CN109395701A - The preparation method and application of a kind of molybdenum, N doping lignocellulosic composite Nano adsorbent material - Google Patents
The preparation method and application of a kind of molybdenum, N doping lignocellulosic composite Nano adsorbent material Download PDFInfo
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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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0218—Compounds of Cr, Mo, W
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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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- 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
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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
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Abstract
The present invention relates to the preparation methods and application of a kind of molybdenum, N doping lignocellulosic composite Nano adsorbent material, include the following steps: that (1) lignocellulosic is calcined under ammonia atmosphere, grind after natural cooling, obtain N doping lignocellulosic；(2) in deionized water by ammonium molybdate dissolution, it is configured to solution I；(3) thioacetamide dissolution in deionized water, is configured to solution II；(4) solution I is mixed well with solution II, is configured to solution III；(5) N doping lignocellulosic is added to solution III, stirs to get solution IV；(6) solution IV is transferred to autoclave, pyroreaction；(7) after the solution IV of pyroreaction is cooling, reaction product is centrifuged, molybdenum, N doping lignocellulosic composite Nano adsorbent material are obtained.Through the invention, the molybdenum, N doping lignocellulosic composites have good adsorption effect to Cr VI, its absorption property is held essentially constant after test is repeated several times, with good stability.
Description
Technical field
The present invention relates to the preparation methods and application of a kind of molybdenum, N doping lignocellulosic composite Nano adsorbent material, belong to
In molybdenum, N doping lignocellulosic composite Nano technical field of adsorption material preparation.
Background technique
The traditional treatment method of chromate waste water is more, and common processing method mainly includes absorption method, ion-exchange, change
Learn the precipitation method, membrane separation process etc., wherein absorption method because its is easy to operate, small investment, high treating effect be acknowledged as it is most effective
One of method.Adsorbent species are various, and there are commonly active carbons, can adsorb contents of many kinds of heavy metal ion, adsorption capacity simultaneously
Greatly, but service life is short, needs regeneration, operating cost high.Therefore, the exploitation of new adsorbent has highly important with application
Meaning.The nano materials such as magnetic nano-particle, metallic compound are because of its large specific surface area, activity height and desorption process simplicity etc.
Advantage receives significant attention, and is successfully applied in the removal process of the heavy metal ion such as Hg, Cr, Pb, As.
Molybdenum disulfide is one of a kind of common sulfide, and popular adsorbent.Lignocellulosic is also a kind of common
Carbon material.Molybdenum dioxide and modified lignocellulosic is compound, its absorption to hexavalent chromium in water body can be improved
Ability,.Therefore, by molybdenum disulfide and modified lignocellulosic is compound will develop good Cr VI adsorbent.
Summary of the invention
It is an object of the present invention to overcome problems of the prior art, a kind of molybdenum, N doping lignocellulosic are provided
The preparation method and application of composite Nano adsorbent material, and in particular to molybdenum, N doping lignocellulosic composite Nano adsorbent material
Preparation method and adsorption technology, this compound have excellent absorption property.
The object of the present invention is achieved like this, the system of a kind of molybdenum, N doping lignocellulosic composite Nano adsorbent material
Preparation Method, which comprises the steps of:
(1) lignocellulosic is calcined under ammonia atmosphere, is ground after natural cooling, obtain N doping lignocellulosic；
(2) ammonium molybdate of 0.1~1mmol is dissolved in the deionized water of 10~100mL, is configured to solution I；
(3) 5~10mmol thioacetamide is dissolved in the deionized water of 10~50mL, is configured to solution II；
(4) solution I and solution II are mixed well, is configured to solution III；
(5) N doping lignocellulosic is added in solution III, is uniformly mixing to obtain solution IV；
(6) solution IV is transferred in autoclave, pyroreaction；
(7) after the solution of pyroreaction IV is cooling, step (6) reaction product is centrifuged, collects precipitating, point
Not Yong deionized water, washes of absolute alcohol, by the reaction product after cleaning be placed in baking oven dry overnight to get molybdenum, N doping
Lignocellulosic composite Nano adsorbent material.
