CN104437546A - Non-homogeneous phase ozone catalyst and preparation method thereof - Google Patents
Non-homogeneous phase ozone catalyst and preparation method thereof Download PDFInfo
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- CN104437546A CN104437546A CN201410743716.0A CN201410743716A CN104437546A CN 104437546 A CN104437546 A CN 104437546A CN 201410743716 A CN201410743716 A CN 201410743716A CN 104437546 A CN104437546 A CN 104437546A
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Abstract
The invention discloses a non-homogeneous phase ozone catalyst and a preparation method thereof. The non-homogeneous phase ozone catalyst comprises the following components in percentage by weight: 36.4%-52.4% of water dreg micropowder, 9.1%-14.3% of magnesium oxide (MgO), 18.2%-23.8% of magnesium chloride hexahydrate (MgCl2.6H2O), 4.8%-9% of foaming agents and 9.1%-19% of catalytic activity mixtures. The preparation method of the non-homogeneous phase ozone catalyst, which is disclosed by the invention, is simple and short in process flow, only requires the maximum temperature at 40-60 DEG C in a product preparation process, and is very low in production cost.
Description
Technical field
The present invention relates to catalyst technical field, especially relate to a kind of heterogeneous ozone catalyst and preparation method thereof.
Background technology
At present, ozone, can various impurity in oxidize water in water treatment as a kind of excellent strong oxidizer, to reach the effect of water purification, and in Water treatment, have advantages such as not producing secondary pollution and be used widely in water treatment.
People utilize the mode of ozone be mainly for sterilization and directly carry out oxidation processes to the pollutant in water the earliest, and find in rear a kind of Land use systems, although ozone oxidation performance is strong, but it has stronger selective to the pollutant process in water, this characteristic limits the popularization of ozonation technology in process organic wastewater with difficult degradation thereby.Given this, have people catalyst preparation to be become certain density solution (i.e. homogeneous catalyst), join in waste water, catalyst is present in waste water with the form of ion, is then passed in waste water by ozone and carries out catalytic oxidation.Although this measure can improve treatment effect, but homogeneous catalyst exists in use, and catalyst is difficult to reclaim, medicament costly, introduce impurity and produce secondary pollution, and ozone utilization rate is low, poor etc. the problems for the treatment of effeciency, limit its application in water treatment and popularization to a great extent.
In recent years, around how designing a class catalyst, it can improve the utilization rate of ozone, strengthen the oxidability of ozone, the polluter of ozone after catalysis in non-selectivity ground oxidation processes water can be made again, catalyst and catalytic activity component do not run off with sewage again simultaneously, thus realize obtaining excellent treatment effect with lower processing cost, become the emphasis of each scientific research institution and the research of relevant enterprises and institutions.
Chinese patent ZL200710121727.5, discloses a kind of method for preparing catalyst of efficient catalytic ozonisation organic pollutants.Its method, for join in deionized water by a certain amount of manganese acetate, then adds a certain amount of Mesoporous zirconia, makes Mn0 in solution
2/ ZrO
2middle Mn(is with Mn0
2meter) percentage composition is 1-15wt%, at room temperature flood 0.5-6 hour, the system obtained is 100-140 DEG C of dry 1-6 hour in an oven, then deionized water is spent, use 100-140 DEG C of dry 1-6 hour again, finally gained powder is calcined 2-6 hour at 300-500 DEG C, finally obtain Mn0
x/ ZrO
2sample.
Chinese patent ZL200510009814.2, disclose the preparation of catalyst of Nano titanium dioxide and the method for catalyst ozonization water treatment, disclose the preparation method of catalyst of Nano titanium dioxide, it is with active alundum (Al2O3), white silica gel, molecular sieve or zeolite for carrier, and active constituent is TiO
2butyl titanate is slowly dissolved in obtained colloidal sol in anhydrous ethanol solvent, active alundum (Al2O3), white silica gel, molecular sieve or zeolite are dipped in this solution, at room temperature shake 5-48 hour, after filtration under 105 DEG C of conditions dry 2-18 hour, then adopt programmed temperature method in muffle furnace, under 550 DEG C of conditions, to sinter 1-10 hour and obtained solid catalyst.
To sum up, the preparation of current ozone catalyst all needs through following steps: 1. screen suitable catalyst carrier; 2. the solution of certain density catalytic activity component is configured; 3. by carrier impregnation to containing catalyst component solution in; 4. the catalyst flooded is taken out and drying at relatively high temperatures; 5. catalyst drying completed carries out sintering, solidifying again; 6. shaping solid catalyst is produced.Above-mentioned Making programme inevitably need use secondary temperature elevation (needing after drying again to sinter), and not only energy consumption is very high, and fuel combustion and active constituent transform all can generation secondary pollution in various degree, be unfavorable for energy-saving and emission-reduction.In addition, the catalytic activity component of catalyst prepared by said method is all more single, and applicable surface is wideless in the treatment of waste water, and Making programme is longer, technique is comparatively complicated, each of which increases the cost of production, current catalytic component is single, and it is low to the utilization rate of ozone.
