CN108178180B - A kind of preparation method of Large ratio surface cerium oxide - Google Patents

A kind of preparation method of Large ratio surface cerium oxide Download PDF

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CN108178180B
CN108178180B CN201810191198.4A CN201810191198A CN108178180B CN 108178180 B CN108178180 B CN 108178180B CN 201810191198 A CN201810191198 A CN 201810191198A CN 108178180 B CN108178180 B CN 108178180B
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蒋央芳
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    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00Compounds of rare earth metals
    • C01F17/20Compounds containing only rare earth metals as the metal element
    • C01F17/206Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
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    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61Surface area
    • B01J35/61310-100 m2/g
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    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J35/615100-500 m2/g
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Abstract

The present invention discloses a kind of preparation method of Large ratio surface cerium oxide.With liquid, ceric sulfate, ammonium carbonate, oxalic acid are configured to solution, the oxalic acid solution of preparation is put into reaction kettle, the sal volatile of 0.1-0.12 times of volume of oxalic acid solution is added, then ceric sulfate solution and sal volatile are added in the liquid of bottom, temperature is at the uniform velocity reduced in simultaneous reactions kettle, reaction kettle stops cooling after charging, and this temperature is maintained to be stirred to react 1-1.5h, it is then separated by solid-liquid separation, obtains the first filtrate and the first filter residue, pure water is added in first filter residue, then it dries, is sieved after broken, obtains sieving materials;Sieving materials are calcined in rotary kiln, then by it is broken, sieve to get.Preparation process of the present invention is simple, there is biggish specific surface area at ambient and elevated temperatures, and catalytic activity is high.

Description

A kind of preparation method of Large ratio surface cerium oxide
Technical field
The present invention relates to a kind of preparation methods of Large ratio surface cerium oxide, belong to catalyst technical field.
Background technique
The cerium oxide of Large ratio surface is applied to petroleum cracking and cracking, the fields such as purifying vehicle exhaust catalysis.Conventional work Skill is prepared using coprecipitation, by the reunion in control powder preparation process and is added stabilizer, is made product at high temperature Still keep biggish specific surface area.The purity of the cerium oxide of Large ratio surface on the market is greater than 99.9%, and granularity is 1-3 microns, Fresh specific surface is to be generally less than 160m2/g, and aging specific surface area (1000 DEG C of 4hr) is less than 25m2/g.
The cerium oxide of general Large ratio surface is used for high-temperature catalytic, and high temperature can make conventional Large ratio surface cerium oxide Specific surface drastically reduces, to affect catalytic effect.
Summary of the invention
In view of this, preparation process is simple, in room temperature the present invention provides a kind of preparation method of Large ratio surface cerium oxide With have biggish specific surface area under high temperature, catalytic activity is high.
The present invention solves above-mentioned technical problem by following technological means:
A kind of preparation method of Large ratio surface cerium oxide, is following steps:
(1) match liquid, technical pure ceric sulfate is configured to the ceric sulfate solution that concentration is 180-185g/L, and constant temperature arrives Temperature is 40 ± 2 DEG C, technical pure ammonium carbonate is configured to the sal volatile that concentration is 550-600g/L, and constant temperature to temperature is 40 ± 2 DEG C, technical pure oxalic acid is configured to the oxalic acid solution that concentration is 100-105g/L, and constant temperature to temperature is 40 ± 2 DEG C;
(2) it reacts, the oxalic acid solution of preparation is put into reaction kettle, and constant temperature to temperature is 40 ± 2 DEG C, in reaction kettle Cooling coil is set, is then stirred, the ammonium carbonate of 0.1-0.12 times of volume of oxalic acid solution is added in mixing speed 100-120r/min Solution, addition, which finishes, to be continued to stir 15-30min, and as bottom liquid, ceric sulfate solution and sal volatile are then added to bottom In liquid, temperature is at the uniform velocity reduced in simultaneous reactions kettle, the rate for reducing temperature is 5-6 DEG C/h, and ceric sulfate solution and ammonium carbonate are molten The volume flow ratio of liquid is 6-6.2:1, and the ceric sulfate solution and sal volatile total volume for amounting to addition are bottom liquid product 1-1.5 times, the time that ceric sulfate solution and sal volatile is added is 3-4 hours, and reaction kettle stops cooling after charging, And this temperature is maintained to be stirred to react 1-1.5h, it is then separated by solid-liquid separation, obtains the first filtrate and the first filter residue, by the first filter residue The conductivity 150-250 μ S/cm of pure water to washing water is added, then dries to moisture content and is lower than 1%, after broken 150-200 mesh is crossed, sieving materials are obtained;
(3) it calcines, step (2) sieving materials is calcined in rotary kiln, calcination temperature is 340-360 DEG C, calcination time 5-6 Hour, then by it is broken, sieve to get.
