CN102153160A - Method for eliminating hexavalent chromium in waste liquid through adsorption by utilizing persimmon residues - Google Patents
Method for eliminating hexavalent chromium in waste liquid through adsorption by utilizing persimmon residues Download PDFInfo
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- CN102153160A CN102153160A CN 201010125925 CN201010125925A CN102153160A CN 102153160 A CN102153160 A CN 102153160A CN 201010125925 CN201010125925 CN 201010125925 CN 201010125925 A CN201010125925 A CN 201010125925A CN 102153160 A CN102153160 A CN 102153160A
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Abstract
The invention relates to a method for eliminating hexavalent chromium in waste liquid through adsorption by utilizing persimmon residues, belonging to the technical field of metal ion eliminating. The method comprises the following steps of: (1) carbonating persimmon juicing residues; (2) washing and drying; and (3) absorbing by adding a waste liquid containing hexavalent chromium ions. The method provided by the invention is reasonable in design, bitter persimmon juicing residues are subjected to direct carbonating at high temperature so as to be prepared into an adsorbent, the pH value of the waste liquid is regulated, and finally the effect of eliminating the hexavalent chromium in the waste liquid through adsorption is achieved. Compared with the prior art, the treatment cost is greatly reduced and is 10-20% of the traditional treatment method; the treatment period is also greatly shortened, the hexavalent chromium can be eliminated in 24 hours; and no pollution is produced, the operation is simple, and the method is easy to popularize.
Description
Technical field
The invention belongs to the technical field that metal ions in waste liquor is removed, be specifically related to a kind of persimmon residue that utilizes carbonizing treatment from the aqueous solution and be dissolved into the wherein each kind of metal selectivity and the chromic method of adsorption removal effectively.
Background technology
Chromium is as chromium plating liquid and stainless material or be used to the skin of tanning, and is used to various fields in recent years.Sexavalent chrome toxicity in the chromium is very strong, is subjected to strict control in a lot of countries.For example, other metals such as sexavalent chrome and ferrous, iron coexist in a large number in chrome plating waste liquor.Therefore, only optionally separate, remove sexavalent chrome from such waste liquid is not easy very much.
In the past, contain the sexavalent chrome waste liquid and be reduced into the lower trivalent chromium of toxicity as reductive agents such as sodium borohydrides by adopting, add highly basic such as calcium hydroxide or sodium hydroxide and other coexistence metals then together as the precipitation of metal hydroxides, handle by the method for from water, removing.But such metal hydroxides water ratio height, and, can't utilize again as metals resources in the non-ferrous metal smeltery, always by management type treatment plant landfill disposal owing to there is multiple metal mixture.
As mentioned above, chromium is applied to various fields, is one of indispensable rare metal of industry and life.But, because its place of production concentrates on part areas such as South Africa, so its supply chain is extremely fragile.Therefore from the waste of wide range of forms, waste liquid chromium being carried out that efficient recovery utilizes again will be to enjoy popular confidence.
The output of the puckery persimmon of China is 5,000,000 tons/year, and major part all is used to make the puckery liquid of persimmon for utilizations such as the skins of tanning.Residue after squeezing the juice or directly discarded perhaps is used as fertilizer.
Tannin is one of organism that constitutes plant, and a lot of PHENOL 99.8 MIN ((CARBOLIC ACID)), benzene phosphorus diphenol and pyrogallol position are arranged in its molecular configuration.Contain in a large number this tannin come from the natural plant material persimmon, green tea and red wine etc. are arranged.It is said that the amount of the polyphenol that contains in the persimmon particularly is about 200 times of red wine.Tannin is the bitter taste of plant or sends out composition puckery, particularly exists the tannin in the persimmon to be called as persimmon tannin in a large number.The period that is suitable for gathering in the crops sophisticated puckery persimmon contain solubility persimmon tannin in the water of 1-2%, contain the persimmon tannin of 5-6% in the immature puckery persimmon.
Persimmon tannin be epicatechin, catechuic acid-3-ester, epigallocatechin, gallocatechin-3-ester this in 4 compound chemistry in conjunction with after material.Their component ratio is 1: 1: 2: 2, have repeating structure.Molecular weight is about about 10,000 5 thousand polymer pycnogenols polymkeric substance.
