CN101817894A - Application of chelating macromolecular resin in removing heavy metal ions in fruit and vegetable juice - Google Patents
Application of chelating macromolecular resin in removing heavy metal ions in fruit and vegetable juice Download PDFInfo
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- CN101817894A CN101817894A CN201010100142A CN201010100142A CN101817894A CN 101817894 A CN101817894 A CN 101817894A CN 201010100142 A CN201010100142 A CN 201010100142A CN 201010100142 A CN201010100142 A CN 201010100142A CN 101817894 A CN101817894 A CN 101817894A
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Abstract
The invention provides an application of chelating macromolecular resin in removing heavy metal ions in fruit and vegetable juice. The resin is polystyrene macromolecular resin of crosslinking benzylamine base dithio-formylation and with ferric ions which are loaded on benzylamine bases, methylene and phosphate group. The successfully developed and obtained functionalized resin of crosslinking benzylamine base dithio-formylation and with the ferric ions which are loaded on the benzylamine bases, the methylene and the phosphate group is used for removing the heavy metal ions in the fruit and vegetable juice. Proved by a result, the resin can simultaneously remove heavy metal elements with more complicated existing modes in the fruit and vegetable juice, has obvious removal effect, high removal rate and convenient use and is suitable for large-scale use on the spot.
Description
Technical field
The present invention relates to the macromolecule resin technical field, specifically, relate to the purposes that a kind of crosslinked benzamido group dithio formic acidization and ferric ion load on the polystyrene chelating high molecular resin on the benzamido group methylene phosphate.
Background technology
The fast development of China's economy has caused the serious environmental pollution over nearly 30 years.Heavy-metal residual is one of the most serious pollution form.Chemically density is called heavy metal greater than the metal of 4.5 gram/cubic centimetres.Nucleidic mass is generally heavy metal greater than 55 metal.Copper, lead, zinc, iron, cobalt, nickel, chromium, vanadium, niobium, tantalum, titanium, manganese, cadmium, mercury, tungsten, molybdenum, gold and silver etc. are main heavy metal elements.Although heavy metals such as manganese, copper, zinc are the essential trace elements of vital movement, most of heavy metal such as mercury, lead, cadmium etc. all are deleterious to human body, and all heavy metals all have very strong toxicity when surpassing finite concentration.Heavy metal contamination is meant the environmental pollution that is caused by heavy metal or its compound, mainly is because due to the human factors such as mining, exhaust gas emission, sewage irrigation and use heavy metal goods.Heavy metal with soil, atmosphere and water pollution after, will enter food chain, finally enter human body.Because biological amplification, to the high-grade progression, content of harmful such as heavy metal are increasing from rudimentary for food chain.Heavy metal ion will be brought the damage that is difficult to repair intravital the accumulating of people to human body, can directly cause death when dosage is big.In " world's ten big pollution incidents ", " minamata disease " incident and " itai-itai " incident are caused by heavy metal Hg and cadmium respectively.The significant damage that heavy-metal residual causes has made people have to face its existence and has striven to find terms of settlement.
Because soil and water body are contaminated by heavy metals, plantation of plant and cultivation undoubtedly will be affected.Can not escape by luck equally with the closely-related fruits and vegetables of human lives.With the apple is example, according to China's researching and analysing of apple that apple main product ground-area, Shandong produces shown: the recall rate of fluorine, mercury and chromium is 100%, the recall rate of lead, tin, arsenic is all above 93%, and the exceeding standard rate of mercury, lead and tin is respectively 1.47%, 11.29% and 8.06%.Heavy metal in the fruits and vegetables is mainly derived from the pollution to " waste water,waste gas and industrial residue " in the enrichment and industrial production of heavy metal of soil, irrigation water, the agricultural chemicals of using and fertilizer, fruits and vegetables self.Heavy metals exceeding standard in the fruits and vegetables has directly had influence on related industrieies such as fruit juice, vegetables juice.Fruit juice and vegetables juice also exist in possibility contaminated by heavy metals in the course of processing.
