change down material, promptly environment is polluted, and also is the waste to resource.Therefore, need handle, after repairing, reuse, also for enterprise saves the raw material spending, create economic benefit simultaneously, realize twice laid, embody the protection theory of Gongxin Huaxin Science & Technology Co., Ltd. environment to material recovery.
Summary of the invention
The embodiment of the invention provides a heavy metal species sorbing material repair process, and the heavy metal sorbing material that absorption property is descended is reused after repairing.
The heavy metal species sorbing material repair process that the embodiment of the invention provides comprises:
Detect amido content, coupling agent content and copper capacity in the heavy metal material to be repaired, wherein said heavy metal sorbing material is: the silica gel of the heavy metal ion adsorbed matrix of grafting;
If said amido content is greater than predetermined amido content lower limit; And said coupling agent content is higher than the lower limit of predetermined coupling agent content, and then: the metal ion that remains in said heavy metal sorbing material surface is removed in desorb, washs to pH value neutral; Dry for usely, otherwise finish;
Mix sodium hydrate methanol solution and 2-chloromethyl pyridine hydrochloride methanol solution; Obtain mixed liquor; Stir while mixing; In mixed process, regulate the pH value of said mixed liquor; Make said pH value remain on predetermined scope, dissolve fully up to said sodium hydrate methanol solution and 2-chloromethyl pyridine hydrochloride methanol solution;
Heavy metal sorbing material to be repaired is added in the said mixed liquor, stir said mixed liquor, the agitated reactor that extracts said heavy metal sorbing material and said mixed liquor place reacts predetermined duration to vacuum under vacuum condition,
Under normal pressure, heat said agitated reactor, reach predetermined temperature up to the temperature of said mixed liquor; The duration that isothermal reaction is confirmed, in the isothermal reaction process, the pH value of mixed liquor in the said agitated reactor of real-time regulated; Make said pH value be no more than preset upper limit, and remain in the predetermined scope;
Stop heating, cooling naturally, the mixeding liquid temperature in said agitated reactor is lower than 30 ℃, stops to stir;
Mixed liquor in the said agitated reactor is evacuated to nutsch filter, collects filtrating, use deionized water to wash said heavy metal sorbing material and remove inorganic salts,
Use weakly acidic solution to wash said heavy metal sorbing material, after the filtrating after the washing becomes faintly acid, reuse deionized water and wash said heavy metal sorbing material,
On said heavy metal sorbing material, add methyl alcohol, heat, stirring, suction filtration remove methyl alcohol, leaves standstill the said heavy metal sorbing material after suction filtration separates, vacuumizing and drying promptly gets.
Alternatively, before amido content, coupling agent content and the copper capacity in detecting heavy metal material to be repaired, also comprise:
Desorb is removed and is remained in the metal ion on the said heavy metal sorbing material, and washing is dried to constant weight for 80 ℃ to neutral.
Alternatively, mixing, stirring sodium hydrate methanol solution and 2-chloromethyl pyridine hydrochloride methanol solution obtain before the mixed liquor, also comprise following preliminary treatment:
In airtight, dry grinder, NaOH is ground to powder;
The pulverous said dissolution of sodium hydroxide of getting the 216kg gram is to 25m
3Methyl alcohol, be stirred to fully dissolving, promptly get said sodium hydrate methanol solution, going into first, to add flow container for use.
The pulverous said dissolution of sodium hydroxide of alternatively, getting the 216kg gram is to 25m
3Methyl alcohol, be stirred to dissolving fully with the rotating speed of 300～500min/r.
Alternatively, mix sodium hydrate methanol solution and 2-chloromethyl pyridine hydrochloride methanol solution and obtain before the mixed liquor, also comprise following preliminary treatment:
To add agitated reactor, with the 2-chloromethyl pyridine hydrochloride adding 1m of 855kg
3Methanol solution, be stirred to dissolving fully with the rotating speed of 300～500min/r, promptly get said 2-chloromethyl pyridine hydrochloride methanol solution, going into second, to add flow container for use.
Alternatively; The mixed liquor that mixes sodium hydrate methanol solution and 2-chloromethyl pyridine hydrochloride methanol solution; Stir while mixing, in mixed process, regulate the pH value of said mixed liquor, make said pH value remain on definite scope; Dissolve fully up to said sodium hydrate methanol solution and 2-chloromethyl pyridine hydrochloride methanol solution, specifically:
Add 115m to agitated reactor
3Said first sodium hydrate methanol solution that adds in the flow container,
Add the said second 2-chloromethyl pyridine hydrochloride methanol solution that add in the flow container while stirring to said agitated reactor, the pH value of the mixed liquor in adition process in the real-time regulated agitated reactor makes the pH value of said mixed liquor remain 10.5 ± 05,
When said second add 2-chloromethyl pyridine hydrochloride methanol solution in the flow container add finish after; Continue to stir the mixed liquor in the said agitated reactor; The pH value of the said mixed liquor of test in the whipping process, if said pH value is less than or equal to 9, then the dropping sodium methanol solution is adjusted to pH value between 9 to 12; PH value until said mixed liquor is invariable, and this moment, said sodium hydrate methanol solution and 2-chloromethyl pyridine hydrochloride methanol solution dissolved fully.
