CN108262029A - A kind of preparation method of Organic-inorganic composite modified straw dephosphorization sorbing material - Google Patents

A kind of preparation method of Organic-inorganic composite modified straw dephosphorization sorbing material Download PDF

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CN108262029A
CN108262029A CN201810066936.2A CN201810066936A CN108262029A CN 108262029 A CN108262029 A CN 108262029A CN 201810066936 A CN201810066936 A CN 201810066936A CN 108262029 A CN108262029 A CN 108262029A
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modified
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solution
filtrate
straw
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CN108262029B (en
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钱程
刘兴勇
曹洪岩
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Sichuan University of Science and Engineering
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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
    • 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
    • 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
    • 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
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • 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
    • C02F2101/105—Phosphorus compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)
  • Fertilizers (AREA)

Abstract

The invention belongs to environment adsorbing materials technical fields, and in particular to a kind of preparation method of organo-mineral complexing modified straw dephosphorization sorbing material.This method is using agricultural crop straw as raw material, using cheap, nontoxic organic acid and calcium salt as modifying agent, under certain condition, agitated, reflux, impregnating process, organo-mineral complexing modified straw dephosphorization sorbing material is prepared, while realizes recycling organic and without modifying agent.This is simple for process and environmentally protective, and can effectively remove phosphor in sewage, promotes the practical value of the present invention.

Description

A kind of preparation method of Organic-inorganic composite modified straw dephosphorization sorbing material
Technical field
The invention belongs to environment adsorbing materials technical fields, and in particular to a kind of Organic-inorganic composite modified straw dephosphorization The preparation method of sorbing material.
Background technology
With China's economic development and the raising of urban life level, water pollution problems is also more serious, many rivers lakes All there is different degrees of eutrophication in pool, and it is the principal element caused to body eutrophication that phosphorus is exceeded.Therefore, The phosphorus in sewage how is effectively removed, is to need to solve the problems, such as it in current China environmental protection and eutrophied water treatment One.At present, the common method of dephosphorization mainly includes bioanalysis, chemical precipitation method, membrane separation process and absorption method etc., wherein absorption method Because its equipment be simple and convenient to operate with processing speed it is very fast the advantages that, and be concerned.It is absorption using absorption method dephosphorization key The selection of material.As a kind of efficient dephosphorization sorbing material, should have that environmental-friendly, stability is good, easy regeneration and cheap Feature.Agricultural crop straw obtains extensive concern because its source is wide, distinctive chemical constitution and the recycling potentiality of waste.
China generates a large amount of stalk as large agricultural country every year, and at present the processing mode of stalk mainly directly and also Field or burning.Though crop straw burning can consume a large amount of stalks, a large amount of flying dusts and pellet can be generated, while is generated a large amount of Toxic and harmful gas causes environmental pollution, therefore, opens up the new application approach of agricultural crop straw, turns waste into wealth, realize its resource Change using be sustainable development there is an urgent need to and be prepared into efficient absorption material, and applied to water treatment field pole by stalk Have economy and social value.
Stalk typically refer to rice, wheat, corn, cotton, etc. remainder of the crops after seed is harvested, be a kind of Agricultural wastes are mainly made of lignin, cellulose and hemicellulose etc., in structure and containing abundant hydroxyl isoreactivity Group has functionalization ability.But at present, agricultural crop straw prepares sorbing material and focuses mostly in the removal of heavy metal ion, and It is less in terms of for dephosphorization.Preparing dephosphorization sorbing material using stalk mainly has following methods：(1) it is transferred using organic synthesis method Amido is connect, and uses the noxious materials such as epoxychloropropane, technique not environmentally protective enough (Xing Xu, Baoyu Gao, Wenyi Wang,et al.Adsorption of phosphate from aqueous solutions onto modified wheat residue:Characteristics,kinetic and column studies[J].Colloids and Surfaces B:Biointerfaces,2009,70:46–52)；(2) it uses high temperature cabonization method by stover for biological activated carbon, carries out dilute Soil is cerium modified, and this method processing early period high energy consumption, costly, economy is relatively poor (103877937 B of CN) for modifying agent； (3) using lanthanum zirconium inorganic salts as modifying agent, activated using microwave-precipitation method prepare inorganic modified rape stalk (CN 107126935) it is less that the method for, Organic-inorganic composite being used to be modified prepares stalk dephosphorization adsorbent, and the present invention is using organic The method of grafting-inorganic compounding prepares modified straw, and uses it for the phosphate radical in removal sewage.