Along with the newest fruits of agricultural science and technology constantly is applied to produce, per unit area yield and the ultimate production of China fruits and vegetables constantly create the all-time new and high.Fruit juice and vegetables juice have been called the important industry of China.According to statistics, the output of China's apple condensed juice has accounted for more than 40% of Gross World Product, and export volume accounts for the over half of quantum of world trade.Therefore, the heavy-metal residual in fruit juice and the vegetables juice must cause enough attention." really, vegetables juice beverages health standard " (the GB 19297-2003) of State Bureau of Standardization's promulgation stipulated that clearly the limit index of heavy metal is: arsenic (As)≤0.2mg/kg, lead (Pb)≤0.05mg/kg, copper (Cu)≤5.0mg/kg.In addition, State Bureau of Standardization has also issued concrete standard with regard to concrete fruit juice, wherein also heavy metal limit has been carried out clear and definite qualification.
Methods such as general at present employing absorption method, ion exchange treatment method and resin method are removed the heavy metal ion in fruit juice or the vegetables juice.
Absorption method is to utilize the unique texture of sorbent material, interacts or forms the method that form such as surperficial hydrogen bond is removed the heavy metal ion in fruit juice or the vegetables juice by surface adsorption, surface electrical.Sorbent material commonly used has activated carbon fiber, wilkinite and macroporous adsorbent resin etc.
The ion exchange treatment method is to utilize ion-exchanger to remove the method for heavy metal ion.Ion-exchange is to exchange by the self-contained ion that can move freely of exchanger and processed fruit juice or the heavy metal ion in the vegetables juice to realize.The power that promotes ion-exchange is that functional group on interionic concentration difference and the exchanger is to the affinity of heavy metal ion.Heavy metal ion in the in most cases processed solution is to be adsorbed earlier, to be exchanged.Therefore, ion-exchanger has absorption, exchange double effects.Ion-exchanger commonly used has ion exchange resin, ion-exchange fiber and zeolite etc.
Resin removal method is to utilize the functional group that contains elements such as aerobic, nitrogen, sulphur on the modified high-molecular resin to reach the purpose of removing heavy metal ion with the principle that heavy metal ion in fruit juice or the vegetables juice forms stable chelate.Chelating resin commonly used comprises that benzyl imine oxalic acid type resin, sulfydryl type resin, amino-type resin, benzamido group phosphatic type resin and load have the benzamido group phosphatic type resin of ferric ion and/or trivalent lanthanum ion.
Along with the continuous progress and the innovation of biological chemistry theory and technology, the method for organism by chemical action removal heavy metal ion appearred at present.The mechanism of this method may be extracellular enrichment/deposition, cell surface absorption or complexing, the interior enrichment of cell etc.The process of removing heavy metal ion may comprise each process such as electrostatic attraction, complexing, ion-exchange, microdeposit, redox reaction.
All there is shortcoming more or less in the method that above-mentioned usefulness removes the heavy metal ion in fruit juice or the vegetables juice, these drawbacks limit they promotion and application in actual production.
For absorption method, the effective ingredient in fruit juice and the vegetables juice more easily is adsorbed, the difficult reason such as be adsorbed of heavy metal ion makes the application of absorption method be subjected to very big restriction.When using activated carbon fiber and wilkinite as sorbent material, fruit juice or vegetables juice are easy to generate secondary pollution; When using macroporous adsorbent resin as sorbent material, adsorption rate and elution rate are all slow, inefficiency.Simultaneously, the reprocessing cycle of sorbent material is difficult for realizing.
For the ion exchange treatment method, ion-exchanger generally all presents certain acid-basicity, and this has certain destruction to the effective ingredient in fruit juice or the vegetables juice; The electric charge that ion-exchanger itself carries also might exert an influence to the effective ingredient in fruit juice or the vegetables juice, may be to cause one of reason muddy after fruit juice or the vegetables juice.This has just limited the application of the heavy metal ions of ion exchange method in removing fruit juice or vegetables juice.