Ceric sulfate solution, sal volatile and the oxalic acid solution prepared in the step (1) make after secondary filter With the aperture of filter medium is 0.5-1 microns.
It is at the uniform velocity to be added that bottom liquid process, which is added, with sal volatile in ceric sulfate solution in the step (2), and equipment is added For at least one of peristaltic pump or metering pump.
Calcium chloride solution is added in first filtrate obtained in the step (2), is stirred to react 1-2 hours, then filters, washes It washs, condensing crystallizing obtains ammonia chloride crystal after filtrate and wash water are merged, and filter residue is added sodium carbonate liquor and carries out pulp, then again Temperature is 70-75 DEG C after reaction 1-2 hours, then filters, obtains the filtrate and calcium carbonate filter residue containing sodium sulphate and sodium oxalate, Containing the filtrate of sodium sulphate and sodium oxalate by being concentrated into Baume degrees as 50-52, being subsequently cooled to temperature is 10-15 DEG C, is carried out It is separated by solid-liquid separation, obtains the oxalic acid sodium crystal that purity is 98% or more, the mother liquor of separation of solid and liquid will obtain pure after moisture evaporating completely The sodium sulfate crystal for spending > 97%, obtained calcium carbonate filter residue are added hydrochloric acid solution and obtain calcium chloride solution return use.
The molal quantity of calcium is the total moles of sulfate radical, oxalate and carbonate in the first filtrate in the calcium chloride solution of addition Several 1.05-1.1 times, the sodium carbonate of addition are 1.05-1.1 times of calcium molal quantity in filter residue.
Present invention utilizes the solubility that the solubility of ammonium oxalate is significantly smaller than oxalic acid, ammonium oxalate is in 40 DEG C of solubility It is 4.45 that 8.18,30 DEG C, which are 6.09,20 DEG C, and the solubility of oxalic acid is 21.2,30 DEG C in 40 DEG C of solubility and is 14.3,20 DEG C and is 9.5, ammonium carbonate is added in oxalic acid, generation obtains ammonium oxalate, so that ammonium oxalate partially crystallizable is precipitated, ceric sulfate is then added Solution and sal volatile, then Ce (IV) ion can be using this ammonium oxalate crystal as nucleus growth, to ammonium oxalate be wrapped up, together When, in continuous reaction process, temperature is gradually decreased, while constantly obtaining Ce (IV) precipitating, also constantly there is oxalic acid The crystal of ammonium is precipitated, so that Ce (IV) precipitating is mixed with ammonium oxalate crystal, in high-temperature burning process, the grass of package The ammonium oxalate of sour ammonium and mixed growth can resolve into ammonia, carbon dioxide gas, vapor and vapor away, to obtain hollow knot The cerium oxide of structure and loose porous Large ratio surface, the cerium oxide hole that the present invention obtains is big, and is hollow structure, at high temperature Its specific surface area is much larger than existing product on the market, and catalytic performance is superior.
The index of finally obtained Large ratio surface cerium oxide of the invention is as follows:
The beneficial effects of the present invention are:
1. so that Ce (IV) precipitating is wrapped on ammonium oxalate nucleus, while constantly existing by using ammonium oxalate as nucleus Then reaction process cooling said high-temperature calcination, so that careless so that ammonium oxalate crystal is constantly precipitated with Ce (IV) precipitating together Sour ammonium decomposes, so that cerium oxide becomes hollow and loose porous structure, and the cerium oxide for other techniques preparation that compares, Hole is bigger, and what hole was blocked at high temperature lacks, and hollow structure, so that specific surface area at ambient and elevated temperatures is all larger than Existing cerium oxide, catalytic effect are more preferable.