In step (1), reaction calcination temperature is 600~800 DEG C, and heating rate is 5~15 DEG C/min, calcination time 1
~3 h.
In step (5), its quality of lignocellulosic is 10~30mg.
In step (6), the liquor capacity of solution IV is 60~100mL, and reaction temperature is 180~220 DEG C, and the reaction time is
16~24 hours.
In step (7), centrifugation rate is 2000~6000r/min, and the wash number of second alcohol and water is 3~6 times, and baking oven is steady
Determining temperature is 60~80 DEG C.
A kind of application of molybdenum, N doping lignocellulosic composite Nano adsorbent material, which is characterized in that including walking as follows
It is rapid:
A) it takes molybdenum, 4~10mg of N doping lignocellulosic composite Nano adsorbent material to be placed in 50mL test tube, volume is added
For the potassium bichromate solution of 20~50mL, with hydrochloric acid or sodium hydrate regulator solution pH, reacts, obtain under the conditions of magnetic agitation
Solution after reaction；
B) solution after answering is negated, takes 2~5mL filtrate in colorimetric cylinder after filtering, is diluted to graticule, volume ratio, which is added, is
Sulfuric acid, 1:1 phosphoric acid and the diphenylcarbazide solution of 1:1, develop the color 5min, measures it at wavelength 540nm with spectrophotometer
Absorbance；
C) the potassium bichromate stoste for configuring 5 various concentrations, detects its absorbance with spectrophotometer respectively, obtains extinction
The standard curve of degree and concentration relationship；
D) adsorption efficiency or hexavalent chromium removal rate=(C are calculated0–Ct)/C0× 100%, C0Before reacting in solution Cr VI from
The concentration mg/L, C of sontReact the concentration mg/L of hexavalent chromium in solution after the t time；
E) material adsorption capacity=(C is calculated0-Ct) V/W, C0The concentration mg/L, Ct of hexavalent chromium are anti-in solution before reacting
Answering the concentration mg/L, V of hexavalent chromium in solution after the t time is that participate in the volume L, W of the potassium bichromate solution of reaction be to participate in
The quality g of the adsorbent of reaction.
In step a), the pH is 2~9, and the concentration of potassium bichromate solution is 20~60ppm, the reaction time is 0~
150min。
In step b), the volume of the addition phosphoric acid is 0.5mL, the volume of addition sulfuric acid is 0.5mL, hexichol card is added
The volume of bar hydrazine solution is 2mL.
The technical solution for realizing the object of the invention is molybdenum, the preparation of N doping lignocellulosic composite Nano adsorbent material
Method and adsorption technology, include the following steps:
(1) lignocellulosic is calcined under ammonia atmosphere, ground after natural cooling, obtain N doping lignocellulosic；
(2) the ammonium molybdate of 0.1~1mmol is dissolved in the deionized water of 10~100mL, is configured to solution I；
(3) 5~10mmol thioacetamide is dissolved in the deionized water of 10~50mL, is configured to solution II；
(4) solution I and solution II are mixed well, are configured to solution III；
(5) N doping lignocellulosic is added in solution III, is uniformly mixing to obtain solution IV；
(6) solution IV is transferred in autoclave, pyroreaction；
(7) after solution is cooling, step (6) reaction product is centrifuged, collects precipitating, respectively with deionized water,
Reaction product after cleaning is placed in dry in baking oven and answer overnight to get molybdenum, N doping lignocellulosic by washes of absolute alcohol
Close nano adsorption material；
(8) take the 4~10mg of product of step to be (7) placed in 50mL test tube, it is molten that the potassium bichromate that volume is 20~50mL is added
Liquid is reacted under the conditions of magnetic agitation with hydrochloric acid or sodium hydrate regulator solution pH；
(9) the solution after answering is negated, takes 2~5mL filtrate in colorimetric cylinder after filtering, is diluted to graticule, volume ratio, which is added, is
Sulfuric acid, 1:1 phosphoric acid and the diphenylcarbazide solution of 1:1, develop the color 5min, measures it at wavelength 540nm with spectrophotometer
Absorbance；
(10) the potassium bichromate stoste for configuring 5 various concentrations, detects its absorbance with spectrophotometer respectively, obtains extinction
The standard curve of degree and concentration relationship；
(11) adsorption efficiency or hexavalent chromium removal rate=(C are calculated0-Ct)/C0× 100% (C0Before reacting in solution Cr VI from
The concentration mg/L of son, Ct react the concentration mg/L of hexavalent chromium in solution after the t time)
(12) material adsorption capacity=(C is calculated0-Ct)V/W(C0The concentration mg/L, Ct of hexavalent chromium are anti-in solution before reacting
Answering the concentration mg/L, V of hexavalent chromium in solution after the t time is that participate in the volume L, W of the potassium bichromate solution of reaction be to participate in
The quality g) of the adsorbent of reaction.
