CN107159151A - The preparation method of modified expanded rice husk spheroid sorbing material - Google Patents
The preparation method of modified expanded rice husk spheroid sorbing material Download PDFInfo
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- CN107159151A CN107159151A CN201710542572.6A CN201710542572A CN107159151A CN 107159151 A CN107159151 A CN 107159151A CN 201710542572 A CN201710542572 A CN 201710542572A CN 107159151 A CN107159151 A CN 107159151A
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- rice husk
- modified
- expanded rice
- sorbing material
- expanded
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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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- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention discloses a kind of preparation method for being modified expanded rice husk spheroid sorbing material, including：Natural rice husk cleaning is taken to remove impurity, grinding and sieving is sieved, and then adds alkaline solution, is stirred, and filtration drying obtains modified natural rice husk；By modified natural rice husk and sodium carbonate liquor, bulking machine, control bulking machine feeding temperature and drop temperature are added, the expanding treatment of natural rice husk is modified, sieving classification process is then carried out, dries, obtains being modified expanded rice husk；Modified expanded rice husk is added into disc-type granulating machine to be granulated, while adding crosslinking agent, expanded rice husk granulation processing is modified, modified expanded rice husk sorbing material is made.In the present invention after the modified expanded modified group of making of rice husk spheroid sorbing material, the new sorbing material with Adsorption of Heavy Metals copper-lead zinc is made, is had a good application prospect in terms of the water process in the fields such as mine wastewater processing, metallurgical liquid waste processing, the processing of heavy metal-containing polluted water.
Description
Technical field
The invention belongs to the biological material utilization of resources and composite adsorbing material technical field, it is related to a kind of modified expanded rice
The preparation method and application of shell spheroid sorbing material.It is particularly suitable for use in biomass modified technology and the application of spheroid sorbing material etc..
Background technology
Expanded rice husk cellulose is a kind of abundance, cheap and easy to get, biodegradable water-soluble fibre cellulosic biomass
Material, belongs to one kind of polyanion linear polymeric, and sodium carbonate is as a kind of alkali compounds, is that one kind has alkalescent
The compound of matter, its synthetic method is simple.The expanded rice husk spheroid sorbing material of modification of preparation have alkalescent, it is acidproof, in height
There is enough stability and corrosion-resistant grade under acid-base value system.Expanded rice husk cellulose is in sodium carbonate alkali compounds
Mode is fully swelled under effect, mutual supplement with each other's advantages, the effect of Synergistic is reached, so that the pelletizing mechanical property of materials formed increases
Plus, while having good adsorptivity.And between alkaline carbonic acid sodium swelling action causes between expanded rice husk cellulose macromolecular
Away from increasing, be conducive to more metal ions to diffuse into the inside of expanded rice husk cellulose, be conducive to more metals to enter
Row exchange adsorption, so as to add more adsorption sites, is combined the adsorbent for preparing high absorption property and is applied to ore deposit
The processing of smelting heavy metals element and extraction field, to solve current Expanded rice husk powder body hardly possible recovery, difficult separation, be difficult to work
The defect of industryization application, while the problem of can solving the wasting of resources that expanded rice husk macromolecule faces, develops renewable money
Source, development for high and new technology, realizes that resources sustainable development is significant.
At present, mainly there are chemical precipitation method, extraction, ion exchange for extracting the method for lead zinc-copper in mining and metallurgy waste water
Method, absorption method etc..Wherein, biomass absorbent method be reclaim trace heavy metal element most efficient method, with cost it is low, processing
Speed is fast, using the wide advantage of scope, but the restricting of its easy sorbent suspension, selectivity be not high.And based on biological material
The spheroidal adsorbent of preparation has the advantages that good selectivity, forming, stability height etc., therefore, studies such efficiently low
The novel biomass micro-sphere absorption material of cost, the finiteness and powder adsorbent of biological material adsorption capacity can be solved simultaneously
The problem of hardly possible separation etc..