2. preparation process waste water yield is few, ammonium root therein, oxalate, sulfate radical realize recycling, so that preparation Environmental friendly property is good.
3. passing through conventional depositing technology and calcine technology, it can it prepares this large surface and accumulates virtue cerium oxide, technique letter It is single, it is at low cost.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in detail, a kind of Large ratio surface cerium oxide of the present embodiment Preparation method, be following steps:
(1) match liquid, technical pure ceric sulfate is configured to the ceric sulfate solution that concentration is 180-185g/L, and constant temperature arrives Temperature is 40 ± 2 DEG C, technical pure ammonium carbonate is configured to the sal volatile that concentration is 550-600g/L, and constant temperature to temperature is 40 ± 2 DEG C, technical pure oxalic acid is configured to the oxalic acid solution that concentration is 100-105g/L, and constant temperature to temperature is 40 ± 2 DEG C;
(2) it reacts, the oxalic acid solution of preparation is put into reaction kettle, and constant temperature to temperature is 40 ± 2 DEG C, in reaction kettle Cooling coil is set, is then stirred, the ammonium carbonate of 0.1-0.12 times of volume of oxalic acid solution is added in mixing speed 100-120r/min Solution, addition, which finishes, to be continued to stir 15-30min, and as bottom liquid, ceric sulfate solution and sal volatile are then added to bottom In liquid, temperature is at the uniform velocity reduced in simultaneous reactions kettle, the rate for reducing temperature is 5-6 DEG C/h, and ceric sulfate solution and ammonium carbonate are molten The volume flow ratio of liquid is 6-6.2:1, and the ceric sulfate solution and sal volatile total volume for amounting to addition are bottom liquid product 1-1.5 times, the time that ceric sulfate solution and sal volatile is added is 3-4 hours, and reaction kettle stops cooling after charging, And this temperature is maintained to be stirred to react 1-1.5h, it is then separated by solid-liquid separation, obtains the first filtrate and the first filter residue, by the first filter residue The conductivity 150-250 μ S/cm of pure water to washing water is added, then dries to moisture content and is lower than 1%, after broken 150-200 mesh is crossed, sieving materials are obtained;
(3) it calcines, step (2) sieving materials is calcined in rotary kiln, calcination temperature is 340-360 DEG C, calcination time 5-6 Hour, then by it is broken, sieve to get.
Ceric sulfate solution, sal volatile and the oxalic acid solution prepared in the step (1) make after secondary filter With the aperture of filter medium is 0.5-1 microns.
It is at the uniform velocity to be added that bottom liquid process, which is added, with sal volatile in ceric sulfate solution in the step (2), and equipment is added For at least one of peristaltic pump or metering pump.
Calcium chloride solution is added in first filtrate obtained in the step (2), is stirred to react 1-2 hours, then filters, washes It washs, condensing crystallizing obtains ammonia chloride crystal after filtrate and wash water are merged, and filter residue is added sodium carbonate liquor and carries out pulp, then again Temperature is 70-75 DEG C after reaction 1-2 hours, then filters, obtains the filtrate and calcium carbonate filter residue containing sodium sulphate and sodium oxalate, Containing the filtrate of sodium sulphate and sodium oxalate by being concentrated into Baume degrees as 50-52, being subsequently cooled to temperature is 10-15 DEG C, is carried out It is separated by solid-liquid separation, obtains the oxalic acid sodium crystal that purity is 98% or more, the mother liquor of separation of solid and liquid will obtain pure after moisture evaporating completely The sodium sulfate crystal for spending > 97%, obtained calcium carbonate filter residue are added hydrochloric acid solution and obtain calcium chloride solution return use.
