CN105582888A - Method for preparing carbon microsphere adsorbent under catalysis of metal salt with low-temperature hydrothermal method - Google Patents
Method for preparing carbon microsphere adsorbent under catalysis of metal salt with low-temperature hydrothermal method Download PDFInfo
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- CN105582888A CN105582888A CN201610041624.7A CN201610041624A CN105582888A CN 105582888 A CN105582888 A CN 105582888A CN 201610041624 A CN201610041624 A CN 201610041624A CN 105582888 A CN105582888 A CN 105582888A
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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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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
- B01J20/28014—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 form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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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
Abstract
The invention discloses a method for preparing a carbon microsphere adsorbent under catalysis of metal salt with a low-temperature hydrothermal method. The method comprises steps as follows: (1) a biomass solution with the concentration being 2wt%-20wt% and a metal salt solution with the concentration being 0.5wt%-2wt% are prepared, then mixed in the mass ratio being (2-5):1 and stirred for 5-10 min, and a reaction solution is obtained; (2) the reaction solution is transferred to a stainless steel reaction kettle, the volume of the reaction solution accounts for 60%-80% of that of the reaction kettle, the reaction solution is heated to 100-160 DEG C at a certain heating speed, reacts at the constant temperature for 8-20 hours and is naturally cooled, separated and dried in vacuum, and hydrothermal carbon microspheres are obtained; (3) the hydrothermal carbon microspheres are calcined and carbonized at the air atmosphere, and the carbon microsphere adsorbent is obtained. The preparation process of the adsorbent is simple, energy consumption is low, the reaction time is shortened to be within 24 hours, and the adsorbent has high adsorption performance for part of positive ions, particularly, uranyl ions, has excellent radioresistance, thermal stability and acid stability and can be widely used for treatment of radioactive wastewater.
Description
Technical field
The invention belongs to biomass resource utilization and biomass absorbent material technology field, be specifically related to a kind of method that slaine catalysis hydrothermal reaction at low temperature is prepared carbosphere adsorbent.
Background technology
Energy-saving and environmental protection, nuclear energy development and utilization are subject to China already deeply, and even global great attention. The radioactive wastewater that nuclear industry produces is to the destruction of ecological environment except chemical toxicity, and also active impact, forms serious threat to plant and the mankind's survival and development. Therefore developing new material and new technology processes Uranium in Waste Water acyl ion and has realistic meaning. Compare with the method such as chemical precipitation method, ion-exchange, embrane method, use absorption method to remove uranyl ion in waste water and there is the easily advantage such as recycling of with low cost, adsorbent. Hydro-thermal carbon adsorbent compared with most of sorbing materials, possesses good radiation resistance, heat endurance and absolute acid stability during for the treatment of uranium-containing waste water. But hydrothermal carbonization legal system requires for carbon adsorbent at present reaction temperature higher (being greater than 180 DEG C), reaction time are grown (being generally a couple of days). In order to solve long shortcoming of preparation high, time of adsorbent temperature, in preparation process, add catalyst, can effectively address the above problem, thereby reduce energy consumption, improved the production efficiency of hydro-thermal carbon adsorbent. For example, patent documentation CN104649246A discloses " a kind of low-temperature hydrothermal method for manufacturing of biomass carbon micro-/ nano ball; it adopts the biomass carbon preparation method of base catalysis or one pot of low-temperature hydrothermal carbonization of lewis acid/Bronsted acid catalysis biomass; this technical scheme; process complexity; catalyst component adds complicated, is unfavorable for the further expansion utilization of carbosphere.
The biomass material that adopts lower temperature to prepare hydro-thermal carbosphere is at present mainly fructose soln, but it is limited to originate, and is unfavorable for industrial applications; Adopt glucose solution as carbon source, 180～220 DEG C of hydrothermal temperatures, the reaction time is greater than 24 hours; Adopt other biological raw material as carbon source, hydrothermal temperature is greater than 220 DEG C, and the reaction time is greater than 24 hours. Biomass material aboundresources, renewable, toxicity is little, is prepared into hydro-thermal carbosphere adsorbent and has good stability, radioresistens, the characteristic such as high temperature resistant. Hydro-thermal carbosphere adsorbent surface contains abundant oxygen-containing functional group (COOH ,-OH etc.), with metal cation (as La, Ce, Sm, Gd etc.), especially with uranyl ion (UO2 2+) can form chelation, and then reach the effect of removing Uranium in Waste Water, be expected to efficiently, prepare to scale the hydro-thermal carbosphere adsorbent of a kind of environmental friendliness, low energy consumption.
Summary of the invention
As the result of various extensive and careful research and experiment, the present inventor has been found that, adopting living beings and slaine is raw material, the carbosphere adsorbent of preparing with hydrothermal reaction at low temperature, particle size is several microns, microballoon pattern is regular, smooth surface, rich surface containing-COOH and-functional groups such as OH, can efficient adsorption Uranium in Waste Water acyl ion. Based on this discovery, complete the present invention.
An object of the present invention is to solve at least the problems referred to above and/or defect, and provide at least below by the advantage of explanation.