For the resin method, arsenic element may exist with positively charged ion or negatively charged ion because lead, cadmium, mercury and copper in fruit juice or the vegetables juice generally exist with cationic form, and the existence form of heavy metal relative complex makes to unite uses multiple resin it could be removed.This has not only increased cost, has prolonged the operating time, also makes the reprocessing cycle of resin to realize easily.
For biochemical method, subject matter be remove the theory of heavy metal element still immature, the cellular component that participates in metal complex is constituted and biosynthetic process is unclear, lack that heavy metal element is adsorbed or the dynamics data of complexing, can't carry out that process design and amplification and economy are accounted etc.These problems make utilize method that biochemical method removes heavy metal ion still difficulty walk out the laboratory.
Summary of the invention
The object of the present invention is to provide the purposes and the application method thereof of the functional resin heavy metal ions in removing garden spgarden stuff that contains multiple chelation group.
The invention provides the purposes of a kind of macromolecule resin heavy metal ions in removing garden spgarden stuff, described chelating high molecular resin, it is that crosslinked benzamido group dithio formic acidization and ferric ion load on the polystyrene macromolecule resin on the benzamido group methylene phosphate.
Chelating high molecular resin of the present invention adopts following method preparation: with crosslinked benzamido group polystyrene resin purifying, swelling; Then under acidic conditions, with phosphorous acid, polyformaldehyde reaction; And then react with liquor ferri trichloridi; Under alkaline condition, make at last with the dithiocarbonic anhydride reaction.
The preparation method of chelating high molecular resin of the present invention specifically comprises the steps:
1) with crosslinked benzamido group polystyrene resin A with pure purifying after, use pure swelling again;
2) under acidic conditions, with the crosslinked benzamido group polystyrene resin A after the swelling and phosphorous acid, polyformaldehyde reaction, make 20%～30% benzamido group be converted into the benzamido group methylene phosphate, and then with liquor ferri trichloridi reaction, obtain crosslinked benzamido group and ferric ion and load on polystyrene resin B on the benzamido group methylene phosphate;
3) under alkaline condition, with resin B and dithiocarbonic anhydride reaction, make that remaining benzamido group is converted into the benzamido group dithio formate in the resin B, obtain crosslinked benzamido group dithio formic acidization and ferric ion and load on polystyrene macromolecule resin C on the benzamido group methylene phosphate.
Specifically, described step 1) comprises: with crosslinked benzamido group polystyrene resin A, with the methyl alcohol or the ethanol repetitive scrubbing of 2.0～5.0 times of Resin A weight, filter, dry, obtain the Resin A behind the purifying; Resin A swelling after using the methyl alcohol of 1.5～2.0 times of Resin A weight or ethanol with purifying then.
Described step 2) comprising:
A, the Resin A after the above-mentioned swelling is joined in the methyl alcohol or ethanol of 5 times of Resin A weight, add phosphorous acid, Paraformaldehyde 96 and concentrated hydrochloric acid then, mix post-heating to 70 ℃, stirring reaction 12～24h, be cooled to room temperature after, filter, be washed with distilled water to washings and be neutral, dry;
Wherein, the weight ratio of Resin A, phosphorous acid, Paraformaldehyde 96 and concentrated hydrochloric acid is 1: 0.82～1.24: 0.30～0.45: 0.27～0.41;
B, then continuously with the deionized water wash of 5% hydrochloric acid of the deionized water of 5% sodium hydroxide solution of the ethanol of 1～3 times of Resin A weight, 0.5 times of Resin A weight, 1～3 times of Resin A weight, 0.5 times of Resin A weight, 1～5 times of Resin A weight to washings pH be 5～7;
C, add concentration expressed in percentage by weight 10% liquor ferri trichloridi then, stir 12～24h down at 30 ℃, filter then, discard filtrate, resin dries till being washed till washings and not having a ferric ion (ferric ion detects with potassium thiocyanate) with deionized water;
Wherein, the weight ratio of liquor ferri trichloridi and Resin A is 0.24～0.37: 1.
