CN108486199A - Water-soluble chelator, preparation method and the process for treating heavy-metal waste water with it - Google Patents
Water-soluble chelator, preparation method and the process for treating heavy-metal waste water with it Download PDFInfo
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- CN108486199A CN108486199A CN201810261038.2A CN201810261038A CN108486199A CN 108486199 A CN108486199 A CN 108486199A CN 201810261038 A CN201810261038 A CN 201810261038A CN 108486199 A CN108486199 A CN 108486199A
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P21/00—Preparation of peptides or proteins
- C12P21/06—Preparation of peptides or proteins produced by the hydrolysis of a peptide bond, e.g. hydrolysate products
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
- C07K1/14—Extraction; Separation; Purification
- C07K1/34—Extraction; Separation; Purification by filtration, ultrafiltration or reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
A kind of water soluble chelate compound, preparation method and use its process for treating heavy-metal waste water.The process for treating heavy-metal waste water includes：Subcritical protein extraction, proteinase hydrolization method and hyperfiltration technique combine and prepare water-soluble chelator solution, chelatropic reaction is occurred into for the solution of preparation and heavy metal in waste water, mixed liquor is concentrated and separated through ultrafiltration membrane after reaction, generate heavy metal chelate concentrate, adjust the pH value of gained heavy metal chelate concentrate, it is concentrated and separated through ultrafiltration membrane, heavy metal concentrate obtains high purity metal through extraction, electrolysis process, and water-soluble chelator solution recycles.Raw material of the present invention is cheap and easy to get, the chelating agent function admirable of preparation, biodegradable；The water-soluble chelator molecular weight of preparation can be controlled according to ultrafiltration membrane aperture feature, adjustable molecular weight and uniform；Heavy metal removing rate in heavy metal wastewater thereby is high, is not influenced by foreign ions such as calcium, magnesium, and the valuable metal purity of recycling is high.
Description
Technical field
The present invention relates to waste water reclaiming process field, more particularly to a kind of water soluble chelate compound, preparation method and
Using its process for treating heavy-metal waste water.
Background technology
Heavy metal is generally widely present in natural concentration in natural environment, but since heavy metal is opened in mankind's activity
Adopt, smelt, processing and business manufacture etc. activities, such as non-ferrous metal mining, ore dressing, non-ferrous metal metallurgy, smelting iron and steel, electricity
Plating, process hides, chlorine industry etc., generate plurality of heavy metal waste water, cause environmental pollution, by various states and in the form of existing for a huge sum of money
Belong to, into environment after can not be degraded by microorganisms, but enter in the biological chain of the ecosystem and precipitate, be enriched with, migrate, it is long-term broken
The eubolism function of bad organism brings serious harm to human society and natural environment, and how cost-effective removal is useless
Heavy metal in water, reduction industrial water drainage is threatened caused by ecological environment has become urgent problem to be solved.
At this stage, mainly there are chemical precipitation method, ion-exchange, absorption method and film to the minimizing technology of heavy metal in waste water
Partition method.Wherein, membrane separation process has easy to operate, without phase-change for heavy metal containing wastewater treatment, to heavy metal ion rejection
The advantages that height, recyclable valuable metal, however, the seperation film currently used for heavy metal-containing wastewater treatment is NF membrane and reverse osmosis
Film, membrane module is expensive, and operating pressure is high, high energy consumption, and processing cost is high；NF membrane and reverse osmosis membrane are by the huge sum of money in waste water
Category retains jointly with impurity such as calcium and magnesium ions, easily formation fouling membrane caused by calcium, magnesium plasma, calcium in heavy metal concentrate,
The impurity ion contents such as magnesium are high, influence the recycling of follow-up valuable metal.
