CN105130509A - Method for removing lead ions and cadmium ions in liquid protein fertilizer - Google Patents
Method for removing lead ions and cadmium ions in liquid protein fertilizer Download PDFInfo
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- CN105130509A CN105130509A CN201510479865.5A CN201510479865A CN105130509A CN 105130509 A CN105130509 A CN 105130509A CN 201510479865 A CN201510479865 A CN 201510479865A CN 105130509 A CN105130509 A CN 105130509A
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Abstract
The invention relates to a method for removing lead ions and cadmium ions in a liquid protein fertilizer. The method comprises liquid protein fertilizer concentration, heavy metal removal agent preparation, lead and cadmium ion removal treatment, heavy metal removal agent separation and other steps, wherein the heavy metal removal agent preparation comprises precursor liquid A preparation, precursor liquid B preparation, precursor solution preparation, precursor zeolite compounding, calcining and other steps. The method of the present invention has the following beneficial effects that: 1, the heavy metal lead and cadmium ions in the liquid protein fertilizer can be completely removed; 2, the used heavy metal removal agent is easy to remove, and the harmful substance affecting the protein fertilizer effect can not be retained after the treatment; and 3, the prepared heavy metal removal agent can be reused after the soaking with the high concentration sodium ion solution.
Description
Technical field
The present invention relates to fishery products field of deep, especially relate to a kind of method removing lead, cadmium ion in liquid protein fertilizer.
Background technology
Liquid protein fertilizer is a kind of Crop fertilizer made of discarded animal/vegetable protein, is normally prepared from Optimization of Low Value Fish or aquatic product leftovers.In recent years because industrial or agricultural sewage is by random discharge into sea, containing the burning of heavy metal fossil oil, sanitary sewage enters sea with river, and it is coastal day by day frequent with offshore activities, cause heavy metal in seawater to increase, particularly plumbous, cadmium ion exceeds standard especially severe, thus causes lead, the cadmium ion content overproof in easy enriching heavy metal fishery products, also can exceed standard accordingly with plumbous in the liquid protein fertilizer that corresponding low-value aquatic product is obtained, cadmium ion content.If do not do de-plumbous, cadmium ion process to liquid protein fertilizer that is plumbous, cadmium ion content overproof, then plumbous, cadmium ion can enter human body along the path of Protein fertilizer, farm crop, human body, the physical and mental health of harm people.But there are no the special processing method removing heavy metal ion for liquid protein fertilizer in prior art, more there are no removing processing method that is plumbous in liquid protein fertilizer, cadmium ion.In other field liquid, the method for heavy-metal ion removal normally adopts chemical precipitation method and ion exchange method merely.Chemical precipitation method adds alkali exactly in required removing heavy metals liquid makes heavy metal ion precipitate, and then remove the heavy metal after precipitation through physical method, the pH value of liquid not only can be changed in this method process, also can introduce some other ion, if use the lead in this method removal liquid protein fertilizer, cadmium ion may affect the result of use of original liquid, if use the lead in this method removal liquid protein fertilizer, cadmium ion, the aluminum ion that precipitation agent is additionally introduced, iron ion can cause protein generation sex change in Protein fertilizer, also the growth that Protein fertilizer uses crop can be affected, ion exchange method is exactly the method utilizing the ion generation exchange interaction in ion-exchanger and liquid and make ion isolation, ion exchange resin is a kind of insoluble macromolecular compound, if use lead, the cadmium ion in this method removal liquid protein fertilizer, ion exchange resin joins and to be difficult to after in liquid protein fertilizer remove, thus the application effect of liquid protein fertilizer after having influence on.
Summary of the invention
The present invention be overcome existingly remove that heavy metal approach application is fertile plumbous to liquid protein, above-mentioned deficiency existing in cadmium removing process, provide that one removes lead, cadmium ion is effective, safe without toxic side effect remove plumbous, cadmium ion method in liquid protein fertilizer.
For achieving the above object, the present invention is by the following technical solutions:
Remove a method that is plumbous in liquid protein fertilizer, cadmium ion, comprise the following steps:
(1) liquid protein fertilizer is concentrated: liquid protein fertilizer is concentrated into 2 ~ 3 times of stoste, and the suitably concentrated of Protein fertilizer can improve the efficiency removing heavy metal lead, cadmium ion.