Reaction calcination temperature described in step (1) is 600~800 DEG C, and heating rate is 5~15 DEG C/min, calcination time
For 1~3 h.
(5) described its quality of lignocellulosic is 10~30mg to step.
Liquor capacity described in step (6) be 60~100mL, reaction temperature be 180~220 DEG C, the reaction time be 16~
24 hours.
(7) the centrifugation rate is 2000~6000r/min to step, and the wash number of second alcohol and water is 3~6 times, is dried
Case equilibrium temperature is 60~80 DEG C.
(8) the pH is 2~9 to step, and the concentration of potassium bichromate solution is 20~60ppm, and the reaction time is 0~150min.
It is 0.5mL that the volume of step (9) the additions phosphoric acid, which is 0.5mL, the volume of sulfuric acid is added, addition hexichol kappa
The volume of hydrazine solution is 2mL.
Compared with the existing technology, the present invention achieve it is following the utility model has the advantages that
1. it is the structure in order to more preferably regulate and control molybdenum sulfide that N doping lignocellulosic is added in molybdenum sulfide synthetic system, promote
Make molybdenum sulfide compound that there is bigger specific surface area and better dispersion performance, molybdenum disulfide and N doping lignocellulosic
Synergistic effect, can have ensure gained compound have more preferable absorption property.
2. calcined lignocellulosic structure is more excellent, performance is more stable, corrosion-resistant, ageing-resistant and reuse rate
It is high.
3. step (7) in first clean the unreacted thioacetamide of removal with ethyl alcohol, then clean with deionized water remove it is not anti-
The inorganic ions answered can obtain pure molybdenum, N doping lignocellulosic composite nano materials.
4. molybdenum, N doping lignocellulosic composite nano materials, have an excellent absorption property, synthetic method it is simple and at
This is lower, has very high removal rate, potential industrial application value with higher for chromate waste water.For initial sexavalence
Chromium concn is lower than the waste water of 50ppm, according to 200mg/L molybdenum, N doping lignocellulosic, hexavalent chromium removal rate up to 80% with
On.
To sum up, the present invention relates to a kind of molybdenum, the preparation and application of N doping lignocellulosic composite Nano antibacterial material, packets
It includes following steps: the nitrating lignocellulosic calcined uniformly being distributed in the system of synthesis of carbon/molybdenum disulfide, reaction under high pressure
It reacts, be centrifugated sediment and dried overnight in kettle, obtain molybdenum, N doping lignocellulosic composites.Take a certain amount of receive
Nano composite material is added in the hexavalent chromium solution of various concentration, magnetic agitation reaction.It reacts the different time, takes out appropriate
Sulfuric acid, phosphoric acid and diphenylcarbazide solution are added into filtrate, detects its absorbance with spectrophotometer for solution, filtering,
And the concentration of hexavalent chromium solution after reaction is calculated by standard curve, obtain removal efficiency.As a result prove: the molybdenum, nitrogen are mixed
Miscellaneous lignocellulosic composites have good suction-operated to Cr VI, and its absorption property is protected substantially after multiplicating test
Hold it is constant, it is with good stability.