Ultrafiltration membrane technique has the advantages that membrane flux is high, operating pressure is low, low energy consumption, processing cost is low, with good investment, does not cut
The foreign ions such as calcium, magnesium are stayed, concentrate recycling valuable metal is simple, and recycling valuable metal purity is high, and ultrafiltration membrane technique is for weight
Metallic wastewater processing is with the obvious advantage.Hyperfiltration technique, which usually requires to couple with other technologies, could be used to handle the huge sum of money in waste water
Belong to, if Ultrafiltration Coupling technology is complexed in water-soluble polymer, with heavy metal ion chela occurs for the water-soluble chelator containing functional group
Reaction is closed, when the molecular weight of water-soluble chelator is more than the molecular weight cut off of ultrafiltration membrane, the weight with water-soluble chelator chelating
Metal ion is trapped, to realize the separation of metal ion.When concentration of heavy metal ion reaches certain in ultrafiltration membrane concentrate
Level adjusts and liquid pH value is concentrated by ultrafiltration, so that water-soluble chelator in ultrafiltration concentration liquid is detached with heavy metal, mixed liquor is through ultrafiltration membrane
Processing, heavy metal generate high concentration heavy metal solution by ultrafiltration membrane, and water-soluble chelator is trapped, and is reused.
The water-soluble polymer that Ultrafiltration Coupling technology is complexed currently used for water-soluble polymer mainly has polyethyleneimine, gathers
Sodium acrylate etc., such water-soluble polymer price are high, it is difficult to realize large-scale use, biological degradability is poor, and there are secondary dirts
Risk is contaminated, therefore, cheap and function admirable biodegradable water soluble chelate compound is prepared and is coupled with hyperfiltration technique to containing weight
Metallic wastewater carries out recycling treatment and is of great significance.
Invention content
In view of the deficiencies of the prior art, the main purpose of the present invention is to provide a kind of water soluble chelate compound, its systems
Preparation Method and use its process for treating heavy-metal waste water, to solve at least partly in above-mentioned technical problem at least it
One.
To achieve the goals above, as one aspect of the present invention, a kind of preparation side of water-soluble chelator is provided
Method includes the following steps：
The raw material of industry, leftover pieces or waste material of containing water-soluble bioprotein are cleaned, are crushed, raw material particle size after being crushed
Less than or equal to 5mm；
It will be pumped into sub-critical extraction device through over cleaning, broken raw material, under certain reaction condition, carried out water-soluble raw
The extraction of object albumen obtains water-soluble biological protein solution；
Water-soluble biological protein concentration in the water-soluble biological protein solution for being obtained above-mentioned steps using ultrafiltration membrane is extremely
0.01~0.1g/mL；
The water-soluble biological protein concentrated solution that above-mentioned steps obtain is taken, a certain amount of neutral proteinase or basic protein is added
Enzyme stirring and dissolving is added sodium hydroxide solution and adjusts pH value to 7~10, solution is put into constant temperature oscillator, under certain temperature
1~4h is reacted, constant temperature oscillator hunting speed is 10~60r/min, and freezing later makes enzyme inactivate, and centrifugal filtration obtains protein peptides
Solution；
The protein peptides in albumen peptide solution are concentrated into 0.05~0.5g/mL using ultrafiltration membrane, ultrafiltration membrane trapped fluid is taken, obtains
Obtain protein peptides concentrate, i.e. the water-soluble chelator solution.
As another aspect of the present invention, a kind of water that basis preparation method as described above is prepared is additionally provided
Dissolubility chelating agent solution.
As another aspect of the invention, a kind of process for treating heavy-metal waste water is additionally provided, is included the following steps：
Step 1, the pH value of pending heavy metal wastewater thereby is adjusted, it is molten that water-soluble chelator as described above is added thereto
Liquid, stirring a period of time obtain water-soluble chelator and the heavy metal chelate solution to be formed are complexed with heavy metal；
Step 2, obtained heavy metal chelate solution is concentrated and separated through ultrafiltration membrane, obtains that liquid, permeate is concentrated by ultrafiltration
Reuse or discharge；
Step 3, the pH value that liquid is concentrated by ultrafiltration is adjusted, the heavy metal chelate decomplexing separation is made；
Step 4, by the solution of decomplexing separation through ultrafiltration membrane treatment, water-soluble chelator, which is enriched with to form concentrate and recycle, to be made
With permeate is heavy metal concentrate；
Step 5, purification reuse is carried out to the heavy metal concentrate.
Based on the above-mentioned technical proposal it is found that compared with the prior art, the advantages of the present invention are as follows：The present invention is used containing water-soluble
The raw material of industry, leftover pieces or the waste material of property bioprotein are that raw material prepares water-soluble chelator, and raw material is cheap and easy to get, preparation
It is chelating agent function admirable, biodegradable；Water-soluble chelator is prepared using sub-critical extraction and hydrolysis by novo method, is made
Standby water-soluble chelator molecular weight can be controlled according to ultrafiltration membrane aperture feature, and fouling membrane is small；By the water-soluble chelator of preparation
It is coupled to heavy metal-containing waste water recycling treatment with hyperfiltration technique, heavy metal removing rate is high, not by the foreign ions shadow such as calcium, magnesium
It rings, the valuable metal purity of recycling is high.