In order to realize according to these objects of the present invention and other advantage, provide a kind of slaine catalysis hydrothermal reaction at low temperature to prepare the method for carbosphere adsorbent, comprise the following steps:
Step 1, get the biomass solution that biomass material compound concentration is 2～20wt%, get the metal salt solution that slaine compound concentration is 0.5～2wt%; Then by biomass solution and metal salt solution in mass ratio 2～5:1 mix, stir 5～10 minutes, obtain reaction solution;
Step 2, reaction solution is transferred to stainless steel cauldron, wherein reaction solution accounts for 60～80% of reactor volume, is then warmed up to 100～160 DEG C with certain heating rate, and isothermal reaction is after 8～20 hours, through naturally cooling, separation, vacuum drying, obtain hydro-thermal carbosphere;
Step 3, by the roasting carbonization in air atmosphere of hydro-thermal carbosphere, obtain carbosphere adsorbent.
Preferably, in described step 1, biomass material is any one in glucose, fructose, starch, inulin, lignocellulosic.
Preferably, in described step 1, slaine is CrCl3、SnCl4、WCl4、B(OH)3、AlCl3In any one.
Preferably, in described step 2, heating rate is 0.1～10 DEG C/min, and vacuum drying temperature is 50～100 DEG C.
Preferably, in described step 3, the roasting carburizing temperature of hydro-thermal carbosphere in air atmosphere is 250～600 DEG C, and the time is 0.5～5h, and heating rate is 0.1～10 DEG C/min.
Preferably, described biomass material is modified inulin, the preparation method of described modified inulin is: inulin is added in deionized water, heating is mixed with the inulin solution of 10～15wt%, by weight, get 100～300 parts of inulin solution, with salt acid for adjusting pH value to 3～4, with 750W microwave treatment 10～30min; Then add the urea liquid of 1～3mol/L, pH value is adjusted to 6～7, obtain acidolysis inulin solution; Get 10～20 parts of terephthalic acid (TPA)s, mix with 80～100 parts of DMAs, then add acidolysis inulin solution and 3～5 parts of pyridines of 20～30 parts to mix, by mixed material be warming up to 75～85 DEG C and at this temperature stirring reaction 5～10 hours, obtain reacting rear mixture; Mixture after reaction is cooled to after room temperature, filters, filtrate through dried over mgso, obtain inulin esterification products again after organic solvent is removed in distillation; Get 10～15 parts of inulin esterification products, be dissolved in 80～100 parts of N, in N-dimethylacetylamide, in inulin esterification products solution, add 5～8 parts of melamines dissolving completely, gained mixed solution back flow reaction under 150～180 DEG C of conditions naturally cooled to room temperature after 3～5 hours, filtered and obtained solid product, used methyl alcohol by after gained solid product washing 3～5 times, dry to constant weight, obtain modified inulin.
Preferably, the solvent of the modified inulin solution of described modified inulin preparation is that volume ratio is DMF and the acetone of 1:1～3.
Preferably, in described step 1, the reaction solution obtaining is placed in to the ultrasonic 30～60min of ultrasonic wave separating apparatus, the adjustable range of ultrasonic power is at 600～1800W, and supersonic frequency is at 25～50KHz.
Preferably, in described step 3, the process of roasting carbonization is: the hydro-thermal carbosphere obtaining is added in rotary roasting furnace, be warming up to 100～200 DEG C with the speed heating using microwave of 0.1～10 DEG C/min, insulation 10～20min, then be warming up to 300～400 DEG C with the speed heating using microwave of 0.1～10 DEG C/min, insulation 1～2h, is then warming up to 500～600 DEG C with the speed heating using microwave of 0.1～10 DEG C/min, insulation 2～3h, obtains carbosphere adsorbent; The frequency of described heating using microwave is 915MHz;
Preferably, the rotary speed of described rotary roasting furnace is 10～15r/min.
The concentration of the biomass material adopting in step 1 of the present invention is 2～20wt%, under this concentration, can promote in hydrothermal carbonization process nucleation and carbon nucleus growth smoothly, finally generate stable, pattern is regular, the micron order carbon ball of structure homogeneous. If concentration, lower than this scope, is not easy to large-scale production, if concentration, higher than this scope, can affect the regularity of carbosphere pattern and surperficial number of functional groups.
The object that adopts slaine in step 1 of the present invention is to play catalytic action, and biomass material hydrothermal carbonization process is divided into following several stages: (1) presoma is hydrolyzed into monomer, and system pH value declines; (2) monomer dewaters and brings out polymerisation; (3) aromatization causes the formation of end product. Wherein in (1), system pH value declines, and be to produce organic acid because some monomer decomposes, and the free hydrogen ion that these acid produce will generate soluble product to dehydration and fragmentation reaction. In the situation that reaction temperature is lower, the biomass material of some resistant to hydrolysis cannot be hydrolyzed into monomer at all, just do not have organic acid to generate yet, by added metal salt as catalyst, effectively promote living beings generation dehydration, generate the higher composition of 5 hydroxymethyl furfural isoreactivity, and then reach the object of Formed material under low temperature.
In step 2 of the present invention, adopting vacuum drying method, is the oxygen-containing functional group in order to protect hydro-thermal carbosphere surface.
