CN110465266A - Threonine is modified montmorillonite used, preparation method and applications - Google Patents

Threonine is modified montmorillonite used, preparation method and applications Download PDF

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Publication number
CN110465266A
CN110465266A CN201810450221.7A CN201810450221A CN110465266A CN 110465266 A CN110465266 A CN 110465266A CN 201810450221 A CN201810450221 A CN 201810450221A CN 110465266 A CN110465266 A CN 110465266A
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montmorillonite
threonine
modified
preparation
montmorillonite used
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王风云
廖川
夏明珠
雷武
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Nanjing Tech University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/285Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

Modified montmorillonite used, preparation method and applications that the invention discloses a kind of threonines.The method first carries out the pretreatments such as sour modification, dried and screened to raw material na-montmorillonite, then modifying agent threonine is soluble in water and adjust pH be 3~5, pretreated sour modified na-montmorillonite is added, it is stirred to react under room temperature, finally it is modified montmorillonite used to obtain threonine for suction filtration, washing, drying and sieving.The modified obtained montmorillonite of the present invention is as adsorbent, there is good adsorption capacity to metal ions such as Pb (II), Cu (II) in water, saturated extent of adsorption can respectively reach 120mg/g and 30mg/g, have a good application prospect in effluent containing heavy metal ions process field.