As can be seen here, in prior art, ozone catalyst with and preparation method thereof all there is significantly not enough and defect, urgently improve further.
Summary of the invention
The object of this invention is to provide a kind of heterogeneous ozone catalyst and preparation method thereof, make it have that cost is low, technological process is simple, consume energy low, decreasing pollution, catalyst application is wide, and catalytic efficiency is high, ozone utilization rate is high, the advantage of long service life.
For solving the problems of the technologies described above, the invention provides a kind of preparation method of heterogeneous ozone catalyst, it comprises the following steps:
Step one: screening grain slag micro mist, and be crushed into particle diameter and be less than 250 orders;
Step 2: be mixed material by the following material Homogeneous phase mixing of mass ratio: grain slag micro mist 36.4%-52.4%, magnesia 9.1%-14.3%, magnesium chloride hexahydrate 18.2%-23.8%, blowing agent 4.8%-9% and catalytic activity mixture 9.1%-19%;
Step 3: described mixed material is delivered to balling disk (-sc) granulation, sprays into atomized water simultaneously, prepares intermediate products in balling disk (-sc);
Step 4: described intermediate products are tanned by the sun 3-6 hour in the sun, then hangs 28-40 hour, obtains heterogeneous ozone catalyst finished product.
The present invention also provides a kind of preparation method of heterogeneous ozone catalyst, and it comprises the following steps:
Step one: screening grain slag micro mist, and be crushed into particle diameter and be less than 250 orders;
Step 2: be mixed material by the following material Homogeneous phase mixing of mass ratio: grain slag micro mist 36.4%-52.4%, magnesia 9.1%-14.3%, magnesium chloride hexahydrate 18.2%-23.8%, blowing agent 4.8%-9% and catalytic activity mixture 9.1%-19%;
Step 3: described mixed material is delivered to balling disk (-sc) granulation, sprays into atomized water simultaneously, prepares intermediate products, by these intermediate products at 40-60 DEG C of laser heating 0.5-3 hour in balling disk (-sc);
Step 4: the intermediate products after heating in step 3 are hung 10-28 hour and obtains heterogeneous ozone catalyst finished product.
In one embodiment of the present of invention, described catalytic activity mixture comprises the first catalytic activity mixture and the second catalytic activity mixture;
Wherein, the first catalytic activity mixture adopts iron making and sintering dedusting ash, and it comprises di-iron trioxide (Fe
2o
3), tri-iron tetroxide (Fe
3o
4), calcium oxide (CaO), silica (SiO
2) and noble metal; This noble metal is at least one in gold (Au), silver (Ag) and cobalt (Co), and this first catalytic activity mixture accounts for the 60%-80% of total catalytic activity mixture quality;
Described second catalytic activity mixture comprises titanium dioxide (TiO
2), cupric oxide (CuO), manganese monoxide (MnO), manganese dioxide (MnO
2), alundum (Al2O3) (A1
2o
3), cobalt oxide (CoO) and cobaltosic oxide (Co
3o
4) at least one, and this second catalytic activity mixture accounts for the 20%-40% of total catalytic activity mixture quality.
In one embodiment of the present of invention, in described first catalytic activity mixture, the mass content ratio of each component is respectively: di-iron trioxide (Fe
2o
3) be 20%-30%, tri-iron tetroxide (Fe
3o
4) be 5%-15%, gold (Au) is 0.0003%-0.001%, and silver (Ag) is 0.03%-0.1%, and surplus is calcium oxide (CaO) and silica (SiO
2).
In one embodiment of the present of invention, in described second catalytic activity mixture, it is 50% that the mass content ratio of each component is respectively cupric oxide (CuO), and manganese monoxide (MnO) is 50%.
In one embodiment of the present of invention, the particle diameter of described catalytic activity mixture is less than 380 orders, and described blowing agent is dry powder carbonic hydroammonium (NH
4hCO
3).
In one embodiment of the present of invention, in described step 3, described in spray into atomized water quality be the 10%-14% of described mixture quality of material.
In addition, the present invention also provides a kind of heterogeneous ozone catalyst prepared by above-mentioned method, and it comprises the material of following masses ratio: grain slag micro mist 36.4%-52.4%, magnesia (MgO) 9.1%-14.3%, magnesium chloride hexahydrate (MgCl
26H
2o) 18.2%-23.8%, blowing agent 4.8%-9% and catalytic activity mixture 9.1%-19%.
