CN109248661A - A kind of chitosan-metal hydroxides composite material, preparation method and application - Google Patents
A kind of chitosan-metal hydroxides composite material, preparation method and application Download PDFInfo
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- CN109248661A CN109248661A CN201710594557.6A CN201710594557A CN109248661A CN 109248661 A CN109248661 A CN 109248661A CN 201710594557 A CN201710594557 A CN 201710594557A CN 109248661 A CN109248661 A CN 109248661A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/001—Runoff or storm water
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
Abstract
The present invention provides a kind of chitosan-metal hydroxides composite materials, including chitosan and the metal hydroxides being carried on the chitosan.Composite material prepared by the present invention for natural water repairing and treating, adsorption capacity is big, and effect is good, will not cause secondary pollution, is a kind of green, environmental protection composite material.
Description
Technical field
The present invention relates to a kind of chitosan-metal hydroxides composite materials, preparation method and application.
Background technique
Water is lifespring, is one of the indispensable physical resources that the mankind depend on for existence and development.With industry
Fast development, the mankind are increasingly frequent to the development and utilization of environmental resource, and global natural water environmental pollution states allow of no optimist,
River contacts the tie on land and lake or ocean as one, and environmental problem also becomes increasingly conspicuous, and river course environment problem is main
Be embodied in the following aspects: (1) soil erosion etc. causes river blocking siltation, flood control capacity to reduce；(2) industry, agricultural and
A large amount of discharges of exhausting sewage cause water body nitrogen and phosphorus content significantly raised, and river water body eutrophication causes water plant
And algal bloom, water quality deterioration；(3) adopt carelessly sand, junk carelessly heap abandon etc. due to cause rivers current by
Resistance, river diversion etc.；(4) since the occupancy and construction waste of the processes such as Human Architecture construction fill river, so that river narrows,
Water capacity reduces.Wherein, water eutrophication pollutes, and is a global problem, it not only seriously destroys ecology of water scape
It sees and water ecological setting, reduces use the function of water body, lead to a large amount of poisonings of the biology such as fish and dead, cause aquatic products feeding
Industry loss etc. is grown, and the pollutants such as the water stink of eutrophication is big, color is deep, bacterium and nitrite, nitrate are more, people and animals
Can cause multiple infectious disease and parasitic disease, also induction cancer of the esophagus, gastric cancer etc. after edible, seriously endanger human and livestock health, at
For important environmental problem urgently to be resolved, and phosphorus is the Main Factors for inducing eutrophication pollution.Therefore, it is effectively reduced water
The content of phosphorus in body is the important channel for preventing water eutrophication, is an extremely urgent task in river repairing and treating.
In view of river to the importance of ecological environment and human lives, people gradually recognize river course environment reparation in recent years
The importance of improvement has done numerous studies in river course environment repairing and treating.Currently, having many technologies applied to phosphorus in river
Removal, such as chemical method, bioanalysis and absorption method.
The basic principle of chemical method dephosphorization is to be allowed to form insoluble phosphoric acid with phosphate radical in water by adding chemical reagent
Salt sediment removes phosphorus after separation of solid and liquid from natural water, and the chemical reagent used is generally molysite, aluminium salt, calcium salt.Benefit
Removal rate with chemical method dephosphorization, phosphorus is higher, and treatment effect is stablized, but higher cost, the sludge quantity of generation are larger.
Bioanalysis dephosphorization service condition is more harsh, larger by natural water water quality impact, and the sludge of generation is more intractable,
And it is not high to the removal efficiency of phosphorus.
Absorption method dephosphorization is to be removed using certain porous or bigger serface substance to the affinity of phosphate radical come what is realized
Phosphorus technique, because its have many advantages, such as it is economical, efficiently, be easy to operate and control, it is without secondary pollution due to be concerned.The pass of absorption method
Key is the selection of adsorbent, and currently used adsorbent mainly includes natural material and its modifier, industrial residue and its changes
Property object, activated alumina and its modifier and artificial synthesized adsorbent etc..Wherein, natural material, industrial residue are because of absorption
Capacity is small, is easy to produce the factors such as secondary pollution, using being restricted；Activated alumina is the dephosphorization absorption being applied at present
Agent, but its adsorption capacity is not high, and the cycle of operation is shorter, regenerates after adsorption saturation costly.Therefore, a kind of efficient dephosphorization is researched and developed
Adsorbent material becomes a kind of trend.
Chitosan (CTS) is the deacetylated obtained product of chitin that nature is widely present, and is powder sorbent molding
Bonds well agent and skeletal support material, active amino and hydroxyl are contained in molecule, many adsorbates can be become
Adsorption site has good reactivity, and its precursor origin is extensive, nontoxic, easily biological-degradable, has very big open
Hair, utility value.The ability of Absorption of Heavy Metal ion with Chitosan affirmed, but it is for existing for anionic form
The adsorption effect of phosphate radical is unsatisfactory, meanwhile, traditional chitosan is generally powdered, difficulty is separated by solid-liquid separation, in acid item
Soluble under part, these factors all limit its application.
Summary of the invention
The present invention provides a kind of chitosan-metal hydroxides composite material, including chitosan and it is carried on the shell
Metal hydroxides on glycan.The present invention utilizes chitosan to the absorption property of metal ion, in situ between chitosan molecule
Metal hydroxides is generated, the obtained composite material of the present invention can effectively remove the phosphorus in natural water, reduce in water
Eutrophication, play the role of administer repair natural water.The natural water includes but is not limited to river water, lake water and river
Water.
As an implementation, the average pore size of the composite material is 2.0~3.8nm.As another embodiment party
Formula, the average pore size of the composite material are 2.0~3.0nm.
As an implementation, the saturated extent of adsorption of the composite material is 15~25mg/g.The saturated extent of adsorption
Refer to institute's adsorbable Solute mass when the adsorbent of Unit Weight reaches adsorption saturation.