In step 3 of the present invention, adopt the object of roasting carbonization in air atmosphere to be, increase the oxygen-containing functional group quantity on hydro-thermal carbosphere surface, pass through the temperature of a little higher than hydro-thermal reaction simultaneously, reach the object of sclerosis hydro-thermal carbosphere, finally obtain hydro-thermal carbosphere adsorbent.
The present invention at least comprises following beneficial effect:
(1) the present invention, taking biomass material, slaine as catalyst, has synthesized hydro-thermal carbosphere adsorbent, after this sorbent treatment waste water, can be repeatedly used, and after use is discarded, easily disposes.
(2) by adding slaine that dehydration occurs under low temperature (100～160 DEG C) as catalyst living beings, and prepare carbosphere adsorbent by carbonization, the metal salt catalyst composition adding is single, catalytic efficiency is high, simple to operate, energy consumption is low, the hydro-thermal carbosphere surface of preparation has and uranyl ion, La, Ce, Sm, a large amount of active groups of the chelatings such as Gd, therefore, hydro-thermal carbon adsorbent preparation method of the present invention energy-conserving and environment-protective, the hydrothermal carbonization method with unique advantage is improved, and the hydro-thermal carbon adsorbent of preparation is to uranyl ion, La, Ce, Sm, Gd etc. have higher adsorption efficiency, adsorption rate faster.
(3) size of hydro-thermal carbosphere adsorbent of the present invention is compared with homogeneous, regular shape, rich surface containing-COOH and-OH, be convenient to subsequent chemistry modification.
(4) preparation method of the present invention is simple to operate, and efficiency is high, and preparation process environmental friendliness is practical, and the raw material sources of adsorbent are abundant, and cost is low, and made adsorbent is a kind of environment-friendly material. Therefore, there is good economic benefit and popularizing application prospect.
Other advantage of the present invention, target and feature embody the explanation of part by below, and part also will be by being understood by those skilled in the art research and practice of the present invention.
Brief description of the drawings:
Fig. 1 is the scanning electron microscope (SEM) photograph of the carbosphere prepared of the embodiment of the present invention 1;
Fig. 2 is that carbosphere adsorbent prepared by the embodiment of the present invention 1 is analyzed the surface-element obtaining containing spirogram by EDX;
Fig. 3 be the pH of uranyl ion solution carbosphere adsorbent prepared by embodiment 1 adsorbance affect figure;
Fig. 4 be the pH of uranyl ion solution carbosphere adsorbent prepared by embodiment 1 uranyl ion clearance affect figure.
Detailed description of the invention:
Below in conjunction with accompanying drawing, the present invention is described in further detail, to make those skilled in the art can implement according to this with reference to description word.
Should be appreciated that use herein do not allot existence or the interpolation of one or more other elements or its combination such as " having ", " comprising " and " comprising " term.
Embodiment 1:
Step 1, get glucose and be dissolved in the water, the glucose solution that compound concentration is 10wt%, gets AlCl3Be dissolved in the water, the AlCl that compound concentration is 2wt%3Solution; Then by glucose solution and AlCl3Solution in mass ratio 3:1 mixes, and stirs 10 minutes, obtains reaction solution;
Step 2, reaction solution is transferred to stainless steel cauldron, wherein reaction solution accounts for 80% of reactor volume, is then warmed up to 120 DEG C with the heating rate of 1 DEG C/min, and isothermal reaction is after 10 hours, through naturally cooling, separation, 60 DEG C of vacuum drying, obtain hydro-thermal carbosphere;
Step 3, hydro-thermal carbosphere is warmed up to 300 DEG C of roastings 2 hours with the heating rate of 1 DEG C/min in air atmosphere, finally obtains carbosphere adsorbent.
Embodiment 2:
Step 1, get glucose and be dissolved in the water, the glucose solution that compound concentration is 10wt%, gets SnCl4Be dissolved in the water, the SnCl that compound concentration is 2wt%4Solution; Then by glucose solution and SnCl4Solution in mass ratio 3:1 mixes, and stirs 10 minutes, obtains reaction solution;
Step 2, reaction solution is transferred to stainless steel cauldron, wherein reaction solution accounts for 80% of reactor volume, is then warmed up to 120 DEG C with the heating rate of 1 DEG C/min, and isothermal reaction is after 10 hours, through naturally cooling, separation, 60 DEG C of vacuum drying, obtain hydro-thermal carbosphere;
Step 3, hydro-thermal carbosphere is warmed up to 300 DEG C of roastings 2 hours with the heating rate of 1 DEG C/min in air atmosphere, finally obtains carbosphere adsorbent.
Embodiment 3:
Step 1, get glucose and be dissolved in the water, the glucose solution that compound concentration is 10wt%, gets CrCl3Be dissolved in the water, the CrCl that compound concentration is 2wt%3Solution; Then by glucose solution and CrCl3Solution in mass ratio 3:1 mixes, and stirs 10 minutes, obtains reaction solution;
Step 2, reaction solution is transferred to stainless steel cauldron, wherein reaction solution accounts for 80% of reactor volume, is then warmed up to 120 DEG C with the heating rate of 1 DEG C/min, and isothermal reaction is after 10 hours, through naturally cooling, separation, 60 DEG C of vacuum drying, obtain hydro-thermal carbosphere;
Step 3, hydro-thermal carbosphere is warmed up to 300 DEG C of roastings 2 hours with the heating rate of 1 DEG C/min in air atmosphere, finally obtains carbosphere adsorbent.