Alternatively, mix the mixed liquor of sodium hydrate methanol solution and 2-chloromethyl pyridine hydrochloride methanol solution, the rotating speed while mixing with 300～500min/r stirs said mixed liquor.
Alternatively, the pH value of the mixed liquor in adition process in the real-time regulated agitated reactor makes the pH value of said mixed liquor remain 10.5 ± 05, specifically:
When the pH value of said mixed liquor less than 10.5 the time, drip said sodium hydrate methanol solution, the pH value of said mixed liquor is remained 10.5 ± 05.
Alternatively, heavy metal sorbing material to be repaired is added in the said mixed liquor, stir said mixed liquor, the agitated reactor that extracts said heavy metal sorbing material and said mixed liquor place reacts predetermined duration to vacuum under vacuum condition, specifically:
Heavy metal sorbing material to be repaired is added in the said mixed liquor, stir said mixed liquor, extract said agitated reactor to vacuum with the rotating speed of 60min/r, under the condition of vacuum-025mPa, stirring reaction 30min.
Alternatively, under normal pressure, heat said agitated reactor; Temperature up to said mixed liquor reaches predetermined temperature, and the duration that isothermal reaction is confirmed is in the isothermal reaction process; The pH value of mixed liquor in the said agitated reactor of real-time regulated; Make said pH value be no more than preset upper limit, and remain in the predetermined scope, specifically:
Under normal pressure, specifically the mode with steam or water-bath heating heats said agitated reactor, reaches 65-70 ℃ up to the temperature of said mixed liquor,
Under 65-70 ℃ of temperature range, said heavy metal sorbing material was said reaction kettle for reaction 22 hours, and the pH value of mixed liquor in the real-time regulated agitated reactor in course of reaction remains between 9 and 12 said pH value.
Alternatively, the pH value of mixed liquor in the real-time regulated agitated reactor in course of reaction makes said pH value remain 10.5 ± 05.
Alternatively, use weakly acidic solution to wash said heavy metal sorbing material, specifically being to use pH value is that 3 acid solution washs said heavy metal sorbing material, and wash time is 10 minutes, and the acid solution consumption is 2m
3
Alternatively, on said heavy metal sorbing material, add methyl alcohol, heat, stirring, suction filtration remove methyl alcohol, specifically:
On said heavy metal sorbing material, add 2m
3Methyl alcohol, heat to 35 ℃, stir after 1 hour, suction filtration is removed said methyl alcohol, if the filtrating that said suction filtration comes out takes on a red color, then returns this step, till the filtrating behind the suction filtration does not take on a red color.
Alternatively, leave standstill the said heavy metal sorbing material after suction filtration separates, vacuumizing and drying, specifically:
Left standstill air-dry said heavy metal sorbing material at least 6 hours, and be not more than under 80 ℃ of conditions, the said heavy metal sorbing material of vacuumizing and drying 2 hours in temperature.
Therefore the technical scheme of using the embodiment of the invention can make it return to the state of can reusing to recycling through long-term use to underproof heavy metal sorbing material (GXA-Cu material).
The specific embodiment
Describe the present invention in detail below in conjunction with specific embodiment, be used for explaining the present invention in this illustrative examples of the present invention and explanation, but not as to qualification of the present invention.
Embodiment 1:
Present embodiment discloses a heavy metal species sorbing material repair process, wherein mainly comprises following flow process:
Get in right amount to reclaim and use that (silica gel of the heavy metal ion adsorbed matrix of grafting is called for short the GXA-Cu material, and wherein GXA is writing a Chinese character in simplified form of silica gel to underproof heavy metal sorbing material from enterprise; CU is a copper); Remove through desorb and to remain in little metal ion on the material, and washing is dried to constant weight to neutral; Detect amido content, the Cu capacity.
Greater than predetermined lower limit, then repair this batch product like amido content and coupling agent content, through desorb, washing is dried to constant weight to neutral with all material that reclaims, and it is to be repaired to go to high-order charging spout (No. 1 charging spout); Otherwise then do not do reparation.