As an implementation, the deacetylation of the chitosan is 80~90%.
As an implementation, the quality of the chitosan is the 75~95% of the composite material quality.As another
A kind of embodiment, the quality of the chitosan are the 80~90% of the composite material quality.
As an implementation, the metallic element in the metal hydroxides in iron, aluminium, magnesium, manganese and nickel extremely
Few one kind.As another embodiment, the metal hydroxides further includes the hydrate of metal hydroxides.As another
Kind embodiment, the metal hydroxides are selected from Fe (OH)3、Al(OH)3、Mg(OH)2、Ni(OH)2、Fe(OH)3·3H2O、Al
(OH)3·5H2O and Mn (OOH) H2At least one of O.
The present invention provides a kind of preparation method of chitosan-metal hydroxides composite material, comprising the following steps: 1) will
The aqueous solution of chitosan and acid is mixed to get modified chitosan；2) aqueous solution of alkali, the chitosan of modification and metal salt are mixed
Chitosan-metal hydroxides composite material is obtained after conjunction.
As an implementation, it is adjusted after step 2) mixes the aqueous solution of alkali, the chitosan of modification and metal salt mixed
The pH of solution is closed to alkalinity, obtains chitosan-metal hydroxides composite material.
As an implementation, it is adjusted after step 2) mixes the aqueous solution of alkali, the chitosan of modification and metal salt mixed
The pH of solution is closed to alkalinity, is then allowed to stand to obtain chitosan-metal hydroxides composite material.
As an implementation, it is adjusted after step 2) mixes the aqueous solution of alkali, the chitosan of modification and metal salt mixed
The pH of solution is closed to alkalinity, is then allowed to stand, is dried to obtain chitosan-metal hydroxides composite material.
The present invention provides a kind of preparation method of chitosan-metal hydroxides composite material, comprising the following steps: 1) will
The aqueous solution of chitosan and acid is mixed to get modified chitosan: 2) it is molten modified chitosan and metal salt to be mixed to get mixing
Liquid A；3) aqueous solution of mixed solution A and alkali is mixed to get chitosan-metal hydroxides composite material.The present invention will be in
Modification of chitosan under solution state is mixed with metal salt, and chitosan and metal ion is made to form complex, then sharp under stiring
Compound is precipitated with the pH value of alkaline solution adjustment complex solution.The present invention utilizes suction of the chitosan to various metals ion
Attached property, the in-situ preparation metal hydroxides between chitosan molecule, compared to direct precipitation method, the present invention is preferably obtained compound
The partial size of product is smaller, doped metal ion is easy, uniform, can realize effective while effectively control Product size
Load；The direct precipitation method is directly to mix the aqueous solution three of chitosan, metal salt, alkali.
As an implementation, the pH of mixed solution is adjusted after step 3) mixes mixed solution A with the aqueous solution of alkali
To alkalinity, chitosan-metal hydroxides composite material is obtained.In the present invention, the aqueous solution that alkali is added obtains reacting metal salt
To complex metal hydroxide, complex metal hydroxide is supported on modification of chitosan under conditions of alkalinity and precipitates analysis
Out.
As an implementation, the pH of mixed solution is adjusted after step 3) mixes mixed solution A with the aqueous solution of alkali
To alkalinity, it is then allowed to stand to obtain chitosan-metal hydroxides composite material.In the present invention, the purpose of standing is to allow just
Raw precipitating (metal hydroxides generated) and mother liquor (refer to and isolate precipitating or crystalline substance in chemical precipitation or crystallization process
Remaining saturated solution after body) a period of time is placed together, the impurity contained in precipitating on the one hand can be removed, on the other hand,
During standing, little crystal grain disappears, and big crystal grain is constantly grown up, and crystal is grown, and reduces other ions in the suction of plane of crystal
It is attached, while the particle diameter distribution of crystal also can be relatively uniform.
As an implementation, the pH of mixed solution is adjusted after step 3) mixes mixed solution A with the aqueous solution of alkali
To alkalinity, it is then allowed to stand, is dried to obtain chitosan-metal hydroxides composite material.
As an implementation, the average grain diameter of chitosan described in step 1) is 60~200 mesh.As another real
Mode is applied, the average grain diameter of chitosan described in step 1) is 100~150 mesh.
As an implementation, the concentration of acid described in step 1) in water is 0.05~0.45mol/L.
As an implementation, acid described in step 1) is selected from least one of hydrochloric acid, citric acid and glacial acetic acid.
As an implementation, the metal salt is selected from least one of molysite, aluminium salt, manganese salt, nickel salt and magnesium salts.
As an implementation, the metal salt is molysite and manganese salt；Or the metal salt is molysite and aluminium salt；Or institute
Stating metal salt is manganese salt and aluminium salt；Or the metal salt is nickel salt and molysite；Or the metal salt is molysite and magnesium salts；Or it is described
Metal salt is molysite, manganese salt and aluminium salt；Or the metal salt is molysite, nickel salt and magnesium salts.
As an implementation, the metal salt is molysite and manganese salt；Or the metal salt is molysite and aluminium salt；Or institute
Stating metal salt is molysite, manganese salt and aluminium salt.
As an implementation, the metal salt is molysite and manganese salt；The quality and manganese of ferro element in the metal salt
The mass ratio of element is 1: 3~5: 1.
When the mass ratio of the quality of the ferro element in metal salt and manganese element is less than 1: 3, due to Mn (OOH) in compound
Content is higher, and Mn (OOH) H2O is compared to Fe (OH)3·3H2It is slightly poor to the adsorption capacity of phosphate radical for O；And when gold
When the quality of ferro element and the mass ratio of manganese element are greater than 5: 1 in category salt, Fe (OH) in compound3·3H2O content is higher, and Fe
(OH)3·3H2O is relative to Mn (OOH) H2For O, specific surface area, void content are relatively small, and leading to adsorption effect not is very
It is ideal.Accordingly, it is preferred that the adsorbance of the quality of the ferro element in metal salt and the obtained adsorbent of the mass ratio of manganese element
It is larger.