Description of the drawings
Fig. 1 is the process flow diagram of the present invention.
Specific implementation mode
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, and reference
Attached drawing, the present invention is described in further detail.
Water-solubility protein is a kind of natural polymer being made of a variety of amino acid, has a large amount of hydroxyl, carboxyl, ammonia
With heavy metal chelatropic reaction can occur for the functional groups such as base, amide groups, these groups.Certain raw materials of industry, leftover pieces or waste material
In contain the waste silk after water-solubility protein, such as husks, filature, silk gum, fish meal, rice bran, mushroom stems, rapeseed dregs, bean dregs, have
Abundance, it is cheap, it is a kind of potential raw material for being used to prepare water-soluble chelator the features such as easily biological-degradable.
In order to make full use of above-mentioned raw materials, the invention discloses a kind of preparation methods of water-soluble chelator solution, including
Following steps：
The raw material of industry, leftover pieces or waste material of containing water-soluble bioprotein are cleaned, are crushed, raw material particle size after being crushed
Less than or equal to 5mm；
It will be pumped into sub-critical extraction device through over cleaning, broken raw material, under certain reaction condition, carried out water-soluble raw
The extraction of object albumen obtains water-soluble biological protein solution；
Water-soluble biological protein concentration in the water-soluble biological protein solution for being obtained above-mentioned steps using ultrafiltration membrane is extremely
0.01~0.1g/mL；
The water-soluble biological protein concentrated solution that above-mentioned steps obtain is taken, a certain amount of neutral proteinase or basic protein is added
Enzyme stirring and dissolving is added sodium hydroxide solution and adjusts pH value to 7~10, solution is put into constant temperature oscillator, under certain temperature
1~4h is reacted, constant temperature oscillator hunting speed is 10~60r/min, and freezing later makes enzyme inactivate, and centrifugal filtration obtains protein peptides
Solution；
The protein peptides in albumen peptide solution are concentrated into 0.05~0.5g/mL using ultrafiltration membrane, ultrafiltration membrane trapped fluid is taken, obtains
Obtain protein peptides concentrate, i.e. the water-soluble chelator solution.
Preferably, the raw material of industry, leftover pieces or the waste material of the containing water-soluble bioprotein are husks, useless after filature
It is one or more in silk, silk gum, fish meal, rice bran, mushroom stems, rapeseed dregs, bean dregs；
Preferably, in the step of raw material of industry, leftover pieces or waste material to containing water-soluble bioprotein clean, first
Using ultrasonic cleaning, reuses the ether that bath raio is 1: 20 and impregnate for 24 hours, take out the raw material after impregnating and cleaned, dried in the air with distilled water
It is dry, soaked in absolute ethyl alcohol 12h is used later, is taken out the raw material distilled water after impregnating and is cleaned and dries；
Preferably, the water-soluble biological albumen sub-critical extraction reaction condition is：It is water-soluble using distilled water, sodium carbonate
In liquid, wet chemical, potassium bicarbonate aqueous solution or aqueous solution of urea it is a kind of be used as extractant, reaction temperature be 100~
320 DEG C, pressure is 2~5.2Mpa；Reaction unit selects nickel alloy, titanium alloy or stainless steel nickel plating material.
Preferably, the amount that neutral proteinase or alkali protease is added is 0.1~2.5mg/mL water-soluble biological albumen
Solution.
Preferably, the ultrafiltration membrane for concentrating sericin peptide solution is Kynoar or polyether sulfone or polyacrylonitrile
Material, ranging from 0.005~0.01 μm of membrane aperture.
The invention also discloses the water-soluble chelator solution that a kind of basis preparation method as described above is prepared.
