CN105327688A - Method for removing heavy metals in sea cucumbers through modified attapulgite composite chelate resin - Google Patents
Method for removing heavy metals in sea cucumbers through modified attapulgite composite chelate resin Download PDFInfo
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- CN105327688A CN105327688A CN201510807178.1A CN201510807178A CN105327688A CN 105327688 A CN105327688 A CN 105327688A CN 201510807178 A CN201510807178 A CN 201510807178A CN 105327688 A CN105327688 A CN 105327688A
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- attapulgite
- sea cucumber
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Abstract
The invention discloses a method for removing heavy metals in sea cucumbers through modified attapulgite composite chelate resin in order to solve the problem that the heavy metals in the sea cucumbers cannot be effectively removed with a conventional sea cucumber cleaning method. The method comprises steps as follows: attapulgite-chelate resin is prepared from preprocessed attapulgite and chelate resin through compositing, an attapulgite-chelate resin water suspension is prepared by the aid of deionized water, the sea cucumbers are cleaned through ultrasonic oscillating of the water suspension, and the heavy metals in the sea cucumbers are adsorbed and removed. The method has the advantages of reasonable technology, good adsorption effect, convenience in operation and low adsorbent cost.
Description
Technical field
The present invention includes the separation method by solid absorbent treat liquid, especially a kind of method utilizing attapulgite modified composite chelate resin to remove sea cucumber heavy metal.
Background technology
Sea cucumber generally lives in the dark marine site of 3-20 rice, perches in the rock at the bottom, silt, sea grass.They are liked eating the silt, the beach face ooze that are deposited on seabed, because wherein containing diatom, zoodetritus, small-sized biological, microorganism etc.Sea cucumber poor growth, generally needs 2-3 from seedling to maturation.Because offshore waters are subject to pollution in various degree in recent years, add the special life habit of sea cucumber, sea cucumber surface and digestion enteron aisle very easily accumulate heavy metal.At present, Holothurian machining process generally through the conventional method that surface washing dissection is washed again, generally can only remove sea cucumber sediments, but effectively can not remove the harmful substances such as heavy metal ion, these harmful substances are stayed in sea cucumber, work the mischief to the mankind.Therefore, how removing the harmful substance such as heavy metal in sea cucumber surface and enteron aisle is a problem demanding prompt solution.
Summary of the invention
Effectively can not remove the deficiency of sea cucumber heavy metal of body to overcome conventional method cleaning sea cucumber, the object of this invention is to provide a kind of rational technology, adsorption effect is good, easy and simple to handle, cost the is low attapulgite modified composite chelate resin that utilizes removes the method for sea cucumber heavy metal.
The technical solution adopted for the present invention to solve the technical problems is: a kind of method utilizing attapulgite modified composite chelate resin to remove sea cucumber heavy metal, is characterized in that: it is through following process steps:
(1) preparation of attapulgite-chelating resin: take 5 ~ 15 parts of pretreated attapulgites by weight, 20 ~ 40 parts of D405 chelating resins are placed in container, add 15 ~ 25 parts, concentration is the HCL solution of 2 ~ 4mol/L, heating is boiled, sonic oscillation shakes up 0.5 ~ 1.5h, it is 20 ~ 48KHZ that supersonic frequency controls, centrifugal 15 ~ 30min, remove supernatant, get precipitate with deionized water and be washed till pH value 6 ~ 8, dry 6 ~ 8h under 70 ~ 80 DEG C of conditions, grinding and sieving, is placed in drier, obtains attapulgite-chelating resin;
(2) preparation of attapulgite-chelating resin aqueous suspensions: in attapulgite quality is the attapulgite-chelating resin aqueous suspensions of 1 ~ 3% with deionized water preparation mass fraction, for subsequent use;
(3) removal of sea cucumber heavy metal: pretreated sea cucumber is put into attapulgite-chelating resin aqueous suspensions, the mass ratio of sea cucumber and attapulgite-chelating resin aqueous suspensions is 1:1 ~ 2, sonic oscillation 20 ~ 30min under room temperature, it is 20 ~ 60KHZ that supersonic frequency controls, then sea cucumber is taken out, rinse 2 ~ 3 times with clear water.