In agitated reactor, add sodium hydrate methanol solution and (be dissolved in the solution of methyl alcohol hereinafter to be referred as NaOH; Be called for short NaOH solution), open and stir, slowly (the 2-chloromethyl pyridine hydrochloride is dissolved in the solution of methyl alcohol to agitated reactor adding 2-chloromethyl pyridine hydrochloride methanol solution by adding flow container; Be called for short the 2-PC methanol solution); Detect the pH value of counting the mixed liquor in the detection reaction still with online pH value, when its pH value is lower than lower limit (being 9 in the present embodiment), begin to drip the NaOH methanol solution; The control pH value remains between 9 to 12 it.In mixing NaOH methanol solution and 2-PC methanol solution process; The rate of addition of NaOH methanol solution and 2-PC methanol solution; Regulate according to pH value by the computer program logic control program, make the pH value of mixed liquor keep constant as far as possible, maintain between the 9-12.
After the 2-PC methanol solution adds; The pH value of the reactant in the detection reaction still (being mixed liquor); If pH value is lower than requirement (being predefined for 9 in the present embodiment); Then add NaOH methanol solution control pH value (this is the requirement of present embodiment reaction), stir and detect pH value once more after 30 minutes, carry out following control: show all not dissolvings fully of one of two kinds of reactants or both if pH value changes.Can not begin next step reaction this moment, dissolves fully but continue to be stirred to it.Under the constant situation of the pH value that has only definite mixed liquor maintenance in long-time; After thinking that just two kinds of above-mentioned reagent all dissolve fully, could begin next step reaction then, in the reaction of present embodiment; PH value must remain on (9-12, preferred 10.5 ± 05) between the claimed range.
GXA-Cu material to be repaired is slowly added in the agitated reactor, opens water circulating vacuum pump simultaneously, keep vacuum, treat that material all adds after, keep this vacuum certain hour.Close vavuum pump, return to normal pressure gradually.Solution in the agitated reactor is begun heating, open condensing reflux.The solution temperature of control in the agitated reactor treats that solution temperature reaches timing after the requirement, reaction certain hour.During reaction; All the time use the online detection meter of pH value, the pH value of the mixed liquor of control and regulation in the agitated reactor, by computer program logic control NaOH methanol solution rate of addition so that pH value is regulated; Guarantee during reaction not allow pH value to surpass the upper limit (being defined as 12 in the present embodiment).
After reaction finishes, stop heating, cooling is lower than 30 ℃ naturally, stops to stir.Material and reactant liquor are gone to nutsch filter by pipeline, and parting material is collected methyl alcohol filtrating and is reused to sealing to reclaim in the storage tank.
Wash the GXA-Cu material with deionized water towards drip washing, after the inorganic salts in the GXA-Cu material are removed, use weakly acidic solution (is 3 such as pH value) instead and have agitator treating.After the filtrating of flowing out after the washing is faintly acid, use the deionized water washing instead.Collection is filtrated to waste liquid pool.The GXA-Cu material that will pass through after above-mentioned deionization washing and weakly acidic solution wash uses methanol wash, heats, and stirs, and suction filtration is collected filtrating.After the washed twice, the GXA-Cu material that suction filtration is good goes to well-ventilated place, and natural air drying is dry, make it be husky appearance after, again material is vacuumized baking to dry.After dry the completion, detect amido content, the Cu capacity is judged and is repaired the back qualified products.
Wherein, amido total content detection method is following:
Sampling is undertaken by the GB5475 regulation.Take by weighing the 15g sample, the HCl solution 100mL that pipettes 01mol/L with pipette shakes up in conical flask, soaks 4h in 50 ℃ of water-baths; Be cooled to room temperature, filter, pipette filtrating 25mL; Place another conical flask; To get ionized water washing bottle bottle wall on a small quantity, add 2 phenolphthalein indicators, with NaOH solution titration to little apparent redness of 01mol/L.
Amido total content computing formula:
In the formula:
N-amido total content, %;
c
1-HCl solution concentration, mol/L;
c
2-NaOH solution concentration, mol/L;
V
1-HCl liquor capacity, L;
V
2-NaOH liquor capacity, L;
The m-product weight, g.
Get 3 parts of parallel sample and measure its arithmetic mean of instantaneous value, be measurement result.
Wherein, Copper Ion Exchange capacity check method is following:
Preparation is regulated pH value ≈ 3 through dilute sulfuric acid, and concentration is the Cu that contains of 50mmol/L
2+Original solution.
Sampling is undertaken by the GB5475 regulation.Accurately take by weighing dry products 02 ± 00005g, in the conical flask of packing into.
Pipette 20mLCu with pipette
2+Original solution adds above-mentioned conical flask, covers bottle stopper.
Place magnetic stirring apparatus, with the stirring at low speed of 30r/min 24 hours.Filter, collect filtrating, dilute 500 times, to be measured.