Described step 3) comprises:
D, in the resin B that makes, add the sodium hydroxide solution of dithiocarbonic anhydride and 4%～6% (weight percent), stir 1～3h down for 20～40 ℃ in temperature, stir 3～5h down for 45～50 ℃ in temperature then, be cooled to room temperature;
Wherein, the weight ratio of resin B, dithiocarbonic anhydride and sodium hydroxide is 1: 0.55～0.75: 0.31～0.34;
E, regulate pH to 6.0～7.0, filter,, dry with distilled water washing resin 3～5 times with concentrated hydrochloric acid.
Chelating high molecular resin of the present invention detects through micro ft-ir spectroscopy and to show, it contains the multiple chelation groups such as benzamido group methylene phosphate that benzamido group dithio formyloxy and load have ferric ion.
As everyone knows, the unoccupied orbital that has of heavy metal ion makes it be equivalent to Lewis acid.If it can form coordinate bond with the Lewis alkali that lone-pair electron can be provided, heavy metal ion just can remove from solution with the form of inner complex.Here it is utilizes resin to remove the theoretical foundation of heavy metal element.Can provide in the functional group of lone-pair electron and generally comprise ligating atoms such as sulphur, oxygen, nitrogen, phosphorus.Sulphur atom in thioether, mercaptan, thiophenol, sulfydryl, dithiocarbamate, the thiocarbamate etc.; Nitrogen-atoms in Sauerstoffatom in ether, phenol, carboxyl, the hydroxyl etc. and acid amides, nitrile, nitro, diazonium compound, azo-compound, primary amine, secondary amine, the tertiary amine can be as forming the strong Lewis alkali of coordination with heavy metal ion.Selectivity in the time of providing the character of the Lewis alkali of lone-pair electron to determine that itself and heavy metal ion coordination form inner complex.According to the ultimate principle and the experimental fact of chelatropic reaction, successfully developed the macromolecule resin of the functionalization of heavy metal cations such as the selectivity removal of mercury, deleading, copper removal at present.
In garden spgarden stuff, heavy metals such as copper, mercury, lead, cadmium generally exist with cationic form.So the resin of above-mentioned functionalization is united use, can remove the heavy metal cations such as copper, mercury, lead and cadmium in the garden spgarden stuff effectively.The existence form more complicated of arsenic in garden spgarden stuff may occur with cationic form, but the form with acid ion (for example arsenate negative ion or arsenous anion negative ion) occurs under the more susceptible condition.Normally heavy metal ion such as iron or lanthanum are loaded on the macromolecule resin by sequestering action at present,, thereby arsenic is removed then by arsenate negative ion or arsenous anion negative ion and these heavy metal ion formation inner complex.
Not only increase cost but unite the heavy metal element that uses multiple resin to remove in the garden spgarden stuff, prolonged the operating time, also made the reprocessing cycle of resin to realize easily.
The present invention succeeds in developing the crosslinked benzamido group dithio formic acidization that obtains and ferric ion with our company and loads on the heavy metal ion that the functional resin that contains multiple chelation group on the benzamido group methylene phosphate is used for removing garden spgarden stuff.The result shows that this resin can be removed by simultaneously that the existence form in the garden spgarden stuff is comparatively complicated heavy metal element simultaneously.Removal effect is obvious, the clearance height.Easy to use.Be fit to on-the-spot, the in enormous quantities use.
The using method that contains the functional resin of multiple chelation group provided by the invention is described below:
Take by weighing a certain amount of functional resin that contains multiple chelation group, join in the garden spgarden stuff that needs to handle, vigorous stirring 30-120 minute, filter and obtain treated garden spgarden stuff.Adopt inductively coupled plasma emission spectrography (ICP-AES) to measure the content of the heavy metal ion in the garden spgarden stuff of handling front and back, to determine effect of the present invention.
Embodiment
Following examples are used for further specifying the present invention, but are not used for limiting the present invention.
