CN108905955A - A kind of method of microwave method synthesis manganese oxide attapulgite composite material - Google Patents
A kind of method of microwave method synthesis manganese oxide attapulgite composite material Download PDFInfo
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- CN108905955A CN108905955A CN201810792544.4A CN201810792544A CN108905955A CN 108905955 A CN108905955 A CN 108905955A CN 201810792544 A CN201810792544 A CN 201810792544A CN 108905955 A CN108905955 A CN 108905955A
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- 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
- B01J20/0222—Compounds of Mn, Re
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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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention belongs to material manufacture technology field, a kind of method of microwave method synthesis manganese oxide attapulgite composite material is disclosed, learning from else's experience handles recessed soil and be added to H2SO4In；Microwave treatment, filtering, distillation are washed to neutrality, and liquid is removed in centrifugation, and microwave drying is ground up, sieved, and save；Recessed soil, adds MnSO after acid activation4Solution and lauryl sodium sulfate, ultrasound, obtain the recessed soil of dispersion；Microwave treatment, moisture evaporating completely, Mn2+It is fully dispersed to arrive recessed native inner surfaces of pores；NaOH solution microwave treatment is added in above-mentioned recessed soil, makes OH‑Ion and the Mn being dispersed in recessed native micropore2+It generates Mn (OH)2, distill and be washed to neutrality, liquid is removed in centrifugation, removes the Mn (OH) of recessed native surface free state2；Microwave drying, acid, alkali in neutralisation treatment waste water.There is the present invention dispersibility for improving manganese oxide can enhance manganese oxide to the degradation capability of intractable nitrobenzene wastewater in conjunction with the absorption property of recessed soil.
Description
Technical field
The invention belongs to material manufacture technology fields more particularly to a kind of microwave method to synthesize manganese oxide attapulgite composite material
Method.
Background technique
Microwave is all electromagnetic wave as radio wave, infrared ray, visible light, and frequency is generally 300MHz-300kMHz,
Electromagnetic wave of the wavelength between 1 meter to 1 millimeter.Dc power needed for DC power supply provides the magnetron of microwave generator, it is micro-
Wave producer generates alternating electric field, and the electric field action is on the object in microwave field, due to unbalanced small point of distribution of charges
Sub electromagnetic wave absorption rapidly and the rotation and collision for so that polar molecule is generated 2,500,000,000 times/s or more, polar molecule change with external electric field
And it swings and generates fuel factor；Again because of the interaction between the warm-up movement and adjacent molecule of molecule itself, make molecule with electricity
Variation and the rule swung receives obstructions, this creates the terminal the effect to rub is similar to, part energy is converted into point
Sub- thermal energy causes the aggravation of molecular motion, and the high speed rotation of molecule and vibration make molecule be in metastable state, this be conducive to molecule into
The ionization of one step or the preparation state in reaction, therefore the temperature of heated material is increased rapidly in a short period of time.
Due to the inside of the deep enough substance of microwave energy, rather than the heat transfer of substance itself is relied on, therefore only need routine
Method ten/and once arriving achievable entire heating process of centesimal time, heat utilization rate is high, saves the energy, no public affairs
Evil, is conducive to improve working conditions.Conventional heating means whether electric heating, steam, hot-air etc., will reach certain temperature
Require a period of time, and utilize microwave heating, adjust microwave output power, substance heating state immediately inertialess with changing
Become, is convenient for automation control in this way.Microwave method is also used for the row such as chemical industry, food, agricultural and sideline product, wood type, building material, paper product
The drying of industry.Microwave heating temperature is uniform, the same outside and inside, and for the object of complex contour, heating uniformity also adds than other
Hot method is good.Some advantageous physically or chemically act on can also be generated for heating synthesis.
The high-penetration of microwave field provides the feasibility of material homogeneous heating, has the work heated to specific region moment
With increasing the freedom degree of material heat treatment, microwave field made to obtain extensive concern in material modification and processing technology.Such as
CN201010022767.6：A kind of method of synthesizing MCM-22 molecular sieve with microwave； CN201310143034.1：Carbon nano
The microwave method synthetic method of material/charcoal-aero gel (CA).
Recessed soil is the abbreviation of attapulgite clay.It is the aqueous rich magnesium aluminosilicate clays mineral of a kind of layer of chain structure,
Due to unique stick crystal structure, there is excellent absorption property, while surface is rich in silicone hydroxyl, it is easily modified prepare it is novel multiple
Condensation material.Recessed soil has obtained more and more attention with the composite modified new function material for preparing of inorganic and organic matter.Such as
CN201610466406.8：The recessed native intercalation modifying graphene of one kind, UHMWPE composite fibre and preparation method thereof；
CN201710559077.6：A kind of recessed soil/sodium alginate hybrid inorganic-organic materials and preparation method thereof and application；
CN201710392901.3：The preparation method and gained of the recessed soil-polystyrene resin of magnetism based on magnetic recessed native surface modification
Product；CN201610768376.6：A kind of magnet composite material and preparation method based on nano concave earth；
CN201510803781.2：The CO of recessed soil matrix surface grafting polyacrylamide2The preparation method of adsorbent material.
Be used as carrier using recessed soil, by manganese oxide load to recessed native stick it is brilliant on, prepare manganese oxide/attapulgite composite material, can be with
The dispersibility for effectively improving manganese oxide can enhance manganese oxide to intractable nitrobenzene wastewater in conjunction with the absorption property of recessed soil
Degradation capability.