Measure Cu in filtrating and the original solution according to GB7475
2+Concentration.Wherein, Copper Ion Exchange calculation of capacity formula:
In the formula:
The example weight that m-takes by weighing, unit: g;
The mensuration concentration of c-original solution after dilution, unit: mg/L;
c
1The mensuration concentration of-filtrating after dilution, unit: mg/L;
The Copper Ion Exchange capacity of Q-product, unit: mmol/g.
Get 3 parts of parallel sample and measure its arithmetic mean of instantaneous value, be measurement result.
Therefore, adopt the present embodiment technical scheme, utilize the present embodiment technical scheme to make it return to the state of can reusing to recycling through long-term use to underproof heavy metal sorbing material (GXA-Cu material).
A kind of concrete application implementation of present embodiment method can be following:
Get to reclaim from enterprise in right amount and use to underproof GXA-Cu material, warp is resolved to remove and is remained in little metal ion on the material, and detection amido content, Cu capacity are dried to constant weight in washing for 80 ℃ to neutral.As amido content and coupling agent content greater than lower limit then this batch product repair, through resolving, washing is dried to constant weight to neutral with all material that reclaims, it is to be repaired to go to No. 1 high-order charging spout.Otherwise then do not do reparation.
In airtight drying and grinding machine, NaOH is ground to powder (helping to accelerate dissolution velocity).Having stirring, heating, airtight 5m
3In the stainless steel cauldron, add 25m earlier
3Methanol solution slowly adds the NaOH after the grinding of 2162kg from the agitated reactor top, and stirs that (rotating speed 300～500min/r) accelerate dissolution treat that all the dissolving back goes to high-order sealing storage with centrifugal pump with solution and adds (No. 1 add flow container) for use in the flow container.
With 1m
3Methanol solution adds in the agitated reactor; Slowly add the 2-chloromethyl pyridine hydrochloride (2PC) of 855kg in the agitated reactor; And stir that (rotating speed 300～500min/r) accelerate dissolution treat that all the dissolving back goes to high-order sealing storage with centrifugal pump with solution and adds (No. 2 add flow container) for use in the flow container.
With adding in the flow container the good NaOH methanol solution of dissolving fully for No. 1, in agitated reactor, add 115m
3The NaOH methanol solution.Open and stir (rotating speed 300～500min/r); Add flow container by No. 2 and slowly add the 2PC methanol solution to agitated reactor; Detect meter with online pH value and detect pH value, when pH value＜10.5, beginning is added dropwise to the NaOH methanol solution and carries out pH value and regulate and (add 05m about 2PC greatly by adding flow container for No. 1
3The time), the control pH value is 10.5 ± 05.
In NaOH methanol solution 2PC methanol solution mixed process; According to pH value control NaOH methanol solution and 2PC methanol solution rate of addition (rate of addition is all by the control of condition valve), keep invariable by the computer program logic control with pH value in the assurance mixed process as far as possible.
After the 2PC methanol solution adds, detecting reactant pH value＞9.If pH value＜9, then adding NaOH methanol solution control pH value is 10.5.Stir and detect pH value once more after 30 minutes, show all not dissolvings fully of one of two kinds of reactants or both if pH value changes, can not begin next step reaction this moment.Only constant for a long time at the pH value of confirming reactant, promptly two kinds of reagent all could begin next step reaction after the dissolving fully.PH value must remain between 9 to 12.
The agitated reactor mixing speed is reduced to 60min/r, GXA-Cu to be repaired in No. 1 charging spout is slowly added in the agitated reactor, open water circulating vacuum pump simultaneously, keep vacuum-025mPa, after material all adds, keep this vacuum 30min.Close positive empty pump, return to normal pressure gradually.Solution in the agitated reactor is begun heating (adopting steam or water-bath heating), open condensing reflux.65～70 ℃ of temperature of control treat that solution temperature reaches timing after the requirement, reaction 22h.Between the stage of reaction, use the online detection of pH value at 22h all the time, the control pH value is 10.5 ± 05, by the rate of addition of computer program logic control NaOH methanol solution.Between the stage of reaction, do not allow pH value＞12.
After reaction finishes, stop heating, cooling is lower than 30 ℃ naturally, stops to stir.Material and reactant liquor are gone to by pipeline, nutsch filter, parting material is collected methyl alcohol filtrating, to sealing in the storage tank.Use deionized water to wash towards drip washing, after inorganic salts were removed in the material, using pH value instead was that 3 acid solutions have agitator treating, wash time 10min, and solution usage is 2m
3After filtrating is washed for weak acid, use the deionized water washing instead once.Collection is filtrated to waste liquid pool, with the neutralization of will filtrating of other workshop spent acid in the factory, and reduces liquor C OD, can discharge after reaching discharge standard.Product is used 2m
3Washed with methanol, heat to 35 ℃, stir 1h after, suction filtration is collected filtrating, washed twice.After washing finished, filtrating should not have redness, as has redness, again washing once, up to the filtrating after washing to the washing not redly till.The silica gel that suction filtration is good goes to the well-ventilated, and air dry makes it be husky appearance back (it is air-dry to be not less than 6h, and material is thoroughly not air-dry, has explosion danger when dry), again to material vacuumizing and drying 2h, and temperature＜80 ℃.