As an implementation, the metal salt is molysite and magnesium salts；The quality and iron of magnesium elements in the metal salt
The mass ratio of element is 0~1: 8.In the present invention, the addition of Ni, Mg can be in the hydroxide generated or its hydrates
Middle formation defect changes crystallinity, can reduce the preparation cost of material after metal composite, and be able to maintain preferable absorption
Performance；Excessive addition Ni, Mg may will affect the structure of the hydroxide or its hydrate that have generated, make crystal structure
It changes, influences the absorption to phosphate radical.
As an implementation, the metal salt is molysite, manganese salt and aluminium salt；Manganese element and aluminium member in the metal salt
The mass ratio of element is 1: 2~2: 1；The quality of ferro element and the mass ratio of manganese element are 1: 3~5: 1.
As an implementation, the metal salt is molysite and nickel salt；Ferro element and nickel element in the metallic element
Mass ratio be 3: 1~1: 2.
As an implementation, the metal salt is molysite, nickel salt and magnesium salts；Ferro element and nickel in the metallic element
The mass ratio of element is 3: 1~1: 2；The mass ratio of nickel element and magnesium elements is 1: 16~8: 3 in the metallic element.
As an implementation, the molysite is selected from iron chloride, ferric chloride (FeCl36H2O), ferric sulfate, nine water ferric nitrates, Asia
At least one of ferric nitrate, thiocyanation iron, ferric bromide and ferric acetate.
As another embodiment, the molysite is selected from iron chloride, ferric chloride (FeCl36H2O), ferric sulfate and nine water ferric nitrates
At least one of.
As an implementation, the aluminium salt is selected from aluminium chloride, aluminium chloride, aluminum sulfate octadecahydrate, nine hydration nitre
At least one of sour aluminium, alum, tartaric acid aluminium, silver iodide, aluminium bromide and aluminum acetate.As another embodiment, the aluminium
Salt is in aluminium chloride, aluminum sulfate octadecahydrate, ANN aluminium nitrate nonahydrate and at least one of alum.
As an implementation, the manganese salt in manganese chloride, manganese sulfate monohydrate, nine water manganese sulfates and manganese nitrate extremely
Few one kind
As an implementation, the nickel salt is selected from least one of nickel nitrate, nickel sulfate hexahydrate and nickel chloride.
As an implementation, the magnesium salts is selected from least one of magnesium nitrate hexahydrate, magnesium sulfate and magnesium chloride.
As an implementation, the alkali is selected from inorganic base and/or organic base.
As an implementation, the inorganic base contains alkali metal element and/or alkali earth metal.
As an implementation, the inorganic base is at least one in sodium hydroxide, potassium hydroxide and calcium hydroxide
Kind.
As an implementation, the organic base is selected from least one of triethylamine, potassium tert-butoxide and n-BuLi.
As an implementation, the aqueous solution of the alkali is selected from ammonium hydroxide.
As an implementation, the concentration of the aqueous solution of the alkali is 0.5~2.5mol/L.
As an implementation, the mass ratio of the quality of metallic element and modification of chitosan is 1: 35 in the metal salt
~1: 10.When the quality of metallic element and the mass values of modification of chitosan are less than 1: 35, illustrate chitosan loaded hydroxide
Object content is lower, indifferent to Phosphateadsorption；When ratio is greater than 1: 10, excessive hydroxide can be enriched in chitosan
Surface is simultaneously assembled, so that adsorption activity center is reduced, absorption property can also decline.
As an implementation, the mass ratio of the quality of metallic element and modification of chitosan is 1: 25 in the metal salt
~1: 15.
As an implementation, the pH is 8~12.
As an implementation, the pH is 9~11.
As an implementation, the incorporation time of step 2) is 10 minutes~90 minutes.
As an implementation, the incorporation time of step 2) is 30 minutes~60 minutes.
As an implementation, the time of the standing is 10~60 minutes；As an implementation, the standing
Time be 10~60 minutes.
As an implementation, the temperature of the drying is 40~120 DEG C.
As an implementation, the incorporation time of step 3) is 10~90 minutes.
As an implementation, step 1) is stirred chitosan and acid to obtain modified chitosan.
As an implementation, the speed of the stirring is 80~160 revs/min.
As an implementation, the speed of the stirring is 100~150 revs/min.
The present invention provides a kind of chitosan-application of the metal hydroxides composite material in natural water, including will answer
Condensation material is mixed with natural water；The mass ratio of the composite material and natural water is 1: 10000~1: 500.
As an implementation, the content of phosphorus is 1~15ppm in the natural water.
As an implementation, the content of phosphorus is 5~12ppm in the natural water.
As an implementation, the mass ratio of phosphorus is 1: 150~1 in the quality of the composite material and natural water:
150。
As an implementation, the mass ratio of phosphorus is 1: 120~2 in the quality of the composite material and natural water:
5。
Compared with prior art, the present invention has following excellent effect:
(1) composite material adsorption capacity prepared by the present invention is big, and adsorptive selectivity is strong；
(2) relative to artificial synthesized organic polymer resin, chitosan of the present invention has precursor widely distributed, next
The advantages that source is abundant, easily biological-degradable；
(3) composite material that lye, the chitosan of modification and metal salt are mixed to get by the present invention is in g., jelly-like, after dry
It is broken into the particle of irregular size, increases the contact area of composite material and natural water, improves composite material to certainly
The absorption property of phosphorus in right water body.
(4) composite material prepared by the present invention for natural water repairing and treating, metal ion is not easy in treatment process
Dissolution, will not cause secondary pollution, be a kind of green, environment-friendly materials adsorbent material.
Specific embodiment
The present invention is described in detail in specific embodiment below, however the present invention is not restricted to following implementation
Example.