As everyone knows, this polyphenolic substance of persimmon tannin and metal ion form fluor-complex, up to the present attempt to utilize this character to modulate metal absorbent from polyphenolic substance in a large number.The sorbent material that can adsorb in this case,, reclaim, remove predetermined substance from water must be water insoluble.Modulate insoluble sorbent material and need be cured processing, be cured processing and need use chemical substances such as Epicholorohydrin, Paraformaldehyde 96.Nakajima etc. extract persimmon tannin from the puckery liquid of persimmon, adopt formaldehyde to be cured, and are modulated into sorbent material.Nakajima etc. have reported the technology that this sorbent material carries out selective adsorption to the sexavalent chrome that is present in the water.
[non-patent literature 1] A.Nakajima and Y.Baba: " Mechanism of haxavalentchromium adsorption by persimmon tannin gel ", Water Research, 38,2859-2864 (2004)
But this sorbent material extracts modulation with above-mentioned tannin composition from the puckery liquid of persimmon and forms, and needs cost great number cost owing to extract and reclaim, so price is high.And the chemical substance of using in the solidification treatment much is an objectionable impurities.Relevant for this, inventor of the present invention does not use aforementioned harmful chemical in the skin with puckery persimmon is the modulation of sorbent material of raw material, but adopts the vitriol oil that the skin of puckery persimmon is cured processing, is modulated into water-fast sorbent material.In patent documentation 1, this is reported.
[patent documentation 1] number of patent application: 2004-126809, title: the manufacture method of Pericarpium Kaki sorbent material: the applying date: on April 22nd, 2004
On this basis, inventor of the present invention finds, the puckery persimmon that will the contain persimmon tannin equally in a large number residue of squeezing the juice is handled through 24 hours 100 ℃ of heated and stirred in the vitriol oil and is modulated into sorbent material, adopt such sorbent material can from water, optionally adsorb, separate, remove sexavalent chrome, for example report done of non-patent literature 2 grades.
[non-patent literature 2] K.Inoue, R.Chand, H.Poudyal, K.Narimura, H.Nakagawa, H.Kawakita, K.Ohto: " Adsorption of chromium (VI) by persimmon and grapewaste ", 5
ThInternational Conference on Hydrometallurgy 2009, Paper A-01, July 6-8,2009, Zhangjiajie, Hunan, China
But, modulate the vitriol oil that uses in such sorbent material process because the moisture dilution that is contained in a large number in the residue of squeezing the juice of puckery persimmon can't be used repeatedly when modulating sorbent material once more, so it is discarded after neutralizing treatment to have to.Need to spend neutralizing treatment and waste treatment cost here again.
Summary of the invention
At the problem that prior art exists, the objective of the invention is to design provides a kind of persimmon residue that utilizes carbonizing treatment selectivity and technical scheme of the chromic method of adsorption removal effectively from waste liquid.This method is simple to operate, the processing cycle is short, pollution-free and processing cost is low.
Described a kind of chromic method in the persimmon residue adsorption removal waste liquid of utilizing is characterized in that comprising following processing step:
1) get the persimmon residue of squeezing the juice and pulverize, under temperature 600-1000 ℃, carbonizing treatment 0.5-3 hour;
2) residue that carbonizing treatment is crossed is clean with flushing with clean water, at room temperature carries out drying, promptly obtains sorbent material;
3) accent contains the pH value of hexavalent chromium waste liquid to 1-4, in this waste liquid, add through step 2 then) sorbent material that obtains, the ratio of hexavalent chromium is 1kg: 0.1-1.7mol in sorbent material consumption and the waste liquid, sorbent material fully adsorbs the hexavalent chromium in the waste liquid, and the hexavalent chromium in the waste liquid is eliminated.
Described a kind of chromic method in the persimmon residue adsorption removal waste liquid of utilizing is characterized in that persimmon is puckery persimmon in the described step 1), carries out carbonizing treatment in the aluminum crucible of secluding air.
Described a kind of chromic method in the persimmon residue adsorption removal waste liquid of utilizing is characterized in that the carbonizing treatment condition is in the described step 1): under temperature 700-900 ℃, and carbonizing treatment 1-2.5 hour.
Described a kind of chromic method in the persimmon residue adsorption removal waste liquid of utilizing is characterized in that the carbonizing treatment condition is in the described step 1): under temperature 800-900 ℃, and carbonizing treatment 1.5-2 hour.
Described a kind of chromic method in the persimmon residue adsorption removal waste liquid of utilizing, when it is characterized in that the pH value 1-2 of waste liquid in the described step 3) or 2.5-4, the ratio of hexavalent chromium is 1kg: 0.1-1.3mol in sorbent material consumption and the waste liquid.