Detailed description of the invention
Fig. 1 is the SEM spectrum of the molybdenum of the embodiment of the present invention 1, N doping lignocellulosic composites.
Fig. 2 is the TEM map of the molybdenum of the embodiment of the present invention 1, N doping lignocellulosic composites.
Fig. 3 is that molybdenum, N doping lignocellulosic react different time to six under the conditions of different initial concentrations in the present invention
The removal rate of valence chromium ion.
Fig. 4 is material when molybdenum, N doping lignocellulosic reach balance under the conditions of different initial concentrations in the present invention
Adsorption capacity.
Specific embodiment
With reference to the accompanying drawing and Detailed description of the invention the present invention is described further.
Embodiment 1
The preparation and application of a kind of molybdenum, N doping lignocellulosic composite Nano adsorbent material of the invention successively include
Following steps:
By lignocellulosic under ammonia atmosphere 800 DEG C of calcining 2h, heating rate be 5 DEG C/min natural cooling after grind,
Obtain N doping lignocellulosic；
(1) the ammonium molybdate of 0.5mmol is dissolved in the deionized water of 40mL, is configured to solution I；
(2) 10mmol thioacetamide is dissolved in the deionized water of 40mL, is configured to solution II；
(3) solution I and solution II are mixed well, are configured to solution III；
(4) 30mg N doping lignocellulosic is added in solution III, is uniformly mixing to obtain solution IV；
(5) the solution of 80mL IV is transferred in 100mL autoclave, 200 DEG C of reaction 20h；
(6) after solution is cooling, step (6) reaction product is centrifuged, collects precipitating, respectively with deionized water,
Washes of absolute alcohol 3 times, the reaction product after cleaning is placed in 60 DEG C of drying in baking oven and is stayed overnight to get molybdenum, the wooden fibre of N doping
Plain composite Nano adsorbent material is tieed up, pattern is as shown in Figure 1, 2；
(7) take the product 6mg of step to be (7) placed in 50mL test tube, the potassium bichromate solution that 30mL concentration is 20ppm be added,
With hydrochloric acid or sodium hydrate regulator solution pH to 2,5,10,20,30min are reacted respectively under the conditions of magnetic agitation；
(8) the solution after answering is negated, takes 2mL filtrate in colorimetric cylinder after filtering, is diluted to graticule, is separately added into the sulphur of 1:1
Acid, 1:1 phosphoric acid 0.5mL and 2mL diphenylcarbazide solution, develop the color 5min, is measured at wavelength 540nm with spectrophotometer
Its absorbance；
(9) it is respectively configured 20,30,40,50, the potassium bichromate stoste of five various concentrations of 60ppm, uses spectrophotometric respectively
Meter detects its absorbance, obtains the standard curve of absorbance and concentration relationship；
(10) adsorption efficiency or hexavalent chromium removal rate=(C are calculated0-Ct)/C0× 100% (C0Before reacting in solution Cr VI from
The concentration mg/L of son, Ct react the concentration mg/L of hexavalent chromium in solution after the t time)
(11) material adsorption capacity=(C is calculated0-Ct)V/W(C0The concentration mg/L, Ct of hexavalent chromium are anti-in solution before reacting
Answering the concentration mg/L, V of hexavalent chromium in solution after the t time is that participate in the volume L, W of the potassium bichromate solution of reaction be ginseng
With the quality g) of the adsorbent reacted
Hexavalent chromium removal efficiency=(C0-C1)/C0× 100%=100%
Embodiment 2
The preparation and application of a kind of molybdenum, N doping lignocellulosic composite Nano adsorbent material of the invention successively include
Following steps:
By lignocellulosic under ammonia atmosphere 800 DEG C of calcining 2h, heating rate be 5 DEG C/min natural cooling after grind
Mill, obtains N doping lignocellulosic；
(2) the ammonium molybdate of 0.5mmol is dissolved in the deionized water of 40mL, is configured to solution I；