Invention content
The goal of the invention of the present invention is to be directed to more than technical problem, provides a kind of Organic-inorganic composite modified straw and remove The preparation method of phosphorus sorbing material.This method prepares a kind of Organic-inorganic composite modified straw and removes using agricultural crop straw as raw material Phosphorus sorbing material, and use it for the phosphate radical in removal sewage, while realizes recycling for modified filtrate, not only straw Recycling and New Phosphorus the sorbing material exploitation of stalk provide a method, are also provided for treatment of Phosphorus Containing Waste Water a kind of effective Approach.
In order to realize more than goal of the invention, the specific technical solution of the present invention is as follows：
A kind of Organic-inorganic composite modified straw dephosphorization sorbing material preparation method, includes the following steps：
1) using any one in wheat and rice straw as raw material, after crushed, the stalk powder of 60-120 mesh is collected, It washs, is spare after 80 DEG C of dry 12h.
2) using any one in oxalic acid, malonic acid, succinic acid and citric acid as organically-modified reagent, using water as solvent, The configuration concentration ranging from aqueous solution of 0.2-2.0mol/L, is denoted as solution A；Using any one in calcium chloride or calcium nitrate as nothing Machine modifying agent prepares the ionic calcium soln of calcium ion concentration range 0.1-1.0mol/L, is denoted as solution B.
3) 5g stalks are weighed, with solution A in 100ml steps 2 in 105-135 DEG C, constant temperature is stirred at reflux reaction 3-12h, warp After natural filtration, liquid phase is denoted as modified filtrate I, is stored for future use after organic acid content detects；Solid phase and 50ml 0.1mol/ LNa2CO31h is stirred at room temperature in solution.Products obtained therefrom is filtered, it is spare after 80 DEG C of freeze-day with constant temperature 12h after washing, it is denoted as organic change Property stalk.
4) solution B in step 3) in the organically-modified stalk input 100mL steps 2) of gained, is stirred to react 2- at room temperature 6h, after suction filtration, filtrate is denoted as modified filtrate II, is stored for future use after calcium ion concentration detects；Solid phase is done in 80 DEG C of constant temperature Organic-inorganic composite modified straw is obtained after dry 12h.
5) phosphorus saturated extent of adsorption measures.0.1g Organic-inorganic composite modified straws are weighed, it is certain density with 25mL NaH2PO4Solution, room temperature shakes absorption 12h in conical flask, measures and calculate the saturated extent of adsorption of phosphorus.
This method can also include 6) mending respectively in modified filtrate II in the modified filtrate I of the middle gained of step 3) and step 4) Fill a certain amount of organic acid and a certain amount of calcium salt be configured to aqueous solution, according to step 2) -5) repetitive operation, it realizes to modified filtrate I and the recycling of modified filtrate II.
The positive effect of the present invention is embodied in：
(1), using agricultural crop straw as raw material, using cheap, nontoxic organic acid and calcium salt as modifying agent, in certain condition Under, through reflux, impregnating process, Organic-inorganic composite modified straw dephosphorization sorbing material is prepared, while realize organic and nothing The recycling of machine modifying agent.
(2), this is simple for process and environmentally protective, and can effectively remove phosphor in sewage, promotes the practical value of the present invention.