The present invention passes through chemistry using expanded rice husk cellulose renewable resource most abundant, cheap and easy to get in nature
The expanded rice husk of itself and organic powder is combined by modified and physical modification prepares the compound dome sorbing material for extracting heavy metal, both
New thinking is provided to extract heavy metal element in mining and metallurgy waste water, and new way can be provided to develop biological material, is solved
Determine resource rational utilization and problem of environmental pollution, met the requirement of sustainable development, with larger use value and wide
Application prospect.
The content of the invention
It is an object of the invention to solve at least the above and/or defect, and provide at least will be described later excellent
Point.
In order to realize that there is provided the modified expanded rice husk spheroid absorption of one kind according to object of the present invention and further advantage
The preparation method of material, comprises the following steps：
Step 1: taking natural rice husk cleaning to remove impurity, grinding and sieving is sieved, then adds alkaline solution, stir
Mix after 1~3h of reaction, filtration drying, obtain modified natural rice husk；
Step 2: by modified natural rice husk and sodium carbonate liquor, adding bulking machine；Control moisture makes charging water content 10
~50%, control bulking machine feeding temperature is at 40~120 DEG C；Drop temperature control at 100~300 DEG C, pH controls 7~8 it
Between, the expanding treatment of natural rice husk is modified, sieving classification process is then carried out, in 30~60 DEG C of dry 8~30h, obtains
Modified expanded rice husk；
Granulated, while adding crosslinking agent, be modified Step 3: modified expanded rice husk is added into disc-type granulating machine
Expanded rice husk granulation processing, is made the expanded rice husk sorbing material of modification of 800 μm~10000 μm of particle diameter.
Preferably, in the step one, sieving uses the sieve of 80~500 mesh.
Preferably, the concentration of the step one neutral and alkali solution is 1~10wt%；The natural rice husk and alkaline solution
With weight ratio be 20:1~5:1；The alkaline solution is in sodium carbonate liquor, sodium bicarbonate solution and hydrated sodium carbonate solution
One kind.
Preferably, in the step 2, the concentration of sodium carbonate liquor is 1~10wt%；The modified natural rice husk with
Sodium carbonate liquor and weight ratio be 20:1~5:1；The alkaline solution is sodium carbonate liquor, sodium bicarbonate solution and hydration carbon
One kind in acid sodium solution.
Preferably, the crosslinking agent is any one in glutaraldehyde, epoxychloropropane, divinylsulfone；It is described to hand over
It is the 10~20% of modified expanded rice husk weight to join the addition of agent.
Preferably, the process in the step one is replaced with：Natural rice husk cleaning is taken to remove impurity, grinding and sieving is entered
Row screening, then, by weight, takes 20~30 parts of natural rice husks, 60~120 parts of alkaline solutions, the chloro- 2- hydroxypropyls of 5~10 parts of 3-
Base trimethyl ammonium chloride and 3~5 diallyldimethylammonium chlorides are placed in the sealing container with stirring, are then held the sealing
Device is placed in progress irradiation stir process in 1.5MeV, 30mA electron accelerator, then filters, and dries, and modified natural rice is made
Shell.By the modification of the process, rice husk is activated, and rice husk surface formation cellular is increased its specific surface area, day is added
The adsorption site of right rice husk, enhances its adsorption capacity to Trace Components in mining and metallurgy waste water.
Preferably, the radiation dose rate that uses of irradiating is 200~500kGy/h, irradiation dose for 1000~
2000kGy, mixing speed is 100~200r/min.
Preferably, the compound method of the alkaline solution is：By weight, 10~20 parts of weight are added in 100 parts of water
Than for 3:1 sodium carbonate and urea.