In one embodiment of the present of invention, described catalytic activity mixture comprises the first catalytic activity mixture and the second catalytic activity mixture;
Wherein, the first catalytic activity mixture adopts iron making and sintering dedusting ash, and it comprises di-iron trioxide (Fe
2o
3), tri-iron tetroxide (Fe
3o
4), calcium oxide (CaO), silica (SiO
2) and noble metal, this noble metal is at least one in gold (Au), silver (Ag) and cobalt (Co), and this first catalytic activity mixture accounts for the 60%-80% of total catalytic activity mixture quality;
Described second catalytic activity mixture comprises titanium dioxide (TiO
2), cupric oxide (CuO), manganese monoxide (MnO), manganese dioxide (MnO
2), alundum (Al2O3) (A1
2o
3), cobalt oxide (CoO) and cobaltosic oxide (Co
3o
4) at least one, and this second catalytic activity mixture accounts for the 20%-40% of total catalytic activity mixture quality;
Described blowing agent is dry powder carbonic hydroammonium (NH
4hCO
3).
In one embodiment of the present of invention, in described first catalytic activity mixture, the mass content ratio of each component is respectively: di-iron trioxide (Fe
2o
3) be 20%-30%, tri-iron tetroxide (Fe
3o
4) be 5%-15%, gold (Au) is 0.0003%-0.001%, and silver (Ag) is 0.03%-0.1%, and surplus is calcium oxide (CaO) and silica (SiO
2);
In described second catalytic activity mixture, the mass content ratio of each component is respectively: cupric oxide (CuO) is 50%, and manganese monoxide (MnO) is 50%.
The heterogeneous ozone catalyst of the present invention has following beneficial effect compared with prior art:
1, in catalyst prod manufacturing process of the present invention, maximum temperature only needs 40-60 DEG C, and preparation method is simple, technological process is short, production cost is very cheap;
2, method for preparing catalyst of the present invention does not need sintering or calcining, avoids the environmental pollution that the conversion because of fuel combustion and active constituent brings;
3, the catalyst prod active catalytic component prepared of the present invention is various, avoid the problem that single the faced adaptive surface of catalyst component is narrow, there is applicability widely, especially as the core product of pre-oxidation means and biochemical process coupling, there is huge advantage in organic wastewater with difficult degradation thereby advanced treating field;
4, present invention achieves the slug detect of steel mill grain slag and the efficiency utilization of iron-smelter iron making and sintering dedusting ash, substantially increase the secondary value of waste material;
5, heterogeneous solid ozone catalyst of the present invention because mechanical strength is high, water insoluble, medium density and catalytic activity component isotropic consolidation among the surface and micropore of catalyst carrier, therefore this catalyst long service life, not easily runs off;
6, this multiple catalyst component significantly improves the utilization rate of ozone than traditional one-component catalyst.
Detailed description of the invention
Below by way of the beneficial effect that specific embodiment is introduced embodiments of the invention further and had, object is to help reader better to understand essence of the present invention and spirit, does not form limiting the scope of the present invention.
Embodiment 1
Heterogeneous solid ozone catalyst refers to the magnesium cement granules to be full of Multimetal oxide in a kind of surface and micropore.The preparation method of this heterogeneous ozone catalyst, specifically comprises the following steps:
Step one: screen the grain slag micro mist after magnetic separation, and be ground into particle diameter and be less than 250 orders, select granularity to be less than the catalytic activity mix powder of 380 object containing metal oxides, selective oxidation magnesium, magnesium chloride hexahydrate powder and dry powder blowing agent;
Step 2: according to a certain percentage described grain slag micro mist and magnesium oxide powder, magnesium chloride hexahydrate powder, dry powder blowing agent and particle diameter are less than 380 object catalytic activity mix powders and add batching tank diameter, utilize mixer Homogeneous phase mixing for mixed material;
Wherein, grain slag micro mist accounts for the 36.4%-52.4% of gross mass, and magnesia (MgO) accounts for the 9.1%-14.3% of gross mass, magnesium chloride hexahydrate (MgCl
26H
2o) account for the 18.2%-23.8% of gross mass, catalytic activity mixture accounts for the 9.1%-19% of gross mass, and dry powder blowing agent accounts for the 4.8%-9% of gross mass, and each component ratio sum is 100%.