Saturated adsorption capacity test is carried out to composite material obtained by embodiment, test method is as follows: m grams of material dosage,
Phosphorus solution initial concentration C0, adsorbed in constant temperature oscillator, adsorption time is that for 24 hours, adsorption temp is 25 DEG C, and absorption terminates
Afterwards, solution concentration Ce after measurement absorption.
Test method is according to the measurement ammonium molybdate spectrophotometric method of GB 11893-1989 water quality total phosphorus.
Saturated adsorption capacity calculation formula q (mg/g)=V* (C of the present invention0- Ce)/m, wherein C0, Ce be respectively phosphorus in solution
Equilibrium concentration (mg/L) after initial concentration and absorption；V is adsorbent solution volume (L)；M is that adsorbent material adds quality (g).
Ion release test method: useless according to People's Republic of China's state environment protecting standard HJ 557-2010 solid
Object Leaching leaching method horizontal vibration method, specific assay method is as follows: weighing the sample that dry weight is 100g, is placed in 2L
Extraction flask (2L have spiral cover and inner cover wide-mouth bottle, by cannot leach or the inert material of adsorption sample ingredient (such as: glass
Or polyethylene etc.) composition) in, by sample: the mass ratio of water be 10: 1 (L/Kg) addition digestion agent (water, GB/T 6682, two
Grade), it is vertically fixed on horizontal shaking device (the adjustable reciprocating horizontal oscillation device of frequency) after covering tightly bottle cap, adjusts oscillation
Frequency is 110 ± 10 times/min, amplitude 40mm, removes extraction flask after vibrating 8h at room temperature, stands 16h.In oscillatory process
In when having gas generation, should timing extraction flask is opened in draught cupboard, discharge excessive pressure；In filter (pressure filtration dress
Set or vacuum apparatus) on install filter membrane (0.45 μm of miillpore filter), filter and collect leachate, be acidified to pH < with nitric acid
2, utilize the constituent contents such as atomic absorption spectrography (AAS) detection Fe, Mn, Al.According to above-mentioned Ion release test method, the present invention will
Chitosan described in Examples 1 to 7-metal hydroxides composite material is tested after handling natural water, Ion release
Content is as shown in table 1.
Embodiment 1:
It is that 0.20mol/L glacial acetic acid mixes that take 80g partial size, which be 60 mesh, the chitosan of deacetylation 90% and 10L concentration,
To modified chitosan, after stirring to dissolve with 120 revs/min of speed, 12.3g Fe (NO is added3)3·9H2O、
2.6gMnSO4·H2O、23.5g Al(NO3)3·9H2O and 200g 0.5mol/L NaOH, is stirred to react and stands 60 after ten minutes
Minute, 40 DEG C of dryings obtain the Fe (OH) that 94g average grain diameter is 2.0nm3·3H2O/Al(OH)3·5H2O/Mn(OOH)·H2O-
Chitosan (CTS) composite material.The composite material 0.025g for taking above-mentioned preparation, being added to 250g initial phosphorous content is 15ppm's
In river water (quality of phosphorus is 3.75g), capacity indicator is carried out, the saturated extent of adsorption for measuring composite material is 18.74mg/g.
Under equal conditions, blank chitosan adsorption capacity is 0.11mg/g, it was found from above-described embodiment: chitosan loaded metal hydrogen-oxygen
After compound, adsorption capacity is greatly improved.
Embodiment 2:
It is that 0.15mol/L HCl is mixed to get that take 70g partial size, which be 120 mesh, the chitosan of deacetylation 80% and 8L concentration,
After stirring to dissolve with 130 revs/min of speed, 5.4g FeCl is added in modified chitosan3·6H2O、5.94g
MnCl2、6.66g Al2(SO4)3·18H2O is 12 with 2mol/L KOH regulation system pH, is stirred to react 60 points after mixing evenly
20 minutes are stood after clock, distillation water washing to eluate is in neutrality, and 100 DEG C of dryings obtain the Fe (OH) of 93.3g3·3H2O/Al
(OH)3·5H2O/Mn(OOH)·H2O-CTS composite material.The composite material 0.1g for taking above-mentioned preparation is added to the initial phosphorus of 50g
In the river water (quality of phosphorus is 0.05g) that content is 1ppm, capacity indicator is carried out, the saturated extent of adsorption of composite material is measured
For 22.44mg/g.
Embodiment 3:
It is 0.25mol/L aqueous citric acid solution that take 30g partial size, which be 100 mesh, the chitosan of deacetylation 85% and 5L concentration,
It is mixed to get modification of chitosan, after stirring to dissolve with 100 revs/min of speed, 4g Fe is added2(SO4)3、1.79gMn
(NO3)2、3.99g AlCl3, it is 13 with 0.8mol/L NaOH regulation system pH after mixing evenly, it is quiet after being stirred to react 50 minutes
Ageing 50 minutes is set, distillation water washing to eluate is in neutrality, and 80 DEG C of dryings obtain the Fe that 31.6g average grain diameter is 3.8nm
(OH)3·3H2O/Al(OH)3·5H2O/Mn(OOH)·H2O-CTS composite material.The composite material 0.3g for taking above-mentioned preparation, adds
Enter into the river water (quality of phosphorus is 1.5g) that 300g initial phosphorous content is 5ppm, carries out capacity indicator, measure composite wood
The saturated extent of adsorption of material is 17.35mg/g.
Embodiment 4:
It is that 0.35mol/L glacial acetic acid mixes that take 75g partial size, which be 200 mesh, the chitosan of deacetylation 88% and 10L concentration,
To modified chitosan, after stirring to dissolve with 150 revs/min of speed, 10g Fe (CH is added3COO)3、
5.91gMnCl2、15g AlBr3, it is 13, after being stirred to react 90 minutes with 0.5mol/L NaOH regulation system pH after mixing evenly
Still aging 60 minutes, distillation water washing to eluate was in neutrality, 120 DEG C of dryings, obtained the Fe that 85g average grain diameter is 2.5nm
(OH)3·3H2O/Al(OH)3·5H2O/Mn(OOH)·H2O-CTS composite material.The composite material 0.2g for taking above-mentioned preparation, adds
Enter into the river water (quality of phosphorus is 1.1g) that 100g initial phosphorous content is 11ppm, carries out capacity indicator, measure composite wood
The saturated extent of adsorption of material is 18.36mg/g.