(3) 10mmol thioacetamide is dissolved in the deionized water of 40mL, is configured to solution II；
(4) solution I and solution II are mixed well, are configured to solution III；
(5) 30mg N doping lignocellulosic is added in solution III, is uniformly mixing to obtain solution IV；
(6) the solution of 80mL IV is transferred in 100mL autoclave, 200 DEG C of reaction 20h；
(7) after solution is cooling, step (6) reaction product is centrifuged, collects precipitating, respectively with deionized water,
Washes of absolute alcohol 3 times, the reaction product after cleaning is placed in 60 DEG C of drying in baking oven and is stayed overnight to get molybdenum, the wooden fibre of N doping
Tie up plain composite Nano adsorbent material；
(8) take the product 6mg of step to be (7) placed in 50mL test tube, the potassium bichromate solution that 30mL concentration is 30ppm be added,
With hydrochloric acid or sodium hydrate regulator solution pH to 2,5,10,20,30min are reacted respectively under the conditions of magnetic agitation；
(9) the solution after answering is negated, takes 2mL filtrate in colorimetric cylinder after filtering, is diluted to graticule, is separately added into the sulphur of 1:1
Acid, 1:1 phosphoric acid 0.5mL and 2mL diphenylcarbazide solution, develop the color 5min, is measured at wavelength 540nm with spectrophotometer
Its absorbance；
(10) it is respectively configured 20,30,40,50, the potassium bichromate stoste of five various concentrations of 60ppm, uses spectrophotometric respectively
Meter detects its absorbance, obtains the standard curve of absorbance and concentration relationship；
(11) adsorption efficiency or hexavalent chromium removal rate=(C are calculated0-Ct)/C0× 100% (C0Before reacting in solution Cr VI from
The concentration mg/L of son, Ct react the concentration mg/L of hexavalent chromium in solution after the t time)
(12) material adsorption capacity=(C is calculated0-Ct)V/W(C0The concentration mg/L, Ct of hexavalent chromium are anti-in solution before reacting
Answering the concentration mg/L, V of hexavalent chromium in solution after the t time is that participate in the volume L, W of the potassium bichromate solution of reaction be ginseng
With the quality g) of the adsorbent reacted
Hexavalent chromium removal efficiency=(C0-C1)/C0× 100%=100%
Embodiment 3
The preparation and application of a kind of molybdenum, N doping lignocellulosic composite Nano adsorbent material of the invention successively include
Following steps:
By lignocellulosic under ammonia atmosphere 800 DEG C of calcining 2h, heating rate be 5 DEG C/min natural cooling after grind
Mill, obtains N doping lignocellulosic；
(2) the ammonium molybdate of 0.5mmol is dissolved in the deionized water of 40mL, is configured to solution I；
(3) 10mmol thioacetamide is dissolved in the deionized water of 40mL, is configured to solution II；
(4) solution I and solution II are mixed well, are configured to solution III；
(5) 30mg N doping lignocellulosic is added in solution III, is uniformly mixing to obtain solution IV；
(6) the solution of 80mL IV is transferred in 100mL autoclave, 200 DEG C of reaction 20h；
(7) after solution is cooling, step (6) reaction product is centrifuged, collects precipitating, respectively with deionized water,
Washes of absolute alcohol 3 times, the reaction product after cleaning is placed in 60 DEG C of drying in baking oven and is stayed overnight to get molybdenum, the wooden fibre of N doping
Tie up plain composite Nano adsorbent material；
(8) take the product 6mg of step to be (7) placed in 50mL test tube, the potassium bichromate solution that 30mL concentration is 40ppm be added,
With hydrochloric acid or sodium hydrate regulator solution pH to 2,5,10,20,30min are reacted respectively under the conditions of magnetic agitation；
(9) the solution after answering is negated, takes 2mL filtrate in colorimetric cylinder after filtering, is diluted to graticule, is separately added into the sulphur of 1:1