(2) heavy metal removing agent preparation: described heavy metal removing agent preparation comprises the following steps:
(1) precursor A liquid preparation: described precursor A liquid is made up of the component of following volume percent: tetrabutyl titanate 20 ~ 30%, dehydrated alcohol 45 ~ 55%, and surplus is anhydrous acetic acid, stirs after each component mixing 5 ~ 15 minutes, prepares to obtain Ti Sol A liquid;
(2) precursor B liquid preparation: described precursor B liquid to be the mass percent prepared by dehydrated alcohol and PVP be 3 ~ 7% PVP ethanolic soln;
(3) precursor solution preparation: obtain precursor solution after stirring 1 ~ 2 hour after precursor A liquid mixes with precursor B liquid, A liquid and B liquid mass ratio are 1:1 ~ 3;
(4) presoma zeolite compound: stir 50 ~ 80 minutes after being mixed with zeolite by precursor solution, obtains mixing presoma, and will mix presoma oven dry, pulverizing, and obtain mixing precursor powder, precursor solution and zeolite mass ratio are 1:1 ~ 2;
(5) calcine: by the mixing precursor powder after pulverizing 550 ~ 650 DEG C of temperature lower calcinations 3 ~ 5 hours, obtain heavy metal removing agent.
After the calcining of mixing precursor powder, titanium elements exists with the form of titanium dioxide.Titanium dioxide is a kind of technology maturation and has the novel photocatalyst of greater catalytic performance, it can under the effect of sunlight particularly sunlight middle-ultraviolet lamp, produce light induced electron, light induced electron and solution weight metal ion react, make heavy metal lead, cadmium ion is reduced to metallic lead, cadmium, thus more easily adsorbed by Zeolite support, then reach the effect of removing heavy metal lead, cadmium ion in solution.PVP is the tetrabutyl titanate that a kind of efficient dispersion agent better can disperse in presoma, thus after making preparation mixing precursor powder in tetrabutyl titanate can be full and uniform mix with zeolite, and mix about 600 DEG C that in precursor powder, organic components boiling point is mostly concentrated, the calcining temperature arranging 550 ~ 650 DEG C both fully can remove the organism in powder, can ensure that again zeolite wherein and titanium dioxide can not free the change of performance because temperature is too high.
(3) remove lead, cadmium ion: mixed 1:10 ~ 15 in mass ratio with liquid protein fertilizer by the heavy metal removing agent prepared, and stir 3 ~ 5 hours under light illumination.
(4) heavy metal removing agent is separated: the method separating-purifying of the reactant press filtration after photochemical catalysis is obtained the liquid protein after removing lead, cadmium fertile.
As preferably, photochemical catalysis light source used is high voltage mercury lamp light source or xenon source.High voltage mercury lamp can simulate ultraviolet illumination environment, and xenon lamp can simulating nature light photoenvironment, if experiment proves that the effect removing heavy metal ion with UV-irradiation photochemical catalysis is better.
As preferably, zeolite is sodium base clinoptilolite or sodium base mordenite.By sodium ion solution-treated mistake, sodium base zeolite is called as from the zeolite for sodium ion in duct, sodium base zeolite has the ion-exchange performance that common zeolite does not have, the sodium ion exchange in the heavy metal lead in solution, cadmium ion and zeolite can be made, thus play the auxiliary effect removing heavy metal lead in liquid, cadmium ion.
As preferably, the molecular weight of PVP is 500000 ~ 1300000.
As preferably, the temperature increasing schedule of calcination process is as follows:
(1) temperature rise rate of 10 DEG C is heated up from room temperature to 400 DEG C with per minute;
(2) 500 DEG C are warming up to the heat up temperature rise rate of 5 DEG C of per minute from 400 DEG C;
(3) holding temperature is warming up to the heat up temperature rise rate of 3 DEG C of per minute from 500 DEG C.
In temperature increasing schedule, early stage, temperature rise rate was very fast, can rapid temperature increases to temperature required, later stage temperature rise rate is comparatively slow, can allow the abundant slow releasing of gas produced in mixed powder, can not be too fast because heating up, and produces gas velocity too soon, causes powder to be ejected.