Described a kind of chromic method in the persimmon residue adsorption removal waste liquid of utilizing, when it is characterized in that the pH value 2-2.5 of waste liquid in the described step 3), the ratio of hexavalent chromium is 1kg: 1-1.7mol in sorbent material consumption and the waste liquid.
Above-mentioned a kind of chromic method in the persimmon residue adsorption removal waste liquid of utilizing, reasonable in design, the residue of squeezing the juice of puckery persimmon is carried out direct carbonizing treatment by high temperature be modulated into sorbent material, again by regulating the pH value of waste liquid, reach chromic effect in the adsorption removal waste liquid at last, the present invention compared with prior art, processing cost significantly reduces, processing cost is the 10-20% of traditional treatment method, the processing cycle also significantly shortens, and only needed just sexavalent chrome can be removed in 24 hours, and the present invention is pollution-free, simple to operate, be easy to promote.
Description of drawings
Fig. 1 for the residue of squeezing the juice of puckery persimmon through 800 ℃ of carbonizing treatment after the absorption percentage of metal ion and the graph of a relation between the pH after the absorption after the sorbent material effect that forms of modulation;
Fig. 2 is the absorption percentage of metal ion after the sorbent material effect that modulation formed after the residue of squeezing the juice of puckery persimmon was handled with the vitriol oil and the graph of a relation between the pH after the absorption;
Fig. 3 is for the adsorption isotherm line chart of modulating the sorbent material hexavalent chromium that forms after the carbonizing treatment under all temps condition;
The adsorption isotherm line chart of the hexavalent chromium of the various pH aqueous solution when Fig. 4 modulates the sorbent material that form after the carbonizing treatment for adopting under 800 ℃ of conditions.
Embodiment
Further specify the present invention below in conjunction with specific embodiment.
The present invention squeezes the juice persimmon after residue pulverizes, in the aluminum crucible that cuts off air, at high temperature pass through 0.5-3, a 1-2.5 or 1.5-2 hour carbonizing treatment after, it is clean to carry out flushing with clean water, at room temperature carries out drying and is modulated into sorbent material.Treatment temp of the present invention is 600-1000 ℃, and best temperature range is 700-900 ℃.
The sorbent material that employing forms through such method carbonizing treatment modulation contacts by batchwise operation or the file operation of adopting in the past with the aqueous solution of the various forms that contain various metal ions, can adsorb, reclaim these metal ions.
And the influence of the state of the aqueous solution such as the absorption active receiving pH of metal ion is very big.PH has nothing in common with each other to the influence of the absorption activity generation of every metal ion species, thus to it be adsorbed separately respectively to each metal ion by the pH that adjusts waste liquid, can be with hexavalent chromium and other separation of metal ions.
When the pH of waste liquid value 1-2 or 2.5-4, the ratio of hexavalent chromium is 1kg: 0.1-1.3mol in sorbent material consumption and the waste liquid.
When the pH of waste liquid value 2-2.5, the ratio of hexavalent chromium is 1kg: 1-1.7mol in sorbent material consumption and the waste liquid.
The influence that embodiment 1pH brings the absorption of each metal ion species
In containing the adjusted aqueous solution 10mL of the metal ion various pH of process of 0.5mmol/L concentration, add the sorbent material 10mg that forms through 800 ℃ of carbonizing treatment modulation, under 30 ℃ of conditions, rock mixing.The ICPS-8100 type ICP atom emission spectroanalysis device that before the absorption and the employing of the metal concentration in the aqueous solution afterwards Tianjin, island produces is measured, the 720A type pH survey meter that pH adopts ORION to produce is measured.
The result has obtained as shown in Figure 1 for the relation between the pH (transverse axis) after the absorption percentage (longitudinal axis) of each metal ion species and the absorption.Absorption percentage such as following formula definition, the ratio that expression reduces owing to adsorbing metal ions concentration for initial concentration of metal ions.
Absorption percentage=(starting point concentration of (metal concentration after the starting point concentration-absorption of metal ion)/metal ion) X100
As can be seen from Figure 1, the metal ion that is adsorbed of low-down pH be adsorbed firmly.In addition, the absorption line of certain metal ion species is far away apart from other the absorption line of metal ion, and this metal ion has selectivity, in other words and other separation of metal ions bigger by preferentially adsorbed.