The invention also discloses a kind of process for treating heavy-metal waste water, include the following steps：
Step 1, the pH value of pending heavy metal wastewater thereby is adjusted, it is molten that water-soluble chelator as described above is added thereto
Liquid, stirring a period of time obtain water-soluble chelator and the heavy metal chelate solution to be formed are complexed with heavy metal；
Step 2, obtained heavy metal chelate solution is concentrated and separated through ultrafiltration membrane, obtains that liquid, permeate is concentrated by ultrafiltration
Reuse or discharge；
Step 3, the pH value that liquid is concentrated by ultrafiltration is adjusted, the heavy metal chelate decomplexing separation is made；
Step 4, by the solution of decomplexing separation through ultrafiltration membrane treatment, water-soluble chelator, which is enriched with to form concentrate and recycle, to be made
With permeate is heavy metal concentrate；
Step 5, purification reuse is carried out to the heavy metal concentrate.
Preferably, in step 1, the pH value of pending heavy metal wastewater thereby is adjusted to 3.5~7；
Preferably, in step 1, the quality of the water-soluble chelator and heavy metal in waste water that are added into heavy metal wastewater thereby
Than being 1.2~10: 1.
Preferably, in step 2,4, it is described be concentrated by ultrafiltration the ultrafiltration membrane material that separating step is selected be Kynoar,
Polyether sulfone or polyacrylonitrile, membrane aperture are 0.001~0.01 μm；
Preferably, in step 2,4, the operating condition of the ultrafiltration membrane concentration is：Room temperature, intake pressure are less than
0.5Mpa。
Preferably, in step 3 when heavy metal chelate decomplexing, the pH value for adjusting solution is 2~6.
Preferably, the step of carrying out purification reuse to heavy metal concentrate described in step 5 includes：Using " extraction-is anti-
Extraction-electrolysis " technique, obtains high purity metal product；
Preferably, in the extraction process, phosphoric acid kind of extractants or chelating extractant are selected；
It is further preferred that in the extraction process, select 30%~40% P204 and 260# kerosene as organic phase,
Or select chelating extractant and kerosene as organic phase；
Preferably, in the extraction process, extractant concentration 10% compares O/A=1: 1.
As a preferred embodiment of the present invention, above-mentioned water-soluble chelator solution is used the invention discloses a kind of
Process for treating heavy-metal waste water, as shown in Figure 1, this approach includes the following steps：The industry of containing water-soluble bioprotein is former
Material, leftover pieces or waste material are added in sub-critical extraction device using cleanings such as distilled water, ether, absolute ethyl alcohols, after drying and are extracted
Water-soluble biological albumen obtains water-soluble biological protein solution, and water-soluble biological protein solution obtained is dense using ultrafiltration membrane
Contracting, concentrate are added protease hydrolytic, obtain albumen peptide solution, albumen peptide solution obtained is concentrated to give water using ultrafiltration membrane
Dissolubility chelating agent solution；Water-soluble chelator solution is added in heavy metal-containing waste water, the heavy metal in waste water and water-soluble chela
Chelatropic reaction occurs for mixture, uses ultrafiltration membrane treatment, permeate discharge or reuse, concentrate that acidolysis is added the solution after reaction
Solution after decomplexing is used ultrafiltration membrane treatment, concentrate to recycle by network, and permeate has by extraction, electrolysis process recycling
Valence metal finally obtains high purity metal product.
More specifically, the preparation of the water-soluble chelator of the present invention and its side for heavy metal-containing waste water recycling treatment
Method is as follows：
(1) preparation of water-soluble chelator：It by the raw material of industry of containing water-soluble bioprotein, leftover pieces or is given up with distilled water
Material cleaning is dried, wherein ultrasonic cleaning for example may be used.The ether for being 1: 20 by bath raio impregnates for 24 hours, takes out after impregnating
Raw material is cleaned with distilled water, is dried.With soaked in absolute ethyl alcohol 12h, takes out the raw material distilled water after impregnating and clean and dry.It will dry in the air
Raw material after dry is put into sub-critical extraction device, carries out the extraction of water-soluble biological albumen, obtains water-soluble biological protein solution；
Water-soluble biological albumen in solution is reduced to 0.05g/mL using ultrafiltration membrane, takes one by obtained water-soluble biological protein solution
A certain amount of neutral proteinase or alkali protease stirring and dissolving is added in the water-soluble biological protein concentrated solution for determining volume, is added
Sodium hydroxide solution adjusts pH value to 7~10, and solution is put into constant temperature oscillator, 2h is reacted under certain temperature, rotating speed is
30r/min, after freezed at -40 DEG C, so that enzyme is inactivated, centrifugal filtration obtains albumen peptide solution, using ultrafiltration membrane by protein peptides in solution
It is concentrated into 0.1g/mL, obtains protein peptides concentrate, i.e. water-soluble chelator solution.