Preferably, procedure below is also included between the step 2 and step 3：By weight, filled in supercritical reaction
Put middle addition 20~30 parts of expanded rice husks of modification, 5~10 parts of itaconic anhydrides, 100~120 parts of DMAC N,N' dimethyl acetamides and 2~3
Part triethylamine, then seals system, stirs anti-under conditions of being passed through at carbon dioxide to 40~60MPa, 80~90 DEG C of temperature
Answer 5~6 hours, reacted material is cooled down, pressure release, filter, dried using microwave radiation, the modification being further modified
Expanded rice husk；Modified expanded rice husk is further modified by the process, makes to be modified expanded rice husk surface and further forms porous
Shape increases its specific surface area, further increases the adsorption site of modified expanded rice husk, further enhancing it to mining and metallurgy waste water
The adsorption capacity of middle Trace Components.
Preferably, the process of the microwave radiation drying is：Modified expanded rice husk is put into quartzy drier, then
It is placed in microwave radiation reacting furnace；Nitrogen is passed through with 80~120mL/min speed, the switch of microwave radiation reacting furnace is opened,
Microwave radiation drying process is carried out to precipitation, room temperature is cooled to after drying process, the expanded rice husk of the modification being further modified；
The condition of the microwave radiation drying process is：Microwave radiation frequencies are 2450 ± 50MHz, and microwave radiation unit power is 0.5
~1.5w/g, microwave irradiation time is 30~60min, and microwave radiation temperature is 50~60 DEG C.
For paper, " straw electromagnetic induction auxiliary heating extruding and puffing technology is ground the bulking machine used in the present invention
Study carefully,《Cellulose Science and technology》,2005,13(3):7-13 " or thesis for the doctorate " uranium and association heavy metal biological matter absorption green wood
The preparation and application research of material, Zhang Yongde, Beijing Non-Ferrous Metal Research General Academy, the bulking machine disclosed in 2016 ".
The present invention at least includes following beneficial effect：
(1) in the present invention after the modified expanded modified group of making of rice husk spheroid sorbing material, being made has high Adsorption of Heavy Metals
The new sorbing material of copper-lead zinc, can operate with the processing of the zinc waste water of copper-lead containing heavy metal；This adsorbent heavy metal has good
Selective adsorption.
(2) the expanded rice husk spheroid sorbing material of modification of the invention has pelletizing size controllability, regular shape, Ke Yitong
Cross control mixed sols concentration, comminutor rotating speed and be controlled spherical size.The complex spherical adsorbent of preparation is easy to from carrying
Take in heavy metal and separate, the problem of solving adsorbent hardly possible separation.
(3) what the present invention was provided a kind of be modified expanded rice husk spheroid sorbing material and have inexpensive cost, good machinery
Stability, good selectivity can be repeatedly used, thus be can be widely applied to heavy metal containing wastewater treatment, extracted metal
In terms of.
(4) preparation method of the present invention is simple to operate, efficiency high, and preparation technology is simple, and practical, cost is low, made
Adsorbent is a kind of environment-friendly material.Therefore, with good economic benefit and popularizing application prospect.
Further advantage, target and the feature of the present invention embodies part by following explanation, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Brief description of the drawings：
Fig. 1 is the scanning electron microscope (SEM) photograph of the expanded rice husk sorbing material of modification prepared by the embodiment of the present invention 3.
Embodiment：
The present invention is described in further detail below in conjunction with the accompanying drawings, to make those skilled in the art with reference to specification text
Word can be implemented according to this.
It should be appreciated that such as " having ", "comprising" and " comprising " term used herein do not allot one or many
The presence or addition of individual other elements or its combination.