Embodiment 5:
It is that 0.45mol/L citric acid water is mixed that take 110g partial size, which be 150 mesh, the chitosan of deacetylation 87% and 16L concentration,
Conjunction obtains modified chitosan, and after stirring to dissolve with 150 revs/min of speed, 32g FeBr is added3、9.43gMn
(NO3)2、14.4g Al(CH3COO)3, after mixing evenly, with 2mol/L NH3.H2O regulation system pH is 12, is stirred to react 70 points
Still aging 50 minutes after clock, distillation water washing to eluate is in neutrality, and 110 DEG C of dryings obtain the Fe (OH) of 130g3·3H2O/
Al(OH)3·5H2O/Mn(OOH)·H2O-CTS composite material.The composite material 0.45g for taking above-mentioned preparation, at the beginning of being added to 225g
In the river water (quality of phosphorus is 2.7g) that beginning phosphorus content is 12ppm, capacity indicator is carried out, the saturation for measuring composite material is inhaled
Attached amount is 17.57mg/g.
Embodiment 6:
It is that 0.05mol/L HCl is mixed to get that take 96g partial size, which be 60 mesh, the chitosan of deacetylation 80% and 30L concentration,
After stirring to dissolve with 120 revs/min of speed, 12g Fe is added in modified chitosan2(SO4)3、7.48g MnCl2、
25g alum is 9 with 0.5mol/L NaOH regulation system pH, is stirred to react still aging 10 points after ten minutes after mixing evenly
Clock, distillation water washing to eluate are in neutrality, and 40 DEG C of dryings obtain the Fe (OH) of 107g3·3H2O/Al(OH)3·5H2O/Mn
(OOH)·H2O-CTS composite material.The composite material 0.18g for taking above-mentioned preparation, being added to 180g initial phosphorous content is 10ppm
River water (quality of phosphorus be 1.8g) in, carry out capacity indicator, the saturated extent of adsorption for measuring composite material is 16.31mg/
g。
Embodiment 7:
It is that 0.45mol/L HCl is mixed that take 120g partial size, which be 200 mesh, the chitosan of deacetylation 90% and 20L concentration,
To modified chitosan, after stirring to dissolve with 150 revs/min of speed, 5.8g FeCl is added3、13.4g MnSO4·
H2O、30g AlI3, it is 13 with 2.5mol/L KOH regulation system pH after mixing evenly, it is still aging after being stirred to react 90 minutes
60 minutes, distillation water washing to eluate was in neutrality, and 120 DEG C of dryings obtain the Fe (OH) of 144g3·3H2O/Al(OH)3·
5H2O/Mn(OOH)·H2O-CTS composite material.The composite material 0.27g for taking above-mentioned preparation, being added to 360g initial phosphorous content is
In the river water (quality of phosphorus is 2.88g) of 8ppm, capacity indicator is carried out, the saturated extent of adsorption for measuring composite material is
19.93mg/g。
Embodiment 8:
It is that 0.35mol/L HCl is mixed that take 160g partial size, which be 200 mesh, the chitosan of deacetylation 88% and 50L concentration,
To modified chitosan, after stirring to dissolve with 150 revs/min of speed, 55g FeCl is added3·6H2O is stirred evenly
Afterwards, it is 8 with 1mol/L NaOH regulation system pH, is stirred to react still aging 30 minutes after sixty minutes, distillation water washing to wash-off
Liquid is in neutrality, 120 DEG C of dryings, obtains the Fe (OH) of 188g3·3H2O-CTS composite material.Take the composite material of above-mentioned preparation
0.15g is added in the lake water (quality of phosphorus is 0.75g) that 750g initial phosphorous content is 1ppm, carries out capacity indicator, is surveyed
The saturated extent of adsorption for obtaining composite material is 8.52mg/g.
Embodiment 9:
It is that 0.20mol/L citric acid mixes that take 150g partial size, which be 60 mesh, the chitosan of deacetylation 90% and 10L concentration,
To modified chitosan, after stirring to dissolve with 140 revs/min of speed, 23g MnSO is added4·H2O, after mixing evenly,
With 1.5mol/L NH3·H2O regulation system pH is 12, still aging 20 minutes after being stirred to react 30 minutes, and distillation water washing is extremely
Eluate is in neutrality, 100 DEG C of dryings, obtains Mn (OOH) H of 178g2O-CTS composite material.Take the composite wood of above-mentioned preparation
Expect 0.40g, be added in the river (quality of phosphorus is 0.2g) that 200g initial phosphorous content is 1ppm, carries out capacity indicator,
The saturated extent of adsorption for measuring composite material is 5.36mg/g.
Embodiment 10:
Taking chitosan that 280g partial size is 160 mesh, deacetylation 90% with 25L concentration is that 0.30mol/L HCl is mixed
To modified chitosan, after stirring to dissolve with 120 revs/min of speed, 40.4g Fe (NO is added3)3·9H2O、50.7g
MnSO4·H2O, after mixing evenly, with 1.8mol/L NH3·H2O regulation system pH be 12, be stirred to react stand after twenty minutes it is old
Change 20 minutes, distillation water washing to eluate is in neutrality, and 90 DEG C of dryings obtain the Fe (OH) of 321g3·3H2O//Mn(OOH)·
H2O-CTS composite material.The composite material 0.16g for taking above-mentioned preparation is added to the river water that 160g initial phosphorous content is 10ppm
In (quality of phosphorus is 1.6g), capacity indicator is carried out, the saturated extent of adsorption for measuring composite material is 15.77mg/g.