Wherein, catalytic activity mixture comprises the first catalytic activity mixture and the second catalytic activity mixture, and wherein, the mass ratio that the first catalytic activity mixture accounts for total catalytic activity mixture is 60%-80%, and it mainly comprises di-iron trioxide (Fe
2o
3) and tri-iron tetroxide (Fe
3o
4), the calcium oxide (CaO) also containing gold (Au), the silver noble metal such as (Ag) and cobalt (Co) and surplus and silica (SiO
2) etc. component; The thing mass ratio that second catalytic activity mixture accounts for total catalytic activity mixture is 20%-40%, and it mainly comprises titanium dioxide (TiO
2), cupric oxide (CuO), manganese monoxide (MnO), manganese dioxide (MnO
2), alundum (Al2O3) (A1
2o
3), cobalt oxide (CoO), cobaltosic oxide (Co
3o
4) in one or more.
Step 3: the mixed material of described mixing is delivered to balling disk (-sc) granulation through conveyer belt, sprays into atomized water simultaneously, obtains intermediate products in balling disk (-sc).Its concrete course of work is:
The first step: ball is formed, and mixed material is the material that hydrophily is higher, and particle surface has the ability of adsorption moisture.Adhesive property is produced after magnesia and magnesium chloride meet water.When the mixed material constantly added rolls in balling disk (-sc), tiny water droplet is also constantly sprinkled upon on mixed material, and particle runs into water droplet, and rapid adsorption infiltrates, and particle surface forms the very thin moisture film of one deck, and adsorbs material in the rolling.Because the surface tension of water and the cementation of mixed material form little ball---mother bulb one by one, there is very thin moisture film on mother bulb surface, this moisture when constantly rolling moves outward gradually and is formed under centrifugal force and Action of Gravity Field, and the amount of water wherein in ball forming process is 10% ~ 14% of mixed material gross mass.
Second step: whole ball is formed, after the ball of pre-add water mixer enters balling disk (-sc), by the effect of centrifugal force, frictional force and gravity in balling disk (-sc), along parabolic motion, due to cohesiveness and the plasticity of mixed material, make ball cohere mutually in motion process and grow up into whole ball gradually, thus prepare intermediate products.
Step 4: placed by the intermediate products obtained in step 3 and tan by the sun 3-6 hour in the sun, then hangs 28-40 hour in feeding warehouse and obtains heterogeneous solid ozone catalyst finished product.
Preferably, in step 4, can select intermediate products in warehouse, hang 36 hours, heterogeneous solid ozone catalyst finished product can be obtained.
Embodiment 2
The preparation method of heterogeneous ozone catalyst of the present invention, specifically comprises the following steps:
Step one: screen the grain slag micro mist after magnetic separation, and be ground into particle diameter and be less than 250 object micro mists, select granularity to be less than the catalytic activity mix powder of 380 object containing metal oxides, selective oxidation magnesium, magnesium chloride hexahydrate powder and dry powder blowing agent;
Step 2: according to a certain percentage described grain slag micro mist and magnesium oxide powder, magnesium chloride hexahydrate powder, dry powder blowing agent and particle diameter are less than 380 object catalytic activity mix powders and add batching tank diameter, utilize mixer Homogeneous phase mixing for mixed material;
Wherein, grain slag micro mist accounts for the 36.4%-52.4% of gross mass, and magnesia (MgO) accounts for the 9.1%-14.3% of gross mass, magnesium chloride hexahydrate (MgCl
26H
2o) account for the 18.2%-23.8% of gross mass, catalytic activity mixture accounts for the 9.1%-19% of gross mass, and dry powder blowing agent accounts for the 4.8%-9% of gross mass, and each component ratio sum is 100%.
Wherein, catalytic activity mixture comprises the first catalytic activity mixture and the second catalytic activity mixture, and wherein, the mass ratio that the first catalytic activity mixture accounts for total catalytic activity mixture is 60%-80%, and it mainly comprises di-iron trioxide (Fe
2o
3) and tri-iron tetroxide (Fe
3o
4), the calcium oxide (CaO) also containing gold (Au), the silver noble metal such as (Ag) and cobalt (Co) and surplus and silica (SiO
2) etc. component; The thing mass ratio that second catalytic activity mixing accounts for total catalytic activity mixture is 20%-40%, and it mainly comprises titanium dioxide (TiO
2), cupric oxide (CuO), manganese monoxide (MnO), manganese dioxide (MnO
2), alundum (Al2O3) (A1
2o
3), cobalt oxide (CoO), cobaltosic oxide (Co
3o
4) in one or more.
Step 3: the mixed material of described mixing is delivered to balling disk (-sc) granulation through conveyer belt, sprays into atomized water simultaneously, obtains intermediate products, these intermediate products are placed in heating cabinet laser heating 0.5-3 hour within the scope of 40-60 DEG C in balling disk (-sc).Wherein, in this step, the amount spraying into atomized water is 10% ~ 14% of mixed material gross mass.
Step 4: the intermediate products feeding warehouse after heating in step 3 is hung 10-28 hour and can obtain heterogeneous solid ozone catalyst finished product.