Manganese oxide load is realized using liquid phase reactor, most of manganese oxide precipitating cannot all be efficiently entering recessed native duct,
Or it is only simply attached to recessed native surface and will result in manganese oxide once being catalyzed for liquid phase adsorption and be largely lost.And it passes
Loading process of uniting is slower, and a hour more than 20 has been used if a kind of method of the towering proposition in Ji, see " Agriculture of Anhui science, 2013,
41(33)".Traditional heating uses baking oven or Muffle furnace simultaneously, and not only the time is long, but also energy consumption is high.
In conclusion problem of the existing technology is：
(1) manganese oxide attapulgite composite material is prepared, the dispersibility of manganese oxide is bad, and the absorption property in conjunction with recessed soil is poor,
The degradation capability of manganese oxide p-nitrophenyl class waste water is poor；
(2) manganese oxide load is realized using liquid phase reactor, most of manganese oxide precipitating cannot all be efficiently entering recessed native hole
Road, or it is only simply attached to recessed native surface, it is catalyzed with liquid phase adsorption, manganese oxide is caused to be largely lost；Traditional heating simultaneously
Using baking oven or Muffle furnace, time consumption and energy consumption.
(3) preparation system of the prior art prepares poor operability in product, and intelligentized control method is poor, to the technique in preparation
Parameter cannot accurately control.
(4) conventional color image contour extraction method interferes vulnerable to initial profile point when extracting object boundary and restrains speed
Degree is slow, big so as to cause the color image profile noise of extraction, has influenced the effect of image segmentation.Microwave method is caused to synthesize oxygen
Change manganese attapulgite composite material poor quality.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of microwave method synthesis manganese oxide attapulgite composite materials
Method can be obviously shortened composite material preparation time, reduce energy consumption, improve payload of the manganese oxide on recessed soil.
Liquid deposition and the thermal decomposition of manganese sulfate and sodium hydroxide is selected to prepare manganese oxide attapulgite composite material, it is main
Reaction equation is：
MnSO4+2NaOH→Mn(OH)2+Na2SO4
Mn(OH)2→Mn2O3·xH2O→MnO2·yH2O
The invention is realized in this way a kind of method of microwave method synthesis manganese oxide attapulgite composite material, including：
Step 1：50g is taken to be added to the H that 500ml concentration is 1mol/L by the recessed native raw material of pulverization process2SO4Solution
In；
Step 2：Solution in step 1 is put into microwave device, 60~80 DEG C, filtered after 15-25min under the conditions of 300W,
It distilling water washing for several times, is washed till neutrality, 12000r/min is centrifuged off supernatant liquid, 60~80 DEG C of drying in microwave device,
It is ground up, sieved, is saved in drier；
Step 3：The MnSO of 100mL 2mol/L is added under stirring condition for recessed soil after taking acid activation4Solution and 1g 12
Sodium alkyl sulfate (SDS), 400W, 30 DEG C, 10-20min ultrasonic disperse it is uniform, the recessed soil dispersed；
Step 4：Finely dispersed recessed soil is put into microwave device, 60~80 DEG C, 300W make moisture evaporating completely, Mn2+
It is fully dispersed to arrive recessed native inner surfaces of pores；
Step 5：The recessed soil of gained in step 4 is added to the NaOH solution of 100mL 5mol/L, 60~80 DEG C, 300W condition
Lower microwave treatment 15-25min, makes OH-Ion and the Mn being dispersed in recessed native micropore2+It generates Mn (OH)2, distill water washing number
It is secondary, it is washed till neutrality, 12000r/min is centrifuged off supernatant liquid, removes the Mn (OH) of recessed native surface free state2；
Step 6：By the recessed soil of gained in step 5,60~80 DEG C of microwave drying 20-30min, Mn (OH) in recessed soil hole2
It decomposes, manganese oxide/attapulgite composite material is made；
Step 7：Step 1 is mixed with the resulting filtrate of step 5 and is put into waste liquid tank, neutralizes acid, alkali in waste water.
Further, in the step 1, controlling is 60~80 DEG C.
Further, dodecyl sodium sulfate is added in step 3 to be dispersed as dispersing agent, and with ultrasonic wave.
Another object of the present invention is to provide a kind of sides using microwave method synthesis manganese oxide attapulgite composite material
The manganese oxide attapulgite composite material of method synthesis.