Embodiment 4:
Step 1, get starch dissolution in water, the starch solution that compound concentration is 10wt%, gets AlCl3Be dissolved in the water, the AlCl that compound concentration is 2wt%3Solution; Then by starch solution and AlCl3Solution in mass ratio 3:1 mixes, and stirs 10 minutes, obtains reaction solution;
Step 2, reaction solution is transferred to stainless steel cauldron, wherein reaction solution accounts for 80% of reactor volume, is then warmed up to 120 DEG C with the heating rate of 1 DEG C/min, and isothermal reaction is after 10 hours, through naturally cooling, separation, 60 DEG C of vacuum drying, obtain hydro-thermal carbosphere;
Step 3, hydro-thermal carbosphere is warmed up to 300 DEG C of roastings 2 hours with the heating rate of 1 DEG C/min in air atmosphere, finally obtains carbosphere adsorbent.
Embodiment 5:
Step 1, get fructose and be dissolved in the water, the fructose soln that compound concentration is 10wt%, gets AlCl3Be dissolved in the water, the AlCl that compound concentration is 2wt%3Solution; Then by fructose soln and AlCl3Solution in mass ratio 3:1 mixes, and stirs 10 minutes, obtains reaction solution;
Step 2, reaction solution is transferred to stainless steel cauldron, wherein reaction solution accounts for 80% of reactor volume, is then warmed up to 120 DEG C with the heating rate of 1 DEG C/min, and isothermal reaction is after 10 hours, through naturally cooling, separation, 60 DEG C of vacuum drying, obtain hydro-thermal carbosphere;
Step 3, hydro-thermal carbosphere is warmed up to 300 DEG C of roastings 2 hours with the heating rate of 1 DEG C/min in air atmosphere, finally obtains carbosphere adsorbent.
Embodiment 6:
Step 1, get fructose and be dissolved in the water, the fructose soln that compound concentration is 10wt%, gets AlCl3Be dissolved in the water, the AlCl that compound concentration is 2wt%3Solution; Then by fructose soln and AlCl3Solution in mass ratio 3:1 mixes, and stirs 10 minutes, obtains reaction solution, and reaction solution is placed in to the ultrasonic 30min of ultrasonic wave separating apparatus, ultrasonic power 1800W, supersonic frequency 28KHz;
Step 2, reaction solution is transferred to stainless steel cauldron, wherein reaction solution accounts for 80% of reactor volume, is then warmed up to 120 DEG C with the heating rate of 1 DEG C/min, and isothermal reaction is after 10 hours, through naturally cooling, separation, 60 DEG C of vacuum drying, obtain hydro-thermal carbosphere;
Step 3, hydro-thermal carbosphere is warmed up to 300 DEG C of roastings 2 hours with the heating rate of 1 DEG C/min in air atmosphere, finally obtains carbosphere adsorbent.
Embodiment 7:
Step 1, get fructose and be dissolved in the water, the fructose soln that compound concentration is 10wt%, gets AlCl3Be dissolved in the water, the AlCl that compound concentration is 2wt%3Solution; Then by fructose soln and AlCl3Solution in mass ratio 3:1 mixes, and stirs 10 minutes, obtains reaction solution;
Step 2, reaction solution is transferred to stainless steel cauldron, wherein reaction solution accounts for 80% of reactor volume, is then warmed up to 120 DEG C with the heating rate of 1 DEG C/min, and isothermal reaction is after 10 hours, through naturally cooling, separation, 60 DEG C of vacuum drying, obtain hydro-thermal carbosphere;
Step 3, the hydro-thermal carbosphere obtaining is added in rotary roasting furnace, be warming up to 100 DEG C with the speed heating using microwave of 1 DEG C/min, insulation 10min, then be warming up to 300 DEG C with the speed heating using microwave of 1 DEG C/min, insulation 1h, then be warming up to 600 DEG C with the speed heating using microwave of 1 DEG C/min, insulation 3h, obtains carbosphere adsorbent; The frequency of described heating using microwave is 915MHz; The rotary speed of described rotary roasting furnace is 15r/min.
Embodiment 8:
Step 2, get inulin and be dissolved in the water, the inulin solution that compound concentration is 10wt%, gets WCl4Be dissolved in the water, the WCl that compound concentration is 2wt%4Solution; Then by inulin solution and WCl4Solution in mass ratio 3:1 mixes, and stirs 10 minutes, obtains reaction solution;
Step 2, reaction solution is transferred to stainless steel cauldron, wherein reaction solution accounts for 80% of reactor volume, is then warmed up to 120 DEG C with the heating rate of 1 DEG C/min, and isothermal reaction is after 10 hours, through naturally cooling, separation, 60 DEG C of vacuum drying, obtain hydro-thermal carbosphere;
Step 3, hydro-thermal carbosphere is warmed up to 300 DEG C of roastings 2 hours with the heating rate of 1 DEG C/min in air atmosphere, finally obtains carbosphere adsorbent.