Preferably, in step 4, the intermediate products after by heating can be selected to send into warehouse and to hang 24 hours.
This embodiment is the limiting factor considered because of season or weather conditions and regional climate, at the highest temperature of environment lower than under the non-fine day weather conditions of 30 DEG C, after heterogeneous solid ozone catalyst intermediate products complete, be placed in heating cabinet laser heating 0.5-3 hour within the scope of 40-60 DEG C according to the intermediate products that actual conditions can utilize factory's waste hot steam granulation to be completed, the intermediate products heated feeding warehouse hangs 10-28 hour and can obtain heterogeneous solid ozone catalyst finished product.
The raw material of heterogeneous catalytic ozonation agent of the present invention mainly removes grain slag micro mist after abrasive grit again after mechanical crushing for aggregate, with magnesia (MgO) powder and magnesium chloride hexahydrate (MgCl with the grain slag of steel mill through magnetic separation
26H
2o) be cementing agent, with dry powder carbonic hydroammonium (NH
4hCO
3) be blowing agent, and with the catalytic active substance containing various metals and metal oxide for catalytic activity mixture.Concretely, in heterogeneous catalytic ozonation agent, the mass percentage of each component is respectively: grain slag micro mist 36.4%-52.4%, magnesia (MgO) 9.1%-14.3%, magnesium chloride hexahydrate (MgCl
26H
2o) 18.2%-23.8%, blowing agent 4.8%-9% and catalytic activity mixture 9.1%-19%, each component ratio sum is 100%.
Wherein, catalytic activity mixture comprises the first catalytic activity mixture and second catalytic activity mixture two parts, and wherein the first catalytic activity mixture is from the ironmaking of iron-smelter
sintering dust separation ash, it mainly comprises the metal oxide of 20%-35%: di-iron trioxide (Fe
2o
3) and tri-iron tetroxide (Fe
3o
4), also containing gold (Au), the silver noble metal such as (Ag) and cobalt (Co) and calcium oxide (CaO) and silica (SiO
2) etc. component, the metal in this first catalytic activity compound and metal oxide are desirable highly active catalytic Component Source, and this first catalytic activity mixture accounts for the 60%-80% of total catalytic activity mixture quality; Concretely, in the first catalytic activity mixture, the mass content of each component is respectively: di-iron trioxide (Fe
2o
3) 20% ~ 30%, tri-iron tetroxide (Fe
3o
4) be 5% ~ 15%, gold (Au) is 0.0003% ~ 0.001%(1 ton content is 3 ~ 10g), silver (Ag) is 0.03% ~ 0.1%(1 ton content is 300 ~ 1000g), surplus is calcium oxide (CaO) and silica (SiO
2) etc. component, each component ratio sum is 100%.Second catalytic activity mixture is metal oxide, comprises titanium dioxide (TiO
2), cupric oxide (CuO), manganese monoxide (MnO), manganese dioxide (MnO
2), alundum (Al2O3) (A1
2o
3), cobalt oxide (CoO), cobaltosic oxide Co
3o
4in one or more, this second catalytic activity mixture accounts for the 20%-40% of total catalytic activity mixture quality.
Embodiment 3
First the grain slag micro mist after magnetic separation is screened, and be ground into particle diameter and be less than 250 object micro mists, then granularity is selected to be less than the catalytic activity mix powder of 380 object containing metals and metal oxide, magnesia, magnesium chloride hexahydrate powder and ammonium hydrogencarbonate dry powder blowing agent, according to mass ratio by grain slag micro mist 47.2%, magnesia (MgO) 12.3%, magnesium chloride hexahydrate (MgCl
26H
2o) 23.5%, catalytic activity mixture 11.3%(wherein, and in the first catalytic activity mixture, the mass ratio of each component is: di-iron trioxide is 30%, tri-iron tetroxide is 5%, gold (Au) is 0.0003%, and silver (Ag) is 0.03%, and surplus is calcium oxide (CaO) and silica (SiO
2), in second catalytic activity mixture, cupric oxide (CuO) accounts for 50%, manganese monoxide (MnO) accounts for 50%) and the dry powder blowing agent of 5.7% join batching tank diameter, then with mixer, mixed material is stirred, the mixed material mixed evenly is sent into balling disk (-sc) through conveyer belt, spray into atomization running water by shower nozzle simultaneously, amount of water accounts for 12% of mixed material gross mass, in balling disk (-sc), there is chemical reaction after mixed material fully contacts with water and caused particle and consolidation, then fully 3-6 hour is tanned by the sun under the intermediate products that granulation completes being inserted sunlight, then feeding warehouse hangs 36 hours and can obtain finished product heterogeneous solid ozone catalyst.