(2) heavy metal-containing waste water pH value is adjusted, water-soluble chelator solution made from step (1), stirring are added thereto
Reaction obtains the chelate solution that water-soluble polymer is formed with heavy metal.
(3) chelate solution that the water-soluble polymer for obtaining step (2) is formed with heavy metal is through ultrafiltration membrane concentration point
From making the chelating agent solution that water-soluble polymer and heavy metal are formed be enriched with to obtain liquid, permeate reuse or row is concentrated by ultrafiltration
It puts.
(4) it adjusts and liquid pH value is concentrated by ultrafiltration, the chelating agent decomplexing separation for making water-soluble polymer be formed with heavy metal.
(5) by the solution of decomplexing separation through ultrafiltration membrane, water-soluble chelator is enriched in concentrate and recycles, and penetrates
Liquid is high concentration heavy metal concentrate.
(6) high concentration concentrate obtains high purity metal solid product through extraction, electrolysis process.
As a further improvement, in above-mentioned steps (1), the raw material of industry, the leftover pieces or useless of containing water-soluble bioprotein
Material is one or more of husks, the waste silk after filature, silk gum, fish meal, rice bran, mushroom stems, rapeseed dregs, bean dregs.
As a further improvement, in above-mentioned steps (1), water-soluble biological protein extract is distilled water, sodium carbonate
One kind in solution, wet chemical, potassium bicarbonate aqueous solution or aqueous solution of urea.
As a further improvement, in above-mentioned steps (1), water-soluble biological protein extraction reaction condition is：Reaction temperature
150~310 DEG C.
As a further improvement, in above-mentioned steps (1), the amount that alkali protease is added is 0.1~2.5mg/mL silk gum
Solution.
As a further improvement, in above-mentioned steps (2), heavy metal-containing waste water pH value is adjusted to 3.5~7.
As a further improvement, in above-mentioned steps (2), in water-soluble chelator solution water-soluble chelator content with it is useless
The mass values of content of beary metal are 1.2~10: 1, preferably 2~10: 1 in water.
As a further improvement, described that cutting for the ultrafiltration membrane selected by separating step is concentrated by ultrafiltration in above-mentioned steps (3)
Molecular weight is stayed to be more than 5000.
As a further improvement, in above-mentioned steps (3), the operating condition of the ultrafiltration concentration separation is：Room temperature, into
Water pressure is less than 0.5Mpa.
As a further improvement, in above-mentioned steps (4), the pH value for adjusting the solution is 2~6, preferably 3~6.
Hereafter technical scheme of the present invention and effect are further elaborated by several specific embodiments.
Embodiment 1
The mass fraction of water-soluble biological albumen is 70% in husks, will be carried out after husks distilled water immersion ultrasonic clear
It washes, is crushed.Cleaning, broken rear raw material 2000g are taken, addition 80L distilled water, which is put into sub-critical extraction device, carries out subcritical carry
It takes, 300 DEG C of reaction temperature, pressure 2.5MPa.Water-soluble biological protein solution is made, cools down at room temperature, will be made using ultrafiltration membrane
Water-soluble biological protein concentration takes 5L water-soluble biological protein concentrated solutions to 0.05g/mL in the solution obtained, and 5g alkalinity eggs are added
White enzyme stirring and dissolving is added sodium hydroxide solution (1mol/L) and adjusts pH value to 9, solution is put into constant temperature oscillator, 35 DEG C
Lower reaction 2h, rotating speed 30r/min, after at -40 DEG C freeze, so that enzyme is inactivated, centrifugal filtration, supernatant is concentrated into using ultrafiltration membrane
0.1g/mL, obtains albumen peptide solution, i.e. water-soluble chelator solution, in solution the weight average molecular weight of protein peptides between 8000~
Between 10000.
Take 50L waste water containing Cu, pH value of waste water 6.5, a concentration of 40mg/L of Cu, calcium concentration 230mg/L, with 1mol/L sulphur
It is 6 that acid solution, which adjusts heavy metal-containing waste water pH value, and water-soluble chelator solution 70mL obtained is added thereto, is stirred to react,
Obtain the chelate solution that water-soluble chelator is formed with heavy metal.