Embodiment 9:
Step 1, inulin is added to the water, heating is mixed with the inulin solution of 10wt%, gets inulin solution 100g, with salt acid for adjusting pH value to 3, with 750W microwave treatment 10min; Then add the urea liquid of 1mol/L, pH value is adjusted to 6, obtain acidolysis inulin solution; Get 20g terephthalic acid (TPA), with 80gN, N-dimethylacetylamide mixes, then adds the acidolysis inulin solution of 20g and 3g pyridine to mix, by mixed material be warming up to 75 DEG C and at this temperature stirring reaction 5 hours, obtain reacting rear mixture; Mixture after reaction is cooled to after room temperature, filters, filtrate through dried over mgso, obtain inulin esterification products again after organic solvent is removed in distillation; Get inulin esterification products 10g, be dissolved in 80gN, in N-dimethylacetylamide, in inulin esterification products solution, add 5g melamine dissolving completely, gained mixed solution back flow reaction under 180 DEG C of conditions naturally cooled to room temperature after 3 hours, filtered and obtained solid product, used methyl alcohol by after gained solid product washing 3 times, dry to constant weight, obtain modified inulin.
Step 2, get modified inulin and be dissolved in the DMF and acetone that volume ratio is 1:1, the modified inulin solution that compound concentration is 10wt%, gets WCl4Be dissolved in the water, the WCl that compound concentration is 2wt%4Solution; Then by modified inulin solution and WCl4Solution in mass ratio 3:1 mixes, and stirs 10 minutes, obtains reaction solution;
Step 2, reaction solution is transferred to stainless steel cauldron, wherein reaction solution accounts for 80% of reactor volume, is then warmed up to 120 DEG C with the heating rate of 1 DEG C/min, and isothermal reaction is after 10 hours, through naturally cooling, separation, 60 DEG C of vacuum drying, obtain hydro-thermal carbosphere;
Step 3, hydro-thermal carbosphere is warmed up to 300 DEG C of roastings 2 hours with the heating rate of 1 DEG C/min in air atmosphere, finally obtains carbosphere adsorbent.
Embodiment 10:
Step 1, get modified inulin prepared by embodiment 9 and be dissolved in the DMF and acetone that volume ratio is 1:1, the modified inulin solution that compound concentration is 10wt%, gets WCl4Be dissolved in the water, the WCl that compound concentration is 2wt%4Solution; Then by modified inulin solution and WCl4Solution in mass ratio 3:1 mixes, and stirs 10 minutes, obtains reaction solution; Reaction solution is placed in to the ultrasonic 30min of ultrasonic wave separating apparatus, ultrasonic power 1800W, supersonic frequency 28KHz;
Step 2, reaction solution is transferred to stainless steel cauldron, wherein reaction solution accounts for 80% of reactor volume, is then warmed up to 120 DEG C with the heating rate of 1 DEG C/min, and isothermal reaction is after 10 hours, through naturally cooling, separation, 60 DEG C of vacuum drying, obtain hydro-thermal carbosphere;
Step 3, hydro-thermal carbosphere is warmed up to 300 DEG C of roastings 2 hours with the heating rate of 1 DEG C/min in air atmosphere, finally obtains carbosphere adsorbent.
Embodiment 11:
Step 1, get modified inulin prepared by embodiment 9 and be dissolved in the DMF and acetone that volume ratio is 1:1, the modified inulin solution that compound concentration is 10wt%, gets WCl4Be dissolved in the water, the WCl that compound concentration is 2wt%4Solution; Then by modified inulin solution and WCl4Solution in mass ratio 3:1 mixes, and stirs 10 minutes, obtains reaction solution;
Step 2, reaction solution is transferred to stainless steel cauldron, wherein reaction solution accounts for 80% of reactor volume, is then warmed up to 120 DEG C with the heating rate of 1 DEG C/min, and isothermal reaction is after 10 hours, through naturally cooling, separation, 60 DEG C of vacuum drying, obtain hydro-thermal carbosphere;
Step 3, the hydro-thermal carbosphere obtaining is added in rotary roasting furnace, be warming up to 100 DEG C with the speed heating using microwave of 1 DEG C/min, insulation 10min, then be warming up to 300 DEG C with the speed heating using microwave of 1 DEG C/min, insulation 1h, then be warming up to 600 DEG C with the speed heating using microwave of 1 DEG C/min, insulation 3h, obtains carbosphere adsorbent; The frequency of described heating using microwave is 915MHz; The rotary speed of described rotary roasting furnace is 15r/min.
Embodiment 12:
Step 1, get modified inulin prepared by embodiment 9 and be dissolved in the DMF and acetone that volume ratio is 1:1, the modified inulin solution that compound concentration is 10wt%, gets WCl4Be dissolved in the water, the WCl that compound concentration is 2wt%4Solution; Then by modified inulin solution and WCl4Solution in mass ratio 3:1 mixes, and stirs 10 minutes, obtains reaction solution; Reaction solution is placed in to the ultrasonic 30min of ultrasonic wave separating apparatus, ultrasonic power 1800W, supersonic frequency 28KHz;
Step 2, reaction solution is transferred to stainless steel cauldron, wherein reaction solution accounts for 80% of reactor volume, is then warmed up to 120 DEG C with the heating rate of 1 DEG C/min, and isothermal reaction is after 10 hours, through naturally cooling, separation, 60 DEG C of vacuum drying, obtain hydro-thermal carbosphere;
Step 3, the hydro-thermal carbosphere obtaining is added in rotary roasting furnace, be warming up to 100 DEG C with the speed heating using microwave of 1 DEG C/min, insulation 10min, then be warming up to 300 DEG C with the speed heating using microwave of 1 DEG C/min, insulation 1h, then be warming up to 600 DEG C with the speed heating using microwave of 1 DEG C/min, insulation 3h, obtains carbosphere adsorbent; The frequency of described heating using microwave is 915MHz; The rotary speed of described rotary roasting furnace is 15r/min.