The molal quantity of calcium is the total moles of sulfate radical, oxalate and carbonate in the first filtrate in the calcium chloride solution of addition Several 1.05-1.1 times, the sodium carbonate of addition are 1.05-1.1 times of calcium molal quantity in filter residue.
Embodiment 1
A kind of preparation method of Large ratio surface cerium oxide, is following steps:
(1) match liquid, technical pure ceric sulfate is configured to the ceric sulfate solution that concentration is 181g/L, and constant temperature is to temperature It is 41 DEG C, technical pure ammonium carbonate is configured to the sal volatile that concentration is 585g/L, and constant temperature to temperature is 41 DEG C, it will be industrial Pure oxalic acid is configured to the oxalic acid solution that concentration is 103g/L, and constant temperature to temperature is 41 DEG C;
(2) it reacts, the oxalic acid solution of preparation is put into reaction kettle, and constant temperature to temperature is 40 DEG C, built in reaction kettle Then cooling coil stirs, mixing speed 110r/min, and the sal volatile of 0.11 times of volume of oxalic acid solution is added, and is added It finishes and continues to stir 20min, as bottom liquid, then ceric sulfate solution and sal volatile are added in the liquid of bottom, while anti- Answering at the uniform velocity reduces temperature in kettle, the rate for reducing temperature is 5.5 DEG C/h, the volume flow of ceric sulfate solution and sal volatile Than for 6.1:1, the ceric sulfate solution and sal volatile total volume that amount to addition are 1.25 times of bottom liquid product, sulfuric acid is added The time of high cerium solution and sal volatile is 3.5 hours, and reaction kettle stops cooling after charging, and this temperature is maintained to stir 1.35h is reacted, is then separated by solid-liquid separation, obtains the first filtrate and the first filter residue, pure water is added to washing in the first filter residue The 180 μ S/cm of conductivity of water is washed, then dries to moisture content and is lower than 1%, 180 meshes are crossed after broken, are sieved Material;
(3) it calcines, step (2) sieving materials is calcined in rotary kiln, calcination temperature is 355 DEG C, and calcination time 5.5 is small When, then by it is broken, sieve to get.
Ceric sulfate solution, sal volatile and the oxalic acid solution prepared in the step (1) make after secondary filter With the aperture of filter medium is 0.8 micron.
It is at the uniform velocity to be added that bottom liquid process, which is added, with sal volatile in ceric sulfate solution in the step (2), and equipment is added For peristaltic pump.
Calcium chloride solution is added in first filtrate obtained in the step (2), is stirred to react 1.5 hours, then filters, washes It washs, condensing crystallizing obtains ammonia chloride crystal after filtrate and wash water are merged, and filter residue is added sodium carbonate liquor and carries out pulp, then again After temperature is 73 DEG C of reactions 1.2 hours, then filters, obtain the filtrate and calcium carbonate filter residue containing sodium sulphate and sodium oxalate, contain Having the filtrate of sodium sulphate and sodium oxalate process to be concentrated into Baume degrees is 51, and being subsequently cooled to temperature is 12 DEG C, is separated by solid-liquid separation, The oxalic acid sodium crystal that purity is 98% or more is obtained, the mother liquor of separation of solid and liquid will obtain purity >'s 97% after moisture evaporating completely Sodium sulfate crystal, obtained calcium carbonate filter residue are added hydrochloric acid solution and obtain calcium chloride solution return use.
The molal quantity of calcium is the total moles of sulfate radical, oxalate and carbonate in the first filtrate in the calcium chloride solution of addition Several 1.08 times, the sodium carbonate of addition are 1.08 times of calcium molal quantity in filter residue.