Attached drawing and subordinate list explanation
The technological process of the preparation method of the heretofore described Organic-inorganic composite modified straw dephosphorization sorbing materials of Fig. 1 Figure
Fig. 2-1 is the electron microscope picture (SEM) of the Organic-inorganic composite modified straw prepared by embodiment 3
Fig. 2-2 is the power spectrum spectrogram (EDS) of the Organic-inorganic composite modified straw prepared by embodiment 3
Fig. 2-3 is the electron microscope picture (SEM) of stalk after phosphorus absorption
Fig. 2-4 is the power spectrum spectrogram (EDS) of stalk after phosphorus absorption
Fig. 2-5 is the 3rd electricity for recycling stalk after prepared Organic-inorganic composite modified straw phosphorus absorption of filtrate Sub- microscope figure (SEM)
Fig. 2-6 is the 3rd energy for recycling stalk after prepared Organic-inorganic composite modified straw phosphorus absorption of filtrate Compose spectrogram (EDS)
Specific embodiment
With reference to specific embodiment and comparative example, the present invention is further explained.It will be appreciated that these embodiments are only used for Illustrate the present invention rather than limit the scope of the invention.It should also be understood that be, after reading the content taught by the present invention, Those skilled in the art can make various modifications or changes to the present invention, and such equivalent forms equally fall within right appended by the application Claim limited range.
Embodiment 1：
A kind of Organic-inorganic composite modified straw dephosphorization sorbing material preparation method, includes the following steps：
1) using wheat stalk as raw material, after crushed, by the stalk powder washing of 60-120 mesh, after 80 DEG C of dry 12h It is spare.
2) using oxalic acid as modifying agent, configuration concentration is the oxalic acid aqueous solution of 0.5mol/L, is denoted as solution A；With calcium chloride For inorganic modified reagent, the ionic calcium soln of calcium ion concentration 0.4mol/L is prepared, is denoted as solution B.
3) 5g stalks are weighed, with solution A in 100ml steps 2 in 105 DEG C, constant temperature is stirred at reflux reaction 10h, often presses through After filter, solid phase and 100ml 0.1mol/L Na2CO31h is stirred at room temperature in solution.Products obtained therefrom is filtered, after washing, in 80 DEG C of perseverances It is spare after the dry 12h of temperature, it is denoted as organically-modified stalk；
4) solution B in step 3) in the organically-modified stalk input 100mL steps 2) of gained, is stirred to react at room temperature Solid phase through filtering and washing, is obtained Organic-inorganic composite modified straw by 2h after 80 DEG C of freeze-day with constant temperature 12h.
5) gained is modified in filtrate I and step 4) and supplements a certain amount of organic acid respectively in modified filtrate II in step 3) Aqueous solution is configured to a certain amount of calcium salt, according to step 2) -5) repetitive operation, it realizes to modified filtrate I and is modified filtrate II Recycling.
0.1g Organic-inorganic composite modified straws are weighed, with NaH2PO4Solution (NaH2PO4A concentration of the 10 of solution~ 150mg/L, similarly hereinafter), room temperature shakes absorption 12h in conical flask, measures the phosphorus saturated extent of adsorption of sorbing material.After testing, have Machine-inorganic compounding modified straw is 23.8mg/g to phosphorus saturated extent of adsorption.Filtrate modified straw prepared after the 3rd cycle Saturated extent of adsorption to phosphorus is 22.6mg/g.
Embodiment 2：
A kind of Organic-inorganic composite modified straw dephosphorization sorbing material preparation method, includes the following steps：
1) using rice straw as raw material, after crushed, the stalk powder of 60-120 mesh washs, after 80 DEG C of dry 12h It is spare.
2) using succinic acid as organically-modified reagent, configuration concentration is the succinic acid aqueous solution of 0.8mol/L, is denoted as solution A； Using calcium nitrate as inorganic modified reagent, the ionic calcium soln of calcium ion concentration 0.2mol/L is prepared, is denoted as solution B.
3) 5g stalks are weighed, with solution A in 100ml steps 2 in 120 DEG C, constant temperature is stirred at reflux reaction 6h, through natural filtration Afterwards, solid phase and 100ml 0.1mol/L Na2CO31h is stirred at room temperature in solution.Products obtained therefrom is filtered, after washing, in 80 DEG C of constant temperature It is spare after dry 12h, it is denoted as organically-modified stalk；
4) solution B in step 3 in the organically-modified stalk input 100mL steps 2 of gained, is stirred to react 1- at room temperature Solid phase through filtering and washing, is obtained Organic-inorganic composite modified straw by 4h after 80 DEG C of freeze-day with constant temperature 12h.