For effect of the present invention is described, inventor provides contrast experiment as follows:
Comparative example 1:
In step 1 of the present invention, do not have metal salt solution to participate in reaction, identical with example 1 of all the other parameters, technical process is also identical.
Comparative example 2:
In step 1 of the present invention, do not have metal salt solution to participate in reaction, identical with example 4 of all the other parameters, technical process is also identical.
Comparative example 3:
In step 1 of the present invention, do not have metal salt solution to participate in reaction, identical with example 5 of all the other parameters, technical process is also identical.
Comparative example 4:
In step 2 of the present invention, hydro-thermal carbosphere takes oven drying to replace vacuum drying method to dry hydro-thermal carbosphere, identical with example 1 of all the other parameters, and technical process is also identical.
Comparative example 5:
In step 3 of the present invention, the not further roasting in air atmosphere of hydro-thermal carbosphere, identical with example 1 of all the other parameters, technical process is also identical.
Adopt the hydro-thermal carbosphere adsorbent of above embodiment 1～12 and comparative example 1～5 preparation do respectively productive rate statistics and uranyl ion solution is carried out to Static Adsorption research.
The hydro-thermal carbosphere adsorbent 0.01g that gets respectively above-described embodiment 1～12 and comparative example 1～5 preparation mixes with the uranyl solution of 20mL140mg/L, and regulating pH is 4.5, is placed in shaking table vibration 24h, and rotating speed is 130rpm, and adsorption temp is 25 DEG C; Record and adsorb uranyl ion concentration in the solution of front and back with ultraviolet specrophotometer;
Adsorption effect to uranyl ion is as shown in table 1, and the clearance of uranyl ion is calculated by following formula (1),
Clearance=(Co-Cm)/Co × 100% (1)
Wherein, Co is the concentration of uranyl ion before absorption, and Cm is the concentration of uranyl ion after absorption.
The adsorbance of sorbing material is calculated by following formula (2),
Adsorbance=(Co-Ce) V/m (2)
Wherein, Co is the concentration of uranyl ion before absorption, and Ce is the concentration of uranyl ion after adsorption equilibrium, and V is the volume that adds uranyl ion solution, and m is the quality of the hydro-thermal carbosphere adsorbent that adds.
Fig. 4 is the adsorption effect figure of the uranyl ion solution of hydro-thermal carbosphere adsorbent to different pH of preparation in the embodiment of the present invention 1, experimentation is: get adsorbent 0.01g and mix with the uranyl solution of 20mL140mg/L, regulating respectively pH is 2.5,3.5,4.5, be placed in shaking table vibration 24h, rotating speed is 130rpm, and adsorption temp is 25 DEG C; Record and adsorb uranyl ion concentration in the solution of front and back with ultraviolet specrophotometer, and calculate adsorbance, as shown in Figure 4, illustrate that at pH be at 4.5 o'clock, the adsorbance maximum of adsorbent.
The hydro-thermal carbosphere adsorbent that embodiment 1～12 and comparative example 1～5 are prepared carries out calculation of yield, and the productive rate that each example and comparative example calculate is as shown in table 1.
Table 1
As known from Table 1, embodiment 1～11 has adopted raw material and the technological parameter in proportion of the present invention, and the productive rate of hydro-thermal carbosphere adsorbent is greater than 16.5%; Its advantages of good adsorption effect to uranyl ion solution, clearance is all greater than 69%, and the adsorbance of uranyl ion is all greater than to 155.5mg/g.
And the ratio of the raw material adopting in comparative example and technological parameter is not within proportion of the present invention, therefore, as described in comparative example 1 and comparative example 2, do not form solid product, and the productive rate of comparative example 3 is also relatively low. Also poor to the adsorption effect of uranyl ion, clearance and adsorbance are all less than example 1～5 respective value.
Comparative example 1 is with comparative example 2 compared with embodiment 1, and in step 1, metal salt-free participates in reaction not in scope of the present invention. Comparative example 1 and comparative example 2 are under cryogenic conditions, and hydrothermal carbonization can not get solid product, and reaction system is just changed to brown a little. Illustrate under low-temperature hydrothermal environment, the reactions such as biomass solution is not hydrolyzed, dehydration, and then in reaction solution, there is no Formed core, also just generate without carbosphere.
Comparative example 3 is compared with embodiment 1, and in step 1, metal salt-free participates in reaction not in scope of the present invention. Comparative example 3 is under cryogenic conditions, although can be hydrolyzed, dehydration, and Formed core and form carbosphere, has many reasons to hinder its industrial applications, such as: (1) raw material sources are limited; (2) hydrothermal carbonization becomes the particle diameter of carbosphere to only have 200 nanometer left and right, and while application as adsorbent, difficulty reclaims and is not easy to repeatedly utilize; (3) this raw material is on the low side compared with other biological raw material as the productive rate of carbon source. Comprehensive above-mentioned reason, comparative example 3 is limited in the application prospect of adsorbing domain.