In Fig. 1, the absorption line of Cr (VI) and the absorption line of other metal ions separate very big, and (low pH side) moves to the left.Show that promptly hexavalent chromium has more optionally by adsorbents adsorb of the present invention than other metal ions.If as can be seen pH is adjusted to 1-2.5 from this figure, hexavalent chromium is adsorbed, and other metal ions are not adsorbed, illustrate hexavalent chromium can with other separation of metal ions.
For relatively, adopt the sorbent material that forms with vitriol oil processing back modulation in the prior art under similarity condition, to carry out adsorption experiment, the result is as shown in Figure 2.
Relatively find that the absorption line of Cr (VI) has moved to very high pH one side (right side) in the back with Fig. 1, absorption lines such and other metal ions are very big at interval in the absence of image pattern 1.The sorbent material that modulation formed after i.e. explanation, the sorbent material that modulation forms after the carbonizing treatment under 800 ℃ of conditions shown in Figure 1 were handled than the vitriol oil shown in Figure 2 is higher to the selectivity of hexavalent chromium.
Be used in modulation forms after the carbonizing treatment under 600 ℃, 700 ℃, 800 ℃, 900 ℃ and the 1000 ℃ of conditions sorbent material carries out hexavalent chromium when pH=2 adsorption experiment, experiment condition is identical during with Fig. 1 situation.Its result, the relation in adsorptive capacity of hexavalent chromium (q, the longitudinal axis) and the absorption rear solution between the concentration (Ce, transverse axis) of remaining hexavalent chromium, promptly the adsorption isothermal line of hexavalent chromium is as shown in Figure 3.Adsorptive capacity is by following formula definition: adsorptive capacity (q)=(concentration of the hexavalent chromium after the starting point concentration-absorption of hexavalent chromium) x is for the dry weight (10mg) of volume (the 10mL)/sorbent material of the aqueous solution of experiment.
All be that adsorptive capacity is followed the increase of concentration and increased under any situation in Fig. 3 in the less field of concentration, and in the high density field, move closer to fixed value.Promptly become the Langmuir type adsorption isothermal line of in a lot of adsorption phenomenas, seeing.Can be according to this asymptotic fixed value in the hope of saturated extent of adsorption (q for each sorbent material that uses
Max), as shown in table 1.
Table 1 carbonizing treatment temperature and for the relation between the saturated extent of adsorption of the sorbent material that forms in this temperature condition modulated
| The carbonizing treatment temperature (℃) | Saturated extent of adsorption (mol/kg) |
| 600 | 0.23 |
| 700 | 0.42 |
| 800 | 1.64 |
| 900 | 1.10 |
| 1000 | 0.44 |
The result of table 1 shows that saturated extent of adsorption is handled the maximum that the back modulation forms under 800 ℃ of conditions.
The adsorption isothermal line of hexavalent chromium in various pH aqueous solution when Fig. 4 represents to adopt the sorbent material that modulation forms after the carbonizing treatment under 800 ℃ of conditions.The absorption of same this moment also is Langmuir type adsorption isothermal line during with Fig. 3.Same with the situation of Fig. 3, obtained the result shown in the table 2 during the saturated extent of adsorption of the hexavalent chromium when asking each pH.
Table 2 for carbonizing treatment under 800 ℃ of conditions after the relation between saturated adsorptive capacity and the pH in the absorption of hexavalent chromium in the aqueous solution of the various pH of sorbent material that form of modulation
| pH | Saturated extent of adsorption (mol/kg) |
| 1 | 0.96 |
| 2 | 1.64 |
| 3 | 0.18 |
| 4 | 0 |
Claims (6)
1. one kind is utilized chromic method in the persimmon residue adsorption removal waste liquid, it is characterized in that comprising following processing step:
1) get the persimmon residue of squeezing the juice and pulverize, under temperature 600-1000 ℃, carbonizing treatment 0.5-3 hour;
2) residue that carbonizing treatment is crossed is clean with flushing with clean water, at room temperature carries out drying, promptly obtains sorbent material;
3) accent contains the pH value of hexavalent chromium waste liquid to 1-4, in this waste liquid, add through step 2 then) sorbent material that obtains, the ratio of hexavalent chromium is 1kg: 0.1-1.7mol in sorbent material consumption and the waste liquid, sorbent material fully adsorbs the hexavalent chromium in the waste liquid, and the hexavalent chromium in the waste liquid is eliminated.
2. a kind of chromic method in the persimmon residue adsorption removal waste liquid of utilizing as claimed in claim 1 is characterized in that persimmon is puckery persimmon in the described step 1), carries out carbonizing treatment in the aluminum crucible of secluding air.