5) supplemented respectively in modified filtrate II in the modified filtrate I of gained and step 4 in step 3 a certain amount of organic acid and A certain amount of calcium salt is configured to aqueous solution, according to step 2) -5) repetitive operation, realize the weight to modified filtrate I and modified filtrate II It is multiple to utilize.After testing, Organic-inorganic composite modified straw is 22.1mg/g to phosphorus saturated extent of adsorption.Filtrate is after the 3rd cycle Prepared modified straw is 21.0mg/g to the saturated extent of adsorption of phosphorus.
Embodiment 3：
A kind of Organic-inorganic composite modified straw dephosphorization sorbing material preparation method, includes the following steps：
1) using wheat stalk as raw material, after crushed, the stalk powder of 60-120 mesh washs, after 80 DEG C of dry 12h It is spare.
2) using citric acid as organically-modified reagent, configuration concentration is the aqueous citric acid solution of 1.0mol/L, is denoted as solution A； Using calcium chloride as inorganic modified reagent, the ionic calcium soln of calcium ion concentration 0.6mol/L is prepared, is denoted as solution B.
3) 5g stalks are weighed, with solution A in 100ml steps 2 in 125 DEG C, constant temperature is stirred at reflux reaction 6h, through natural filtration Afterwards, solid phase and 100ml 0.1mol/L Na2CO31h is stirred at room temperature in solution.Products obtained therefrom is filtered, after washing, in 80 DEG C of constant temperature It is spare after dry 12h, it is denoted as organically-modified stalk.
4) solution B in step 3 in the organically-modified stalk input 100mL steps 2 of gained, is stirred to react 5h at room temperature, Through filtering and washing, solid phase is obtained into Organic-inorganic composite modified straw after 80 DEG C of freeze-day with constant temperature 12h.
5) supplemented respectively in modified filtrate II in the modified filtrate I of gained and step 4 in step 3 a certain amount of organic acid and A certain amount of calcium salt is configured to aqueous solution, according to step 2) -5) repetitive operation, realize the weight to modified filtrate I and modified filtrate II It is multiple to utilize.After testing, Organic-inorganic composite modified straw is 28.6mg/g to phosphorus saturated extent of adsorption.Filtrate is after the 3rd cycle Prepared modified straw is 27.2mg/g to the saturated extent of adsorption of phosphorus.
Embodiment 4：
A kind of Organic-inorganic composite modified straw dephosphorization sorbing material preparation method, includes the following steps：
1) using rice straw as raw material, after crushed, the stalk powder of 60-120 mesh washs, after 80 DEG C of dry 12h It is spare.
2) using malonic acid as modifying agent, using water as solvent, configuration concentration is the malonic acid aqueous solution of 1.0mol/L, is denoted as Solution A；Using calcium nitrate as inorganic modified reagent, the ionic calcium soln of calcium ion concentration 0.3mol/L is prepared, is denoted as solution B.
3) 5g stalks are weighed, with solution A in 100ml steps 2) in 135 DEG C, constant temperature is stirred at reflux reaction 3h, often presses through After filter, solid phase and 100ml 0.1mol/L Na2CO3Solution is stirred to react 1h at room temperature.Products obtained therefrom is filtered, after washing, It is spare after 80 DEG C of freeze-day with constant temperature 12h, it is denoted as organically-modified stalk；
4) solution B in step 3 in the organically-modified stalk input 100mL steps 2 of gained, is stirred to react 6h at room temperature, Through filtering and washing, solid phase is obtained into Organic-inorganic composite modified straw after 80 DEG C of freeze-day with constant temperature 12h.
5) gained is modified in filtrate I and step 4 and supplements a certain amount of organic acid respectively in modified filtrate II in step 3) Aqueous solution is configured to a certain amount of calcium salt, according to step 2) -5) repetitive operation, it realizes to modified filtrate I and is modified filtrate II Recycling.After testing, Organic-inorganic composite modified straw is 23.6mg/g to phosphorus saturated extent of adsorption.Filtrate is through the 3rd cycle Prepared modified straw is 23.3mg/g to the saturated extent of adsorption of phosphorus afterwards.