Comparative example 4 is compared with embodiment 1, in step 2, drying means is not in scope of the present invention, and comparative example 4 adopts the method for oven drying that the hydro-thermal carbon in step 1 is dried to processing, do not investigate vacuum drying and baking oven on hydro-thermal carbosphere surface-COOH and-impact of OH. Cause functional group's partial destruction in dry run, reduced the chelation success rate between group and uranyl ion, therefore comparative example 1～5, obviously reduces uranyl ion adsorption effect.
Comparative example 5 is compared with embodiment 1, in step 2, not further in air atmosphere carbonization not in scope of the present invention, in comparative example 5, hydro-thermal carbosphere does not have further carbonization and sclerosis, between hydro-thermal carbosphere, reunite serious, microsphere surface group does not increase, and is that group part is by embedding on the contrary, thereby comparative example 1～5, obviously affect the adsorption effect to uranyl ion.
Embodiment 6 is compared with embodiment 5, adopt and ultrasonic reaction solution has been processed, ultrasonic wave energy discharges huge energy, the localized hyperthermia's hyperbaric environment producing and the microjet with intense impact power, easily realize each evenly mixing mutually, elimination local concentration is inhomogeneous, improve reaction speed, stimulate the formation of cenotype, and can also play shear action to reuniting, be conducive to the formation of molecule, product is dispersed in microemulsion with the form of nano particle, and existence that can be stable, and the carbosphere adsorbent obtaining to the adsorption effect of uranyl ion apparently higher than the adsorption effect that does not apply the carbosphere that ultrasonic processing obtains in embodiment 5, illustrate that hyperacoustic applying played useful effect to the absorption property of carbosphere.
Embodiment 7 is compared with embodiment 5, the carbonization mode adopting is the process that program microwave heats up, temperature programming can be brought into play the greatest benefit of each temperature section, reduce the mean temperature of whole process, reduce total energy loss, improve overall capacity usage ratio, simultaneously, temperature programming has reduced the heater working time at high temperature, thereby has reduced the requirement to heater high-temperature stability, has improved utilization rate and the reliability of firing equipment, adopt heating using microwave to heat up simultaneously, microwave is a kind of electromagnetic wave with special nature, its frequency is between radio wave and light wave, its rate of heat addition is fast, can make raw material in short-term, reach carbonization and activate temperature required, therefore energy consumption is lower, time is also shorter, simultaneously in microwave heating process, material is self-heating, with respect to the mode of existing air heat conduction, the projecting environment temperature of temperature of charge, therefore adopt heating using microwave can reduce sintering temperature, and provide material inside and outside temperature uniform hot environment, can fully penetrate into the inside of material, improve substance characteristics, adjust material structure and shape, obtain high-quality product, in addition, rotation roasting at roasting process, can integrate the pattern of carbosphere adsorbent, obtain the uniform carbosphere of pattern, can find out from adsorption effect, carbosphere adsorbent prepared by embodiment 7 is the adsorption effect apparently higher than the carbosphere obtaining in embodiment 5 to the adsorption effect of uranyl ion, the process that read-me heats up has played useful effect to the absorption property of carbosphere.
Embodiment 8 is compared with embodiment 9, in embodiment 9, adopt modified inulin as biomass material, can find out from adsorption effect, carbosphere adsorbent prepared by embodiment 9 is the adsorption effect apparently higher than the carbosphere that adopts in embodiment 8 inulin to obtain as biomass material to the adsorption effect of uranyl ion, illustrates that the absorption property of the carbosphere to preparation to the modification of inulin has played useful effect.
Embodiment 10 is compared with embodiment 9, embodiment 10 has adopted and ultrasonic reaction solution has been processed, the carbosphere adsorbent that embodiment 10 obtains apparently higher than the adsorption effect that does not apply the carbosphere that ultrasonic processing obtains in embodiment 9, illustrates that hyperacoustic applying played useful effect to the absorption property of carbosphere to the adsorption effect of uranyl ion.
Embodiment 11 is compared with embodiment 9, the carbonization mode that embodiment 11 adopts is the process that program microwave heats up, can find out from adsorption effect, carbosphere adsorbent prepared by embodiment 11 is the adsorption effect apparently higher than the carbosphere obtaining in embodiment 9 to the adsorption effect of uranyl ion, and the process that read-me heats up has played useful effect to the absorption property of carbosphere.
Embodiment 12 is compared with embodiment 9, embodiment 10, embodiment 11, embodiment 12 adopts and ultrasonic reaction solution is processed, utilize again program microwave to heat up, its carbosphere adsorbent of preparing is the adsorption effect apparently higher than the carbosphere obtaining in embodiment 9, embodiment 10, embodiment 11 to the adsorption effect of uranyl ion, illustrates that ultrasonic and process temperature programming has played useful effect to the absorption property of carbosphere.
Visible, the raw material adopting in the present invention is in described ratio, and in the preparation process of sorbing material, parameters is in described scope, and the sorbing material productive rate of preparation is higher, better to the absorption property of uranyl ion.