Embodiment 4
First the grain slag after magnetic separation is screened, and be ground into particle diameter and be less than 250 object micro mists, granularity is selected to be less than the catalytic activity mix powder of 380 object containing metals and metal oxide, magnesia, magnesium chloride hexahydrate powder and ammonium hydrogencarbonate dry powder blowing agent, according to mass ratio by grain slag micro mist 48.6%, magnesia (MgO) 13.2%, magnesium chloride hexahydrate (MgCl
26H
2o) 22.6%, catalytic activity mix powder 9.1%(wherein, the mass ratio of each component in the first catalytic activity mixture: di-iron trioxide (Fe
2o
3) be 20%, tri-iron tetroxide (Fe
3o
4) be 15%, gold (Au) is 0.001%, and silver (Ag) is 0.1%, and surplus is calcium oxide (CaO) and silica (SiO
2), the mass ratio of each component in second catalytic activity mixture: titanium dioxide (TiO
2) be 50%, manganese dioxide (MnO
2) be 50%) and 6.5% dry powder blowing agent join batching tank diameter, then with mixer, mixed material is stirred, the mixed material mixed evenly is sent into balling disk (-sc) through conveyer belt, spray into atomization running water by shower nozzle simultaneously, amount of water accounts for 13% of mixed material gross mass, in balling disk (-sc), there is chemical reaction after mixed material fully contacts with water and caused particle and consolidation, then the intermediate products utilizing factory's waste hot steam granulation to be completed are placed in heating cabinet laser heating 0.5 ~ 3 hour within the scope of 40 ~ 60 DEG C, the product feeding warehouse heated hangs 10 ~ 28 hours and can obtain heterogeneous solid ozone catalyst finished product.
Embodiment 5
First the grain slag micro mist after magnetic separation is screened, and be ground into particle diameter and be less than 250 object micro mists, then granularity is selected to be less than the catalytic activity mix powder of 380 object containing metals and metal oxide, magnesia, magnesium chloride hexahydrate powder and ammonium hydrogencarbonate dry powder blowing agent, according to mass ratio by grain slag micro mist 38.1%, magnesia (MgO) 14.3%, magnesium chloride hexahydrate (MgCl
26H
2o) 23.8%, catalytic activity mixture 19%(wherein, the mass ratio of each component in the first catalytic activity mixture: di-iron trioxide (Fe
2o
3) be 30%, tri-iron tetroxide (Fe
3o
4) be 5%, gold (Au) content is 0.0003%, and silver (Ag) content is 0.03%, and surplus is calcium oxide (CaO) and silica (SiO
2), in second catalytic activity mixture, cupric oxide (CuO) is 50%, manganese monoxide (MnO) is 50%) and the dry powder blowing agent of 4.8% join batching tank diameter, then with mixer, mixed material is stirred, the mixed material mixed evenly is sent into balling disk (-sc) through conveyer belt, spray into atomization running water by shower nozzle simultaneously, amount of water is 10% of mixed material gross mass, in balling disk (-sc), there is chemical reaction after mixed material fully contacts with water and caused particle and consolidation, then fully 3-6 hour is tanned by the sun under the intermediate products that granulation completes being inserted sunlight, then feeding warehouse hangs 28 hours and can obtain finished product heterogeneous solid ozone catalyst.
Embodiment 6
First the grain slag micro mist after magnetic separation is screened, and be ground into particle diameter and be less than 250 object micro mists, then granularity is selected to be less than the catalytic activity mix powder of 380 object containing metals and metal oxide, magnesia, magnesium chloride hexahydrate powder and ammonium hydrogencarbonate dry powder blowing agent, according to mass ratio by grain slag micro mist 52.4%, magnesia (MgO) 9.1%, magnesium chloride hexahydrate (MgCl
26H
2o) 18.2%, catalytic activity mixture 11.3%(wherein, and in the first catalytic activity mixture, the mass ratio of each component is respectively: di-iron trioxide (Fe
2o
3) be 30%, tri-iron tetroxide (Fe
3o
4) be 5%, gold (Au) content is 0.001%, and silver (Ag) content is 0.1%, and surplus is calcium oxide (CaO) and silica (SiO
2), in second catalytic activity mixture, the mass ratio of each component is: cupric oxide (CuO) is 50%, manganese monoxide (MnO) is 50%) and the dry powder blowing agent of 9% join batching tank diameter, then with mixer, mixed material is stirred, the mixed material mixed evenly is sent into balling disk (-sc) through conveyer belt, spray into atomization running water by shower nozzle simultaneously, amount of water is 14% of mixed material gross mass, in balling disk (-sc), there is chemical reaction after mixed material fully contacts with water and caused particle and consolidation, then fully 3-6 hour is tanned by the sun under the intermediate products that granulation completes being inserted sunlight, then feeding warehouse hangs 40 hours and can obtain heterogeneous solid ozone catalyst finished product.