Embodiment 11:
Taking chitosan that 280g partial size is 160 mesh, deacetylation 90% with 25L concentration is that 0.30mol/L glacial acetic acid mixes
Modified chitosan is obtained, after being stirred to dissolve with 130 revs/min of speed, is added, 50.5g Fe (NO3)3·9H2O、
8.6g MnSO4·H2O, after mixing evenly, with 1.8mol/L NH3·H2O regulation system pH is 12, after being stirred to react 50 minutes
Still aging 30 minutes, distillation water washing to eluate was in neutrality, and 90 DEG C of dryings obtain the Fe (OH) of 350g3·3H2O/Mn
(OOH)·H2O-CTS composite material.The composite material 0.23g for taking above-mentioned preparation, being added to 460g initial phosphorous content is 6ppm's
In river water (quality of phosphorus is 2.76g), capacity indicator is carried out, the saturated extent of adsorption for measuring composite material is 17.53mg/g.
Embodiment 12:
It is that 0.20mol/L glacial acetic acid mixes that take 50g partial size, which be 180 mesh, the chitosan of deacetylation 89% and 13L concentration,
To modified chitosan, after stirring to dissolve with 120 revs/min of speed, 24g Mg (NO is added3)2·6H2O, stirring are equal
It is 11, still aging 15 minutes after being stirred to react 30 minutes with 1mol/L NaOH regulation system pH after even, distillation water washing is extremely
Eluate is in neutrality, 80 DEG C of dryings, obtains the Mg (OH) of 55g2- CTS composite material.The composite material 0.21g of above-mentioned preparation is taken,
It is added in the river water (quality of phosphorus is 3.78g) that 630g initial phosphorous content is 6ppm, carries out capacity indicator, measure compound
The saturated extent of adsorption of material is 3.87mg/g.
Embodiment 13:
Taking chitosan that 180g partial size is 160 mesh, deacetylation 90% with 15L concentration is that 0.30mol/L HCl is mixed
To modified chitosan, after stirring to dissolve with 140 revs/min of speed, 80.8g Fe (NO is added3)3·9H2O、
14.94g Mg(NO3)2·6H2O, after mixing evenly, with 2mol/L NH3·H2O regulation system pH is 11, is stirred to react 55 minutes
Still aging 25 minutes afterwards, distillation water washing to eluate was in neutrality, and 110 DEG C of dryings obtain the Fe (OH) of 209g3·3H2O/Mg
(OH)2- CTS composite material.The composite material 0.28g for taking above-mentioned preparation is added to the river water that 350g initial phosphorous content is 7ppm
In (quality of phosphorus is 2.45g), capacity indicator is carried out, the saturated extent of adsorption for measuring composite material is 16.62mg/g.
Embodiment 14:
Take 210g partial size be 200 mesh, the chitosan of deacetylation 88% and 20L concentration be 0.27mol/L citric acid mixing
Modified chitosan is obtained, after stirring to dissolve with 100 revs/min of speed, 23.05g MnSO is added4·H2O、33.3g
Al2(SO4)3·18H2O is 8 with 0.8mol/L NaOH regulation system pH, stands after being stirred to react 35 minutes after mixing evenly
Ageing 15 minutes, distillation water washing to eluate are in neutrality, and 100 DEG C of dryings obtain the Fe (OH) of 238g3·3H2O-CTS is compound
Material.The composite material 0.33g for taking above-mentioned preparation, being added to river water that 660g initial phosphorous content is 5ppm, (quality of phosphorus is
In 3.3g), capacity indicator is carried out, the saturated extent of adsorption for measuring composite material is 5.15mg/g.
Embodiment 15:
Take 210g partial size be 200 mesh, the chitosan of deacetylation 88% and 20L concentration be 0.27mol/L citric acid mixing
Modified chitosan is obtained, after stirring to dissolve with 100 revs/min of speed, 67.55g FeCl is added3·6H2O、27.9g
AlCl3, it is 8, still aging 15 points after being stirred to react 35 minutes with 0.8mol/L triethylamine regulation system pH after mixing evenly
Clock, distillation water washing to eluate are in neutrality, and 100 DEG C of dryings obtain the Fe (OH) of 233g3·3H2O-CTS composite material.It takes
The material 0.20g for stating preparation is added in the river water (quality of phosphorus is 5g) that 1000g initial phosphorous content is 5ppm, is adsorbed
Volume test, the saturated extent of adsorption for measuring composite material is 1.13mg/g.
Embodiment 16:
It is that 0.26mol/L glacial acetic acid mixes that take 100g partial size, which be 180 mesh, the chitosan of deacetylation 90% and 6L concentration,
To modified chitosan, after stirring to dissolve with 130 revs/min of speed, 36.23g FeCl is added3·6H2O、4.61g
MnSO4·H2O is after mixing evenly 8, still aging 25 points after being stirred to react 50 minutes with 1.2mol/L KOH regulation system pH
Clock, distillation water washing to eluate are in neutrality, and 90 DEG C of dryings obtain the Fe (OH) of 119g3·3H2O/Mn (OOH)-CTS composite wood
Material.The material 0.26g for taking above-mentioned preparation is added in the river water (quality of phosphorus is 1.3g) that 130g initial phosphorous content is 10ppm,
Capacity indicator is carried out, the saturated extent of adsorption for measuring composite material is 9.53mg/g.
Embodiment 17:
It is that 0.26mol/L glacial acetic acid mixes that take 100g partial size, which be 180 mesh, the chitosan of deacetylation 90% and 6L concentration,
To modified chitosan, after stirring to dissolve with 130 revs/min of speed, 26.57g FeCl is added3·6H2O、7.39g
MnSO4·H2O is after mixing evenly 8, still aging 25 after being stirred to react 50 minutes with 1.2mol/L NaOH regulation system pH
Minute, distillation water washing to eluate is in neutrality, and 90 DEG C of dryings obtain the Fe (OH) of 120g3·3H2O-CTS composite material.It takes
The composite material 0.25g of above-mentioned preparation is added in the river water (quality of phosphorus is 1.5g) that 300g initial phosphorous content is 5ppm, into
Row capacity indicator, the saturated extent of adsorption for measuring composite material is 5.53mg/g.