A kind of preparation system another object of the present invention is to provide manganese oxide attapulgite composite material includes：
Mix H2SO4Solution preparation system, being added to concentration for the recessed native raw material by pulverization process is 1mol/L's
H2SO4In solution；
Drying is ground up, sieved system, is used for mixing H obtained2SO4Solution is put into microwave device, 60~80 DEG C, 300W
Under the conditions of filter, distillation water washing for several times, be washed till neutrality, be centrifuged off supernatant liquid, in microwave device 60~80 DEG C drying,
It is ground up, sieved, is saved in drier；
The MnSO of 2mol/L is added for taking the recessed soil after acid activation in the recessed native acquisition system of dispersion under stirring condition4
Solution and lauryl sodium sulfate SDS, 400W, 30 DEG C of ultrasonic disperses are uniform, the recessed soil dispersed；
Recessed soil inner surfaces of pores decentralized system, for finely dispersed recessed soil to be put into microwave device, 60~80 DEG C,
300W makes moisture evaporating completely, Mn2+It is fully dispersed to arrive recessed native inner surfaces of pores；
The Mn (OH) of recessed soil surface free state2Removing system is used for recessed soil obtained by recessed native inner surfaces of pores decentralized system
The NaOH solution of 5mol/L is added, 60~80 DEG C, microwave treatment under the conditions of 300W make OH-It ion and is dispersed in recessed native micropore
Mn2+It generates Mn (OH)2, distill water washing for several times, be washed till neutrality, be centrifuged off supernatant liquid, remove recessed native surface free state
Mn (OH)2；
System is made in manganese oxide/attapulgite composite material, for by the Mn (OH) of recessed native surface free state2Institute in removing system
Recessed soil, 60~80 DEG C of microwave dryings, it is recessed soil hole in Mn (OH)2It decomposes, manganese oxide/attapulgite composite material is made；
Acid, alkali neutralization system in waste water, for H will to be mixed2SO4The Mn of solution preparation system, recessed native surface free state
(OH)2The resulting filtrate mixing of removing system is put into waste liquid tank, neutralizes acid, alkali in waste water；
Control system, and mixes H2SO4Solution preparation system, drying be ground up, sieved system, the recessed native acquisition system of dispersion,
The Mn (OH) of recessed soil inner surfaces of pores decentralized system, recessed native surface free state2Removing system, manganese oxide/attapulgite composite material system
Acid, the connection of alkali neutralization system in the system of obtaining, waste water, for controlling the operating parameter of all systems.
Another object of the present invention is to provide a kind of manganese oxide attapulgite composite material preparation control methods to include：
Control system is using particle filter algorithm to mixing H2SO4Solution preparation system, drying are ground up, sieved system, dispersion
Recessed native acquisition system, recessed native inner surfaces of pores decentralized system, recessed native surface free state Mn (OH)2Removing system, oxidation
Manganese/attapulgite composite material be made system, acid in waste water, alkali neutralization system operating parameter controlled；Particle filter algorithm packet
It includes：
1) predicted value of objective contour is calculated based on spatial clustering method with Sobel operator or color：
2) image object profile is considered as to the collection { dl being made of N number of unit line segmenti}1,2 ..., N, for i=1,2 ..., N；
3) in C0In find and dliCorresponding position, according to C0The tangent line of middle corresponding position is as dliSampled reference value,
Generate primary collection；
4) constantly assemble to known optimum solution direction according to state transition model guidance particle, standard particle is avoided to filter
The method degenerated during wave realizes particle state transfer, and calculates the corresponding profile point set of each particle；
5) particle weights are calculated according to the observation model of foundation；
6) the parameter dl obtained with the weighted average calculation current iteration of particle collectionj (i)=(kj (i), bj (i))；
If 7) ‖ dlj (i)-dlj ( - i) 1‖ < ε, wherein take ε=0.5, then obtain using the weighted average of particle collection as dli
Otherwise 4) estimation of parameter is gone to step.
Control method is prepared using the manganese oxide attapulgite composite material another object of the present invention is to provide a kind of,
State transition model avoids the method degenerated in standard particle filtering from including：
It is located at and calculates i-th of unit line segment l of image outlineiParameterWhen, particle when iteration to s walks
Collection is
Wherein Θs (i)For straight line parameter set, Ws (i)For particle weights, Es (i)It is calculated for Snake energy function model
Profile validity estimate, be the foundation of granular Weights Computing；Based on conditions above, local optimum particle is:
Global optimum's particle is:
Then PSO state transition model is as follows：
Wherein rk, rk1, rk2, rb, rb1, rb2Equal Normal Distribution, and
The method for establishing observation model includes：
If the estimates of parameters of estimated the 1st to the (i-1)-th obtained unit line segment is:
Corresponding point sequence of an outline is:
Calculating i-th of unit line segment l of image object profileiParameter when, iteration to s walk when particle collection be:
Thus particle collection obtains image object profile point and is
Local Snake energy value is calculated as follows:
Global Snake energy value is calculated as follows:
Or only take { Ψj}J=1,2 ..., i-1In withSeveral nearest point sets calculate overall situation Snake energy jointly
Value；
For RGB color image or HSI spatial color image, each component has corresponding Snake energy value, i.e.,
It is right respectivelyWithIt is normalized,
Localized particle weight is calculated as follows；
Particle overall situation weight is calculated as follows:
Taking particle weights is the arithmetic average of part and global value, i.e.,
Finally, particle weights are normalized, to realize the Minimum Mean Squared Error estimation of parameter.
Realize that the manganese oxide attapulgite composite material prepares control method another object of the present invention is to provide a kind of
Computer program.
Realize that the manganese oxide attapulgite composite material prepares control method another object of the present invention is to provide a kind of
Computer.
Another object of the present invention is to provide a kind of computer readable storage mediums, including instruction, when it is in computer
When upper operation, so that computer executes the manganese oxide attapulgite composite material and prepares control method.
In conclusion advantages of the present invention and good effect：
The method of microwave method synthesis manganese oxide attapulgite composite material provided by the invention, has the dispersion for improving manganese oxide
Property, in conjunction with the absorption property of recessed soil, manganese oxide can be enhanced to the degradation capability of intractable nitrobenzene wastewater；Manganese oxide can have
Effect enters recessed native duct, and this method prepares composite material manganese oxide good dispersion, and time-consuming short, low energy consumption, and utilization rate of raw materials is high,
It can control acid-base neutralization discharge simultaneously, effectively reduce the pressure of acid in later period waste water, alkali process.