Embodiment 7
First the grain slag micro mist after magnetic separation is screened, and be ground into particle diameter and be less than 250 object micro mists, then granularity is selected to be less than the catalytic activity mix powder of 380 object containing metals and metal oxide, magnesia, magnesium chloride hexahydrate powder and ammonium hydrogencarbonate dry powder blowing agent, proportionally by grain slag micro mist 36.4%, magnesia (MgO) 14%, magnesium chloride hexahydrate (MgCl
26H
2o) 23.8%, catalytic activity mixture 19%(wherein, the mass ratio of each component in the first catalytic activity mixture: di-iron trioxide (Fe
2o
3) be 20%, tri-iron tetroxide (Fe
3o
4) be 15%, gold (Au) is 0.001%, and silver (Ag) is 0.1%, and surplus is calcium oxide (CaO) and silica (SiO
2), the mass ratio of each component in second catalytic activity mixture: titanium dioxide (TiO
2) be 50%, manganese dioxide (MnO
2) content is 50%) and the dry powder blowing agent of 6.8% join batching tank diameter, then with mixer, mixed material is stirred, the mixed material mixed evenly is sent into balling disk (-sc) through conveyer belt, spray into atomization running water by shower nozzle simultaneously, amount of water is 12% of mixed material gross mass, in balling disk (-sc), there is chemical reaction after mixed material fully contacts with water and caused particle and consolidation, then fully 3-6 hour is tanned by the sun under the intermediate products that granulation completes being inserted sunlight, then feeding warehouse hangs 36 hours and can obtain finished product heterogeneous solid ozone catalyst.
The relevant experimental data of heterogeneous solid ozone catalyst of the present invention to petrochemical wastewater shows: traditional one-component ozone catalyst is about 1:3 to the removal amount of COD with the corresponding proportionate relationship of ozone dosage, and heterogeneous multicomponent ozone catalyst of the present invention is under equal conditions about 1:1.5 ~ 2 to the removal amount of COD and the corresponding proportionate relationship of ozone dosage, it can improve the ozone utilization rate of 30% ~ 50%, makes ozone overall utilization reach more than 95%.
Find through research of the present invention, the proportion of composing of Reasonable adjustment first catalytic active component and the second catalytic active component, make heterogeneous solid ozone catalyst of the present invention under use the same terms, than the utilization rate using the catalyst of any one one-component all greatly to improve ozone.
Secondly, the preparation process of heterogeneous solid ozone catalyst of the present invention does not need sintering, compares traditional catalyst, and its product cost manufacturing every cubic metre can reduce fuel cost about 300 ~ 500 yuan.
As can be seen here, heterogeneous solid ozone catalyst of the present invention and preparation method thereof, can improve ozone oxidation ability and catalyst utilization, can the organic substance of difficult degradation in accelerated decomposition water.This ozone catalyst preparation technology is simple, consumes energy low, possesses various active component, and do not flow away with waste water, can reuse, thus reduce the operation processing cost of ozone, decrease secondary pollution, catalyst of the present invention substantially increases ozone utilization rate than single catalyst component.
These are only preferred embodiment of the present invention, limiting technical scope of the invention process when not being able to this, therefore all with reference to description of the present invention do simple equivalence change with modify, all still should belong to protection scope of the present invention.
Claims (10)
1. a preparation method for heterogeneous ozone catalyst, is characterized in that comprising the following steps:
Step one: screening grain slag micro mist, and be crushed into particle diameter and be less than 250 orders;
Step 2: be mixed material by the following material Homogeneous phase mixing of mass ratio: grain slag micro mist 36.4%-52.4%, magnesia 9.1%-14.3%, magnesium chloride hexahydrate 18.2%-23.8%, blowing agent 4.8%-9% and catalytic activity mixture 9.1%-19%;
Step 3: described mixed material is delivered to balling disk (-sc) granulation, sprays into atomized water simultaneously, prepares intermediate products in balling disk (-sc);
Step 4: described intermediate products are tanned by the sun 3-6 hour in the sun, then hangs 28-40 hour, obtains heterogeneous ozone catalyst finished product.