Comparative example 1：
It is reference with embodiment 3, prepares individually organically-modified stalk, the specific steps are：
1) using wheat stalk as raw material, after crushed, the stalk powder of 60-120 mesh washs, after 80 DEG C of dry 12h It is spare.
2) using citric acid as organically-modified reagent, configuration concentration is the aqueous citric acid solution of 1.0mol/L, is denoted as solution A.
3) 5g stalks are weighed, with solution A in 100ml steps 2 in 125 DEG C, constant temperature is stirred at reflux reaction 6h, through natural filtration Afterwards, solid phase and 100ml 0.1mol/L Na2CO31h is stirred at room temperature in solution.Products obtained therefrom is filtered, after washing, in 80 DEG C of constant temperature It is spare after dry 12h, it is denoted as organically-modified stalk.
After testing, organically-modified stalk is and 0.8mg/g to phosphorus saturated extent of adsorption.
Comparative example 2：
It is reference with embodiment 3, preparing individually inorganic modified wheat stalk, actual conditions is：
A kind of Organic-inorganic composite modified straw dephosphorization sorbing material preparation method, includes the following steps：
1) using wheat stalk as raw material, after crushed, the stalk powder of 60-120 mesh washs, after 80 DEG C of dry 12h It is spare.
2) using calcium chloride as inorganic modified reagent, the ionic calcium soln of calcium ion concentration 0.6mol/L is prepared, is denoted as solution B。
3) solution B in stalk input 100mL steps 2, is stirred to react 5h at room temperature, through filtering and washing, by solid phase in After 80 DEG C of freeze-day with constant temperature 12h, inorganic modified stalk is obtained.
After testing, inorganic modified stalk is 1.1mg/g to phosphorus saturated extent of adsorption.
Comparative example 3
It is reference with embodiment 3, prepares Organic-inorganic composite modified wheat stalk, actual conditions is：
1) using wheat stalk as raw material, after crushed, the stalk powder of 60-120 mesh washs, after 80 DEG C of dry 12h It is spare.
2) using citric acid as organically-modified reagent, configuration concentration is the aqueous citric acid solution of 0.01mol/L, is denoted as solution A； Using calcium chloride as inorganic modified reagent, the ionic calcium soln of calcium ion concentration 0.6mol/L is prepared, is denoted as solution B.
3) 5g stalks are weighed, with solution A in 100ml steps 2 in 125 DEG C, constant temperature is stirred at reflux reaction 6h, through natural filtration Afterwards, solid phase and 100ml 0.1mol/L Na2CO31h is stirred at room temperature in solution.Products obtained therefrom is filtered, after washing, in 80 DEG C of constant temperature It is spare after dry 12h, it is denoted as organically-modified stalk.
4) solution B in step 3 in the organically-modified stalk input 100mL steps 2 of gained, is stirred to react 5h at room temperature, Through filtering, washing, solid phase is obtained into Organic-inorganic composite modified straw after 80 DEG C of freeze-day with constant temperature 12h.
5) supplemented respectively in modified filtrate II in the modified filtrate I of gained and step 4 in step 3 a certain amount of organic acid and A certain amount of calcium salt is configured to aqueous solution, according to step 2-5 repetitive operations, realizes the repetition to modified filtrate I and modified filtrate II It utilizes.After testing, Organic-inorganic composite modified straw is 3.8mg/g to phosphorus saturated extent of adsorption.
Comparative example 4
It is reference with embodiment 3, prepares Organic-inorganic composite modified wheat stalk, actual conditions is：
1) using wheat stalk as raw material, after crushed, the stalk powder of 60-120 mesh washs, after 80 DEG C of dry 12h It is spare.
2) using citric acid as organically-modified reagent, configuration concentration is the aqueous citric acid solution of 1.0mol/L, is denoted as solution A； Using calcium chloride as inorganic modified reagent, the ionic calcium soln of calcium ion concentration 0.01mol/L is prepared, is denoted as solution B.