Therefore, the present invention has following beneficial effect:
1. fully can remove heavy metal lead, the cadmium ion in liquid protein fertilizer;
2. used heavy metal removing agent is easily removed, after treatment can not the objectionable impurities of remaining influence Protein fertilizer effect;
3. preparation and the heavy metal removing agent that obtain can be reused after with the immersion of sodium at high concentration solion.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1
Remove a method that is plumbous in liquid protein fertilizer, cadmium ion, comprise the following steps:
(1) liquid protein fertilizer is concentrated: the moisture in evaporation raw material liq Protein fertilizer, makes its water content become the half of stoste.
(2) heavy metal removing agent preparation: described heavy metal removing agent preparation comprises the following steps:
(1) precursor A liquid preparation: described precursor A liquid is made up of the component of following volume percent: tetrabutyl titanate 20%, dehydrated alcohol 45%, anhydrous acetic acid 35%, stirs after each component mixing 5 minutes, prepares to obtain Ti Sol A liquid;
(2) precursor B liquid preparation: described precursor B liquid to be the mass percent prepared by dehydrated alcohol and PVP be 3% PVP ethanolic soln, wherein, the molecular weight of PVP is 500000;
(3) precursor solution preparation: obtain precursor solution after stirring 1 hour after precursor A liquid mixes with precursor B liquid, A liquid and B liquid mass ratio are 1:1;
(4) presoma zeolite compound: stir 50 minutes after being mixed with sodium base clinoptilolite by precursor solution, obtain mixing presoma, and presoma oven dry, pulverizing will be mixed, obtain mixing precursor powder, precursor solution and sodium base clinoptilolite mass ratio are 1:1;
(5) calcine: by the mixing precursor powder after pulverizing 550 DEG C of temperature lower calcinations 3 hours, obtain heavy metal removing agent;
Wherein the temperature increasing schedule of calcination process is as follows:
A) temperature rise rate of 10 DEG C is heated up from room temperature to 400 DEG C with per minute;
B) 500 DEG C are warming up to the heat up temperature rise rate of 5 DEG C of per minute from 400 DEG C;
C) holding temperature is warming up to the heat up temperature rise rate of 3 DEG C of per minute from 500 DEG C.
(3) remove lead, cadmium ion process: by the heavy metal removing agent prepared and liquid protein fertilizer in mass ratio 1:10 mix, and high voltage mercury lamp light source light according under stir 3 hours.
(4) heavy metal removing agent is separated: the method separating-purifying of the reactant press filtration after photochemical catalysis is obtained the liquid protein after removing lead, cadmium fertile.
Embodiment 2
Remove a method that is plumbous in liquid protein fertilizer, cadmium ion, comprise the following steps:
(1) liquid protein fertilizer is concentrated: the moisture in evaporation raw material liq Protein fertilizer, makes its water content become the half of stoste;
(2) heavy metal removing agent preparation: described heavy metal removing agent preparation comprises the following steps:
(1) precursor A liquid preparation: described precursor A liquid is made up of the component of following volume percent: tetrabutyl titanate 25%, dehydrated alcohol 50%, anhydrous acetic acid 25%, stirs after each component mixing 10 minutes, prepares to obtain Ti Sol A liquid;
(2) precursor B liquid preparation: described precursor B liquid to be the mass percent prepared by dehydrated alcohol and PVP be 5% PVP ethanolic soln, wherein, the molecular weight of PVP is 800000;
(3) precursor solution preparation: obtain precursor solution after stirring 1.5 hours after precursor A liquid mixes with precursor B liquid, A liquid and B liquid mass ratio are 1:2.5;
(4) presoma zeolite compound: stir 65 minutes after being mixed with sodium base mordenite by precursor solution, obtain mixing presoma, and presoma oven dry, pulverizing will be mixed, obtain mixing precursor powder, precursor solution and sodium base mordenite mass ratio are 1:1.5;
(5) calcine: by the mixing precursor powder after pulverizing 600 DEG C of temperature lower calcinations 4 hours, obtain heavy metal removing agent;
Wherein the temperature increasing schedule of calcination process is as follows:
A) temperature rise rate of 10 DEG C is heated up from room temperature to 400 DEG C with per minute;
B) 500 DEG C are warming up to the heat up temperature rise rate of 5 DEG C of per minute from 400 DEG C;
C) holding temperature is warming up to the heat up temperature rise rate of 3 DEG C of per minute from 500 DEG C.