Acid, 1:1 phosphoric acid 0.5mL and 2mL diphenylcarbazide solution, develop the color 5min, is measured at wavelength 540nm with spectrophotometer
Its absorbance；
(10) it is respectively configured 20,30,40,50, the potassium bichromate stoste of five various concentrations of 60ppm, uses spectrophotometric respectively
Meter detects its absorbance, obtains the standard curve of absorbance and concentration relationship；
(11) adsorption efficiency or hexavalent chromium removal rate=(C are calculated0-Ct)/C0× 100% (C0Before reacting in solution Cr VI from
The concentration mg/L of son, Ct react the concentration mg/L of hexavalent chromium in solution after the t time)
(12) material adsorption capacity=(C is calculated0-Ct)V/W(C0The concentration mg/L, Ct of hexavalent chromium are anti-in solution before reacting
Answering the concentration mg/L, V of hexavalent chromium in solution after the t time is that participate in the volume L, W of the potassium bichromate solution of reaction be ginseng
With the quality g) of the adsorbent reacted
Hexavalent chromium removal efficiency=(C0-C1)/C0× 100%=94.0%
Embodiment 4
The preparation and application of a kind of molybdenum, N doping lignocellulosic composite Nano adsorbent material of the invention successively include
Following steps:
By lignocellulosic under ammonia atmosphere 800 DEG C of calcining 2h, heating rate be 5 DEG C/min natural cooling after grind
Mill, obtains N doping lignocellulosic；
(2) the ammonium molybdate of 0.5mmol is dissolved in the deionized water of 40mL, is configured to solution I；
(3) 10mmol thioacetamide is dissolved in the deionized water of 40mL, is configured to solution II；
(4) solution I and solution II are mixed well, are configured to solution III；
(5) 30mg N doping lignocellulosic is added in solution III, is uniformly mixing to obtain solution IV；
(6) the solution of 80mL IV is transferred in 100mL autoclave, 200 DEG C of reaction 20h；
(7) after solution is cooling, step (6) reaction product is centrifuged, collects precipitating, respectively with deionized water,
Washes of absolute alcohol 3 times, the reaction product after cleaning is placed in 60 DEG C of drying in baking oven and is stayed overnight to get molybdenum, the wooden fibre of N doping
Tie up plain composite Nano adsorbent material；
(8) take the product 6mg of step to be (7) placed in 50mL test tube, the potassium bichromate solution that 30mL concentration is 50ppm be added,
With hydrochloric acid or sodium hydrate regulator solution pH to 2,5,10,20,30min are reacted respectively under the conditions of magnetic agitation；
(9) the solution after answering is negated, takes 2mL filtrate in colorimetric cylinder after filtering, is diluted to graticule, is separately added into the sulphur of 1:1
Acid, 1:1 phosphoric acid 0.5mL and 2mL diphenylcarbazide solution, develop the color 5min, is measured at wavelength 540nm with spectrophotometer
Its absorbance；
(10) it is respectively configured 20,30,40,50, the potassium bichromate stoste of five various concentrations of 60ppm, uses spectrophotometric respectively
Meter detects its absorbance, obtains the standard curve of absorbance and concentration relationship；
(11) adsorption efficiency or hexavalent chromium removal rate=(C are calculated0-Ct)/C0× 100% (C0 react before in solution Cr VI from
The concentration mg/L of son, Ct react the concentration mg/L of hexavalent chromium in solution after the t time)
(12) material adsorption capacity=(C is calculated0-Ct)V/W(C0The concentration mg/L, Ct of hexavalent chromium are anti-in solution before reacting
Answering the concentration mg/L, V of hexavalent chromium in solution after the t time is that participate in the volume L, W of the potassium bichromate solution of reaction be ginseng
With the quality g) of the adsorbent reacted
Hexavalent chromium removal efficiency=(C0-C1)/C0× 100%=80.4%
Embodiment 5
The preparation and application of a kind of molybdenum, N doping lignocellulosic composite Nano adsorbent material of the invention successively include
Following steps:
By lignocellulosic under ammonia atmosphere 800 DEG C of calcining 2h, heating rate be 5 DEG C/min natural cooling after grind