3) 5g stalks are weighed, with solution A in 100ml steps 2 in 125 DEG C, constant temperature is stirred at reflux reaction 6h, through natural filtration Afterwards, solid phase and 100ml 0.1mol/L Na2CO31h is stirred at room temperature in solution.Products obtained therefrom is filtered, after washing, in 80 DEG C of constant temperature It is spare after dry 12h, it is denoted as organically-modified stalk.
4) solution B in step 3 in the organically-modified stalk input 100mL steps 2 of gained, is stirred to react 5h at room temperature, Through filtering and washing, solid phase is obtained into Organic-inorganic composite modified straw after 80 DEG C of freeze-day with constant temperature 12h.
5) supplemented respectively in modified filtrate II in the modified filtrate I of gained and step 4 in step 3 a certain amount of organic acid and A certain amount of calcium salt is configured to aqueous solution, according to step 2-5 repetitive operations, realizes the repetition to modified filtrate I and modified filtrate II It utilizes.After testing, Organic-inorganic composite modified straw is 4.5mg/g to phosphorus saturated extent of adsorption.
Stalk in embodiment 1 to embodiment 4 and documents 1 to 4 is summarized as follows the saturated extent of adsorption of phosphorus, is shown in Table 1：
Stalk is to the full adsorbance of phosphorus in 1 embodiment and comparative example of table
Example described above is only the preferred embodiment of this patent, but the protection domain of this patent is not limited thereto. It should be pointed out that for those skilled in the art, under the premise of this patent principle is not departed from, according to this specially The technical solution and its inventional idea of profit, can also make several improvements and modifications, these improvements and modifications also should be regarded as this specially The protection domain of profit.

Claims (3)

1. a kind of preparation method of Organic-inorganic composite modified straw dephosphorization sorbing material, it is characterised in that include the following steps：
1) using any one in wheat and rice straw as raw material, after crushed, the stalk powder of 60-120 mesh is collected, is washed Wash, dry after it is spare；
2) using any one in oxalic acid, malonic acid, succinic acid and citric acid as organically-modified reagent, using water as solvent, configuration Concentration range is the aqueous solution of 0.5-2.0 mol/L, is denoted as solution A；Using any one in calcium chloride or calcium nitrate to be inorganic Modifying agent prepares the ionic calcium soln of calcium ion concentration range 0.1-1.0mol/L, is denoted as solution B；
3) 5g stalks are weighed, with 100ml solution As in 105-135 oC, constant temperature is stirred at reflux reaction 3-12h, after natural filtration, Liquid phase is denoted as modified filtrate I, is stored for future use after organic acid content detects；Solid phase and 0.2 mol/L Na of 50ml2CO3Solution room Temperature stirring 1h, products obtained therefrom is filtered, after washing, in 80oIt is spare after C freeze-day with constant temperature 12h, it is denoted as organically-modified stalk；
4) step 3）The middle organically-modified stalk of gained puts into 100 mL steps 2）In solution B, be stirred to react 2- at room temperature 6h, after suction filtration, filtrate is denoted as modified filtrate II, is stored for future use after calcium ion concentration detects；By solid phase in 80oC constant temperature is done Organic-inorganic composite modified straw is obtained after dry 12h.
2. the preparation method of Organic-inorganic composite modified straw dephosphorization sorbing material as described in claim 1, it is characterised in that should Method further includes：It is supplemented respectively in modified filtrate II in modified filtrate I obtained by step 3) and step 4) a certain amount of organic Sour and a certain amount of calcium salt is configured to aqueous solution, according to step 2）-5 ）Repetitive operation is realized to modified filtrate I and modified filtrate II Recycling.
3. it is further removed using the Organic-inorganic composite modified straw dephosphorization sorbing material being prepared in claim 1 The method of phosphorus, it is characterised in that include the following steps：
0.1g Organic-inorganic composite modified straws are weighed, with NaH2PO4Solution, room temperature concussion absorption 12h, measures in conical flask The phosphorus saturated extent of adsorption of sorbing material.
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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN109225153A (en) * 2018-10-22 2019-01-18 北京科技大学 The preparation and its application method of the adsorbent material of trace amounts of phosphorus in a kind of removing water
CN109553171A (en) * 2019-01-04 2019-04-02 湖南科技大学 Charcoal flocculant and its preparation method and application

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