(3) remove lead, cadmium ion process: by the heavy metal removing agent prepared and liquid protein fertilizer in mass ratio 1:13 mix, and high voltage mercury lamp light source light according under stir 4 hours;
(4) heavy metal removing agent is separated: the method separating-purifying of the reactant press filtration after photochemical catalysis is obtained the liquid protein after removing lead, cadmium fertile.
Embodiment 3
Remove a method that is plumbous in liquid protein fertilizer, cadmium ion, comprise the following steps:
(1) liquid protein fertilizer is concentrated: the moisture in evaporation raw material liq Protein fertilizer, makes its water content become the half of stoste;
(2) heavy metal removing agent preparation: described heavy metal removing agent preparation comprises the following steps:
(1) precursor A liquid preparation: described precursor A liquid is made up of the component of following volume percent: tetrabutyl titanate 30%, dehydrated alcohol 55%, anhydrous acetic acid 15%, stirs after each component mixing 15 minutes, prepares to obtain Ti Sol A liquid;
(2) precursor B liquid preparation: described precursor B liquid to be the mass percent prepared by dehydrated alcohol and PVP be 7% PVP ethanolic soln, wherein, the molecular weight of PVP is 1300000;
(3) precursor solution preparation: obtain precursor solution after stirring 2 hours after precursor A liquid mixes with precursor B liquid, A liquid and B liquid mass ratio are 1:3;
(4) presoma zeolite compound: stir 80 minutes after being mixed with sodium base clinoptilolite by precursor solution, obtain mixing presoma, and presoma oven dry, pulverizing will be mixed, obtain mixing precursor powder, precursor solution and sodium base clinoptilolite mass ratio are 1:2;
(5) calcine: by the mixing precursor powder after pulverizing 650 DEG C of temperature lower calcinations 5 hours, obtain heavy metal removing agent;
Wherein the temperature increasing schedule of calcination process is as follows:
A) temperature rise rate of 10 DEG C is heated up from room temperature to 400 DEG C with per minute;
B) 500 DEG C are warming up to the heat up temperature rise rate of 5 DEG C of per minute from 400 DEG C;
C) holding temperature is warming up to the heat up temperature rise rate of 3 DEG C of per minute from 500 DEG C.
(3) remove lead, cadmium ion process: by the heavy metal removing agent prepared and liquid protein fertilizer in mass ratio 1:15 mix, and high voltage mercury lamp light source light according under stir 3 ~ 5 hours;
(4) heavy metal removing agent is separated: the method separating-purifying of the reactant press filtration after photochemical catalysis is obtained the liquid protein after removing lead, cadmium fertile.
The liquid protein fertilizer adopted in above-described embodiment is by obtained after the molten pulp-water solution of fish.
Following technical indicator can be realized by the present invention:
1. fertile according to standard GB/T/T12496.22-1999 wood activated charcoal test determining heavy metals method detects the liquid protein removed in liquid protein fertilizer after lead, the process of cadmium ion method through the present invention, the content of its heavy metal lead, cadmium all reaches the requirement about heavy metal lead, cadmium residual quantity in agricultural industry criteria NY884-2012 biological organic fertilizer standard, namely in cadmium, cadmium residual quantity is less than or equal to 3mg/kg, in lead, plumbous residual quantity is less than or equal to 50mg/kg;
2. use the crop through removing liquid protein fertilizer after lead, the process of cadmium ion method in liquid protein fertilizer in the present invention, about the requirement of heavy metal lead, cadmium residual quantity limit index in the GB2762-2012 national food safety standard that is all up to state standards of its heavy metal lead, cadmium ion.