Embodiment 1：
A kind of preparation method for being modified expanded rice husk spheroid sorbing material, comprises the following steps：
Step 1: taking natural rice husk cleaning to remove impurity, the sieve that 100 mesh are crossed after crushing is sieved, and is then added
After 1wt% sodium carbonate liquor, stirring reaction 1h, filtration drying obtains modified natural rice husk；The natural rice husk and sodium carbonate
The weight ratio of solution is 20:1；
Step 2: by modified natural rice husk and 1wt% sodium carbonate liquor, adding bulking machine；Control moisture contains charging
Water is 10%, and control bulking machine feeding temperature is at 40 DEG C；Drop temperature control is at 100 DEG C, and pH is controlled 7, is modified day
The expanding treatment of right rice husk, then carries out sieving classification process, in 30 DEG C of dry 30h, obtains being modified expanded rice husk；The modification
Natural rice husk and sodium carbonate liquor and weight ratio be 20:1；
Granulated, while adding crosslinking agent glutaraldehyde, entered Step 3: modified expanded rice husk is added into disc-type granulating machine
The modified expanded rice husk granulation processing of row, is made the expanded rice husk sorbing material of modification of 800 μm~10000 μm of particle diameter；The crosslinking
The addition of agent glutaraldehyde is the 10% of modified expanded rice husk weight.
Embodiment 2：
A kind of preparation method for being modified expanded rice husk spheroid sorbing material, comprises the following steps：
Step 1: taking natural rice husk cleaning to remove impurity, the sieve that 80 mesh are crossed after crushing is sieved, and is then added
After 10wt% sodium carbonate liquor, stirring reaction 3h, filtration drying obtains modified natural rice husk；The natural rice husk and carbonic acid
The weight ratio of sodium solution is 5:1；
Step 2: by modified natural rice husk and 1wt% sodium carbonate liquor, adding bulking machine；Control moisture contains charging
Water is 50%, and control bulking machine feeding temperature is at 120 DEG C；Drop temperature control is at 300 DEG C, and pH is controlled 7, is modified day
The expanding treatment of right rice husk, then carries out sieving classification process, in 60 DEG C of dry 8h, obtains being modified expanded rice husk；The modification
Natural rice husk and sodium carbonate liquor and weight ratio be 5:1；
Granulated, while adding crosslinking agent glutaraldehyde, entered Step 3: modified expanded rice husk is added into disc-type granulating machine
The modified expanded rice husk granulation processing of row, is made the expanded rice husk sorbing material of modification of 800 μm~10000 μm of particle diameter；The crosslinking
The addition of agent glutaraldehyde is the 20% of modified expanded rice husk weight.
Embodiment 3：
A kind of preparation method for being modified expanded rice husk spheroid sorbing material, comprises the following steps：
Step 1: taking natural rice husk cleaning to remove impurity, the sieve that 6mm is crossed after crushing is sieved, and then adds 5wt%
Sodium carbonate liquor, after stirring reaction 2h, filtration drying obtains modified natural rice husk；The natural rice husk and sodium carbonate liquor
Weight ratio be 10:1；
Step 2: by modified natural rice husk and 5wt% sodium carbonate liquor, adding bulking machine；Control moisture contains charging
Water is 30%, and control bulking machine feeding temperature is at 100 DEG C；Drop temperature control is at 200 DEG C, and pH is controlled 7, is modified day
The expanding treatment of right rice husk, then carries out sieving classification process, in 50 DEG C of dry 12h, obtains being modified expanded rice husk；The modification
Natural rice husk and sodium carbonate liquor and weight ratio be 10:1；
Granulated, while adding crosslinking agent glutaraldehyde, entered Step 3: modified expanded rice husk is added into disc-type granulating machine
The modified expanded rice husk granulation processing of row, is made the expanded rice husk sorbing material of modification of 800 μm~10000 μm of particle diameter；The crosslinking
The addition of agent glutaraldehyde is the 15% of modified expanded rice husk weight.