Embodiment 1
Take by weighing the commercially available crosslinked benzamido group polystyrene resin A of 100g,, filter, obtain the Resin A behind the purifying after drying with 500mL ethanol repetitive scrubbing.With the 250mL ethanol swelling of the Resin A behind the purifying.Resin A after the swelling is joined in the 625mL ethanol, add 103.3g phosphorous acid, 37.8g Paraformaldehyde 96 and 34.2g concentrated hydrochloric acid, be heated to 70 ℃, stir 16h, be cooled to room temperature then, filter, be neutral until washings with distilled water washing resin.After this resin dried, use 250mL dehydrated alcohol, 50g 5% sodium hydroxide solution, 300mL deionized water, 50g 5% hydrochloric acid, 500mL deionized water wash continuously up to washings pH=6.0.This resin is joined in the solution of 30.5g iron trichloride and 275mL water composition.Stir down 12h at 30 ℃, filter, be washed till washings with deionized water and can not detect (detecting) till the ferric ion, dry, obtain the 128.2g resin B with potassium thiocyanate.
In above-mentioned 128.2g resin B, add the solution that 85.7g dithiocarbonic anhydride, 42.1g sodium hydroxide and 800mL water are formed, stir 2h down for 25 ℃ in temperature, stir 4h down at 45 ℃ then, be cooled to room temperature, regulate pH=6.0, filter with concentrated hydrochloric acid, discard filtrate, resin distilled water wash 3 times are dried, and obtain 171g chelating high molecular resin C.
Detect through micro ft-ir spectroscopy, find that resin C is at 2084cm
-1(benzamido group dithio formyloxy) and 1641cm
-1(load has the benzamido group methylene phosphate of ferric ion) locates to have respectively the obvious characteristic peak to occur, and shows that resin C contains the multiple chelation groups such as benzamido group methylene phosphate that benzamido group dithio formyloxy and load have ferric ion really.
Embodiment 2
Get 500 milliliters of the sea buckthorn juices that certain company produces, add the functional resin that contains multiple chelation group that the 40 gram embodiment of the invention 1 make, vigorous stirring was filtered after 60 minutes, collected filtrate.
With the heavy metal content in the sea buckthorn juice before and after the processing of Varian 700 type inductively coupled plasma emission spectrographies (ICP-AES) mensuration, the result is as follows:
| The heavy metal element of being measured | Before handling (mg/Kg) | Handle back (mg/Kg) | Clearance (%) |
| Mercury | ??0.06 | ??0.0 | Do not detect |
| Plumbous | ??0.76 | ??0.0 | Do not detect |
| Arsenic | ??0.15 | ??0.0 | Do not detect |
| Copper | ??4.58 | ??0.0 | Do not detect |
This shows that the heavy metal content in the juice of Fructus Hippophae after the functional resin through containing multiple chelation group is handled can't detect, reaches " really, vegetables juice beverages health standard " (GB 19297-2003).
Embodiment 3
Get 250 milliliters of the juice of Fructus Mori that certain company produces, add the functional resin that contains multiple chelation group that 15 gram the present invention make, vigorous stirring was filtered after 50 minutes, collected filtrate.
With the heavy metal content in the juice of Fructus Mori before and after the processing of Varian 700 type inductively coupled plasma emission spectrographies (ICP-AES) mensuration, the result is as follows:
| The heavy metal element of being measured | Before handling (mg/Kg) | Handle back (mg/Kg) | Clearance (%) |
| Mercury | ??0.0 | ??0.0 | Do not detect |
| Plumbous | ??0.06 | ??0.0 | Do not detect |
| Arsenic | ??0.22 | ??0.0 | Do not detect |
| Copper | ??5.36 | ??0.0 | Do not detect |
This shows that the heavy metal content in the juice of Fructus Mori after the functional resin through containing multiple chelation group is handled can't detect, reaches " really, vegetables juice beverages health standard " (GB 19297-2003).
Embodiment 4
Get 5000 milliliters of the Radix Dauci Sativae juices that certain company produces, add the functional resin that contains multiple chelation group that 200 gram the present invention make, vigorous stirring was filtered after 90 minutes, collected filtrate.