Preparation system of the invention prepares strong operability in product, and intelligentized control method is high, to the technological parameter in preparation
It can accurately control.
It interferes and restrains vulnerable to initial profile point when extracting object boundary for conventional color image contour extraction method
Speed is slow, big so as to cause the color image profile noise of extraction, the effect of image segmentation has been influenced, in consideration of it, of the invention
Propose the color image contours extract algorithm based on particle filter.Firstly, providing the prediction of image outline and establishing two herein
Dimension space, to make full use of image information；Then, the state transition model based on PSO optimization method is constructed, which promotees
It is close to known optimum state into particle, the distribution of particle is improved, convergence rate is accelerated；It finally establishes and is based on
The observation model of Snake energy function, the observation model are capable of the effect of preferable quantitative description contour extraction of objects.
By simulation result it is found that its background is all more complicated in the color image of experiment, and come from experimental result
It sees, predicts that the profile of color image is very important, if the profile predicted is stable and accurate, to subsequent profile
It extracts and image segmentation is very helpful.Present invention employs the measurement models based on Snake energy function, although
Interfered when predicting profile more, but image object profile still can accurately be predicted and be extracted to its algorithm, this is to subsequent
Very big effect is played in figure segmentation.
Compared with traditional color image contour extraction method, effectively alleviates and interfered and restrained speed by initial profile point
The problems such as slow is spent, the image outline especially under Low SNR extracts, and the image object profile extracted also extremely makes us
It is satisfied, it is better than general contours extract algorithm.Guarantee that the manganese oxide attapulgite composite material obtained is superior in quality.
Detailed description of the invention
Fig. 1 is the method flow diagram of microwave method synthesis manganese oxide attapulgite composite material provided in an embodiment of the present invention；
Fig. 2 is the preparation system schematic diagram of microwave method synthesis manganese oxide attapulgite composite material provided in an embodiment of the present invention；
In figure：1, H is mixed2SO4Solution preparation system；2, drying is ground up, sieved system；3, the recessed native acquisition system of dispersion；
4, recessed native inner surfaces of pores decentralized system；5, the Mn (OH) of recessed native surface free state2Removing system；6, manganese oxide/recessed soil is compound
System is made in material；7, acid, alkali neutralization system in waste water；8, control system.
Specific embodiment
In order to further understand the content, features and effects of the present invention, the following examples are hereby given, and cooperate attached drawing
Detailed description are as follows.
Step of the invention is explained in detail with reference to the accompanying drawing.
As shown in Figure 1, the step of microwave method synthesis manganese oxide attapulgite composite material method, is：
S101：50g is taken to be added to the H that 500ml concentration is 1mol/L by the recessed native raw material of pulverization process2SO4In solution；
S102：Solution in step 1 is put into microwave device, 60~80 DEG C, microwave treatment 15--30min under the conditions of 300W
After filter, distillation water washing for several times, is washed till neutrality, and 12000r/min centrifuge removes supernatant liquid, 60 in microwave device~
80 DEG C of drying, are ground up, sieved, save in drier；
S103：The MnSO of 100mL 2mol/L is added under stirring condition for recessed soil after taking acid activation4Solution and 1g dodecane
Base sodium sulphate (SDS), 400W, 30 DEG C, 10-20min ultrasonic disperse it is uniform, the recessed soil dispersed；
S104：Finely dispersed recessed soil is put into microwave device, 60~80 DEG C, 300W make moisture evaporating completely, Mn2+It fills
It is distributed to recessed native inner surfaces of pores；
S105：The recessed soil of gained in step 4 is added to the NaOH solution of 100mL 5mol/L, 60~80 DEG C, 300W condition
Lower microwave treatment 15-25min, makes OH-Ion and the Mn being dispersed in recessed native micropore2+It generates Mn (OH)2, distill water washing number
It is secondary, it is washed till neutrality, 12000r/min centrifuge removes supernatant liquid, removes the Mn (OH) of recessed native surface free state2；
S106：By the recessed soil of gained in step 5,60~80 DEG C of microwave drying 20-30min, Mn (OH) in recessed soil hole2Point
Manganese oxide attapulgite composite material is made in solution；
S107：Step 1 is mixed with the resulting filtrate of step 5 and is put into waste liquid tank, neutralizes acid, alkali in waste water.
In step S101, control temperature provided in an embodiment of the present invention accelerates acid activation speed at 60~80 DEG C；
In step S101, the embodiment of the present invention provides the attapulgite material of sulfuric acid treatment, and it is miscellaneous to remove carbonate in recessed soil etc.
Matter, the lesser H of radius+Part K in attapulgite can be displaced+、Na+、Ca2+And Mg2+Equal metal cations, thus dredging hole
Road, the specific surface area for increasing recessed soil；It is able to achieve acid-base neutralization discharge simultaneously, reduces the pressure to environment；
Dodecyl sodium sulfate is added in step S103 to be dispersed as dispersing agent, and with ultrasonic wave；
In step S107, step 1 is mixed with the resulting filtrate of step 5 and is put into waste liquid tank, can played in well
And effect, reduce the pressure of acid in later period waste water, alkali process.
The oxygen of method synthesis provided in an embodiment of the present invention using microwave method synthesis manganese oxide attapulgite composite material
Change manganese attapulgite composite material.