Claims (6)
1. remove a method that is plumbous in liquid protein fertilizer, cadmium ion, it is characterized in that comprising the following steps:
(1) liquid protein fertilizer is concentrated: the moisture in evaporation raw material liq Protein fertilizer, makes its water content become the half of stoste;
(2) remove lead, cadmium ion process: mixed 1:10 ~ 15 in mass ratio with liquid protein fertilizer by heavy metal removing agent, and stir under light illumination and carry out light-catalyzed reaction in 3 ~ 5 hours;
(3) heavy metal removing agent is separated: the method separating-purifying of the reactant press filtration after photochemical catalysis is obtained the liquid protein after removing lead, cadmium fertile.
2. a heavy metal removing agent, is characterized in that, this heavy metal removing agent is obtained by following steps:
(1) precursor A liquid preparation: described precursor A liquid is made up of the component of following volume percent: tetrabutyl titanate 20 ~ 30%, dehydrated alcohol 45 ~ 55%, and surplus is anhydrous acetic acid, stirs after each component mixing 5 ~ 15 minutes, prepares to obtain Ti Sol A liquid;
(2) precursor B liquid preparation: described precursor B liquid to be the mass percent prepared by dehydrated alcohol and PVP be 3 ~ 7% PVP ethanolic soln;
(3) precursor solution preparation: obtain precursor solution after stirring 1 ~ 2 hour after precursor A liquid mixes with precursor B liquid, A liquid and B liquid mass ratio are 1:1 ~ 3;
(4) presoma zeolite compound: stir 50 ~ 80 minutes after being mixed with zeolite by precursor solution, obtains mixing presoma, and will mix presoma oven dry, pulverizing, and obtain mixing precursor powder, precursor solution and zeolite mass ratio are 1:1 ~ 2;
(5) calcine: by the mixing precursor powder after pulverizing 550 ~ 650 DEG C of temperature lower calcinations 3 ~ 5 hours, obtain heavy metal removing agent.
3. a kind ofly according to claim 1 to remove in liquid protein fertilizer method that is plumbous, cadmium ion, it is characterized in that: described photochemical catalysis light source used is high voltage mercury lamp light source or xenon source.
4. a kind ofly according to claim 2 to remove in liquid protein fertilizer method that is plumbous, cadmium ion, it is characterized in that: described zeolite is sodium base clinoptilolite or sodium base mordenite.
5. a kind ofly according to claim 2 to remove in liquid protein fertilizer method that is plumbous, cadmium ion, it is characterized in that: the molecular weight of described PVP is 500000 ~ 1300000.
6. a kind ofly according to claim 2 to remove in liquid protein fertilizer method that is plumbous, cadmium ion, it is characterized in that: the temperature increasing schedule of described calcination process is as follows:
(1) temperature rise rate of 10 DEG C is heated up from room temperature to 400 DEG C with per minute;
(2) 500 DEG C are warming up to the heat up temperature rise rate of 5 DEG C of per minute from 400 DEG C;
(3) holding temperature is warming up to the heat up temperature rise rate of 3 DEG C of per minute from 500 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510479865.5A CN105130509A (en) | 2015-08-07 | 2015-08-07 | Method for removing lead ions and cadmium ions in liquid protein fertilizer |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510479865.5A CN105130509A (en) | 2015-08-07 | 2015-08-07 | Method for removing lead ions and cadmium ions in liquid protein fertilizer |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1532295A (en) * | 1976-07-29 | 1978-11-15 | British Petroleum Co | Process for the removal of metals from organic solutions |
| CN104437495A (en) * | 2014-12-23 | 2015-03-25 | 河北工业大学 | Hierarchical alpha-Fe2O3/TiO2 hollow sphere dual-functional photocatalyst and application thereof |
-
2015
- 2015-08-07 CN CN201510479865.5A patent/CN105130509A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1532295A (en) * | 1976-07-29 | 1978-11-15 | British Petroleum Co | Process for the removal of metals from organic solutions |
| CN104437495A (en) * | 2014-12-23 | 2015-03-25 | 河北工业大学 | Hierarchical alpha-Fe2O3/TiO2 hollow sphere dual-functional photocatalyst and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李进辉等: "沸石负载型TiO2的制备及其降解含酚废水的研究", 《广州化工》 * |
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Application publication date: 20151209 |