The index of finally obtained Large ratio surface cerium oxide of the invention is as follows:
Embodiment 2
A kind of preparation method of Large ratio surface cerium oxide, is following steps:
(1) match liquid, technical pure ceric sulfate is configured to the ceric sulfate solution that concentration is 182g/L, and constant temperature is to temperature It is 40 DEG C, technical pure ammonium carbonate is configured to the sal volatile that concentration is 585g/L, and constant temperature to temperature is 40 DEG C, it will be industrial Pure oxalic acid is configured to the oxalic acid solution that concentration is 103g/L, and constant temperature to temperature is 40 DEG C;
(2) it reacts, the oxalic acid solution of preparation is put into reaction kettle, and constant temperature to temperature is 41 DEG C, built in reaction kettle Then cooling coil stirs, mixing speed 108r/min, and the sal volatile of 0.105 times of volume of oxalic acid solution is added, and is added It finishes and continues to stir 23min, as bottom liquid, then ceric sulfate solution and sal volatile are added in the liquid of bottom, while anti- Answering at the uniform velocity reduces temperature in kettle, the rate for reducing temperature is 5.3 DEG C/h, the volume flow of ceric sulfate solution and sal volatile Than for 6.05:1, the ceric sulfate solution and sal volatile total volume that amount to addition are 1.45 times of bottom liquid product, sulphur is added The time of the high cerium solution of acid and sal volatile is 3.8 hours, and reaction kettle stops cooling after charging, and this temperature is maintained to stir Reaction 1.15h is mixed, is then separated by solid-liquid separation, obtains the first filtrate and the first filter residue, pure water is added extremely in the first filter residue Then the 225 μ S/cm of conductivity of washing water is dried to moisture content and is lower than 1%, 185 meshes are crossed after broken, are sieved Material;
(3) it calcines, step (2) sieving materials is calcined in rotary kiln, calcination temperature is 352 DEG C, and calcination time 5.7 is small When, then by it is broken, sieve to get.
Ceric sulfate solution, sal volatile and the oxalic acid solution prepared in the step (1) make after secondary filter With the aperture of filter medium is 0.85 micron.
It is at the uniform velocity to be added that bottom liquid process, which is added, with sal volatile in ceric sulfate solution in the step (2), and equipment is added For metering pump.
Calcium chloride solution is added in first filtrate obtained in the step (2), is stirred to react 1.4 hours, then filters, washes It washs, condensing crystallizing obtains ammonia chloride crystal after filtrate and wash water are merged, and filter residue is added sodium carbonate liquor and carries out pulp, then again After temperature is 73 DEG C of reactions 1.8 hours, then filters, obtain the filtrate and calcium carbonate filter residue containing sodium sulphate and sodium oxalate, contain Having the filtrate of sodium sulphate and sodium oxalate process to be concentrated into Baume degrees is 51, and being subsequently cooled to temperature is 13 DEG C, is separated by solid-liquid separation, The oxalic acid sodium crystal that purity is 98% or more is obtained, the mother liquor of separation of solid and liquid will obtain purity >'s 97% after moisture evaporating completely Sodium sulfate crystal, obtained calcium carbonate filter residue are added hydrochloric acid solution and obtain calcium chloride solution return use.
The molal quantity of calcium is the total moles of sulfate radical, oxalate and carbonate in the first filtrate in the calcium chloride solution of addition Several 1.08 times, the sodium carbonate of addition are 1.09 times of calcium molal quantity in filter residue.
The index of finally obtained Large ratio surface cerium oxide of the invention is as follows:
Embodiment 3
A kind of preparation method of Large ratio surface cerium oxide, is following steps:
(1) match liquid, technical pure ceric sulfate is configured to the ceric sulfate solution that concentration is 184g/L, and constant temperature is to temperature It is 40.5 DEG C, technical pure ammonium carbonate is configured to the sal volatile that concentration is 585g/L, and constant temperature to temperature is 40 DEG C, by work The pure oxalic acid of industry is configured to the oxalic acid solution that concentration is 101g/L, and constant temperature to temperature is 40 DEG C;
(2) it reacts, the oxalic acid solution of preparation is put into reaction kettle, and constant temperature to temperature is 41 DEG C, built in reaction kettle Then cooling coil stirs, mixing speed 115r/min, and the sal volatile of 0.115 times of volume of oxalic acid solution is added, and is added It finishes and continues to stir 25min, as bottom liquid, then ceric sulfate solution and sal volatile are added in the liquid of bottom, while anti- Answering at the uniform velocity reduces temperature in kettle, the rate for reducing temperature is 5.3 DEG C/h, the volume flow of ceric sulfate solution and sal volatile Than for 6.12:1, the ceric sulfate solution and sal volatile total volume that amount to addition are 1.35 times of bottom liquid product, sulphur is added The time of the high cerium solution of acid and sal volatile is 3.8 hours, and reaction kettle stops cooling after charging, and this temperature is maintained to stir Reaction 1.3h is mixed, is then separated by solid-liquid separation, obtains the first filtrate and the first filter residue, pure water is added to washing in the first filter residue The 215 μ S/cm of conductivity of water is washed, then dries to moisture content and is lower than 1%, 190 meshes are crossed after broken, are sieved Material;
(3) it calcines, step (2) sieving materials is calcined in rotary kiln, calcination temperature is 355 DEG C, and calcination time 5.7 is small When, then by it is broken, sieve to get.