Embodiment 4：
A kind of preparation method for being modified expanded rice husk spheroid sorbing material, comprises the following steps：
Step 1: taking natural rice husk cleaning to remove impurity, the sieve that 6mm is crossed after crushing is sieved, and then adds 8wt%
Sodium bicarbonate solution, after stirring reaction 2h, filtration drying obtains modified natural rice husk；The natural rice husk and sodium acid carbonate
The weight ratio of solution is 10:1；
Step 2: by modified natural rice husk and 6wt% sodium bicarbonate solution, adding bulking machine；Control moisture makes charging
Water content is 40%, and control bulking machine feeding temperature is at 100 DEG C；Drop temperature control is at 250 DEG C, and pH is controlled 7, is modified
The expanding treatment of natural rice husk, then carries out sieving classification process, in 50 DEG C of dry 12h, obtains being modified expanded rice husk；It is described to change
Property natural rice husk and sodium carbonate liquor and weight ratio be 10:1；
Granulated Step 3: modified expanded rice husk is added into disc-type granulating machine, while adding crosslinking agent epoxy chloropropionate
Alkane, is modified expanded rice husk granulation processing, the expanded rice husk sorbing material of modification of 800 μm~10000 μm of particle diameter is made；It is described
The addition of crosslinking agent epoxychloropropane is the 12% of modified expanded rice husk weight.
Embodiment 5：
Process in the step one is replaced with：Natural rice husk cleaning is taken to remove impurity, grinding and sieving is sieved, so
Afterwards, by weight, 25 parts of natural rice husks, 100 parts of alkaline solutions, 8 parts of 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides and 4 diene are taken
Diallyidimethylammonium chloride is placed in the sealing container with stirring, and then the sealing container is placed in 1.5MeV, 30mA electronics
Irradiation stir process is carried out in accelerator, is then filtered, is dried, modified natural rice husk is made；The irradiation agent that the irradiation is used
Dose rate is 200kGy/h, and irradiation dose is 1400kGy, and mixing speed is 150r/min；The compound method of the alkaline solution is：
By weight, it is 3 that 15 parts of weight ratios are added in 100 parts of water:1 sodium carbonate and urea.
Remaining technological parameter and method with it is identical in embodiment 3.
Embodiment 6：
Process in the step one is replaced with：Natural rice husk cleaning is taken to remove impurity, grinding and sieving is sieved, so
Afterwards, by weight, 30 parts of natural rice husks, 120 parts of alkaline solutions, 8 parts of 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides and 5 diene are taken
Diallyidimethylammonium chloride is placed in the sealing container with stirring, and then the sealing container is placed in 1.5MeV, 30mA electronics
Irradiation stir process is carried out in accelerator, is then filtered, is dried, modified natural rice husk is made；The irradiation agent that the irradiation is used
Dose rate is 500kGy/h, and irradiation dose is 2000kGy, and mixing speed is 150r/min；The compound method of the alkaline solution is：
By weight, it is 3 that 20 parts of weight ratios are added in 100 parts of water:1 sodium carbonate and urea.
Remaining technological parameter and method with it is identical in embodiment 3.
Embodiment 7：
Also include procedure below between the step 2 and step 3：By weight, added in supercritical reaction apparatus
25 parts of expanded rice husks of modification, 10 parts of itaconic anhydrides, 100 parts of DMAs and 2 parts of triethylamines, it is then that system is close
Envelope, stirring reaction 5 hours, reacted material is cooled down, let out under conditions of being passed through at carbon dioxide to 60MPa, 80 DEG C of temperature
Pressure, filtering, is dried, the expanded rice husk of the modification being further modified using microwave radiation；
The process that the microwave radiation is dried is：Modified expanded rice husk is put into quartzy drier, microwave is subsequently placed in
In radioreaction stove；Nitrogen is passed through with 80mL/min speed, the switch of microwave radiation reacting furnace is opened, microwave is carried out to precipitation
Radiant drying processing, is cooled to room temperature, the expanded rice husk of the modification being further modified after drying process；The microwave radiation is done
The condition of dry processing is：Microwave radiation frequencies are 2450 ± 50MHz, and microwave radiation unit power is 1w/g, microwave irradiation time
For 60min, microwave radiation temperature is 60 DEG C.
Remaining technological parameter and method with it is identical in embodiment 3.