Mill, obtains N doping lignocellulosic；
(2) the ammonium molybdate of 0.5mmol is dissolved in the deionized water of 40mL, is configured to solution I；
(3) 10mmol thioacetamide is dissolved in the deionized water of 40mL, is configured to solution II；
(4) solution I and solution II are mixed well, are configured to solution III；
(5) 30mg N doping lignocellulosic is added in solution III, is uniformly mixing to obtain solution IV；
(6) the solution of 80mL IV is transferred in 100mL autoclave, 200 DEG C of reaction 20h；
(7) after solution is cooling, step (6) reaction product is centrifuged, collects precipitating, respectively with deionized water,
Washes of absolute alcohol 3 times, the reaction product after cleaning is placed in 60 DEG C of drying in baking oven and is stayed overnight to get molybdenum, the wooden fibre of N doping
Tie up plain composite Nano adsorbent material；
(8) take the product 6mg of step to be (7) placed in 50mL test tube, the potassium bichromate solution that 30mL concentration is 60ppm be added,
With hydrochloric acid or sodium hydrate regulator solution pH to 2,5,10,20,30min are reacted respectively under the conditions of magnetic agitation；
(9) the solution after answering is negated, takes 2mL filtrate in colorimetric cylinder after filtering, is diluted to graticule, is separately added into the sulphur of 1:1
Acid, 1:1 phosphoric acid 0.5mL and 2mL diphenylcarbazide solution, develop the color 5min, is measured at wavelength 540nm with spectrophotometer
Its absorbance；
(10) it is respectively configured 20,30,40,50, the potassium bichromate stoste of five various concentrations of 60ppm, uses spectrophotometric respectively
Meter detects its absorbance, obtains the standard curve of absorbance and concentration relationship；
(11) adsorption efficiency or hexavalent chromium removal rate=(C are calculated0-Ct)/C0× 100% (C0Before reacting in solution Cr VI from
The concentration mg/L of son, Ct react the concentration mg/L of hexavalent chromium in solution after the t time)
(12) material adsorption capacity=(C is calculated0- Ct) (C0 reacts the concentration mg/L, Ct of hexavalent chromium in preceding solution to V/W
It is ginseng that the concentration mg/L, V of hexavalent chromium, which are the volume L, W of the potassium bichromate solution of participation reaction, in solution after the reaction t time
With the quality g) of the adsorbent reacted
Hexavalent chromium removal efficiency=(C0-C1)/C0× 100%=68.6%
The data of Examples 1 to 5 are calculated, and calculates removal efficiency according to the data of Examples 1 to 5 and is depicted as
Fig. 3, adsorption capacity when calculating adsorption equilibrium according to the data of Examples 1 to 5, drafting pattern 4.
As can be seen that being less than the hexavalent chromium solution of 30ppm for concentration when material concentration is 200mg/L from Fig. 3,
Removal efficiency can reach 100%, and when hexavalent chromium concentration is less than 50ppm, removal efficiency is greater than 80%, and reaches in 150min
To balance, as Cr VI initial concentration increases, adsorption capacity constantly increases, but is reaching 60ppm in hexavalent chromium concentration
When, adsorption capacity reaches maximum, maintains 266mg/g.
Absorbance detection is all made of Spectrum ultraviolet-visible spectrophotometer in text.
The foregoing is merely the preferable possible embodiments of the present invention, non-therefore limitation patent protection model of the invention
It encloses.In addition to the implementation, the present invention can also have other embodiments, such as can be by the quality of each ingredient and volume etc.
Ratio enlargement several times.All technical solutions formed using equivalent substitution or equivalent transformation, all fall within the claims in the present invention
In protection scope.Technical characteristic of the present invention without description can realize that details are not described herein by or using the prior art.