Ceric sulfate solution, sal volatile and the oxalic acid solution prepared in the step (1) make after secondary filter With the aperture of filter medium is 0.8 micron.
It is at the uniform velocity to be added that bottom liquid process, which is added, with sal volatile in ceric sulfate solution in the step (2), and equipment is added For peristaltic pump.
Calcium chloride solution is added in first filtrate obtained in the step (2), is stirred to react 1.7 hours, then filters, washes It washs, condensing crystallizing obtains ammonia chloride crystal after filtrate and wash water are merged, and filter residue is added sodium carbonate liquor and carries out pulp, then again After temperature is 73 DEG C of reactions 1.7 hours, then filters, obtain the filtrate and calcium carbonate filter residue containing sodium sulphate and sodium oxalate, contain Having the filtrate of sodium sulphate and sodium oxalate by being concentrated into Baume degrees is 51.5, and being subsequently cooled to temperature is 13 DEG C, carries out solid-liquid point From obtaining the oxalic acid sodium crystal that purity is 98% or more, the mother liquor of separation of solid and liquid will obtain purity > after moisture evaporating completely 97% sodium sulfate crystal, obtained calcium carbonate filter residue are added hydrochloric acid solution and obtain calcium chloride solution return use.
The molal quantity of calcium is the total moles of sulfate radical, oxalate and carbonate in the first filtrate in the calcium chloride solution of addition Several 1.06 times, the sodium carbonate of addition are 1.09 times of calcium molal quantity in filter residue.
The index of finally obtained Large ratio surface cerium oxide of the invention is as follows:
The products application of the embodiment 1 of phase homogenous quantities, embodiment 2, embodiment 3 is catalyzed in purifying vehicle exhaust, is implemented Example 1 makes nitrogen oxides in vehicle exhaust, carbon monoxide, hydrocarbon oxidation catalyst conversion ratio be respectively 99%, 99.1% and 98.7%, embodiment 2 makes nitrogen oxides in vehicle exhaust, carbon monoxide, the hydrocarbon oxidation catalyst conversion ratio to be respectively 99.1%, 99.2% and 98.8%, embodiment, 3 make nitrogen oxides in vehicle exhaust, carbon monoxide, hydrocarbon oxidation catalyst Conversion ratio is respectively 99.2%, 99.2% and 98.9%, and the Large ratio surface cerium oxide conventional on the market of phase homogenous quantities makes The equal < 96% of nitrogen oxides, carbon monoxide, hydrocarbon oxidation catalyst conversion ratio in vehicle exhaust.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this In the scope of the claims of invention.