As shown in Fig. 2, the preparation system of manganese oxide attapulgite composite material provided in an embodiment of the present invention includes：
Mix H2SO4Solution preparation system 1, being added to concentration for the recessed native raw material by pulverization process is 1mol/L's
H2SO4In solution；
Drying is ground up, sieved system 2, is used for mixing H obtained2SO4Solution is put into microwave device, 60~80 DEG C, 300W
Under the conditions of filter, distillation water washing for several times, be washed till neutrality, be centrifuged off supernatant liquid, in microwave device 60~80 DEG C drying,
It is ground up, sieved, is saved in drier；
The MnSO of 2mol/L is added for taking the recessed soil after acid activation in the recessed native acquisition system 3 of dispersion under stirring condition4
Solution and lauryl sodium sulfate SDS, 400W, 30 DEG C of ultrasonic disperses are uniform, the recessed soil dispersed；
Recessed soil inner surfaces of pores decentralized system 4, for finely dispersed recessed soil to be put into microwave device, 60~80 DEG C,
300W makes moisture evaporating completely, Mn2+It is fully dispersed to arrive recessed native inner surfaces of pores；
The Mn (OH) of recessed soil surface free state2Removing system 5 is used for recessed soil obtained by recessed native inner surfaces of pores decentralized system
The NaOH solution of 5mol/L is added, 60~80 DEG C, microwave treatment under the conditions of 300W make OH-It ion and is dispersed in recessed native micropore
Mn2+It generates Mn (OH)2, distill water washing for several times, be washed till neutrality, be centrifuged off supernatant liquid, remove recessed native surface free state
Mn (OH)2；
System 6 is made in manganese oxide/attapulgite composite material, for by the Mn (OH) of recessed native surface free state2In removing system
The recessed soil of gained, 60~80 DEG C of microwave dryings, it is recessed soil hole in Mn (OH)2It decomposes, manganese oxide/attapulgite composite material is made；
Acid, alkali neutralization system 7 in waste water, for H will to be mixed2SO4The Mn of solution preparation system, recessed native surface free state
(OH)2The resulting filtrate mixing of removing system is put into waste liquid tank, neutralizes acid, alkali in waste water；
Control system 8, and mixes H2SO4Solution preparation system, drying be ground up, sieved system, the recessed native acquisition system of dispersion,
The Mn (OH) of recessed soil inner surfaces of pores decentralized system, recessed native surface free state2Removing system, manganese oxide/attapulgite composite material system
Acid, the connection of alkali neutralization system in the system of obtaining, waste water, for controlling the operating parameter of all systems.
Manganese oxide attapulgite composite material provided in an embodiment of the present invention prepares control method：
Control system is using particle filter algorithm to mixing H2SO4Solution preparation system, drying are ground up, sieved system, dispersion
Recessed native acquisition system, recessed native inner surfaces of pores decentralized system, recessed native surface free state Mn (OH)2Removing system, oxidation
Manganese/attapulgite composite material be made system, acid in waste water, alkali neutralization system operating parameter controlled；Particle filter algorithm packet
It includes：
1) predicted value of objective contour is calculated based on spatial clustering method with Sobel operator or color：
2) image object profile is considered as to the collection { dl being made of N number of unit line segmenti}1,2 ..., N, for i=1,2 ..., N；
3) in C0In find and dliCorresponding position, according to C0The tangent line of middle corresponding position is as dliSampled reference value,
Generate primary collection；
4) constantly assemble to known optimum solution direction according to state transition model guidance particle, standard particle is avoided to filter
The method degenerated during wave realizes particle state transfer, and calculates the corresponding profile point set of each particle；
5) particle weights are calculated according to the observation model of foundation；
6) the parameter dl obtained with the weighted average calculation current iteration of particle collectionj (i)=(kj (i), bj (i))；
If 7)Wherein, ε=0.5 is taken, then is obtained with the weighting of particle collection
Averagely it is used as dliOtherwise 4) estimation of parameter is gone to step.
Control method is prepared using the manganese oxide attapulgite composite material another object of the present invention is to provide a kind of,
State transition model avoids the method degenerated in standard particle filtering from including：
It is located at and calculates i-th of unit line segment l of image outlineiParameterWhen, particle when iteration to s walks
Collection is
Wherein Θs (i)For straight line parameter set, Ws (i)For particle weights, Es (i)It is calculated for Snake energy function model
Profile validity estimate, be the foundation of granular Weights Computing；Based on conditions above, local optimum particle is:
Global optimum's particle is:
Then PSO state transition model is as follows：
Wherein rk, rk1, rk2, rb, rb1, rb2Equal Normal Distribution, and
The method for establishing observation model includes：
If the estimates of parameters of estimated the 1st to the (i-1)-th obtained unit line segment is:
Corresponding point sequence of an outline is:
Calculating i-th of unit line segment l of image object profileiParameter when, iteration to s walk when particle collection be:
Thus particle collection obtains image object profile point and is
Local Snake energy value is calculated as follows:
Global Snake energy value is calculated as follows:
Or it only takesIn withSeveral nearest point sets calculate overall situation Snake jointly
Energy value；
For RGB color image or HSI spatial color image, each component has corresponding Snake energy value, i.e.,
It is right respectivelyWithIt is normalized,
Localized particle weight is calculated as follows；
Particle overall situation weight is calculated as follows:
Taking particle weights is the arithmetic average of part and global value, i.e.,
Finally, particle weights are normalized, to realize the Minimum Mean Squared Error estimation of parameter.