The chelate solution that obtained water-soluble chelator and heavy metal are formed is through polyvinylidene fluoride (PVDF) ultrafiltration membrane (retention point
Son is measured 6000) to be concentrated and separated, and the chelate solution that water-soluble polymer is formed with heavy metal is made to be enriched with to obtain ultrafiltration concentration liquid,
A concentration of 0.003mg/L of Cu in permeate, permeate discharge or reuse.
It is 4.5 to be adjusted with 1mol/L sulfuric acid solutions and liquid pH value is concentrated by ultrafiltration, and water-soluble chelator is made to be formed with heavy metal
Chelate decomplexing separation.
By the solution of decomplexing separation through polyvinylidene fluoride (PVDF) ultrafiltration membrane (molecular cut off 7000), water-soluble chelator is rich
It combines in concentrate and recycles, the water-soluble chelator rate of recovery is 100%, and permeate is high concentration heavy metal concentrate, dense
A concentration of 1200mg/L of Cu in contracting liquid.
High concentration concentrate obtains high purity metal solid product through extraction, electrolysis process, and products C u grades are 98%.
Embodiment 2
Waste silk after filature is dried wash with distilled water, the mass fraction of water-soluble biological albumen in the waste silk after filature
It is 40%, waste silk raw material is cleaned by ultrasonic with distilled water.It takes and cleans broken raw material 8000g, distilled water 320L is added to
Sub-critical extraction, centrifugation, precipitation are carried out in sub-critical extraction device, 310 DEG C of sub-critical extraction reaction temperature, pressure 3MPa obtains water
Dissolubility bioprotein solution, cools down at room temperature, using ultrafiltration membrane by water-soluble biological protein concentration in solution obtained extremely
0.05g/mL takes 20L water-soluble biological protein concentrated solutions, and 12g alkali protease stirring and dissolvings are added, and sodium hydroxide solution is added
(1mol/L) adjust pH value to 9, solution is put into constant temperature oscillator, 2h, rotating speed 30r/min are reacted at 35 DEG C, after -40
DEG C freezing, so that enzyme is inactivated, centrifugal filtration, supernatant is concentrated through ultrafiltration membrane, and protein peptides in solution are concentrated into 0.1g/mL, obtain
Albumen peptide solution, i.e., the weight average molecular weight of protein peptides is between 10000~15000 in water-soluble chelator solution.
Take 50L nickel-containing waste waters, pH value of waste water 7.4, a concentration of 60mg/L of Ni, calcium concentration 350mg/L, magnesium density is
180mg/L, it is 6 to adjust heavy metal-containing waste water pH value with 1mol/L sulfuric acid solutions, and water-soluble chelator obtained is added thereto
Solution 150mL, is stirred to react, and obtains the chelate solution that water-soluble polymer is formed with heavy metal.
The chelate solution that obtained water-soluble polymer and heavy metal are formed is through polyvinylidene fluoride (PVDF) ultrafiltration membrane (retention point
Son is measured 7000) to be concentrated and separated, and the chelate solution that water-soluble chelator is formed with heavy metal is made to be enriched with to obtain ultrafiltration concentration liquid,
A concentration of 0.06mg/L of Ni in permeate, permeate discharge or reuse.
It is 5 to be adjusted with 1mol/L sulfuric acid solutions and liquid pH value is concentrated by ultrafiltration, the chela for making water-soluble chelator be formed with heavy metal
Close object decomplexing separation.
By the solution of decomplexing separation through polyvinylidene fluoride (PVDF) ultrafiltration membrane (molecular cut off 7000), water-soluble chelator is rich
It combines in concentrate and recycles, the water-soluble chelator rate of recovery is 100%, and permeate is high concentration heavy metal concentrate, dense
Nickel concentration is 1800mg/L in contracting liquid.
High concentration concentrate obtains high purity metal solid product through extraction, electrolysis process, and product Ni grades are 97%.