The pretreatment of described attapulgite is by the attapulgite alcohol immersion 10 ~ 15h of 60 ~ 80%, cleans up with distilled water.
The pretreatment of described sea cucumber is drawn except enteraden after being cut open by sea cucumber belly, with clear water eccysis sea cucumber surface silt particle, dirt and internal organ.
The present invention adopts pretreated attapulgite and chelating resin compound to prepare attapulgite-chelating resin, attapulgite-chelating resin aqueous suspensions is prepared again by deionized water, this aqueous suspensions sonic oscillation is adopted to clean sea cucumber, remove the heavy metal in sea cucumber, after absorption, obtain the beche-de-mer products that content of beary metal declines to a great extent.Its attapulgite adopted has larger specific area, and adsorb least concentration low, reach time of equilibrium adsorption short, to adsorption conditions without rigors, to Cu (II), Cd (II), Ni (II) and Cr (VI), there is good adsorption effect, wherein the highest to the adsorption capacity of Cr (VI), and low price, raw material are easy to get; Chelating resin (chelateresins) is that a class can form the crosslinked functional high molecule material of polygamy position network and thing with metal ion, the mechanism of its adsorbing metal ions is function atom on resin and metal ion generation complexation reaction, form the rock-steady structure of similar Small molecular chelate, and the mechanism of ion exchange resin absorption is electrostatic interaction, therefore the adhesion of chelating resin and metal ion is stronger, selective higher.Chelating resin combines with attapulgite by the present invention, has both added the surface area of absorption, increases again effective adsorption site, and thus adsorbance increases.The beche-de-mer products through absorption that the present invention obtains through above-mentioned steps, detect according to the atomic absorption spectrophotometry in " Chinese Pharmacopoeia " annex lead, cadmium, arsenic, determination method, content of beary metal in sea cucumber significantly reduces, and reaches food sanitation standard, greatly improves the security of product.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
embodiment 1
Utilize attapulgite modified composite chelate resin to remove a method for sea cucumber heavy metal, it is through following process steps:
(1) preparation of attapulgite-chelating resin: take 9 parts of pretreated attapulgites by weight, 30 parts of D405 chelating resins are placed in there-necked flask, add 20 parts, concentration is the HCL solution of 3mol/L, heating is boiled, sonic oscillation shakes up 1h, supersonic frequency controls as 30KHZ, control centrifuge speed 5000r/min, centrifugal 20min, remove supernatant, get precipitate with deionized water and be washed till pH value 7, dry 7h under 75 DEG C of conditions, after pulverizing, cross 100 mesh sieves, be placed in drier, obtain attapulgite-chelating resin; Wherein, the pretreatment of attapulgite is by the attapulgite alcohol immersion 12h of 75%, cleans up with distilled water;
(2) preparation of attapulgite-chelating resin aqueous suspensions: in attapulgite quality is the attapulgite-chelating resin aqueous suspensions of 2% with deionized water preparation mass fraction, for subsequent use;
(3) removal of sea cucumber heavy metal: draw except enteraden after sea cucumber belly is cut open, after clear water eccysis sea cucumber surface silt particle, dirt and internal organ, put into attapulgite-chelating resin aqueous suspensions, the mass ratio of sea cucumber and attapulgite-chelating resin aqueous suspensions is 1:1.5, sonic oscillation 25min under room temperature, supersonic frequency controls, for 50KHZ, then to be taken out by sea cucumber, 3 times are rinsed with clear water.