Contrast on effect of the invention is further described below with reference to embodiment.
The present invention is synthesized compared with traditional heating synthesis using microwave method, have it is time-consuming short, simple and easy, energy saving and
Efficient advantage.
Embodiment 1
Microwave method synthesize manganese oxide attapulgite composite material method the step of be：
Step 1：50g is taken to be added to the H that 500ml concentration is 1mol/L by the recessed native raw material of pulverization process2SO4Solution
In；
Step 2：Solution in step 1 is put into microwave device, 60 DEG C, filtered after 15min under the conditions of 300W, distillation washing
It washs for several times, is washed till neutrality, 12000r/min centrifuge removes supernatant liquid, and 60 DEG C of drying, are ground up, sieved in microwave device, does
It is saved in dry device；
Step 3：The MnSO of 100mL 2mol/L is added under stirring condition for recessed soil after taking acid activation4Solution and 1g 12
Sodium alkyl sulfate (SDS), 400W, 30 DEG C, 10-20min ultrasonic disperse it is uniform, the recessed soil dispersed；
Step 4：Finely dispersed recessed soil is put into microwave device, 60 DEG C, 300W make moisture evaporating completely, Mn2+Sufficiently
It is distributed to recessed native inner surfaces of pores；
Step 5：The recessed soil of gained in step 4 is added to the NaOH solution of 100mL 5mol/L, 60 DEG C, under the conditions of 300W
Microwave treatment 15min, makes OH-Ion and the Mn being dispersed in recessed native micropore2+It generates Mn (OH)2, distill water washing for several times, wash
To neutrality, 12000r/min centrifuge removes supernatant liquid, removes the Mn (OH) of recessed native surface free state2；
Step 6：By the recessed soil of gained in step 5,60 DEG C of microwave drying 20min, Mn (OH) in recessed soil hole2It decomposes, system
Obtain manganese oxide/attapulgite composite material；
Step 7：Step 1 is mixed with the resulting filtrate of step 5 and is put into waste liquid tank, neutralizes acid, alkali in waste water.
The performance of manganese oxide attapulgite composite material is verified.
With manganese oxide/attapulgite composite material specific surface area of U.S. Mike company's T riStar II 3020BET test preparation
For 96.76m2/g。
The nitrobenzene 100mL of 10mg/L is added into stuffed conical flask in the 1g attapulgite composite material for taking above-mentioned steps to prepare,
On 25 DEG C of constant-temperature tables, concussion absorption 30min, measures filtrate with reduction-azo photometry after filtering under revolving speed 100r/min
Middle nitro phenenyl concentration, nitrobenzene removal rate are 81.35%.It can be seen that acid activation concentration is too low, the material property of preparation is bad.
Embodiment 2
Microwave method synthesize manganese oxide attapulgite composite material method the step of be：
Step 1：50g is taken to be added to the H that 500ml concentration is 1mol/L by the recessed native raw material of pulverization process2SO4Solution
In；
Step 2：Solution in step 1 is put into microwave device, 80 DEG C, filtered after 15-25min under the conditions of 300W, is distilled
Water washing for several times, is washed till neutrality, and 12000r/min centrifuge removes supernatant liquid, and 80 DEG C of drying, ground in microwave device
It sieves, is saved in drier；
Step 3：The MnSO of 100mL 2mol/L is added under stirring condition for recessed soil after taking acid activation4Solution and 1g 12
Sodium alkyl sulfate (SDS), 400W, 30 DEG C, 20min ultrasonic disperse it is uniform, the recessed soil dispersed；
Step 4：Finely dispersed recessed soil is put into microwave device, 80 DEG C, 300W make moisture evaporating completely, Mn2+Sufficiently
It is distributed to recessed native inner surfaces of pores；
Step 5：The recessed soil of gained in step 4 is added to the NaOH solution of 100mL 5mol/L, 80 DEG C, under the conditions of 300W
Microwave treatment 25min, makes OH-Ion and the Mn being dispersed in recessed native micropore2+It generates Mn (OH)2, distill water washing for several times, wash
To neutrality, 12000r/min centrifuge removes supernatant liquid, removes the Mn (OH) of recessed native surface free state2；
Step 6：By the recessed soil of gained in step 5,80 DEG C of microwave drying 30min, Mn (OH) in recessed soil hole2It decomposes, system
Obtain manganese oxide/attapulgite composite material；
Step 7：Step 1 is mixed with the resulting filtrate of step 5 and is put into waste liquid tank, neutralizes acid, alkali in waste water.
The performance of manganese oxide attapulgite composite material is verified.
With manganese oxide/attapulgite composite material specific surface area of U.S. Mike company's T riStar II 3020BET test preparation
For 127.52m2/g。
The nitrobenzene 100mL of 10mg/L is added into stuffed conical flask in the 1g attapulgite composite material for taking above-mentioned steps to prepare,
On 25 DEG C of constant-temperature tables, concussion absorption 30min, measures filtrate with reduction-azo photometry after filtering under revolving speed 100r/min
Middle nitro phenenyl concentration, nitrobenzene removal rate are 65.39%.It can be seen that MnO is the key factor of attapulgite composite material degrading nitrobenzene.