Embodiment 3
Bean dregs are dried wash with distilled water, the mass fraction of water-soluble biological albumen is 20% in bean dregs, and raw material steams
Distilled water is cleaned by ultrasonic.Raw material 2000g after cleaning is put into progress sub-critical extraction (reaction temperature 260 in 80L aqueous solutions
DEG C, pressure 2MPa), it centrifuges, precipitation takes supernatant to obtain water-soluble biological protein solution, cools down at room temperature, uses ultrafiltration membrane
By water-soluble biological protein concentration in solution obtained to 0.05g/mL, 5L water-soluble biological protein concentrated solutions are taken, are added in 3g
Property protease stirring and dissolving, be added sodium hydroxide solution (1mol/L) adjust pH value to 7, solution is put into constant temperature oscillator,
2h, rotating speed 30r/min are reacted at 35 DEG C, after at -40 DEG C freeze, so that enzyme is inactivated, centrifugal filtration, supernatant is concentrated through ultrafiltration membrane
Albumen peptide concentration obtains protein peptides concentrate, i.e. water-soluble chelator solution to 0.1g/mL, and protein peptides divides equally again in solution
Son amount is between 9000~14000.
Take 50L zinc-containing waters, pH value of waste water 7.8, a concentration of 90mg/L of Zn, calcium concentration 230mg/L, magnesium density is
110mg/L, it is 5.5 to adjust heavy metal-containing waste water pH with 1mol/L sulfuric acid solutions, and water-soluble chelator obtained is added thereto
Solution 180mL, is stirred to react, and obtains the chelate solution that water-soluble chelator is formed with heavy metal.
The chelate solution that obtained water-soluble chelator and heavy metal are formed is through polyvinylidene fluoride (PVDF) ultrafiltration membrane (retention point
Son is measured 6000) to be concentrated and separated, and the chelate solution that water-soluble chelator is formed with heavy metal is made to be enriched with to obtain ultrafiltration concentration liquid,
A concentration of 0.02mg/L of Zn in permeate, permeate discharge or reuse.
It is 4.8 to be adjusted with 1mol/L sulfuric acid solutions and liquid pH value is concentrated by ultrafiltration, and water-soluble polymer is made to be formed with heavy metal
Chelate decomplexing separation.
By the solution of decomplexing separation through polyvinylidene fluoride (PVDF) ultrafiltration membrane (molecular cut off 7000), water-soluble chelator is rich
It combines in concentrate and recycles, the water-soluble polymer rate of recovery is 100%, and permeate is high concentration heavy metal concentrate, dense
Zinc concentration is 2600mg/L in contracting liquid.
High concentration concentrate obtains high purity metal solid product through extraction, electrolysis process, and product zinc grade is 99%.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical solution and advantageous effect
Describe in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the protection of the present invention
Within the scope of.
Claims (10)
1. a kind of preparation method of water-soluble chelator, which is characterized in that include the following steps：
The raw material of industry, leftover pieces or waste material of containing water-soluble bioprotein are cleaned, are crushed, broken rear raw material particle size is less than
Equal to 5mm；
It will be pumped into sub-critical extraction device through over cleaning, broken raw material, under certain reaction condition, carries out water-soluble biological egg
White extraction obtains water-soluble biological protein solution；
Water-soluble biological protein concentration in the water-soluble biological protein solution for being obtained above-mentioned steps using ultrafiltration membrane is to 0.01
~0.1g/mL；
The water-soluble biological protein concentrated solution that above-mentioned steps obtain is taken, a certain amount of neutral proteinase is added or alkali protease stirs
Dissolving is mixed, sodium hydroxide solution is added and adjusts pH value to 7~10, solution is put into constant temperature oscillator, reacts 1 under certain temperature
~4h, constant temperature oscillator hunting speed are 10~60r/min, and freezing later makes enzyme inactivate, and centrifugal filtration obtains albumen peptide solution；
The protein peptides in albumen peptide solution are concentrated into 0.05~0.5g/mL using ultrafiltration membrane, take ultrafiltration membrane trapped fluid, obtain egg
White peptide concentrate, i.e. the water-soluble chelator solution.