2. a preparation method for heterogeneous ozone catalyst, is characterized in that comprising the following steps:
Step one: screening grain slag micro mist, and be crushed into particle diameter and be less than 250 orders;
Step 2: be mixed material by the following material Homogeneous phase mixing of mass ratio: grain slag micro mist 36.4%-52.4%, magnesia 9.1%-14.3%, magnesium chloride hexahydrate 18.2%-23.8%, blowing agent 4.8%-9% and catalytic activity mixture 9.1%-19%;
Step 3: described mixed material is delivered to balling disk (-sc) granulation, sprays into atomized water simultaneously, prepares intermediate products, by these intermediate products at 40-60 DEG C of laser heating 0.5-3 hour in balling disk (-sc);
Step 4: the intermediate products after heating in step 3 are hung 10-28 hour and obtains heterogeneous ozone catalyst finished product.
3. the preparation method of heterogeneous ozone catalyst according to claim 1 and 2, is characterized in that,
Described catalytic activity mixture comprises the first catalytic activity mixture and the second catalytic activity mixture;
Wherein, the first catalytic activity mixture adopts iron making and sintering dedusting ash, and it comprises di-iron trioxide (Fe
2o
3), tri-iron tetroxide (Fe
3o
4), calcium oxide (CaO), silica (SiO
2) and noble metal; This noble metal is at least one in gold (Au), silver (Ag) and cobalt (Co), and this first catalytic activity mixture accounts for the 60%-80% of total catalytic activity mixture quality;
Described second catalytic activity mixture comprises titanium dioxide (TiO
2), cupric oxide (CuO), manganese monoxide (MnO), manganese dioxide (MnO
2), alundum (Al2O3) (A1
2o
3), cobalt oxide (CoO) and cobaltosic oxide (Co
3o
4) at least one, and this second catalytic activity mixture accounts for the 20%-40% of total catalytic activity mixture quality.
4. the preparation method of heterogeneous ozone catalyst according to claim 3, is characterized in that,
In described first catalytic activity mixture, the mass content ratio of each component is respectively: di-iron trioxide (Fe
2o
3) be 20%-30%, tri-iron tetroxide (Fe
3o
4) be 5%-15%, gold (Au) is 0.0003%-0.001%, and silver (Ag) is 0.03%-0.1%, and surplus is calcium oxide (CaO) and silica (SiO
2).
5. the preparation method of heterogeneous ozone catalyst according to claim 3, is characterized in that,
In described second catalytic activity mixture, it is 50% that the mass content ratio of each component is respectively cupric oxide (CuO), and manganese monoxide (MnO) is 50%.
6. the preparation method of heterogeneous ozone catalyst according to claim 3, is characterized in that,
The particle diameter of described catalytic activity mixture is less than 380 orders, and described blowing agent is dry powder carbonic hydroammonium (NH
4hCO
3).
7. the preparation method of heterogeneous ozone catalyst according to claim 1, is characterized in that,
In described step 3, described in spray into atomized water quality be the 10%-14% of described mixture quality of material.
8. a heterogeneous ozone catalyst prepared by the method according to any one of claim 1 to 7, is characterized in that the material comprising following masses ratio: grain slag micro mist 36.4%-52.4%, magnesia (MgO) 9.1%-14.3%, magnesium chloride hexahydrate (MgCl
26H
2o) 18.2%-23.8%, blowing agent 4.8%-9% and catalytic activity mixture 9.1%-19%.
9. heterogeneous ozone catalyst according to claim 8, is characterized in that,
Described catalytic activity mixture comprises the first catalytic activity mixture and the second catalytic activity mixture;
Wherein, the first catalytic activity mixture adopts iron making and sintering dedusting ash, and it comprises di-iron trioxide (Fe
2o
3), tri-iron tetroxide (Fe
3o
4), calcium oxide (CaO), silica (SiO
2) and noble metal, this noble metal is at least one in gold (Au), silver (Ag) and cobalt (Co), and this first catalytic activity mixture accounts for the 60%-80% of total catalytic activity mixture quality;
Described second catalytic activity mixture comprises titanium dioxide (TiO
2), cupric oxide (CuO), manganese monoxide (MnO), manganese dioxide (MnO
2), alundum (Al2O3) (A1
2o
3), cobalt oxide (CoO) and cobaltosic oxide (Co
3o
4) at least one, and this second catalytic activity mixture accounts for the 20%-40% of total catalytic activity mixture quality;
Described blowing agent is dry powder carbonic hydroammonium (NH
4hCO
3).
10. heterogeneous ozone catalyst according to claim 9, is characterized in that,
In described first catalytic activity mixture, the mass content ratio of each component is respectively: di-iron trioxide (Fe
2o
3) be 20%-30%, tri-iron tetroxide (Fe
3o
4) be 5%-15%, gold (Au) is 0.0003%-0.001%, and silver (Ag) is 0.03%-0.1%, and surplus is calcium oxide (CaO) and silica (SiO
2);
In described second catalytic activity mixture, the mass content ratio of each component is respectively: cupric oxide (CuO) is 50%, and manganese monoxide (MnO) is 50%.
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