Embodiment 3
Microwave method synthesize manganese oxide attapulgite composite material method the step of be：
Step 1：50g is taken to be added to the H that 500ml concentration is 1mol/L by the recessed native raw material of pulverization process2SO4Solution
In；
Step 2：Solution in step 1 is put into microwave device, 70 DEG C, filtered after 15-25min under the conditions of 300W, is distilled
Water washing for several times, is washed till neutrality, and 12000r/min centrifuge removes supernatant liquid, and 70 DEG C of drying, ground in microwave device
It sieves, is saved in drier；
Step 3：The MnSO of 100mL 2mol/L is added under stirring condition for recessed soil after taking acid activation4Solution and 1g 12
Sodium alkyl sulfate (SDS), 400W, 30 DEG C, 15min ultrasonic disperse it is uniform, the recessed soil dispersed；
Step 4：Finely dispersed recessed soil is put into microwave device, 70 DEG C, 300W make moisture evaporating completely, Mn2+Sufficiently
It is distributed to recessed native inner surfaces of pores；
Step 5：The recessed soil of gained in step 4 is added to the NaOH solution of 100mL 5mol/L, 70 DEG C, under the conditions of 300W
Microwave treatment 20min, makes OH-Ion and the Mn being dispersed in recessed native micropore2+It generates Mn (OH)2, distill water washing for several times, wash
To neutrality, 12000r/min centrifuge removes supernatant liquid, removes the Mn (OH) of recessed native surface free state2；
Step 6：By the recessed soil of gained in step 5,70 DEG C of microwave drying 25min, Mn (OH) in recessed soil hole2It decomposes, system
Obtain manganese oxide attapulgite composite material；
Step 7：Step 1 is mixed with the resulting filtrate of step 5 and is put into waste liquid tank, neutralizes acid, alkali in waste water.
The performance of manganese oxide attapulgite composite material is verified.
With manganese oxide/attapulgite composite material specific surface area of U.S. Mike company's T riStar II 3020BET test preparation
For 139.52m2/g。
The nitrobenzene 100mL of 10mg/L is added into stuffed conical flask in the 1g attapulgite composite material for taking above-mentioned steps to prepare,
On 25 DEG C of constant-temperature tables, concussion absorption 30min, measures filtrate with reduction-azo photometry after filtering under revolving speed 100r/min
Middle nitro phenenyl concentration, nitrobenzene removal rate are 96.35%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of method of microwave method synthesis manganese oxide attapulgite composite material, which is characterized in that the microwave method synthesizes oxidation
The method of manganese attapulgite composite material includes：
Step 1：50g is taken to be added to the H that 500ml concentration is 1mol/L by the recessed native raw material of pulverization process2SO4In solution；
Step 2：Solution in step 1 is put into microwave device, 60~80 DEG C, filtered after 15-25min under the conditions of 300W, is distilled
Water washing for several times, is washed till neutrality, and 12000r/min is centrifuged off supernatant liquid, 60~80 DEG C of drying in microwave device, grinding
It is sieved, is saved in drier；
Step 3：The MnSO of 100mL 2mol/L is added under stirring condition for recessed soil after taking acid activation4Solution and 1g dodecyl
Sodium sulphate (SDS), 400W, 30 DEG C, 10-20min ultrasonic disperse it is uniform, the recessed soil dispersed；
Step 4：Finely dispersed recessed soil is put into microwave device, 60~80 DEG C, 300W make moisture evaporating completely, Mn2+Sufficiently
It is distributed to recessed native inner surfaces of pores；
Step 5：The recessed soil of gained in step 4 is added to the NaOH solution of 100mL 5mol/L, 60~80 DEG C, micro- under the conditions of 300W
Wave handles 15-25min, makes OH-Ion and the Mn being dispersed in recessed native micropore2+It generates Mn (OH)2, distill water washing for several times, wash
To neutrality, 12000r/min is centrifuged off supernatant liquid, removes the Mn (OH) of recessed native surface free state2；
Step 6：By the recessed soil of gained in step 5,60~80 DEG C of microwave drying 20-30min, Mn (OH) in recessed soil hole2It decomposes,
Manganese oxide/attapulgite composite material is made；
Step 7：Step 1 is mixed with the resulting filtrate of step 5 and is put into waste liquid tank, neutralizes acid, alkali in waste water.
2. the method for microwave method synthesis manganese oxide attapulgite composite material as described in claim 1, which is characterized in that the step
In one, controlling is 60~80 DEG C.
3. the method for microwave method synthesis manganese oxide attapulgite composite material as described in claim 1, which is characterized in that in step 3
Dodecyl sodium sulfate is added to be dispersed as dispersing agent, and with ultrasonic wave.
4. a kind of recessed soil of manganese oxide of the method synthesis using the synthesis manganese oxide attapulgite composite material of microwave method described in claim 1
Composite material.