Claims (8)
1. the preparation method of a kind of molybdenum, N doping lignocellulosic composite Nano adsorbent material, which is characterized in that including walking as follows
It is rapid:
(1) lignocellulosic is calcined under ammonia atmosphere, is ground after natural cooling, obtain N doping lignocellulosic；
(2) ammonium molybdate of 0.1~1mmol is dissolved in the deionized water of 10~100mL, is configured to solution I；
(3) 5~10mmol thioacetamide is dissolved in the deionized water of 10~50mL, is configured to solution II；
(4) solution I and solution II are mixed well, is configured to solution III；
(5) N doping lignocellulosic is added in solution III, is uniformly mixing to obtain solution IV；
(6) solution IV is transferred in autoclave, pyroreaction；
(7) after the solution of pyroreaction IV is cooling, step (6) reaction product is centrifuged, precipitating is collected, uses respectively
It is wooden to get molybdenum, N doping overnight to be placed in drying in baking oven by deionized water, washes of absolute alcohol for reaction product after cleaning
Cellulose composite Nano adsorbent material.
2. the preparation method of a kind of molybdenum according to claim 1, N doping lignocellulosic composite Nano adsorbent material is used,
It is characterized in that, reaction calcination temperature is 600~800 DEG C in step (1), heating rate is 5~15 DEG C/min, calcination time
For 1~3h.
3. the preparation method of a kind of molybdenum according to claim 1, N doping lignocellulosic composite Nano adsorbent material is used,
It is characterized in that, its quality of lignocellulosic is 10~30mg in step (5).
4. the preparation method of a kind of molybdenum according to claim 1, N doping lignocellulosic composite Nano adsorbent material is used,
It is characterized in that, in step (6), the liquor capacity of solution IV is 60~100mL, and reaction temperature is 180~220 DEG C, when reaction
Between be 16~24 hours.
5. the preparation method of a kind of molybdenum according to claim 1, N doping lignocellulosic composite Nano adsorbent material is used,
It is characterized in that, centrifugation rate is 2000~6000r/min in step (7), the wash number of second alcohol and water is 3~6 times, is dried
Case equilibrium temperature is 60~80 DEG C.
6. the application of a kind of molybdenum, N doping lignocellulosic composite Nano adsorbent material, which comprises the steps of:
A) molybdenum, 4~10mg of N doping lignocellulosic composite Nano adsorbent material is taken to be placed in 50mL test tube, it is 20 that volume, which is added,
The potassium bichromate solution of~50mL is reacted, after obtaining reaction under the conditions of magnetic agitation with hydrochloric acid or sodium hydrate regulator solution pH
Solution；
B) solution after answering is negated, takes 2~5mL filtrate in colorimetric cylinder after filtering, is diluted to graticule, addition volume ratio is 1:1
Sulfuric acid, 1:1 phosphoric acid and diphenylcarbazide solution, develop the color 5min, its extinction is measured at wavelength 540nm with spectrophotometer
Degree；
C) configure 5 various concentrations potassium bichromate stoste, detect its absorbance with spectrophotometer respectively, obtain absorbance with
The standard curve of concentration relationship；
D) adsorption efficiency or hexavalent chromium removal rate=(C are calculated0–Ct)/C0× 100%, C0Hexavalent chromium in solution before reacting
Concentration mg/L, CtReact the concentration mg/L of hexavalent chromium in solution after the t time；
E) material adsorption capacity=(C is calculated0-Ct) V/W, C0The concentration mg/L, Ct of hexavalent chromium react t in solution before reacting
It is to participate in reaction that the concentration mg/L, V of hexavalent chromium, which are the volume L, W of the potassium bichromate solution of participation reaction, in solution after time
Adsorbent quality g.
7. the application of a kind of molybdenum according to claim 6, N doping lignocellulosic composite Nano adsorbent material, feature
It is, in step a), the pH is 2~9, and the concentration of potassium bichromate solution is 20~60ppm, and the reaction time is 0~150min.
8. the application of a kind of molybdenum according to claim 6, N doping lignocellulosic composite Nano adsorbent material, feature
It is, in step b), the volume of the addition phosphoric acid is 0.5mL, the volume of addition sulfuric acid is 0.5mL, hexichol kappa is added
The volume of hydrazine solution is 2mL.
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