Although embodiment of the present invention are open as above, but it is not restricted to listed utilization in description and embodiment, it can be applied to various applicable the field of the invention completely, for those skilled in the art, can easily realize other amendment, therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific details and illustrates here and the legend of describing.
Claims (10)
1. slaine catalysis hydrothermal reaction at low temperature is prepared a method for carbosphere adsorbent, it is characterized in that: comprise the following steps:
Step 1, get the biomass solution that biomass material compound concentration is 2～20wt%, get the metal salt solution that slaine compound concentration is 0.5～2wt%; Then by biomass solution and metal salt solution in mass ratio 2～5:1 mix, stir 5～10 minutes, obtain reaction solution;
Step 2, reaction solution is transferred to stainless steel cauldron, wherein reaction solution accounts for 60～80% of reactor volume, is then warmed up to 100～160 DEG C with certain heating rate, and isothermal reaction is after 8～20 hours, through naturally cooling, separation, vacuum drying, obtain hydro-thermal carbosphere;
Step 3, by the roasting carbonization in air atmosphere of hydro-thermal carbosphere, obtain carbosphere adsorbent.
2. slaine catalysis hydrothermal reaction at low temperature as claimed in claim 1 is prepared the method for carbosphere adsorbent, it is characterized in that, in described step 1, biomass material is any one in glucose, fructose, starch, inulin, lignocellulosic.
3. slaine catalysis hydrothermal reaction at low temperature as claimed in claim 1 is prepared the method for carbosphere adsorbent, it is characterized in that, in described step 1, slaine is CrCl3、SnCl4、WCl4、B(OH)3、AlCl3In any one.
4. slaine catalysis hydrothermal reaction at low temperature as claimed in claim 1 is prepared the method for carbosphere adsorbent, it is characterized in that, in described step 2, heating rate is 0.1～10 DEG C/min, and vacuum drying temperature is 50～100 DEG C.
5. slaine catalysis hydrothermal reaction at low temperature as claimed in claim 1 is prepared the method for carbosphere adsorbent, it is characterized in that, in described step 3, the roasting carburizing temperature of hydro-thermal carbosphere in air atmosphere is 250～600 DEG C, time is 0.5～5h, and heating rate is 0.1～10 DEG C/min.
6. slaine catalysis hydrothermal reaction at low temperature as claimed in claim 1 is prepared the method for carbosphere adsorbent, it is characterized in that, described biomass material is modified inulin, the preparation method of described modified inulin is: inulin is added in deionized water, heating is mixed with the inulin solution of 10～15wt%, by weight, gets 100～300 parts of inulin solution, with salt acid for adjusting pH value to 3～4, with 750W microwave treatment 10～30min; Then add the urea liquid of 1～3mol/L, pH value is adjusted to 6～7, obtain acidolysis inulin solution; Get 10～20 parts of terephthalic acid (TPA)s, mix with 80～100 parts of DMAs, then add acidolysis inulin solution and 3～5 parts of pyridines of 20～30 parts to mix, by mixed material be warming up to 75～85 DEG C and at this temperature stirring reaction 5～10 hours, obtain reacting rear mixture; Mixture after reaction is cooled to after room temperature, filters, filtrate through dried over mgso, obtain inulin esterification products again after organic solvent is removed in distillation; Get 10～15 parts of inulin esterification products, be dissolved in 80～100 parts of N, in N-dimethylacetylamide, in inulin esterification products solution, add 5～8 parts of melamines dissolving completely, gained mixed solution back flow reaction under 150～180 DEG C of conditions naturally cooled to room temperature after 3～5 hours, filtered and obtained solid product, used methyl alcohol by after gained solid product washing 3～5 times, dry to constant weight, obtain modified inulin.
7. slaine catalysis hydrothermal reaction at low temperature as claimed in claim 6 is prepared the method for carbosphere adsorbent, it is characterized in that, the solvent of the modified inulin solution of described modified inulin preparation is that volume ratio is DMF and the acetone of 1:1～3.
8. slaine catalysis hydrothermal reaction at low temperature as claimed in claim 1 is prepared the method for carbosphere adsorbent, it is characterized in that, in described step 1, the reaction solution obtaining is placed in to the ultrasonic 30～60min of ultrasonic wave separating apparatus, the adjustable range of ultrasonic power is at 600～1800W, and supersonic frequency is at 25～50KHz.
9. slaine catalysis hydrothermal reaction at low temperature as claimed in claim 1 is prepared the method for carbosphere adsorbent, it is characterized in that, in described step 3, the process of roasting carbonization is: the hydro-thermal carbosphere obtaining is added in rotary roasting furnace, be warming up to 100～200 DEG C with the speed heating using microwave of 0.1～10 DEG C/min, insulation 10～20min, then be warming up to 300～400 DEG C with the speed heating using microwave of 0.1～10 DEG C/min, insulation 1～2h, then be warming up to 500～600 DEG C with the speed heating using microwave of 0.1～10 DEG C/min, insulation 2～3h, obtains carbosphere adsorbent; The frequency of described heating using microwave is 915MHz.
10. slaine catalysis hydrothermal reaction at low temperature as claimed in claim 1 is prepared the method for carbosphere adsorbent, it is characterized in that, the rotary speed of described rotary roasting furnace is 10～15r/min.
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