Description

Threonine is modified montmorillonite used, preparation method and applications
Technical field
The present invention relates to a kind of amino-acid modified montmorillonites, preparation method and applications, belong to modified mineral adsorbing material Preparation and technical field of heavy metal wastewater treatment.
Background technique
Battery manufacture industry, metallurgy industry involved in electronic manufacture and the daily vehicle spray painting involved in, plating Etc. industries can all produce a large amount of heavy metal-containing waste water.Heavy metal due to can not be decomposed by animal body, with biological chain into Row has extremely strong organism enrichment effect, once into human body, nervous system and liver of the meeting to human body under long-term accumulation Kidney and other organs cause serious harm.
The method of conventional process heavy metal-containing waste water include membrane separation process, chemical precipitation, ion-exchange, electrochemical process, Biological degradation method and absorption method.Wherein comprehensively consider from economical and practical, convenient, removal efficiency of operation etc., absorption method is mesh The preceding common method of industrial treatment heavy metal ion-containing waste water.
Montmorillonite is a kind of silicate mineral that nature is widely present, and layer structure possessed by it makes it have centainly Adsorbing metal ions ability.Its stratiform constituted mode is that one layer of alumina (Al- (O, OH)) octahedron is clipped in two layers of silicon oxygen (Si-O) in tetrahedron, octahedral and tetrahedral is connected using shared oxygen atom.Montmorillonite is mainly derived from swollen Moisten Tu Kuang, has the advantages that hydrophily, high temperature resistant, abundance and absorption property are good.Compared to industrial common activity The price of carbon adsorbent, montmorillonite is cheaper, and compared to bentonite, montmorillonite is as its effective ingredient, and natural purity is more High montmorillonite absorption property is more outstanding.
Although having had the preparation and application study of some modified mineral soil at present, all in place of Shortcomings.As in Modified alta-mud is prepared as modifying agent by using 18,16 tertiary amines in state patent CN03964453A, but lacks corresponding Application study, and preparation process use a large amount of organic solvents, preparation spend it is higher.Patent application CN106031858A is only right Montmorillonite has carried out sour processing, does not use remaining special modifying agent, has reached 92% to the removal rate of dyeing waste water.Patent Apply for that CN105664838A is 120ug/m in mercury concentration using pillared montmorillonite as the mercury in absorption exhaust gas3When, demercuration Efficiency is 98%, but the poor dispersion of inorganic modified montmorillonite in water, and is related to calcination process, and energy consumption is larger.
Summary of the invention
The purpose of the present invention is to provide the high threonine of a kind of favorable dispersibility, high temperature resistant, heavy metal adsorption rate is modified Montmorillonite, preparation method and applications.
To achieve the above object, technical scheme is as follows:
The modified montmorillonite used preparation method of threonine, the specific steps are as follows:
Step 1, na-montmorillonite powder is added to the water, dropwise addition salt acid for adjusting pH to 4~6, and stirring at normal temperature 12~for 24 hours, it takes out Filter, drying and sieving, obtain sour modified na-montmorillonite;
It step 2, is 0.153~0.229 times of na-montmorillonite sun by the mass ratio of threonine and sour modified na-montmorillonite Ion exchange capacity: 1, by threonine stirring and dissolving Yu Shuizhong, adjusting pH value of solution is 3~5, and sour modified na-montmorillonite powder is added End is stirred at room temperature, is filtered, and is washed, and drying is ground up, sieved, it is modified montmorillonite used to obtain threonine.
Preferably, in step 1, the cation exchange capacity of the na-montmorillonite is 70~110mmoL/100g.
Preferably, in step 1 and 2, sieving condition be 100~200 meshes, more preferably 200 meshes.
Preferably, in step 1 and 2, the drying temperature is 70~80 DEG C.
Preferably, in step 1, the mass volume ratio of the na-montmorillonite and hydrochloric acid solution is 15~20:1, g:L.
Preferably, the mass ratio of the threonine and sour modified na-montmorillonite be 0.191 times of na-montmorillonite sun from Sub- exchange capacity: 1.
The present invention also provides threonine made from above-mentioned preparation method is modified montmorillonite used
Further, the present invention provides above-mentioned threonine modified montmorillonite used answering in absorption heavy metal ion-containing waste water With.
Compared with prior art, the present invention having the advantage that
(1) raw material of the present invention is that natural minerals soil, cheap and easy to get, abundance, and the special construction of itself make its tool There is the ability of adsorbing metal ions;
(2) the modifying agent threonine that the present invention selects is a kind of substance with mating capability itself, and modified insertion is covered de- After between rock layers, adsorbent can be reinforced to a certain extent to the adsorption capacity and stability of metal ion, absorption containing Pb (II), The saturated extent of adsorption of the metal ions waste water such as Cu (II) can respectively reach 120 and 30mg/g, and comparing unmodified montmorillonite has very Big raising has a good application prospect in effluent containing heavy metal ions process field.
Detailed description of the invention
Fig. 1 is the modified montmorillonite used XRD characterization figure of na-montmorillonite and different modifying agent dosages;
Fig. 2 is na-montmorillonite and modified montmorillonite used FT-IR phenogram;
Fig. 3 is the modified montmorillonite used adsorbance variation diagram to lead in solution and copper of different modifying agent dosages;
Fig. 4 be the dosage of threonine be one times of base cationic exchange capacity it is modified montmorillonite used to lead adsorption in water with The variation diagram of pH value of solution and initial concentration;
Fig. 5 be the dosage of threonine be one times of base cationic exchange capacity it is modified montmorillonite used to polluted by copper amount in water with The variation diagram of pH value of solution and initial concentration;
The SEM scanning electron microscope (SEM) photograph of Fig. 6 na-montmorillonite;
Fig. 7 is the modified montmorillonite used SEM scanning electron microscope (SEM) photograph that the dosage of threonine is one times of base cationic exchange capacity.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
Embodiment 1
The modified montmorillonite used preparation method of threonine, comprising the following steps:
(1) pretreatment of na-montmorillonite: na-montmorillonite powder is distributed in the hydrochloric acid solution that pH is 4, room temperature 12h is stirred, suspension is obtained by filtering, drying and grind, sieves with 100 mesh sieve.
(2) threonine is modified: by threonine stirring and dissolving that mole is 2.88mmoL in aqueous solution, modifying agent Soviet Union The mole of propylhomoserin is the 80% of montmorillonite cation exchange capacity, adjusts pH value of solution to 5, then takes sodium base obtained by step (1) Montmorillonite powder 4g is distributed in the aqueous solution of 200mL, is stirred, and reaction is stirred at room temperature for 24 hours, is filtered, distilled water Washing, drying and grinding, finally sieve with 100 mesh sieve, the modified montmorillonite used finished product of threonine can be obtained.
Embodiment 2
The modified montmorillonite used preparation method of threonine, comprising the following steps:
(1) pretreatment of na-montmorillonite: na-montmorillonite powder is distributed in the hydrochloric acid solution that pH is 6, room temperature 12h is stirred, suspension is obtained by filtering, drying and grind, sieves with 100 mesh sieve.