5. a kind of preparation system of manganese oxide attapulgite composite material as claimed in claim 4, which is characterized in that the manganese oxide is recessed
The preparation system of soil composite material includes：
Mix H2SO4Solution preparation system, for being added to the H that concentration is 1mol/L by the recessed native raw material of pulverization process2SO4It is molten
In liquid；
Drying is ground up, sieved system, is used for mixing H obtained2SO4Solution is put into microwave device, and 60~80 DEG C, under the conditions of 300W
Filtering, distillation water washing for several times, are washed till neutrality, are centrifuged off supernatant liquid, and 60~80 DEG C of drying, ground in microwave device
It sieves, is saved in drier；
The MnSO of 2mol/L is added for taking the recessed soil after acid activation in the recessed native acquisition system of dispersion under stirring condition4Solution and
Lauryl sodium sulfate SDS, 400W, 30 DEG C of ultrasonic disperses are uniform, the recessed soil dispersed；
Recessed soil inner surfaces of pores decentralized system, for finely dispersed recessed soil to be put into microwave device, 60~80 DEG C, 300W make
Moisture evaporating completely, Mn2+It is fully dispersed to arrive recessed native inner surfaces of pores；
The Mn (OH) of recessed soil surface free state2Removing system, for recessed soil obtained by recessed native inner surfaces of pores decentralized system to be added
The NaOH solution of 5mol/L, 60~80 DEG C, microwave treatment under the conditions of 300W, makes OH-Ion and the Mn being dispersed in recessed native micropore2+
It generates Mn (OH)2, distill water washing for several times, be washed till neutrality, be centrifuged off supernatant liquid, remove the Mn of recessed native surface free state
(OH)2；
System is made in manganese oxide/attapulgite composite material, for by the Mn (OH) of recessed native surface free state2Gained is recessed in removing system
Soil, 60~80 DEG C of microwave dryings, it is recessed soil hole in Mn (OH)2It decomposes, manganese oxide/attapulgite composite material is made；
Acid, alkali neutralization system in waste water, for H will to be mixed2SO4The Mn (OH) of solution preparation system, recessed native surface free state2It removes
It goes the resulting filtrate mixing of system to be put into waste liquid tank, neutralizes acid, alkali in waste water；
Control system, and mixes H2SO4Solution preparation system, drying are ground up, sieved system, the recessed native acquisition system of dispersion, recessed soil
The Mn (OH) of inner surfaces of pores decentralized system, recessed native surface free state2System is made in removing system, manganese oxide/attapulgite composite material
Acid, the connection of alkali neutralization system in system, waste water, for controlling the operating parameter of all systems.
6. a kind of manganese oxide attapulgite composite material using preparation system described in claim 5 prepares control method, feature exists
In the manganese oxide attapulgite composite material preparation control method includes：
Control system is using particle filter algorithm to mixing H2SO4Solution preparation system, drying be ground up, sieved system, dispersion it is recessed
Native acquisition system, recessed native inner surfaces of pores decentralized system, recessed native surface free state Mn (OH)2Removing system, manganese oxide/recessed soil
Composite material be made system, acid in waste water, alkali neutralization system operating parameter controlled；Particle filter algorithm includes：
1) predicted value of objective contour is calculated based on spatial clustering method with Sobel operator or color：
2) image object profile is considered as to the collection { dl being made of N number of unit line segmenti}1,2 ..., N, for i=1,2 ..., N；
3) in C0In find and dliCorresponding position, according to C0The tangent line of middle corresponding position is as dliSampled reference value, generate
Primary collection；
4) constantly assemble to known optimum solution direction according to state transition model guidance particle, standard particle is avoided to filter
The method degenerated in journey realizes particle state transfer, and calculates the corresponding profile point set of each particle；
5) particle weights are calculated according to the observation model of foundation；
6) the parameter dl obtained with the weighted average calculation current iteration of particle collectionj (i)=(kj (i), bj (i))；
If 7)Wherein, ε=0.5 is taken, then is obtained with the weighted average of particle collection
As dliOtherwise 4) estimation of parameter is gone to step.
7. a kind of prepare control method using manganese oxide attapulgite composite material as claimed in claim 6, which is characterized in that state turns
Shifting formwork type avoids the method degenerated in standard particle filtering from including：
It is located at and calculates i-th of unit line segment l of image outlineiParameterWhen, particle collection is when iteration to s walks
Wherein Θs (i)For straight line parameter set, Ws (i)For particle weights, Es (i)The wheel being calculated for Snake energy function model
Wide validity is estimated, and is the foundation of granular Weights Computing；Based on conditions above, local optimum particle is:
Global optimum's particle is:
Then PSO state transition model is as follows：
Wherein rk, rk1, rk2, rb, rb1, rb2Equal Normal Distribution, and
The method for establishing observation model includes：
If the estimates of parameters of estimated the 1st to the (i-1)-th obtained unit line segment is:
Corresponding point sequence of an outline is:
Calculating i-th of unit line segment l of image object profileiParameter when, iteration to s walk when particle collection be:
Thus particle collection obtains image object profile point and is
Local Snake energy value is calculated as follows:
Global Snake energy value is calculated as follows:
Or only take { Ψj}J=1,2 ..., i-1In withSeveral nearest point sets calculate overall situation Snake energy value jointly；
For RGB color image or HSI spatial color image, each component has corresponding Snake energy value, i.e.,
It is right respectivelyWithIt is normalized, presses
Formula calculates localized particle weight；
Particle overall situation weight is calculated as follows:
Taking particle weights is the arithmetic average of part and global value, i.e.,
Finally, particle weights are normalized, to realize the Minimum Mean Squared Error estimation of parameter.
8. a kind of realize that manganese oxide attapulgite composite material described in claim 6~7 any one prepares control method XXX method
Computer program.
9. a kind of computer for realizing the preparation control method of manganese oxide attapulgite composite material described in claim 6~7 any one.
10. a kind of computer readable storage medium, including instruction, when run on a computer, so that computer executes such as
Manganese oxide attapulgite composite material described in claim 6~7 any one prepares control method.
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