Claims (5)

1. a kind of preparation method of bigger serface cerium oxide, which is characterized in that be following steps:
(1) match liquid, technical pure ceric sulfate is configured to the ceric sulfate solution that concentration is 180-185g/L, and constant temperature is to temperature Be 40 ± 2 DEG C, by technical pure ammonium carbonate be configured to concentration be 550-600g/L sal volatile, and constant temperature to temperature be 40 ± 2 DEG C, technical pure oxalic acid is configured to the oxalic acid solution that concentration is 100-105g/L, and constant temperature to temperature is 40 ± 2 DEG C;
(2) it reacts, the oxalic acid solution of preparation is put into reaction kettle, and constant temperature to temperature is 40 ± 2 DEG C, it is cold built in reaction kettle But then coil pipe stirs, mixing speed 100-120r/min, and the ammonium carbonate that 0.1-0.12 times of volume of oxalic acid solution is added is molten Liquid, addition, which finishes, to be continued to stir 15-30min, and as bottom liquid, ceric sulfate solution and sal volatile are then added to bottom liquid In, temperature is at the uniform velocity reduced in simultaneous reactions kettle, the rate for reducing temperature is 5-6 DEG C/h, ceric sulfate solution and sal volatile Volume flow ratio be 6-6.2:1, amount to addition ceric sulfate solution and sal volatile total volume be bottom liquid product 1- 1.5 times, the time that ceric sulfate solution and sal volatile is added is 3-4 hours, and reaction kettle stops cooling after charging, and It maintains this temperature to be stirred to react 1-1.5h, is then separated by solid-liquid separation, obtain the first filtrate and the first filter residue, the first filter residue is added Enter the conductivity 150-250 μ S/cm of pure water to washing water, then dries to moisture content and be lower than 1%, the mistake after broken 150-200 mesh, obtains sieving materials;
(3) it calcines, step (2) sieving materials is calcined in rotary kiln, calcination temperature is 340-360 DEG C, and calcination time 5-6 is small When, then by it is broken, sieve to get.
2. a kind of preparation method of bigger serface cerium oxide according to claim 1, it is characterised in that: the step (1) ceric sulfate solution, sal volatile and the oxalic acid solution prepared in use after secondary filter, the aperture of filter medium It is 0.5-1 microns.
3. a kind of preparation method of bigger serface cerium oxide according to claim 1, it is characterised in that: the step (2) it is at the uniform velocity to be added that bottom liquid process, which is added, with sal volatile in ceric sulfate solution in, and it is peristaltic pump or metering pump that equipment, which is added, At least one of.
4. a kind of preparation method of bigger serface cerium oxide according to claim 1, it is characterised in that: the step (2) calcium chloride solution is added in the first filtrate obtained in, is stirred to react 1-2 hours, is then filtered, washed, by filtrate and wash water Condensing crystallizing obtains ammonia chloride crystal after merging, and filter residue is added sodium carbonate liquor and carries out pulp, and then temperature is 70-75 DEG C anti-again It after answering 1-2 hours, then filters, obtains the filtrate and calcium carbonate filter residue containing sodium sulphate and sodium oxalate, contain sodium sulphate and grass The filtrate of sour sodium is 50-52 by being concentrated into Baume degrees, and being subsequently cooled to temperature is 10-15 DEG C, is separated by solid-liquid separation, is obtained pure The oxalic acid sodium crystal that degree is 98% or more, the mother liquor of separation of solid and liquid will obtain the sodium sulphate of purity > 97% after moisture evaporating completely Crystal, obtained calcium carbonate filter residue are added hydrochloric acid solution and obtain calcium chloride solution return use.
5. a kind of preparation method of bigger serface cerium oxide according to claim 4, it is characterised in that: the chlorine of addition The molal quantity for changing calcium in calcium solution is 1.05-1.1 times of the total mole number of sulfate radical, oxalate and carbonate in the first filtrate, The sodium carbonate of addition is 1.05-1.1 times of calcium molal quantity in filter residue.
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CN104386732A (en) * 2014-11-17 2015-03-04 赣州有色冶金研究所 Method and system for preparing nano cerium oxide by adopting adsorption and isolation agent
CN106800307A (en) * 2017-01-22 2017-06-06 海城海美抛光材料制造有限公司 A kind of preparation method of particle in the small apparent density cerias of more than 60um
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JPH05270823A (en) * 1992-03-23 1993-10-19 Santoku Kinzoku Kogyo Kk Multiple oxide capable of absorbing and desorbing oxygen and its production
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CN106953111A (en) * 2016-12-09 2017-07-14 北京科技大学 A kind of preparation method of samarium doping cerium oxide solid electrolyte powder
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