Embodiment 18:
It is that 0.33mol/L HCl is mixed to get that take 50g partial size, which be 160 mesh, the chitosan of deacetylation 90% and 7L concentration,
After stirring to dissolve with 110 revs/min of speed, 5.80g FeCl is added in modified chitosan3·6H2O、2.46g
MnSO4·H2O is 8 with 2.0mol/L NaOH regulation system pH, is stirred to react after forty minutes still aging 20 after mixing evenly
Minute, distillation water washing to eluate is in neutrality, and 110 DEG C of dryings obtain the Fe (OH) of 56g3·3H2O/Mn (OOH)-CTS is compound
Material.The composite material 0.21g for taking above-mentioned preparation, being added to river water that 210g initial phosphorous content is 8ppm, (quality of phosphorus is
In 1.68g), capacity indicator is carried out, the saturated extent of adsorption for measuring composite material is 6.73mg/g.
Embodiment 19:
It is that 0.28mol/L glacial acetic acid mixes that take 75g partial size, which be 160 mesh, the chitosan of deacetylation 90% and 12L concentration,
To modified chitosan, after stirring to dissolve with 130 revs/min of speed, 20.28g FeCl is added3·6H2O、3.07g
NiCl2, it is 8, still aging 15 minutes after being stirred to react 35 minutes with 1.6mol/L NaOH regulation system pH after mixing evenly,
Distillation water washing to eluate is in neutrality, and 100 DEG C of dryings obtain the Fe (OH) of 92g3/Ni(OH)2- CTS composite material.It takes above-mentioned
The material 0.5g of preparation is added in the river water (quality of phosphorus is 5.5g) that 500g initial phosphorous content is 11ppm, carries out absorption appearance
Examination is measured, the saturated extent of adsorption for measuring composite material is 8.11mg/g.
Embodiment 20:
It is that 0.37mol/L citric acid mixes that take 90g partial size, which be 180 mesh, the chitosan of deacetylation 88% and 8L concentration,
To modified chitosan, after stirring to dissolve with 110 revs/min of speed, 20.15g NiSO is added4·6H2O, stirring are equal
After even, it is 10, still aging 15 minutes after being stirred to react 30 minutes with 1.0mol/L NaOH regulation system pH, distills water washing
It is in neutrality to eluate, 90 DEG C of dryings, obtains the Ni (OH) of 100g2- CTS composite material.The material 0.32g of above-mentioned preparation is taken,
It is added in the river water (quality of phosphorus is 3.84g) that 640g initial phosphorous content is 6ppm, carries out capacity indicator, measure compound
The saturated extent of adsorption of material is 3.62mg/g.
Embodiment 21:
It is that 0.37mol/L citric acid mixes that take 190g partial size, which be 180 mesh, the chitosan of deacetylation 88% and 8L concentration,
To modified chitosan, after stirring to dissolve with 110 revs/min of speed, 16.91g FeCl is added3·6H2O、6.72g
NiSO4·6H2O and 7.2g Mg (NO3)2·6H2O is after mixing evenly 12 with 1.0mol/L NaOH regulation system pH, stirring
Still aging 15 minutes after reaction 30 minutes, distillation water washing to eluate is in neutrality, and 90 DEG C of dryings obtain the Fe of 212g
(OH)3·3H2O/Mg(OH)2/Ni(OH)2·H2O-CTS composite material.The composite material 0.32g for taking above-mentioned preparation, is added to
In the river water (quality of phosphorus is 3.84g) that 640g initial phosphorous content is 6ppm, capacity indicator is carried out, composite material is measured
Saturated extent of adsorption is 3.62mg/g.
Ion release content is as shown in table 1 after composite material described in Examples 1 to 7 handles river water:
As seen from the table: to be below GB 8978-1996 sewage comprehensive for each Ion release content in water sample after composite material absorption
Close each pollutant emission limit specified in discharge standard, it is believed that prepared by the method adsorption and dephosphorization composite material,
Metal ion is not easy to dissolve out in the adsorption process of river water, will not cause secondary pollution, is a kind of green, environment-friendly composite material.
Claims (39)
1. a kind of chitosan-metal hydroxides composite material, including chitosan and the metallic hydrogen being carried on the chitosan
Oxide.
2. composite material as described in claim 1, it is characterised in that: the average pore size of the composite material be 2.0~
3.8nm。
3. composite material as described in claim 1, it is characterised in that: the saturated extent of adsorption of the composite material be 15~
25mg/g。
4. composite material as described in claim 1, it is characterised in that: the deacetylation of the chitosan is 80~90%.
5. composite material as described in claim 1, it is characterised in that: the quality of the chitosan is the composite material quality
75~95%.
6. composite material as described in claim 1, it is characterised in that: the metallic element in the metal hydroxides is selected from
At least one of iron, aluminium, magnesium, manganese and nickel.
7. a kind of chitosan-metal hydroxides composite material preparation method, comprising the following steps: 1) by chitosan and acid
Aqueous solution is mixed to get modified chitosan；2) shell is obtained after mixing the aqueous solution of alkali, the chitosan of modification and metal salt to gather
Sugar-metal hydroxides composite material.
8. preparation method as claimed in claim 7, it is characterised in that: step 2) by the aqueous solution of alkali, modification chitosan and
The pH for adjusting mixed solution after metal salt mixing obtains chitosan-metal hydroxides composite material to alkalinity.
9. preparation method as claimed in claim 8, it is characterised in that: step 2) by the aqueous solution of alkali, modification chitosan and
The pH for adjusting mixed solution after metal salt mixing is then allowed to stand to alkalinity, is dried to obtain chitosan-metal hydroxides composite wood
Material.