Embodiment 8：
Also include procedure below between the step 2 and step 3：By weight, added in supercritical reaction apparatus
30 parts of expanded rice husks of modification, 8 parts of itaconic anhydrides, 120 parts of DMAs and 3 parts of triethylamines, then seal system,
Stirring reaction 5 hours, reacted material is cooled down, pressure release under conditions of being passed through at carbon dioxide to 50MPa, 90 DEG C of temperature,
Filtering, is dried, the expanded rice husk of the modification being further modified using microwave radiation；
The process that the microwave radiation is dried is：Modified expanded rice husk is put into quartzy drier, microwave is subsequently placed in
In radioreaction stove；Nitrogen is passed through with 80mL/min speed, the switch of microwave radiation reacting furnace is opened, microwave is carried out to precipitation
Radiant drying processing, is cooled to room temperature, the expanded rice husk of the modification being further modified after drying process；The microwave radiation is done
The condition of dry processing is：Microwave radiation frequencies are 2450 ± 50MHz, and microwave radiation unit power is 1.5w/g, during microwave radiation
Between be 50min, microwave radiation temperature be 60 DEG C.
Remaining technological parameter and method with it is identical in embodiment 3.
Embodiment 9：
Also include procedure below between the step 2 and step 3：By weight, added in supercritical reaction apparatus
20 parts of expanded rice husks of modification, 10 parts of itaconic anhydrides, 100 parts of DMAs and 2.5 parts of triethylamines, it is then that system is close
Envelope, stirring reaction 6 hours, reacted material is cooled down, let out under conditions of being passed through at carbon dioxide to 60MPa, 80 DEG C of temperature
Pressure, filtering, is dried, the expanded rice husk of the modification being further modified using microwave radiation；
The process that the microwave radiation is dried is：Modified expanded rice husk is put into quartzy drier, microwave is subsequently placed in
In radioreaction stove；Nitrogen is passed through with 100mL/min speed, the switch of microwave radiation reacting furnace is opened, precipitation is carried out micro-
Room temperature is cooled to after wave radiation drying process, drying process, the expanded rice husk of the modification being further modified；The microwave radiation
The condition of drying process is：Microwave radiation frequencies are 2450 ± 50MHz, and microwave radiation unit power is 0.5w/g, microwave radiation
Time is 60min, and microwave radiation temperature is 50 DEG C.
Remaining technological parameter and method with it is identical in embodiment 5.
Embodiment 10：
Also include procedure below between the step 2 and step 3：By weight, added in supercritical reaction apparatus
30 parts of expanded rice husks of modification, 5 parts of itaconic anhydrides, 120 parts of DMAs and 3 parts of triethylamines, then seal system,
Stirring reaction 5 hours, reacted material is cooled down, pressure release under conditions of being passed through at carbon dioxide to 55MPa, 90 DEG C of temperature,
Filtering, is dried, the expanded rice husk of the modification being further modified using microwave radiation；
The process that the microwave radiation is dried is：Modified expanded rice husk is put into quartzy drier, microwave is subsequently placed in
In radioreaction stove；Nitrogen is passed through with 120mL/min speed, the switch of microwave radiation reacting furnace is opened, precipitation is carried out micro-
Room temperature is cooled to after wave radiation drying process, drying process, the expanded rice husk of the modification being further modified；The microwave radiation
The condition of drying process is：Microwave radiation frequencies are 2450 ± 50MHz, and microwave radiation unit power is 1w/g, during microwave radiation
Between 40min, microwave radiation temperature be 50 DEG C.
Remaining technological parameter and method with it is identical in embodiment 6.
It is dense that the expanded rice husk spheroid sorbing material 0.05g of modification for taking above-described embodiment 1~10 to prepare is added separately to 100mL
Spend in the copper for 20mg/L, lead, zinc ion solution, the pH value for adjusting solution (is found through experiments that when pH value is 4, absorption to 4
Effect is best)；Shaking table vibration 2h is placed in, rotating speed is 150rpm, and adsorption temp is 25 DEG C；Suction is measured with flame atomic absorption spectrometry
Copper, lead, the concentration of zinc ion in attached front and rear solution；And clearance is calculated with below equation (1), as a result as shown in table 1~3：
Wherein, Re% is clearance, and C0 is the concentration of ion before absorption, and Ce is the concentration of ion after adsorption equilibrium.