(2) threonine is modified: by threonine stirring and dissolving that mole is 2.88mmoL in aqueous solution, modifying agent Soviet Union The mole of propylhomoserin is the 80% of montmorillonite cation exchange capacity, adjusts pH value of solution to 5, then takes sodium base obtained by step (1) Montmorillonite powder 4g is distributed in the aqueous solution of 200mL, is stirred, and reaction is stirred at room temperature for 24 hours, is filtered, distilled water Washing, drying and grinding, finally sieve with 100 mesh sieve, the modified montmorillonite used finished product of threonine can be obtained.
Embodiment 3
The modified montmorillonite used preparation method of threonine, comprising the following steps:
(1) pretreatment of na-montmorillonite: na-montmorillonite powder is distributed in the hydrochloric acid solution that pH is 6, room temperature Stirring for 24 hours, obtains suspension by filtering, drying and grind, sieves with 100 mesh sieve.
(2) threonine is modified: by threonine stirring and dissolving that mole is 2.88mmoL in aqueous solution, modifying agent Soviet Union The mole of propylhomoserin is the 80% of montmorillonite cation exchange capacity, adjusts pH value of solution to 5, then takes sodium base obtained by step (1) Montmorillonite powder 4g is distributed in the aqueous solution of 200mL, is stirred, and reaction is stirred at room temperature for 24 hours, is filtered, distilled water Washing, drying and grinding, finally sieve with 100 mesh sieve, the modified montmorillonite used finished product of threonine can be obtained.
Embodiment 4
The modified montmorillonite used preparation method of threonine, comprising the following steps:
(1) pretreatment of na-montmorillonite: na-montmorillonite powder is distributed in the hydrochloric acid solution that pH is 6, room temperature Stirring for 24 hours, obtains suspension by filtering, drying and grind, crosses 200 meshes.
(2) threonine is modified: by threonine stirring and dissolving that mole is 2.88mmoL in aqueous solution, modifying agent Soviet Union The mole of propylhomoserin is the 80% of montmorillonite cation exchange capacity, adjusts pH value of solution to 5, then takes sodium base obtained by step (1) Montmorillonite powder 4g is distributed in the aqueous solution of 200mL, is stirred, and reaction is stirred at room temperature for 24 hours, is filtered, distilled water Washing, drying and grinding, finally cross 200 meshes, the modified montmorillonite used finished product of threonine can be obtained.
Embodiment 5
The modified montmorillonite used preparation method of threonine, comprising the following steps:
(1) pretreatment of na-montmorillonite: na-montmorillonite powder is distributed in the hydrochloric acid solution that pH is 6, room temperature Stirring for 24 hours, obtains suspension by filtering, drying and grind, crosses 200 meshes.
(2) threonine is modified: by threonine stirring and dissolving that mole is 3.6mmoL in aqueous solution, modifying agent Soviet Union The mole of propylhomoserin is the 100% of montmorillonite cation exchange capacity, adjusts pH value of solution to 5, then takes sodium base obtained by step (1) Montmorillonite powder 4g is distributed in the aqueous solution of 200mL, is stirred, and reaction is stirred at room temperature for 24 hours, is filtered, distilled water Washing, drying and grinding, finally cross 200 meshes, the modified montmorillonite used finished product of threonine can be obtained.
Embodiment 6
The modified montmorillonite used preparation method of threonine, comprising the following steps:
(1) pretreatment of na-montmorillonite: na-montmorillonite powder is distributed in the hydrochloric acid solution that pH is 6, room temperature Stirring for 24 hours, obtains suspension by filtering, drying and grind, crosses 200 meshes.
(2) threonine is modified: by threonine stirring and dissolving that mole is 3.6mmoL in aqueous solution, modifying agent Soviet Union The mole of propylhomoserin is the 100% of montmorillonite cation exchange capacity, adjusts pH value of solution to 3, then takes sodium base obtained by step (1) Montmorillonite powder 4g is distributed in the aqueous solution of 200mL, is stirred, and reaction is stirred at room temperature for 24 hours, is filtered, distilled water Washing, drying and grinding, finally cross 200 meshes, the modified montmorillonite used finished product of threonine can be obtained.
Embodiment 7
The modified montmorillonite used preparation method of threonine, comprising the following steps:
(1) pretreatment of na-montmorillonite: na-montmorillonite powder is distributed in the hydrochloric acid solution that pH is 6, room temperature Stirring for 24 hours, obtains suspension by filtering, drying and grind, crosses 200 meshes.
(2) threonine is modified: by threonine stirring and dissolving that mole is 3.6mmoL in aqueous solution, modifying agent Soviet Union The mole of propylhomoserin is the 100% of montmorillonite cation exchange capacity, adjusts pH value of solution to 5, then takes sodium base obtained by step (1) Montmorillonite powder 3g is distributed in the aqueous solution of 200mL, is stirred, and reaction is stirred at room temperature for 24 hours, is filtered, distilled water Washing, drying and grinding, finally cross 200 meshes, the modified montmorillonite used finished product of threonine can be obtained.
The modified montmorillonite used adsorption experiment of 8 threonine of embodiment.
It is as shown in table 1 below that leaded or copper waste water removal rate is adsorbed using the sample that embodiment 1-7 is prepared:
Table 1
Embodiment 1 2 3 4 5 6 7
Lead 67.7% 70.8% 73.1% 76.3% 78.2% 72.6% 75.4%
Copper 48.3% 50.4% 52.0% 54.3% 55.6% 51.7% 53.6%
It is seen from the above data that absorption property obtains after carrying out acid appropriate to na-montmorillonite and being modified A degree of promotion, the subsequent amino-acid modified Soviet Union for further improving the performance of product, being prepared by this method The modified montmorillonite used metal ion in water of propylhomoserin has preferable removal rate.
The modified montmorillonite used adsorbance to lead in solution and copper of the different modifying agent dosages of embodiment 9 changes.
What integrated embodiment 4,5 etc. was prepared below is modified montmorillonite used for sample, and XRD and FITR analysis has been done to it, As shown in Figure 1, the interlamellar spacing of product has been increased to 1.56nm from 1.23nm, illustrates threonine after being modified using threonine Through entering the interlayer of montmorillonite.On the above basis, Fig. 2 is further confirmed, by having contained Soviet Union's ammonia in modified product Acid.Different modifying agent additional amounts influence the performance of product, and specific data are as shown in figure 3, when threonine dosage and acid are modified The mass ratio of na-montmorillonite is 0.191 times of cation exchange capacity: when 1, in the lead ion of 100mg/L and the copper of 100mg/L The adsorption effect of product is best in solion, has respectively reached 63mg/g and 29mg/g.
The modified montmorillonite used influence factor to lead or polluted by copper effect of 10 threonine of embodiment
For modified montmorillonite used made from the embodiment 5 below, different adsorption conditions are probed into the shadow of adsorbent adsorbance It rings.The pH value of lead solution or copper solution is first fixed, then by certain gradient change, its initial concentration obtains adsorbance curve, with The pH value for changing appeal solution afterwards is tested again, and it is as shown in Figure 4,5 that synthesis obtains a series of curves.It can from figure Out, modified montmorillonite used absorption property increases with the raising of solution ph, on the other hand, under the conditions of identical pH, changes Property product adsorbance first with solution ion concentration increase and increase rapidly, finally keep stablize.When pH value of solution is 5, The modified montmorillonite used optimal adsorption amount to lead and copper made from embodiment 5 can reach 120mg/g and 30mg/g respectively.