After dry the completion, amido content detects, the Cu capacity in censorship cls analysis section.Judge that it is all qualified repairing the back product.
Heavy metal sorbing material after process of the present invention is handled; Heavy metal ion in liquid there is very strong selective adsorption capacity; Formed huge legendary turtle compound is fixed on the silica gel active surface; But it can not close other light metal ion by huge legendary turtle, and like sodium, potassium, calcium, zinc etc., and the existence of these ions can not influence the absorption to heavy metal ion yet.The heavy metal sorbing material that the present invention obtained only needs the shirtsleeve operation condition just can be used for handling heavy metal ion, like mercury, chromium, good fortune, lead, copper etc., and can recycle for 3000 times, and its adsorption capacity just descends 10%.Since its unique selectivity and adsorption capacity, and desorption process is very simple, the poisonous and harmful heavy metallic ion obtains recycling through concentrating, and treated water quality is effectively improved.So river in Jiangsu Province which flows into the Huangpu River of Shanghai waste water was particularly examined down the removal of processing, food industry water and the drinking water trace heavy metal ion of industry waste water under this inorganic agent can be widely used in; The fields such as elementary recovery of heavy metal ore deposit exploitation; To environmental improvement and human health, realize that the resources sustainable development strategy is very useful.
The heavy metal sorbing material that present embodiment obtains is than the about soon 1-2 of adsorption function times of traditional huge legendary turtle mould assembly ion exchange resin.Functional group on silica gel, has special performance with the covalent bond form fix, only needs the shirtsleeve operation condition just to can be used to handle heavy metal cation and oxygen metal anion, especially the chromium of removing in the sewage is left
More than the technical scheme that the embodiment of the invention provided is described in detail; Used specific case herein the principle and the embodiment of the embodiment of the invention are set forth, the explanation of above embodiment only is applicable to the principle that helps to understand the embodiment of the invention; Simultaneously, for one of ordinary skill in the art, according to the embodiment of the invention, the part that on the specific embodiment and range of application, all can change, in sum, this description should not be construed as limitation of the present invention.
Claims (14)
1. a heavy metal species sorbing material repair process is characterized in that, comprising:
Detect amido content and copper capacity in the heavy metal material to be repaired, wherein said heavy metal sorbing material is: the silica gel of the heavy metal ion adsorbed matrix of grafting;
If said amido content is greater than predetermined amido content lower limit; And said coupling agent content is higher than the lower limit of predetermined coupling agent content, and then: the metal ion that remains in said heavy metal sorbing material surface is removed in desorb, washs to pH value neutral; Dry for usely, otherwise finish;
Mix sodium hydrate methanol solution and 2-chloromethyl pyridine hydrochloride methanol solution; Obtain mixed liquor; Stir while mixing; In mixed process, regulate the pH value of said mixed liquor; Make said pH value remain on predetermined scope, dissolve fully up to said sodium hydrate methanol solution and 2-chloromethyl pyridine hydrochloride methanol solution;
Heavy metal sorbing material to be repaired is added in the said mixed liquor, stir said mixed liquor, the agitated reactor that extracts said heavy metal sorbing material and said mixed liquor place reacts predetermined duration to vacuum under vacuum condition,
Under normal pressure, heat said agitated reactor, reach predetermined temperature up to the temperature of said mixed liquor; The duration that isothermal reaction is confirmed, in the isothermal reaction process, the pH value of mixed liquor in the said agitated reactor of real-time regulated; Make said pH value be no more than preset upper limit, and remain in the predetermined scope;
Stop heating, cooling naturally, the mixeding liquid temperature in said agitated reactor is lower than 30 ℃, stops to stir;
Mixed liquor in the said agitated reactor is evacuated to nutsch filter, collects filtrating, use deionized water to wash said heavy metal sorbing material and remove inorganic salts,
Use weakly acidic solution to wash said heavy metal sorbing material, after the filtrating after the washing becomes faintly acid, reuse deionized water and wash said heavy metal sorbing material,
On said heavy metal sorbing material, add methyl alcohol, heat, stirring, suction filtration remove methyl alcohol, leaves standstill the said heavy metal sorbing material after suction filtration separates, vacuumizing and drying promptly gets.