3. a kind of chromic method in the persimmon residue adsorption removal waste liquid of utilizing as claimed in claim 1 is characterized in that the carbonizing treatment condition is in the described step 1): under temperature 700-900 ℃, and carbonizing treatment 1-2.5 hour.
4. a kind of chromic method in the persimmon residue adsorption removal waste liquid of utilizing as claimed in claim 1 is characterized in that the carbonizing treatment condition is in the described step 1): under temperature 800-900 ℃, and carbonizing treatment 1.5-2 hour.
5. a kind of chromic method in the persimmon residue adsorption removal waste liquid of utilizing as claimed in claim 1, when it is characterized in that the pH value 1-2 of waste liquid in the described step 3) or 2.5-4, the ratio of hexavalent chromium is 1kg: 0.1-1.3mol in sorbent material consumption and the waste liquid.
6. a kind of chromic method in the persimmon residue adsorption removal waste liquid of utilizing as claimed in claim 1, when it is characterized in that the pH value 2-2.5 of waste liquid in the described step 3), the ratio of hexavalent chromium is 1kg: 1-1.7mol in sorbent material consumption and the waste liquid.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104921301A (en) * | 2015-06-05 | 2015-09-23 | 滁州卷烟材料厂 | Composite adsorbent with persimmon peel for cigarette filter tips and method for preparing composite adsorbent |
| CN107442066A (en) * | 2017-08-07 | 2017-12-08 | 荆楚理工学院 | A kind of microwave charing persimmon skin biological adsorption agent and its production and use |
| CN110314652A (en) * | 2018-03-29 | 2019-10-11 | 河北农业大学 | A kind of absorption and recovery method using persimmon slag to noble metal gold |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004330005A (en) * | 2003-05-01 | 2004-11-25 | Katsutoshi Inoue | Absorbent using peelings of persimmon as raw material and method for separating uranium and thorium using it |
| JP2005305330A (en) * | 2004-04-22 | 2005-11-04 | Katsutoshi Inoue | Production method for adsorbent of persimmon peel |
| WO2007023521A1 (en) * | 2005-08-22 | 2007-03-01 | Saga University | Method of separating gold |
| CN101091907A (en) * | 2007-04-19 | 2007-12-26 | 浙江大学 | Preparation of multistage natural adsorbent for treating organic waste gas, and method of use |
| CN101215163A (en) * | 2007-01-04 | 2008-07-09 | 蔡镇州 | Porosity burnt product |
| JP3157241U (en) * | 2009-11-24 | 2010-02-04 | ベストプロダクツ株式会社 | Deodorant sheets |
-
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- 2010-03-17 CN CN2010101259250A patent/CN102153160B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004330005A (en) * | 2003-05-01 | 2004-11-25 | Katsutoshi Inoue | Absorbent using peelings of persimmon as raw material and method for separating uranium and thorium using it |
| JP2005305330A (en) * | 2004-04-22 | 2005-11-04 | Katsutoshi Inoue | Production method for adsorbent of persimmon peel |
| WO2007023521A1 (en) * | 2005-08-22 | 2007-03-01 | Saga University | Method of separating gold |
| CN101215163A (en) * | 2007-01-04 | 2008-07-09 | 蔡镇州 | Porosity burnt product |
| CN101091907A (en) * | 2007-04-19 | 2007-12-26 | 浙江大学 | Preparation of multistage natural adsorbent for treating organic waste gas, and method of use |
| JP3157241U (en) * | 2009-11-24 | 2010-02-04 | ベストプロダクツ株式会社 | Deodorant sheets |
Non-Patent Citations (1)
| Title |
|---|
| 《Adsorption》 20070921 Xue-Pin Liao et al Adsorption of metal anions of vanadium(V) and chromium(VI) on Zr(IV)-impregnated collagen fiber 第55-64页 1-6 第14卷, * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104921301A (en) * | 2015-06-05 | 2015-09-23 | 滁州卷烟材料厂 | Composite adsorbent with persimmon peel for cigarette filter tips and method for preparing composite adsorbent |
| CN107442066A (en) * | 2017-08-07 | 2017-12-08 | 荆楚理工学院 | A kind of microwave charing persimmon skin biological adsorption agent and its production and use |
| CN110314652A (en) * | 2018-03-29 | 2019-10-11 | 河北农业大学 | A kind of absorption and recovery method using persimmon slag to noble metal gold |
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