Claims (8)

1. the modified montmorillonite used preparation method of threonine, which is characterized in that specific step is as follows:
Step 1, na-montmorillonite powder is added to the water, dropwise addition salt acid for adjusting pH to 4~6, and stirring at normal temperature 12~for 24 hours, it filters, dries Dry and sieving, obtains sour modified na-montmorillonite;
It step 2, is 0.153~0.229 times of na-montmorillonite cation by the mass ratio of threonine and sour modified na-montmorillonite Exchange capacity: 1, by threonine stirring and dissolving Yu Shuizhong, adjusting pH value of solution is 3~5, sour modified na-montmorillonite powder is added, It stirs, filters at room temperature, wash, drying is ground up, sieved, it is modified montmorillonite used to obtain threonine.
2. preparation method according to claim 1, which is characterized in that in step 1, the cation of the na-montmorillonite Exchange capacity is 70~110mmoL/100g.
3. preparation method according to claim 1, which is characterized in that in step 1 and 2, sieving condition is 100~200 mesh Sieve, more preferably 200 meshes.
4. preparation method according to claim 1, which is characterized in that in step 1 and 2, the drying temperature be 70~ 80℃。
5. preparation method according to claim 1, which is characterized in that in step 1, the na-montmorillonite and hydrochloric acid are molten The mass volume ratio of liquid is 15~20:1, g:L.
6. preparation method according to claim 1, which is characterized in that the threonine and sour modified na-montmorillonite Mass ratio is 0.191 times of na-montmorillonite cation exchange capacity: 1.
7. threonine made from preparation method according to any one of claims 1 to 6 is modified montmorillonite used.
8. the modified montmorillonite used application in absorption heavy metal ion-containing waste water of threonine according to claim 7.
CN201810450221.7A 2018-05-11 2018-05-11 Threonine is modified montmorillonite used, preparation method and applications Pending CN110465266A (en)

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CN113797885A (en) * 2021-09-07 2021-12-17 广东省科学院生态环境与土壤研究所 Organic modified montmorillonite composite material and application thereof
CN114570327A (en) * 2022-03-01 2022-06-03 泰州医药城国科化物生物医药科技有限公司 Traditional Chinese medicine heavy metal removal method based on novel amino acid modified attapulgite

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Application publication date: 20191119