2. heavy metal sorbing material repair process according to claim 1 is characterized in that,
Before amido content, coupling agent content and the copper capacity in detecting heavy metal material to be repaired, also comprise:
Desorb is removed and is remained in the metal ion on the said heavy metal sorbing material, and washing is dried to constant weight for 80 ℃ to neutral.
3. heavy metal sorbing material repair process according to claim 1 is characterized in that,
Mixing, stirring sodium hydrate methanol solution and 2-chloromethyl pyridine hydrochloride methanol solution obtain before the mixed liquor, also comprise following preliminary treatment:
In airtight, dry grinder, NaOH is ground to powder;
The pulverous said dissolution of sodium hydroxide of getting the 216kg gram is to 25m
3Methyl alcohol, be stirred to fully dissolving, promptly get said sodium hydrate methanol solution, going into first, to add flow container for use.
4. heavy metal sorbing material repair process according to claim 3 is characterized in that,
The pulverous said dissolution of sodium hydroxide of getting the 216kg gram is to 25m
3Methyl alcohol, be stirred to dissolving fully with the rotating speed of 300～500min/r.
5. heavy metal sorbing material repair process according to claim 4 is characterized in that,
Mix sodium hydrate methanol solution and 2-chloromethyl pyridine hydrochloride methanol solution and obtain before the mixed liquor, also comprise following preliminary treatment:
To add agitated reactor, with the 2-chloromethyl pyridine hydrochloride adding 1m of 855kg
3Methanol solution, be stirred to dissolving fully with the rotating speed of 300～500min/r, promptly get said 2-chloromethyl pyridine hydrochloride methanol solution, going into second, to add flow container for use.
6. heavy metal sorbing material repair process according to claim 5 is characterized in that,
The mixed liquor that mixes sodium hydrate methanol solution and 2-chloromethyl pyridine hydrochloride methanol solution; Stir while mixing; In mixed process, regulate the pH value of said mixed liquor; Make said pH value remain on definite scope, dissolve fully up to said sodium hydrate methanol solution and 2-chloromethyl pyridine hydrochloride methanol solution, specifically:
Add 115m to agitated reactor
3Said first sodium hydrate methanol solution that adds in the flow container,
Add the said second 2-chloromethyl pyridine hydrochloride methanol solution that add in the flow container while stirring to said agitated reactor, the pH value of the mixed liquor in adition process in the real-time regulated agitated reactor makes the pH value of said mixed liquor remain 10.5 ± 05,
When said second add 2-chloromethyl pyridine hydrochloride methanol solution in the flow container add finish after; Continue to stir the mixed liquor in the said agitated reactor; The pH value of the said mixed liquor of test in the whipping process, if said pH value is less than or equal to 9, then the dropping sodium methanol solution is adjusted to pH value between 9 to 12; PH value until said mixed liquor is invariable, and this moment, said sodium hydrate methanol solution and 2-chloromethyl pyridine hydrochloride methanol solution dissolved fully.
7. heavy metal sorbing material repair process according to claim 6 is characterized in that,
The mixed liquor that mixes sodium hydrate methanol solution and 2-chloromethyl pyridine hydrochloride methanol solution, the rotating speed while mixing with 300～500min/r stirs said mixed liquor.
8. heavy metal sorbing material repair process according to claim 6 is characterized in that,
The pH value of the mixed liquor in adition process in the real-time regulated agitated reactor makes the pH value of said mixed liquor remain 10.5 ± 05, specifically:
When the pH value of said mixed liquor less than 10.5 the time, drip said sodium hydrate methanol solution, the pH value of said mixed liquor is remained 10.5 ± 05.
9. heavy metal sorbing material repair process according to claim 1 is characterized in that,
Heavy metal sorbing material to be repaired is added in the said mixed liquor, stir said mixed liquor, the agitated reactor that extracts said heavy metal sorbing material and said mixed liquor place reacts predetermined duration to vacuum under vacuum condition, specifically:
Heavy metal sorbing material to be repaired is added in the said mixed liquor, stir said mixed liquor, extract said agitated reactor to vacuum with the rotating speed of 60min/r, under the condition of vacuum-025mPa, stirring reaction 30min.
10. heavy metal sorbing material repair process according to claim 1 is characterized in that,
Under normal pressure, heat said agitated reactor, reach predetermined temperature up to the temperature of said mixed liquor; The duration that isothermal reaction is confirmed; In the isothermal reaction process, the pH value of mixed liquor in the said agitated reactor of real-time regulated makes said pH value be no more than preset upper limit; And remain in the predetermined scope, specifically:
Under normal pressure, specifically the mode with steam or water-bath heating heats said agitated reactor, reaches 65-70 ℃ up to the temperature of said mixed liquor,
Under 65-70 ℃ of temperature range, said heavy metal sorbing material was said reaction kettle for reaction 22 hours, and the pH value of mixed liquor in the real-time regulated agitated reactor in course of reaction remains between 9 and 12 said pH value.