embodiment 2
Utilize attapulgite modified composite chelate resin to remove a method for sea cucumber heavy metal, it is through following process steps:
(1) preparation of attapulgite-chelating resin: take 5 parts of pretreated attapulgites by weight, 40 parts of D405 chelating resins are placed in there-necked flask, add 15 parts, concentration is the HCL solution of 4mol/L, heating is boiled, sonic oscillation shakes up 1.5h, supersonic frequency controls as 20KHZ, control centrifuge speed 6000r/min, centrifugal 15min, remove supernatant, get precipitate with deionized water and be washed till pH value 6, dry 6h under 80 DEG C of conditions, after pulverizing, cross 120 mesh sieves, be placed in drier, obtain attapulgite-chelating resin; Wherein, the pretreatment of attapulgite is by the attapulgite alcohol immersion 10h of 80%, cleans up with distilled water;
(2) preparation of attapulgite-chelating resin aqueous suspensions: in attapulgite quality is the attapulgite-chelating resin aqueous suspensions of 1% with deionized water preparation mass fraction, for subsequent use;
(3) removal of sea cucumber heavy metal: draw except enteraden after sea cucumber belly is cut open, after clear water eccysis sea cucumber surface silt particle, dirt and internal organ, put into attapulgite-chelating resin aqueous suspensions, the mass ratio of sea cucumber and attapulgite-chelating resin aqueous suspensions is 1:2, sonic oscillation 20min under room temperature, supersonic frequency controls, for 60KHZ, then to be taken out by sea cucumber, 2 times are rinsed with clear water.
embodiment 3
Utilize attapulgite modified composite chelate resin to remove a method for sea cucumber heavy metal, it is through following process steps:
(1) preparation of attapulgite-chelating resin: take 15 parts of pretreated attapulgites by weight, 20 parts of D405 chelating resins are placed in there-necked flask, add 25 parts, concentration is the HCL solution of 2mol/L, heating is boiled, sonic oscillation shakes up 0.5h, supersonic frequency controls as 48KHZ, control centrifuge speed 5000r/min, centrifugal 30min, remove supernatant, get precipitate with deionized water and be washed till pH value 8, dry 8h under 70 DEG C of conditions, after pulverizing, cross 80 mesh sieves, be placed in drier, obtain attapulgite-chelating resin; Wherein, the pretreatment of attapulgite is by the attapulgite alcohol immersion 15h of 60%, cleans up with distilled water;
(2) preparation of attapulgite-chelating resin aqueous suspensions: in attapulgite quality is the attapulgite-chelating resin aqueous suspensions of 3% with deionized water preparation mass fraction, for subsequent use;
(3) removal of sea cucumber heavy metal: draw except enteraden after sea cucumber belly is cut open, after clear water eccysis sea cucumber surface silt particle, dirt and internal organ, put into attapulgite-chelating resin aqueous suspensions, the mass ratio of sea cucumber and attapulgite-chelating resin aqueous suspensions is 1:1, sonic oscillation 30min under room temperature, supersonic frequency controls, for 20KHZ, then to be taken out by sea cucumber, 3 times are rinsed with clear water.
The effect that the present invention removes sea cucumber heavy metal is further illustrated below by experiment.
Control group: under room temperature, sea cucumber: deionized water=1:1.5(mass ratio), sonic oscillation 20min, supersonic frequency controls, for 50KHZ, to detect its aqueous solution content of beary metal, in triplicate, get arithmetic average C
0(unit, mg/kg).
Experimental group: by the method for the removing sea cucumber heavy metal given by embodiment 1, sampling detects the content of heavy metal in suspension, in triplicate, gets arithmetic average C(unit, mg/kg).
By formulae discovery cleaning performance=(C-C
0)/C
0.
Detect according to the atomic absorption spectrophotometry in " Chinese Pharmacopoeia " annex lead, arsenic, cadmium determination method, experimentally result calculates the cleaning performance difference 12.56,8.34 and 16.75 of lead, arsenic, cadmium.As can be seen here, cleaning Adsorption of Heavy Metals Be very effective, shows that the heavy metal of attapulgite-chelating resin suspension to process sea cucumber surface and internal organ accumulation has good elimination effect.
Of the present inventionly utilize attapulgite modified composite chelate resin operation easy, cost is low, can be used for the sea cucumber removing heavy metals technique containing heavy metal, effectively can reduce content of beary metal, reach food sanitation standard, have wide market application foreground.