Table 1：To copper absorption effect
| Embodiment | 1 | 2 | 3 | 4 | 5 |
| Clearance (%) | 92.5 | 92.7 | 92.8 | 92.4 | 97.5 |
| Embodiment | 6 | 7 | 8 | 9 | 10 |
| Clearance (%) | 97.6 | 98.8 | 98.7 | 99.6 | 99.5 |
Table 2：To lead ion adsorption effect
| Embodiment | 1 | 2 | 3 | 4 | 5 |
| Clearance (%) | 91.3 | 91.6 | 91.7 | 91.5 | 96.6 |
| Embodiment | 6 | 7 | 8 | 9 | 10 |
| Clearance (%) | 96.5 | 97.5 | 97.8 | 98.8 | 98.9 |
Table 3：To zinc ion adsorption effect
| Embodiment | 1 | 2 | 3 | 4 | 5 |
| Clearance (%) | 93.3 | 93.5 | 93.6 | 93.4 | 97.8 |
| Embodiment | 6 | 7 | 8 | 9 | 10 |
| Clearance (%) | 97.9 | 98.9 | 99.2 | 99.7 | 99.8 |
It was found from table 1~3, embodiment 1~10 as a result of the raw material and technique in proportion of the present invention, its
Preferable to the adsorption effect of copper, lead, zinc ion, clearance is all higher than 91%, and by the process in embodiment 5~6 to day
Right rice husk carries out pretreatment modification, by the modification of the process, and adsorption effect is apparently higher than unmodified natural rice husk, the process
Rice husk has been activated, and rice husk surface is formed cellular and has increased its specific surface area, the adsorption site of natural rice husk has been added, increases
Its strong adsorption capacity to Trace Components in mining and metallurgy waste water.By further changing to modified expanded rice husk in embodiment 7~8
Property, its adsorption effect makes to be modified expanded rice husk surface and further formed apparently higher than unmodified natural rice husk by the process
Cellular increases its specific surface area, further increases the adsorption site of modified expanded rice husk, further enhancing it to mining and metallurgy
The adsorption capacity of Trace Components in waste water.
It can be seen that, the raw material that uses is in the ratio in the present invention, and in the preparation process of sorbing material, each
Parameter is in described scope, and the sorbing material of preparation is preferable to the absorption property of copper, lead, zinc ion.
Although embodiment of the present invention is disclosed as above, it is not restricted in specification and embodiment listed
With it can be applied to various suitable the field of the invention completely, can be easily for those skilled in the art
Other modification is realized, therefore under the universal limited without departing substantially from claim and equivalency range, the present invention is not limited
In specific details and shown here as the legend with description.
Claims (10)
1. a kind of preparation method for being modified expanded rice husk spheroid sorbing material, it is characterised in that comprise the following steps：
Step 1: taking natural rice husk cleaning to remove impurity, grinding and sieving is sieved, and then adds alkaline solution, and stirring is anti-
Answer after 1~3h, filtration drying, obtain modified natural rice husk；
Step 2: by modified natural rice husk and sodium carbonate liquor, adding bulking machine；Control moisture make charging water content 10~
50%, control bulking machine feeding temperature is at 40~120 DEG C；Drop temperature control is at 100~300 DEG C, and pH is controlled between 7~8,
The expanding treatment of natural rice husk is modified, sieving classification process is then carried out, in 30~60 DEG C of dry 8~30h, is modified
Expanded rice husk；
Granulated, while adding crosslinking agent, be modified expanded Step 3: modified expanded rice husk is added into disc-type granulating machine
Rice husk granulation is handled, and the expanded rice husk sorbing material of modification of 800 μm~10000 μm of particle diameter is made.