10. a kind of chitosan-metal hydroxides composite material preparation method, comprising the following steps: 1) by chitosan and acid
Aqueous solution be mixed to get modified chitosan；2) modified chitosan and metal salt are mixed to get mixed solution A；3) it will mix
The aqueous solution for closing solution A and alkali is mixed to get chitosan-metal hydroxides composite material.
11. preparation method as claimed in claim 10, it is characterised in that: step 3) mixes the aqueous solution of mixed solution A and alkali
The pH of mixed solution is adjusted after conjunction to alkalinity, obtains chitosan-metal hydroxides composite material.
12. preparation method as claimed in claim 11, it is characterised in that: step 3) mixes the aqueous solution of mixed solution A and alkali
The pH of mixed solution is adjusted after conjunction to alkalinity, is then allowed to stand, is dried to obtain chitosan-metal hydroxides composite material.
13. the preparation method as described in claim 7 or 10, it is characterised in that: the average grain diameter of chitosan described in step 1)
For 60~200 mesh.
14. the preparation method as described in claim 7 or 10, it is characterised in that: the concentration of acid described in step 1) in water is
0.05~0.45mol/L
15. the preparation method as described in claim 7 or 10, it is characterised in that: acid described in step 1) is selected from hydrochloric acid, citric acid
And at least one of glacial acetic acid.
16. the preparation method as described in claim 7 or 10, it is characterised in that: the metal salt be selected from molysite, aluminium salt, manganese salt,
At least one of nickel salt and magnesium salts.
17. preparation method as claimed in claim 16, it is characterised in that: the metal salt is molysite and manganese salt；Or the gold
Belonging to salt is molysite and aluminium salt；Or the metal salt is manganese salt and aluminium salt；Or the metal salt is nickel salt and molysite；Or the metal
Salt is molysite and magnesium salts；Or the metal salt is molysite, manganese salt and aluminium salt；Or the metal salt is molysite, nickel salt and magnesium salts.
18. preparation method as claimed in claim 17, it is characterised in that: the metal salt is molysite and manganese salt；Or the gold
Belonging to salt is molysite and aluminium salt；Or the metal salt is molysite, manganese salt and aluminium salt.
19. preparation method as claimed in claim 17, it is characterised in that: the metal salt is molysite and manganese salt；The metal
The mass ratio of the quality of ferro element and manganese element is 1: 3~5: 1 in salt.
20. preparation method as claimed in claim 17, it is characterised in that: the metal salt is molysite and magnesium salts；The metal
The quality of magnesium elements and the mass ratio of ferro element are less than 1: 8 in salt.
21. preparation method as claimed in claim 17, it is characterised in that: the metal salt is molysite, manganese salt and aluminium salt；It is described
The mass ratio of manganese element and aluminium element is 1: 2~5: 1 in metal salt；The quality of ferro element and the mass ratio of manganese element are 1: 3~5
∶1。
22. preparation method as claimed in claim 16, it is characterised in that: the molysite be selected from iron chloride, ferric chloride (FeCl36H2O),
At least one of ferric sulfate, nine water ferric nitrates, nitrous acid iron, thiocyanation iron, ferric bromide and ferric acetate.
23. preparation method as claimed in claim 16, it is characterised in that: the aluminium salt is selected from aluminium chloride, aluminium chloride, ten
At least one of eight water aluminum sulfate, ANN aluminium nitrate nonahydrate, alum, tartaric acid aluminium, silver iodide, aluminium bromide and aluminum acetate.
24. preparation method as claimed in claim 16, it is characterised in that: the manganese salt be selected from manganese chloride, manganese sulfate monohydrate and
At least one of manganese nitrate.
25. preparation method as claimed in claim 16, it is characterised in that: the nickel salt be selected from nickel nitrate, nickel sulfate hexahydrate and
At least one of nickel chloride.
26. preparation method as claimed in claim 16, it is characterised in that: the magnesium salts be selected from magnesium nitrate hexahydrate, magnesium sulfate and
At least one of magnesium chloride.
27. the preparation method as described in claim 7 or 10, it is characterised in that: the alkali is selected from inorganic base and/or organic base.
28. preparation method as claimed in claim 27, it is characterised in that: the inorganic base contains alkali metal element and/or alkali
Earth metal element.
29. preparation method as claimed in claim 27, it is characterised in that: the inorganic base be selected from sodium hydroxide, potassium hydroxide,
And at least one of calcium hydroxide.
30. preparation method as claimed in claim 27, it is characterised in that: the organic base be selected from triethylamine, potassium tert-butoxide and
At least one of n-BuLi.
31. the preparation method as described in claim 7 or 10, it is characterised in that: the aqueous solution of the alkali is selected from ammonium hydroxide.
32. the preparation method as described in claim 7 or 10, it is characterised in that: the concentration of the aqueous solution of the alkali be 0.5~
2.5mol/L。
33. the preparation method as described in claim 7 or 10, it is characterised in that: in the metal salt quality of metallic element with
The mass ratio of modification of chitosan is 1: 35~1: 10.
34. the preparation method as described in claim 8 or 11, it is characterised in that: the pH is 8~12.
35. the preparation method as described in claim 9 or 12, it is characterised in that: the time of the standing is 10~60 minutes.
36. the preparation method as described in claim 9 or 12, it is characterised in that: the temperature of the drying is 40~120 DEG C.
37. a kind of chitosan-application of the metal hydroxides composite material in natural water, including by composite material and nature
Water mixing；The mass ratio of the composite material and natural water is 1: 10000~1: 500.
38. application as claimed in claim 37, it is characterised in that: the content of phosphorus is 1~15ppm in the natural water.
39. application as claimed in claim 37, it is characterised in that: the matter of phosphorus in the quality and natural water of the composite material
Amount is than being 1: 150~2: 1.
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