Claims (3)
1. utilize attapulgite modified composite chelate resin to remove a method for sea cucumber heavy metal, it is characterized in that: it is through following process steps:
(1) preparation of attapulgite-chelating resin: take 5 ~ 15 parts of pretreated attapulgites by weight, 20 ~ 40 parts of D405 chelating resins are placed in container, add 15 ~ 25 parts, concentration is the HCL solution of 2 ~ 4mol/L, heating is boiled, sonic oscillation shakes up 0.5 ~ 1.5h, it is 20 ~ 48KHZ that supersonic frequency controls, centrifugal 15 ~ 30min, remove supernatant, get precipitate with deionized water and be washed till pH value 6 ~ 8, dry 6 ~ 8h under 70 ~ 80 DEG C of conditions, grinding and sieving, is placed in drier, obtains attapulgite-chelating resin;
(2) preparation of attapulgite-chelating resin aqueous suspensions: in attapulgite quality is the attapulgite-chelating resin aqueous suspensions of 1 ~ 3% with deionized water preparation mass fraction, for subsequent use;
(3) removal of sea cucumber heavy metal: pretreated sea cucumber is put into attapulgite-chelating resin aqueous suspensions, the mass ratio of sea cucumber and attapulgite-chelating resin aqueous suspensions is 1:1 ~ 2, sonic oscillation 20 ~ 30min under room temperature, it is 20 ~ 60KHZ that supersonic frequency controls, then sea cucumber is taken out, rinse 2 ~ 3 times with clear water.
2. a kind of method utilizing attapulgite modified composite chelate resin to remove sea cucumber heavy metal according to claim 1, it is characterized in that: the pretreatment of described attapulgite is by the attapulgite alcohol immersion 10 ~ 15h of 60 ~ 80%, cleans up with distilled water.
3. a kind of method utilizing attapulgite modified composite chelate resin to remove sea cucumber heavy metal according to claim 1, it is characterized in that: the pretreatment of described sea cucumber is drawn except enteraden after being cut open by sea cucumber belly, with clear water eccysis sea cucumber surface silt particle, dirt and internal organ.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106890720A (en) * | 2017-03-30 | 2017-06-27 | 兰州坤仑环保科技有限公司 | A kind of alkali chelates the preparation method of palygorskite base heavy metal passivating material |
| CN108101276A (en) * | 2017-11-23 | 2018-06-01 | 南京悠谷新材料科技有限公司 | Industrial wastewater treatment device |
| CN112354366A (en) * | 2020-11-17 | 2021-02-12 | 江苏泷膜环境科技有限公司 | High-flux composite reverse osmosis membrane and preparation method thereof |
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|---|---|---|---|---|
| JPH02187143A (en) * | 1989-01-13 | 1990-07-23 | Japan Atom Energy Res Inst | Production of chelate resin adsorbent having iminodiacetate group |
| CN102247807A (en) * | 2011-05-17 | 2011-11-23 | 江苏麦阁吸附剂有限公司 | Preparation method and usage of modified attapulgite adsorption material |
| CN102391399A (en) * | 2011-10-10 | 2012-03-28 | 中国地质大学（武汉） | Preparation method for chelating ion exchange resin using inorganic substance as matrix |
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2015
- 2015-11-22 CN CN201510807178.1A patent/CN105327688B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02187143A (en) * | 1989-01-13 | 1990-07-23 | Japan Atom Energy Res Inst | Production of chelate resin adsorbent having iminodiacetate group |
| CN102247807A (en) * | 2011-05-17 | 2011-11-23 | 江苏麦阁吸附剂有限公司 | Preparation method and usage of modified attapulgite adsorption material |
| CN102391399A (en) * | 2011-10-10 | 2012-03-28 | 中国地质大学（武汉） | Preparation method for chelating ion exchange resin using inorganic substance as matrix |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106890720A (en) * | 2017-03-30 | 2017-06-27 | 兰州坤仑环保科技有限公司 | A kind of alkali chelates the preparation method of palygorskite base heavy metal passivating material |
| CN108101276A (en) * | 2017-11-23 | 2018-06-01 | 南京悠谷新材料科技有限公司 | Industrial wastewater treatment device |
| CN112354366A (en) * | 2020-11-17 | 2021-02-12 | 江苏泷膜环境科技有限公司 | High-flux composite reverse osmosis membrane and preparation method thereof |
| CN112354366B (en) * | 2020-11-17 | 2021-08-27 | 江苏泷膜环境科技有限公司 | High-flux composite reverse osmosis membrane and preparation method thereof |
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