2. preparation method according to claim 1, which is characterized in that the raw material of industry of the containing water-soluble bioprotein,
Leftover pieces or waste material are waste silk after husks, filature, silk gum, fish meal, rice bran, mushroom stems, rapeseed dregs, one kind in bean dregs or more
Kind；
Preferably, in the step of raw material of industry, leftover pieces or waste material to containing water-soluble bioprotein clean, first use
Ultrasonic cleaning reuses the ether that bath raio is 1: 20 and impregnates for 24 hours, takes out the raw material after impregnating and cleaned, dried with distilled water, it
Soaked in absolute ethyl alcohol 12h is used afterwards, is taken out the raw material distilled water after impregnating and is cleaned and dries；
Preferably, the water-soluble biological albumen sub-critical extraction reaction condition is：Using distilled water, aqueous sodium carbonate,
A kind of as extractant in wet chemical, potassium bicarbonate aqueous solution or aqueous solution of urea, reaction temperature is 100~320
DEG C, pressure is 2~5.2Mpa；Reaction unit selects nickel alloy, titanium alloy or stainless steel nickel plating material.
3. preparation method according to claim 1, which is characterized in that the amount that neutral proteinase or alkali protease is added is
0.1~2.5mg/mL water-soluble biological protein solutions.
4. preparation method according to claim 1, which is characterized in that the ultrafiltration membrane for concentrating sericin peptide solution is
Kynoar or polyether sulfone or polyacrylonitrile material, ranging from 0.005~0.01 μm of membrane aperture.
5. a kind of water-soluble chelator solution that preparation method according to any one of claims 1 to 4, is prepared.
6. a kind of process for treating heavy-metal waste water, which is characterized in that include the following steps：
Step 1, the pH value of pending heavy metal wastewater thereby is adjusted, water-soluble chelating as claimed in claim 6 is added thereto
Agent solution, stirring a period of time obtain water-soluble chelator and the heavy metal chelate solution to be formed are complexed with heavy metal；
Step 2, obtained heavy metal chelate solution is concentrated and separated through ultrafiltration membrane, obtains that liquid, permeate reuse is concentrated by ultrafiltration
Or discharge；
Step 3, the pH value that liquid is concentrated by ultrafiltration is adjusted, the heavy metal chelate decomplexing separation is made；
Step 4, by the solution of decomplexing separation through ultrafiltration membrane treatment, water-soluble chelator is enriched with to form concentrate recycling, thoroughly
It is heavy metal concentrate to cross liquid；
Step 5, purification reuse is carried out to the heavy metal concentrate.
7. process for treating heavy-metal waste water according to claim 6, which is characterized in that in step 1, adjust pending weight
The pH value of metallic wastewater is to 3.5~7；
Preferably, in step 1, the mass ratio of the water-soluble chelator and heavy metal in waste water that are added into heavy metal wastewater thereby is
1.2~10: 1.
8. process for treating heavy-metal waste water according to claim 6, which is characterized in that in step 2,4, the ultrafiltration concentration
The ultrafiltration membrane material that separating step is selected is Kynoar, polyether sulfone or polyacrylonitrile, and membrane aperture is 0.001~0.01 μm；
Preferably, in step 2,4, the operating condition of the ultrafiltration membrane concentration is：Room temperature, intake pressure are less than 0.5Mpa.
9. process for treating heavy-metal waste water according to claim 6, which is characterized in that heavy metal chelate solution in step 3
When network, the pH value for adjusting solution is 2~6.
10. process for treating heavy-metal waste water according to claim 6, which is characterized in that dense to heavy metal described in step 5
Contracting liquid carries out the step of purification reuse and includes：Using " extraction and back extraction-electrolysis " technique, high purity metal product is obtained；
Preferably, in the extraction process, phosphoric acid kind of extractants or chelating extractant are selected；
It is further preferred that in the extraction process, select 30%~40% P204 and 260# kerosene as organic phase, or
Select chelating extractant and kerosene as organic phase；
Preferably, in the extraction process, extractant concentration 10% compares O/A=1: 1.
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| CN111892515A (en) * | 2019-12-29 | 2020-11-06 | 山东远联化工股份有限公司 | Production method and production device of carbamido chelating agent |
| CN115400603A (en) * | 2022-09-16 | 2022-11-29 | 天津大学 | Nanofiltration membrane prepared based on dissociation of plant polyphenol-metal ion complex and preparation method thereof |
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| CN115400603A (en) * | 2022-09-16 | 2022-11-29 | 天津大学 | Nanofiltration membrane prepared based on dissociation of plant polyphenol-metal ion complex and preparation method thereof |
| CN115400603B (en) * | 2022-09-16 | 2023-12-22 | 天津大学 | Nanofiltration membrane prepared based on dissociation of plant polyphenol-metal ion complex and preparation method thereof |
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