11. heavy metal sorbing material repair process according to claim 1 is characterized in that,
The pH value of mixed liquor in the real-time regulated agitated reactor in course of reaction makes said pH value remain 10.5 ± 05.
12. heavy metal sorbing material repair process according to claim 1 is characterized in that,
Use weakly acidic solution to wash said heavy metal sorbing material, specifically being to use pH value is that 3 acid solution washs said heavy metal sorbing material, and wash time is 10 minutes, and the acid solution consumption is 2m
3
13. heavy metal sorbing material repair process according to claim 1 is characterized in that,
On said heavy metal sorbing material, add methyl alcohol, heat, stirring, suction filtration remove methyl alcohol, specifically:
On said heavy metal sorbing material, add 2m
3Methyl alcohol, heat to 35 ℃, stir after 1 hour, suction filtration is removed said methyl alcohol, if the filtrating that said suction filtration comes out takes on a red color, then returns this step, till the filtrating behind the suction filtration does not take on a red color.
14. heavy metal sorbing material repair process according to claim 1 is characterized in that,
Leave standstill the said heavy metal sorbing material after suction filtration separates, vacuumizing and drying, specifically:
Left standstill air-dry said heavy metal sorbing material at least 6 hours, and be not more than under 80 ℃ of conditions, the said heavy metal sorbing material of vacuumizing and drying 2 hours in temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110150939.2A CN102814159B (en) | 2011-06-08 | 2011-06-08 | Heavy metal adsorption material reparation process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110150939.2A CN102814159B (en) | 2011-06-08 | 2011-06-08 | Heavy metal adsorption material reparation process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102814159A true CN102814159A (en) | 2012-12-12 |
| CN102814159B CN102814159B (en) | 2015-01-14 |
Family
ID=47298818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110150939.2A Expired - Fee Related CN102814159B (en) | 2011-06-08 | 2011-06-08 | Heavy metal adsorption material reparation process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102814159B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1597552A (en) * | 2003-09-21 | 2005-03-23 | 邱建宁 | Technological Method of producing toxic heaving metal waste water treatment agent |
| US20050247635A1 (en) * | 2001-08-27 | 2005-11-10 | Vo Toan P | Adsorbents for removing heavy metal cations and methods for producing and using these adsorbents |
| CN101306347A (en) * | 2008-02-19 | 2008-11-19 | 浙江大学 | Preparation method and renovation method of treatment tea for absorbing heavy metal ion in waste water |
| CN101362072A (en) * | 2008-09-27 | 2009-02-11 | 大连理工大学 | Absorbent for removing trace benzene in carbon dioxide and preparation method thereof |
| CN101362076A (en) * | 2007-08-06 | 2009-02-11 | 中国石油化工股份有限公司 | Regeneration method of active carbon absorbent |
| CN101664672A (en) * | 2008-09-04 | 2010-03-10 | 中国科学院兰州化学物理研究所 | Heavy metal composite adsorbent and method for preparing same |
| CN101898107A (en) * | 2010-07-09 | 2010-12-01 | 宁波工程学院 | Method for treating chromium-containing wastewater by using barite adsorbent |
-
2011
- 2011-06-08 CN CN201110150939.2A patent/CN102814159B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050247635A1 (en) * | 2001-08-27 | 2005-11-10 | Vo Toan P | Adsorbents for removing heavy metal cations and methods for producing and using these adsorbents |
| CN1597552A (en) * | 2003-09-21 | 2005-03-23 | 邱建宁 | Technological Method of producing toxic heaving metal waste water treatment agent |
| CN101362076A (en) * | 2007-08-06 | 2009-02-11 | 中国石油化工股份有限公司 | Regeneration method of active carbon absorbent |
| CN101306347A (en) * | 2008-02-19 | 2008-11-19 | 浙江大学 | Preparation method and renovation method of treatment tea for absorbing heavy metal ion in waste water |
| CN101664672A (en) * | 2008-09-04 | 2010-03-10 | 中国科学院兰州化学物理研究所 | Heavy metal composite adsorbent and method for preparing same |
| CN101362072A (en) * | 2008-09-27 | 2009-02-11 | 大连理工大学 | Absorbent for removing trace benzene in carbon dioxide and preparation method thereof |
| CN101898107A (en) * | 2010-07-09 | 2010-12-01 | 宁波工程学院 | Method for treating chromium-containing wastewater by using barite adsorbent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102814159B (en) | 2015-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Recovery of hydrochloric acid from the waste acid solution by diffusion dialysis | |
| CN102531233B (en) | Heavy-metal-containing electroplating wastewater treatment and heavy metal recycling method | |
| CN106277006B (en) | A kind of method for refined crystalline aluminium chloride deliming | |