With the heavy metal content in the Radix Dauci Sativae juice before and after the processing of Varian 700 type inductively coupled plasma emission spectrographies (ICP-AES) mensuration, the result is as follows:
| The heavy metal element of being measured | Before handling (mg/Kg) | Handle back (mg/Kg) | Clearance (%) |
| Mercury | ?0.07 | ??0.0 | Do not detect |
| Plumbous | ?0.08 | ??0.0 | Do not detect |
| Arsenic | ?0.13 | ??0.0 | Do not detect |
| Copper | ?5.52 | ??0.0 | Do not detect |
This shows that the heavy metal content in the Radix Dauci Sativae juice after the functional resin through containing multiple chelation group is handled can't detect, reaches " really, vegetables juice beverages health standard " (GB19297-2003).
Though, above with general explanation, embodiment and use experiment, the present invention is described in detail, but on basis of the present invention, can make some modifications or improvements it, as: use the trivalent heavy metals ion, particularly trivalent lanthanide ion such as trivalent lanthanum ion replaces the ferric ion among the present invention, and this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (5)
1. the purposes of chelating high molecular resin heavy metal ions in removing garden spgarden stuff, it is characterized in that described chelating high molecular resin is that crosslinked benzamido group dithio formic acidization and ferric ion load on the polystyrene macromolecule resin on the benzamido group methylene phosphate.
2. purposes according to claim 1 is characterized in that, described macromolecule resin adopts following method preparation: with crosslinked benzamido group polystyrene resin purifying, swelling; Then under acidic conditions, with phosphorous acid, polyformaldehyde reaction; And then react with liquor ferri trichloridi; Under alkaline condition, make at last with the dithiocarbonic anhydride reaction.
3. purposes according to claim 2 is characterized in that the preparation method of described macromolecule resin comprises the steps:
1) with crosslinked benzamido group polystyrene resin A with pure purifying after, use pure swelling again;
2) under acidic conditions, with the crosslinked benzamido group polystyrene resin A after the swelling and phosphorous acid, polyformaldehyde reaction, make 20%～30% benzamido group be converted into the benzamido group methylene phosphate, and then with liquor ferri trichloridi reaction, obtain crosslinked benzamido group and ferric ion and load on polystyrene resin B on the benzamido group methylene phosphate;
3) under alkaline condition, with resin B and dithiocarbonic anhydride reaction, make that remaining benzamido group is converted into the benzamido group dithio formate in the resin B, obtain crosslinked benzamido group dithio formic acidization and ferric ion and load on polystyrene macromolecule resin C on the benzamido group methylene phosphate.
4. according to claim 1 or 2 or 3 described purposes, it is characterized in that described macromolecule resin joins in the described garden spgarden stuff by the consumption that 4-8 restrains resin/100 milliliter garden spgarden stuff.
5. purposes as claimed in claim 4 is characterized in that, behind the described macromolecule resin of adding, stirs 0.5-2 hour after-filtration in the described garden spgarden stuff.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101001427A CN101817894B (en) | 2010-01-22 | 2010-01-22 | Application of chelating macromolecular resin in removing heavy metal ions in fruit and vegetable juice |
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|---|---|---|---|
| CN2010101001427A CN101817894B (en) | 2010-01-22 | 2010-01-22 | Application of chelating macromolecular resin in removing heavy metal ions in fruit and vegetable juice |
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| CN101817894A true CN101817894A (en) | 2010-09-01 |
| CN101817894B CN101817894B (en) | 2012-03-28 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101803784A (en) * | 2010-04-26 | 2010-08-18 | 北京欧凯纳斯科技有限公司 | Method for removing heavy metal ions in fruit and vegetable juice by using chelate resin in cooperative treatment |
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2010
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101803784A (en) * | 2010-04-26 | 2010-08-18 | 北京欧凯纳斯科技有限公司 | Method for removing heavy metal ions in fruit and vegetable juice by using chelate resin in cooperative treatment |
| CN101803784B (en) * | 2010-04-26 | 2012-07-25 | 北京欧凯纳斯科技有限公司 | Method for removing heavy metal ions in fruit and vegetable juice by using chelate resin in cooperative treatment |
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| CN101817894B (en) | 2012-03-28 |
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