2. the preparation method of expanded rice husk spheroid sorbing material is modified as claimed in claim 1, it is characterised in that the step
In one, sieving uses the sieve of 80~500 mesh.
3. the preparation method of expanded rice husk modified absorbing material as claimed in claim 1, it is characterised in that in the step one
The concentration of alkaline solution is 1~10wt%；The natural rice husk and alkaline solution and weight ratio be 20:1~5:1；The alkali
Property solution be sodium carbonate liquor, sodium bicarbonate solution and hydrated sodium carbonate solution in one kind.
4. the preparation method of expanded rice husk spheroid sorbing material is modified as claimed in claim 1, it is characterised in that the step
In two, the concentration of sodium carbonate liquor is 1~10wt%；The modified natural rice husk and sodium carbonate liquor and weight ratio be 20:1
~5:1；The sodium carbonate liquor replaces with one kind in sodium bicarbonate solution and hydrated sodium carbonate solution.
5. the preparation method of expanded rice husk spheroid sorbing material is modified as claimed in claim 1, it is characterised in that the crosslinking
Agent is any one in glutaraldehyde, epoxychloropropane, divinylsulfone；The addition of the crosslinking agent is modified expanded rice husk
The 10~20% of weight.
6. the preparation method of expanded rice husk spheroid sorbing material is modified as claimed in claim 1, it is characterised in that the step
Process in one is replaced with：Natural rice husk cleaning is taken to remove impurity, grinding and sieving is sieved, and then, by weight, takes 20
~30 parts of natural rice husks, 60~120 parts of alkaline solutions, 5~10 parts of 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides and 3~5 two allyls
Base alkyl dimethyl ammonium chloride is placed in the sealing container with stirring, and the electronics that the sealing container then is placed in into 1.5MeV, 30mA adds
Irradiation stir process is carried out in fast device, is then filtered, is dried, modified natural rice husk is made.
7. the preparation method of expanded rice husk spheroid sorbing material is modified as claimed in claim 6, it is characterised in that the irradiation
The radiation dose rate used is 200~500kGy/h, and irradiation dose is 1000~2000kGy, and mixing speed is 100~200r/
min。
8. expanded rice husk spheroid sorbing material preparation method is modified as claimed in claim 6, it is characterised in that the alkalescence is molten
The compound method of liquid is：By weight, it is 3 that 10~20 parts of weight ratios are added in 100 parts of water:1 sodium carbonate and urea.
9. the preparation method of expanded rice husk spheroid sorbing material is modified as claimed in claim 1, it is characterised in that the step
Also include procedure below between two and step 3：By weight, 20~30 parts of modifications are added in supercritical reaction apparatus expanded
Rice husk, 5~10 parts of itaconic anhydrides, 100~120 parts of DMAs and 2~3 parts of triethylamines, then seal system,
Stirring reaction 5~6 hours under conditions of being passed through at carbon dioxide to 40~60MPa, 80~90 DEG C of temperature, by reacted material
Cooling, pressure release, filtering is dried, the expanded rice husk of the modification being further modified using microwave radiation.
10. the preparation method of expanded rice husk spheroid sorbing material is modified as claimed in claim 9, it is characterised in that described micro-
Wave radiation dry process be：Modified expanded rice husk is put into quartzy drier, is subsequently placed in microwave radiation reacting furnace；With
80~120mL/min speed is passed through nitrogen, opens the switch of microwave radiation reacting furnace, and precipitation is carried out at microwave radiation drying
Reason, is cooled to room temperature, the expanded rice husk of the modification being further modified after drying process；The bar of the microwave radiation drying process
Part is：Microwave radiation frequencies are 2450 ± 50MHz, and microwave radiation unit power is 0.5~1.5w/g, and microwave irradiation time is 30
~60min, microwave radiation temperature is 50~60 DEG C.
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