| CN107262072A (en) | A kind of industrial production process for carrying zirconium nanocomposite adsorbent | |
| CN105061311B (en) | A kind of process for refining of caprolactam | |
| CN102671642B (en) | Polyamine composite adsorbing material loaded on silica gel and preparation method thereof | |
| CN108047361B (en) | A kind of Properties of Magnetic Chelating Resins, preparation method and its application in combined pollution water body purification | |
| CN108766611A (en) | The zero discharge treatment device and its processing method of strong nitric acid system uranium-bearing waste liquid | |
| CN106927539B (en) | UF (ultra filtration factor)6Treatment method of production tail gas leacheate | |
| CN102814159B (en) | Heavy metal adsorption material reparation process | |
| CN105561954B (en) | A kind of design preparation of chelating resin and its research application for cadmium ion in rice | |
| CN103613146A (en) | Innocent treatment method of ferrous chloride | |
| CN109292817A (en) | The method for preparing ammonium metavanadate | |
| CN102836696B (en) | Preparation method of magnetic nano solid-phase extracting agent for Pb<2+> separation | |
| CN104789803A (en) | Method for separating uranium from uranium-containing alkaline sodium carbonate solution | |
| CN102671643B (en) | Polyamine and pyridine difunctional group composite adsorbing material loaded on silica gel and preparation method thereof | |
| Liu et al. | Clean & environmentally friendly regeneration of Fe-surface cleaning pickling solutions | |
| CN102688748B (en) | Silica gel loaded polyamine and carboxyl bifunctional group composite adsorbing material and preparation method thereof | |
| CN103818915A (en) | Method for preparing high-transparency liquid soluble silicate | |
| CN105597661A (en) | Preparation method of magnetic nucleus covered potassium titanium hexacyanoferrate adsorbent and product as well as application | |
| CN103395746B (en) | Method for purifying byproduct hydrochloric acid in 3, 4-dichloronitrobenzene production process | |
| CN109988915B (en) | Preparation method of solid phase extractant for plutonium separation | |
| CN105948294B (en) | A kind of waste acid resource treatment process blocking method based on nano combined carrier | |
| CN215506798U (en) | S-Zorb spent adsorbent reviving system | |
| Özdemir et al. | Boron recovery from borax sludge using solid–liquid extraction followed by sorption with a boron selective resin in column |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20150407 Granted publication date: 20150114 |
|
| RINS | Preservation of patent right or utility model and its discharge | ||
| DD01 | Delivery of document by public notice |
Addressee: Gongxin Huaxin Technology Co., Ltd. Document name: Notification to Pay the Fees |
|
| PD01 | Discharge of preservation of patent |
Date of cancellation: 20160407 Granted publication date: 20150114 |
|
| PP01 | Preservation of patent right |
Effective date of registration: 20160407 Granted publication date: 20150114 |
|
| RINS | Preservation of patent right or utility model and its discharge | ||
| DD01 | Delivery of document by public notice |
Addressee: Gongxin Huaxin Technology Co., Ltd. Document name: Notification of Termination of Procedure Addressee: Gongxin Huaxin Technology Co., Ltd. Document name: Notice of preservation procedure |
|
| DD01 | Delivery of document by public notice |
Addressee: Gongxin Huaxin Technology Co., Ltd. Document name: Notification to Pay the Fees |
|
| DD01 | Delivery of document by public notice |
Addressee: Gongxin Huaxin Technology Co., Ltd. Document name: Notice of preservation proceeding |
|
| DD01 | Delivery of document by public notice | ||
| DD01 | Delivery of document by public notice |
Addressee: Gongxin Huaxin Technology Co., Ltd. Document name: Notice of preservation procedure Addressee: Gongxin Huaxin Technology Co., Ltd. Document name: Notice of amendment |
|
| DD01 | Delivery of document by public notice | ||
| DD01 | Delivery of document by public notice |
Addressee: Gongxin Huaxin Technology Co., Ltd. Document name: Notification to Pay the Fees |
|
| PD01 | Discharge of preservation of patent | ||
| PD01 | Discharge of preservation of patent |
Date of cancellation: 20171007 Granted publication date: 20150114 |
|
| DD01 | Delivery of document by public notice | ||
| DD01 | Delivery of document by public notice |
Addressee: Gongxin Huaxin Technology Co., Ltd. Document name: Notification of Termination of Procedure |
|
| DD01 | Delivery of document by public notice | ||
| DD01 | Delivery of document by public notice |
Addressee: Gongxin Huaxin Technology Co., Ltd. Document name: Notification of Termination of Patent Right |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150114 Termination date: 20170608 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |