CN109354068A - A kind of chromium oxide and preparation method thereof - Google Patents
A kind of chromium oxide and preparation method thereof Download PDFInfo
- Publication number
- CN109354068A CN109354068A CN201811550247.5A CN201811550247A CN109354068A CN 109354068 A CN109354068 A CN 109354068A CN 201811550247 A CN201811550247 A CN 201811550247A CN 109354068 A CN109354068 A CN 109354068A
- Authority
- CN
- China
- Prior art keywords
- chromium
- chromium oxide
- reaction
- preparation
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/02—Oxides or hydrates thereof
- C01G37/033—Chromium trioxide; Chromic acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/62—L* (lightness axis)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/63—Optical properties, e.g. expressed in CIELAB-values a* (red-green axis)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)
Abstract
The present invention provides a kind of chromium oxide and preparation method thereof, which comprises sexavalence chromium salt solution is added in reaction unit, is passed through closed heating after protective gas, reaches and is continually fed into reducibility gas after target temperature and reacts, obtain mixed slurry；Gained mixed slurry is separated by solid-liquid separation, chromium oxyhydroxide powder is obtained；Chromium oxyhydroxide powder is subjected to calcination processing again, obtains chromium oxide.The present invention prepares chromium oxide by sexavalence chromic salts using hydrothermal reduction method, pass through the regulation to reducibility gas and reaction condition, the controllability of intensified response process, reduction rate is up to 99% or more, gained reduzate object is mutually uniform, narrower particle size distribution, gained chromium oxide product quality is higher, can reach the standard of pigment-level chromium oxide；The method process is short, energy consumption and at low cost, non-pollutant discharge, is a kind of process for cleanly preparing, has significant economic benefit.
Description
Technical field
The invention belongs to technical field of material, it is related to a kind of chromium oxide and preparation method thereof more particularly to one kind is adopted
The method for preparing pigment-level chromium oxide with hydrothermal reduction.
Background technique
Chromium oxide (Cr2O3) it is a kind of important raw material of industry, it is widely used in metallurgy, pigment, ceramics, coating, green and throws
The fields such as light and organic catalysis synthesis.Currently, industrially producing Cr2O3Method mainly include chromic anhybride thermal decomposition method and six
Valence chromic salts reduction method.Chromic anhybride thermal decomposition method is using chromic anhybride as raw material, and calcining prepares Cr at high temperature2O3, this method cost compared with
It is high and seriously polluted.Sexavalence chromic salts reduction method is using sulphur or sulfide as reducing agent, through wet process or dry reduction sexavalence chromic salts
Prepare Cr2O3, mainly there is chromium acid sodium alkaline liquid sulphur or vulcanization sodium reduction, potassium bichromate sulphur roast reduction process, sodium dichromate
Ammonium sulfate reduction method etc., there are long flow paths for the above method, introduce sulfur impurity, it is difficult to the problems such as obtaining high-quality product, Er Qie
Low value-added byproduct can be generated in production process.
Based on defect existing for the above method and problem, researcher has developed a variety of preparation Cr at present2O3New process,
Wherein, hydro-thermal method receives extensive research and concern as a kind of process for cleanly preparing.100999335 A of CN discloses one
The method that kind prepares chromium oxide powder using water heat reducing chromate, using chromate aqueous solution as raw material, CO2Gas is acidification
Agent is handled by surfactant, and direct-reduction obtains hydration Cr under hydrothermal conditions2O3Slurry, and then calcine and obtain Cr2O3
Superfine powder, but the process is using oxalic acid, sucrose, methanol, formaldehyde, formic acid or ethyl alcohol as reducing agent, after reaction remaining reducing agent and
Surfactant can enter filtrate, and filtrate component complexity is caused to be not easy to recycle, and Cr obtained by the process2O3Powder thing phase
It forms inhomogenous.101456588 A of CN discloses a kind of hydrothermal reduction sodium chromate or sodium dichromate prepares the technique of chromium oxide,
Sodium chromate or sodium dichromate aqueous solutio and starch or derivatives thereof are subjected to hydrothermal reduction in a high pressure reaction kettle, obtained hydrogen-oxygen
Change chromium to roast to obtain chromium oxide product, this method hydrothermal reduction rate is too fast, is difficult to control, and products therefrom purity is lower, circulation
Filtrate component is equally complicated.
In order to reduce the introducing of hydrothermal reduction byproduct in process object and impurity, 102010005 A of CN discloses a kind of oxygen
The production method for changing chromium is passed through hydrogen using the alkali metal salt of chromic acid or dichromic acid as raw material in high-temperature high-pressure reaction kettle
Reducibility gas carries out reduction reaction, and reaction residual liquor is separated by solid-liquid separation through decrease temperature and pressure, obtains hydrated chromium oxide and corresponding severe
Property aqueous slkali.Reducibility gas is passed through in this method in advance, then heating reaction, reaction process is difficult to control, and causes product
Form inhomogenous, performance is bad, exists simultaneously the higher problem of reaction temperature, pressure.
In conclusion the controllability of enhancing chromium oxide preparation process, is allowed to that product can be regulated and controled by changing reaction condition
Composition and pattern, so that the quality for improving product is current urgent problem, while guaranteeing that preparation process is easy to operate, clear
Clean environmental protection.
Summary of the invention
In view of the problems of the existing technology, the purpose of the present invention is to provide a kind of chromium oxide and preparation method thereof, originally
Invention prepares chromium oxide by sexavalence chromic salts using hydrothermal reduction method, passes through the regulation to reducibility gas and response parameter, enhancing
The controllability of reaction process, so that the object of reaction product is mutually uniform, color characteristics are excellent, meanwhile, cost is relatively low for reaction process, behaviour
Make simple, clean and effective.
To achieve this purpose, the present invention adopts the following technical scheme:
On the one hand, it the present invention provides a kind of preparation method of chromium oxide, the described method comprises the following steps:
(1) sexavalence chromium salt solution is added in reaction unit, is passed through closed heating after protective gas, reaches target temperature
After be continually fed into reducibility gas and react, obtain mixed slurry；
(2) mixed slurry for obtaining step (1) is separated by solid-liquid separation, and obtains chromium oxyhydroxide powder；
(3) the chromium oxyhydroxide powder for obtaining step (2) carries out calcination processing, obtains chromium oxide.
It in the present invention, using sexavalence chromic salts as raw material, does not need that any additive is added, passes through the logical of control reducibility gas
Enter opportunity, sexavalence chromium salt solution is restored to obtain the uniform chromium oxyhydroxide powder of object phase composition, then pigment can be prepared through calcining
The chromium oxide of grade.
First the air in reaction unit and pipeline is discharged with protective gas by the present invention, then is passed through at a set temperature also
Originality gas, it is possible to prevente effectively from temperature-rise period other side reactions generation, and existing hydrothermal reduction technology be typically all exist
Reducing agent is added before not up to setting reaction temperature, has had reduzate generation in not up to set temperature, with temperature
It increases, reduzate changes, and causes the object phase composition of finally obtained reduzate inhomogenous.The present invention is in set temperature
Single object phase can be obtained in lower addition reducing agent, is conducive to subsequent calcination and obtains color characteristics preferably chromium oxide product.
It is used as currently preferred technical solution below, but not as the limitation of technical solution provided by the invention, passes through
Following technical scheme can preferably reach and realize technical purpose and beneficial effect of the invention.
As currently preferred technical solution, step (1) the sexavalence chromic salts includes chromate and/or bichromate.
Preferably, the chromate includes the alkali metal salt of chromic acid, preferably sodium chromate and/or potassium chromate.
Preferably, the bichromate includes the alkali metal salt of dichromic acid, preferably sodium dichromate and/or potassium bichromate.
Preferably, the concentration of chromium ion is 0.18~4.5mol/L in step (1) the sexavalence chromium salt solution, such as
0.18mol/L、0.5mol/L、1.0mol/L、1.5mol/L、2.0mol/L、2.5mol/L、3.0mol/L、3.5mol/L、
4.0mol/L or 4.5mol/L etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same
Sample is applicable in, preferably 0.61~3.7mol/L.
As currently preferred technical solution, step (1) described reaction unit includes vertical response kettle, horizontal reacting kettle
Or any one in bubble tower, preferably bubble tower.
Preferably, step (1) described protective gas includes any one in nitrogen, helium, neon or argon gas or at least
Two kinds of combination, the combination is typical but non-limiting example has: the combination of the combination of nitrogen and helium, helium and neon, helium
The combination of gas, neon and argon gas, nitrogen, helium and combination of argon gas etc..
Preferably, step (1) described reducibility gas includes hydrogen.
As currently preferred technical solution, the temperature of step (1) described reaction is 180~350 DEG C, such as 180 DEG C,
200 DEG C, 225 DEG C, 250 DEG C, 280 DEG C, 300 DEG C, 320 DEG C or 350 DEG C etc., it is not limited to cited numerical value, the numerical value
Other unlisted numerical value are equally applicable in range, preferably 200~350 DEG C, further preferably 200~250 DEG C.
In the present invention, the height of hydrothermal reduction reaction temperature mutually has an impact to the object of product hydroxy chromium oxide, when reaction temperature
When degree is higher than 250 DEG C, the product that hydrothermal reduction obtains is the preferable chromium oxyhydroxide of crystallinity；When reaction temperature is 230~250
DEG C when, the product that hydrothermal reduction obtains exists simultaneously crystalline hydroxy chromium oxide and amorphous chromium oxyhydroxide；When reaction temperature is low
When 230 DEG C, hydrothermal reduction obtains being amorphous chromium oxyhydroxide.The excessively high granularity that will cause reaction product of reaction temperature is inclined
Greatly, make the a* value of its corresponding color performance bigger than normal, apparent colour is partially red, and corresponding b* value is less than normal, and apparent colour is partially blue；And react temperature
It spends that the low granularity that will cause reaction product is less than normal, can equally make the a* value of corresponding color performance bigger than normal, apparent colour is partially red,
Corresponding b* value is less than normal, and apparent colour is partially blue.
Preferably, step (1) target temperature is reaction temperature.
Preferably, the time of step (1) described reaction is 0.5~10h, such as 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 8h
Or 10h etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, preferably 1
~6h, further preferably 2~4h.
Preferably, the pressure of step (1) described reaction be 4~16MPa, such as 4MPa, 6MPa, 7MPa, 8MPa, 9MPa,
10MPa, 12MPa, 14MPa or 16MPa etc., it is not limited to cited numerical value, other are unlisted in the numberical range
Numerical value is equally applicable, preferably 4~13MPa, further preferably 6~11MPa.
Preferably, in step (1) described reaction process, pressure 1~15MPa of maintenance of reducibility gas, such as 1MPa,
2MPa, 3MPa, 4MPa, 5MPa, 6MPa, 8MPa, 10MPa, 12MPa or 15MPa etc., it is not limited to cited numerical value,
Other unlisted numerical value are equally applicable in the numberical range, preferably 1~8MPa, further preferably 1~5MPa.
In the present invention, the operating pressure of reaction is more slightly higher than hydrogen partial pressure, mainly due to can also there is water in reaction process
Partial vapour pressure.Need constantly to supplement the hydrogen of reaction consumption in hydrothermal reduction reaction process, to maintain the partial pressure of hydrogen basic
It is constant, be conducive to increase the solubility of hydrogen in the solution, improve the activity of active hydrogen molecule, and then reaction institute can be reduced
Temperature is needed, the reaction time is shortened.
In the present invention, regulate and control by adjusting reaction temperature and hydrogen partial pressure the reduction and chromium oxyhydroxide of Cr VI
Nucleation, it is generally the case that improve the activity that reaction temperature and hydrogen partial pressure are conducive to improve reactant, promote product nucleation and
It grows up, therefore, by controlling the granule size of the controllable chromium oxyhydroxide of hydrothermal reduction condition, and then realizes the control of reaction process
System.
As currently preferred technical solution, step (1) reaction carries out under agitation.
Preferably, the stirring rate is 80~500r/min, such as 80r/min, 100r/min, 150r/min, 200r/
Min, 250r/min, 300r/min, 350r/min, 400r/min or 500r/min etc., it is not limited to cited numerical value,
Other unlisted numerical value are equally applicable in the numberical range, preferably 100~400r/min, further preferably 200~
350r/min。
Preferably, step (1) is described is quickly cooled down cooling after reaction.
Preferably, the type of cooling is water cooling.
Preferably, it is described cool rate be 1~20 DEG C/min, such as 1 DEG C/min, 3 DEG C/min, 5 DEG C/min, 8 DEG C/
Min, 10 DEG C/min, 12 DEG C/min, 15 DEG C/min, 18 DEG C/min or 20 DEG C/min etc., it is not limited to cited numerical value,
Other unlisted numerical value are equally applicable in the numberical range, preferably 5~10 DEG C/min.
As currently preferred technical solution, described be separated by solid-liquid separation of step (2) includes filtering.
Preferably, described that chromium oxyhydroxide and filtrate is obtained by filtration.
Preferably, the filtrate includes sodium hydroxide and/or potassium hydroxide.
Preferably, the filtrate is used for the preparation of step (1) sexavalence chromium salt solution.
As currently preferred technical solution, after step (2) described separation of solid and liquid, also washed, it is dry, obtain hydroxyl
Base chromium oxide powder.
Preferably, the drying mode includes any one in vacuum drying, forced air drying or freeze-drying, preferably cold
It is lyophilized dry.
Preferably, the partial size of chromium oxyhydroxide powder obtained by step (2) is 45~120nm, for example, 45nm, 50nm, 60nm,
70nm, 80nm, 90nm, 100nm, 110nm or 120nm etc., it is not limited to cited numerical value, in the numberical range other
Unlisted numerical value is equally applicable.
As currently preferred technical solution, the temperature of step (3) described calcination processing is 550~1250 DEG C, such as
550 DEG C, 600 DEG C, 700 DEG C, 800 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C, 1200 DEG C or 1250 DEG C etc., it is not limited to listed
The numerical value of act, other interior unlisted numerical value of the numberical range are equally applicable, and preferably 800~1000 DEG C.
Preferably, the time of step (3) described calcination processing be 0.3~6h, such as 0.3h, 0.5h, 1h, 1.5,2h, 3h,
4h, 5h or 6h etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, excellent
It is selected as 0.5~2h.
As currently preferred technical solution, the described method comprises the following steps:
(1) reaction dress is added in chromate and/or dichromate solution that the concentration of chromium ion is 0.18~4.5mol/L
In setting, it is passed through closed heating after protective gas, is reached and is continually fed into hydrogen after target temperature and reacts, the reaction temperature
It is 180~350 DEG C, the reaction time is 0.5~10h, and reaction pressure is 4~16MPa, and wherein hydrogen partial pressure is 1~15MPa, instead
Quick water-cooled cooling after answering, rate of temperature fall are 1~20 DEG C/min, obtain mixed slurry；
(2) mixed slurry that step (1) obtains successively is filtered, is washed, it is dry, obtain chromium oxyhydroxide powder and
Filtrate, the partial size of gained chromium oxyhydroxide powder are 45~120nm；
(3) the chromium oxyhydroxide powder obtained step (2) carries out calcination processing, and the calcination processing temperature is 550~
1250 DEG C, the calcination processing time is 0.3~6h, obtains chromium oxide.
On the other hand, the present invention provides a kind of chromium oxide being prepared using above-mentioned preparation method, the chromium oxide
For pigment-level chromium oxide.
Preferably, the colorimetric parameter of the chromium oxide are as follows: L*=40~60, such as 40,42,45,48,50,53,55,57
Or 60 etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable；A*=-14
~-21, such as -14, -15, -16, -17, -18, -19, -20 or -21 etc., it is not limited to cited numerical value, the numerical value
Other unlisted numerical value are equally applicable in range；B*=10~19, such as 10,11,12,13,14,15,16,17,18 or 19
Deng it is not limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
In the present invention, the colorimetric parameter of chromium oxide is obtained referring to CIE 1976L*a*b* system, and wherein L* indicates brightness value；
A* indicates red green angle value, and a*, which is positive, indicates red, and a*, which is negative, indicates green；B* indicates champac chromatic value, and b*, which is positive, indicates yellow
Color, b*, which is negative, indicates blue.
Compared with prior art, the invention has the following advantages:
(1) sexavalence chromic salts is carried out hydrothermal reduction by the present invention, reduction rate up to 99% or more, chromium oxide product qualities compared with
Height, purity reach the standard of pigment-level chromium oxide up to 99.6% or more；
(2) present invention, which is passed through in reducibility gas and reaction process at a temperature of goal response, maintains its partial pressure constant, instead
It answers process control strong, helps to reduce reaction temperature, reduce operating pressure, shorten the reaction time, obtained chromium oxyhydroxide
Object is mutually uniform, narrower particle size distribution；
(3) the method for the invention process is short, energy consumption and cost is relatively low, and non-pollutant discharge is, it can be achieved that by-product alkaloids
It recycles, environment-friendly high-efficiency, is a kind of process for cleanly preparing, there is significant economic benefit.
Detailed description of the invention
Fig. 1 is the XRD diagram for the chromium oxide product that the embodiment of the present invention 1 provides and the XRD standard card figure of chromium oxide.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, below further specifically to the present invention
It is bright.But following embodiments is only simple example of the invention, does not represent or limit the scope of the present invention, this hair
Bright protection scope is subject to claims.
Specific embodiment of the invention part provides a kind of preparation method of chromium oxide, and the method includes following steps
It is rapid:
(1) sexavalence chromium salt solution is added in reaction unit, is passed through closed heating after protective gas, reaches target temperature
After be continually fed into reducibility gas and react, obtain mixed slurry；
(2) mixed slurry for obtaining step (1) is separated by solid-liquid separation, and obtains chromium oxyhydroxide powder；
(3) the chromium oxyhydroxide powder for obtaining step (2) carries out calcination processing, obtains chromium oxide.
The following are typical but non-limiting embodiments of the invention:
Embodiment 1:
The preparation method for present embodiments providing a kind of chromium oxide, the described method comprises the following steps:
(1) chromium acid sodium solution that 200mL concentration is 0.2mol/L is placed in the vertical response kettle that volume is 500mL, is led to
Enter the air in nitrogen discharge reaction kettle and pipeline, temperature programming after sealing starts to be passed through after reaching 250 DEG C of goal response temperature
Hydrogen reacts, and maintenance hydrogen partial pressure is 5MPa, reacts quick water-cooled cooling after 2h, and rate of temperature fall is 10 DEG C/min, obtains
Mixed slurry；
(2) mixed slurry that step (1) obtains is filtered, obtains solid and filtrate, obtained solid is washed, does
It is dry, obtain chromium oxyhydroxide powder；
(3) the chromium oxyhydroxide powder for obtaining step (2) handles 3h in 800 DEG C of temperature lower calcinations, obtains pigment-level oxygen
Change chromium.
Using the content of Cr VI in filtrate obtained by Inductively coupled plasma optical emission spectrometer (ICP) determination step (2), and
Utilize the concentration of sodium hydroxide in acid base neutralization titration reaction assay filtrate；It is measured using the examination criteria of GB/T2078-2006
The purity of step (3) chromium oxide product, and X-ray diffraction (XRD) analysis, and the XRD with chromium oxide are carried out to chromium oxide product
Standard card (PDF:01-082-1484) is compared, as a result as shown in Figure 1；Using 110 type color difference meter of Datacolor, D65 light
Source, 10 ° of viewing angles measure the colorimetric parameter of chromium oxide product.
In the present embodiment, it is up to 99.16% according to the reduction rate that the content of Cr VI in step (2) filtrate calculates chromium, filter
The concentration of sodium hydroxide is 0.395mol/L in liquid, the particle diameter distribution of chromium oxyhydroxide powder obtained by step (2) is 70~
100nm；The purity of step (3) chromium oxide product is 99.92%, as shown in Figure 1, the diffraction maximum of chromium oxide product and chromium oxide
Base peak is nearly identical, further proves that its purity is higher；After tested, the colorimetric parameter of chromium oxide product is L*=42,
A*=-14, b*=13.
Embodiment 2:
The preparation method for present embodiments providing a kind of chromium oxide, the described method comprises the following steps:
(1) potassium chromate solution that 200mL concentration is 0.6mol/L is placed in the horizontal reacting kettle that volume is 500mL, is led to
Enter the air in helium discharge reaction kettle and pipeline, temperature programming after sealing starts to be passed through after reaching 200 DEG C of goal response temperature
Hydrogen reacts, and maintenance hydrogen partial pressure is 8MPa, reacts quick water-cooled cooling after 4h, and rate of temperature fall is 5 DEG C/min, is mixed
Close slurry；
(2) mixed slurry that step (1) obtains is filtered, obtains solid and filtrate, obtained solid is washed, does
It is dry, obtain chromium oxyhydroxide powder；
(3) the chromium oxyhydroxide powder for obtaining step (2) handles 1h in 1000 DEG C of temperature lower calcinations, obtains pigment-level oxygen
Change chromium.
It is reacted using the content of Cr VI in filtrate obtained by ICP spectrometer determination step (2), and using acid base neutralization titration
Measure the concentration of potassium hydroxide in filtrate；Using examination criteria determination step (3) chromium oxide product of GB/T 2078-2006
Purity；The colorimetric parameter of chromium oxide product is measured using 110 type color difference meter of Datacolor, D65 light source, 10 ° of viewing angles.
In the present embodiment, it is up to 99.94% according to the reduction rate that the content of Cr VI in step (2) filtrate calculates chromium, filter
The concentration of potassium hydroxide is 1.194mol/L in liquid, and chromium oxyhydroxide powder obtained by step (2) is amorphous chromium oxyhydroxide,
Particle diameter distribution is 80~110nm；The purity of step (3) chromium oxide product is 99.94%；After tested, the coloration of chromium oxide product
Parameter is L*=45, a*=-16, b*=15.
Embodiment 3:
The preparation method for present embodiments providing a kind of chromium oxide, the described method comprises the following steps:
(1) sodium dichromate solution that 1200mL concentration is 2.0mol/L is placed in volume is to lead in the bubble tower of 2000mL
Enter the air in neon discharge bubble tower and pipeline, temperature programming after sealing starts to be passed through after reaching 300 DEG C of goal response temperature
Hydrogen reacts, and maintenance hydrogen partial pressure is 3MPa, reacts quick water-cooled cooling after 3h, and rate of temperature fall is 15 DEG C/min, obtains
Mixed slurry；
(2) mixed slurry that step (1) obtains is filtered, obtains solid and filtrate, obtained solid is washed, does
It is dry, obtain chromium oxyhydroxide powder；
(3) the chromium oxyhydroxide powder for obtaining step (2) handles 6h in 550 DEG C of temperature lower calcinations, obtains pigment-level oxygen
Change chromium.
It is reacted using the content of Cr VI in filtrate obtained by ICP spectrometer determination step (2), and using acid base neutralization titration
Measure the concentration of sodium hydroxide in filtrate；Using examination criteria determination step (3) chromium oxide product of GB/T 2078-2006
Purity；The colorimetric parameter of chromium oxide product is measured using 110 type color difference meter of Datacolor, D65 light source, 10 ° of viewing angles.
In the present embodiment, it is up to 99.85% according to the reduction rate that the content of Cr VI in step (2) filtrate calculates chromium, filter
The concentration of sodium hydroxide is 3.95mol/L in liquid, and the particle diameter distribution of chromium oxyhydroxide powder obtained by step (2) is 50~80nm；
The purity of step (3) chromium oxide product is 99.91%；After tested, the colorimetric parameter of chromium oxide product be L*=50, a*=-18,
B*=16.
Embodiment 4:
The preparation method for present embodiments providing a kind of chromium oxide, the described method comprises the following steps:
(1) potassium chromate solution that 2000mL concentration is 4.5mol/L is placed in volume is to be passed through in the bubble tower of 5000mL
The air in bubble tower and pipeline is discharged in nitrogen, and temperature programming after sealing starts to be passed through hydrogen after reaching 350 DEG C of goal response temperature
Gas reacts, and maintenance hydrogen partial pressure is 10MPa, reacts quick water-cooled cooling after 6h, and rate of temperature fall is 20 DEG C/min, is mixed
Close slurry；
(2) mixed slurry that step (1) obtains is filtered, obtains solid and filtrate, obtained solid is washed, does
It is dry, obtain chromium oxyhydroxide powder；
(3) the chromium oxyhydroxide powder for obtaining step (2) handles 0.3h in 1250 DEG C of temperature lower calcinations, obtains pigment-level
Chromium oxide.
It is reacted using the content of Cr VI in filtrate obtained by ICP spectrometer determination step (2), and using acid base neutralization titration
Measure the concentration of potassium hydroxide in filtrate；Using examination criteria determination step (3) chromium oxide product of GB/T 2078-2006
Purity；The colorimetric parameter of chromium oxide product is measured using 110 type color difference meter of Datacolor, D65 light source, 10 ° of viewing angles.
In the present embodiment, it is up to 99.26% according to the reduction rate that the content of Cr VI in step (2) filtrate calculates chromium, filter
The concentration of potassium hydroxide is 8.933mol/L in liquid, and the particle diameter distribution of chromium oxyhydroxide powder obtained by step (2) is 60~90nm；
The purity of step (3) chromium oxide product is 99.86%；After tested, the colorimetric parameter of chromium oxide product be L*=55, a*=-20,
B*=19.
Embodiment 5:
The preparation method for present embodiments providing a kind of chromium oxide, the described method comprises the following steps:
(1) potassium bichromate solution that 2300mL concentration is 3.7mol/L is placed in the horizontal reacting kettle that volume is 5000mL
In, the air being passed through in nitrogen discharge reaction kettle and pipeline, temperature programming after sealing is opened after reaching 180 DEG C of goal response temperature
Beginning is passed through hydrogen and reacts, and maintenance hydrogen partial pressure is 15MPa, reacts water-cooled cooling after 10h, and rate of temperature fall is 1 DEG C/min, obtains
To mixed slurry；
(2) mixed slurry that step (1) obtains is filtered, obtains solid and filtrate, obtained solid is washed, does
It is dry, obtain chromium oxyhydroxide powder；
(3) the chromium oxyhydroxide powder for obtaining step (2) handles 2h in 900 DEG C of temperature lower calcinations, obtains pigment-level oxygen
Change chromium.
It is reacted using the content of Cr VI in filtrate obtained by ICP spectrometer determination step (2), and using acid base neutralization titration
Measure the concentration of potassium hydroxide in filtrate；Using examination criteria determination step (3) chromium oxide product of GB/T 2078-2006
Purity；The colorimetric parameter of chromium oxide product is measured using 110 type color difference meter of Datacolor, D65 light source, 10 ° of viewing angles.
In the present embodiment, it is up to 99.98% according to the reduction rate that the content of Cr VI in step (2) filtrate calculates chromium, filter
The concentration of potassium hydroxide is 7.39mol/L in liquid, and chromium oxyhydroxide powder obtained by step (2) is amorphous chromium oxyhydroxide,
Particle diameter distribution is 90~120nm；The purity of step (3) chromium oxide product is 99.92%；After tested, the coloration of chromium oxide product
Parameter is L*=40, a*=-15, b*=10.
Embodiment 6:
The preparation method for present embodiments providing a kind of chromium oxide, the described method comprises the following steps:
(1) sodium dichromate solution that 200mL concentration is 0.18mol/L is placed in the vertical response kettle that volume is 500mL,
The air being passed through in argon gas discharge reaction kettle and pipeline, temperature programming after sealing start to lead to after reaching 280 DEG C of goal response temperature
Enter hydrogen to react, maintenance hydrogen partial pressure is 1MPa, reacts water-cooled cooling after 1h, and rate of temperature fall is 8 DEG C/min, is mixed
Slurry；
(2) mixed slurry that step (1) obtains is filtered, obtains solid and filtrate, obtained solid is washed, does
It is dry, obtain chromium oxyhydroxide powder；
(3) the chromium oxyhydroxide powder for obtaining step (2) handles 4h in 700 DEG C of temperature lower calcinations, obtains pigment-level oxygen
Change chromium.
It is reacted using the content of Cr VI in filtrate obtained by ICP spectrometer determination step (2), and using acid base neutralization titration
Measure the concentration of sodium hydroxide in filtrate；Using examination criteria determination step (3) chromium oxide product of GB/T 2078-2006
Purity；The colorimetric parameter of chromium oxide product is measured using 110 type color difference meter of Datacolor, D65 light source, 10 ° of viewing angles.
In the present embodiment, it is up to 99.21% according to the reduction rate that the content of Cr VI in step (2) filtrate calculates chromium, filter
The concentration of sodium hydroxide is 0.356mol/L in liquid, and the particle diameter distribution of chromium oxyhydroxide powder obtained by step (2) is 45~75nm；
The purity of step (3) chromium oxide product is 99.94%；After tested, the colorimetric parameter of chromium oxide product be L*=60, a*=-21,
B*=17.
Comparative example 1:
This comparative example provides a kind of preparation method of chromium oxide, and referring to embodiment 1, difference is only that the method: step
Suddenly obstructed nitrogen before heating up in (1), is passed directly into hydrogen, until reaction terminates.
Using the content of Cr VI in filtrate obtained by ICP spectrometer determination step (2)；Using the inspection of GB/T2078-2006
The purity of the quasi- determination step of mark (3) chromium oxide product；Using 110 type color difference meter of Datacolor, D65 light source, 10 ° of viewing angles
Measure the colorimetric parameter of chromium oxide product.
In this comparative example, due to being passed through reducibility gas before reaching reaction temperature, reduction reaction occurs in advance, with temperature
The variation of degree can be such that reduzate changes, and cause the object phase composition of reduzate inhomogenous, the color of gained chromium oxide product
Can be bad, the reduction rate of chromium is only 95.78% at this time, and the purity of chromium oxide product is 96.23%, colorimetric parameter L*=53,
A*=-12, b*=9.
It can be seen that the present invention with comparative example based on the above embodiments and chromium oxide, Cr VI prepared using hydrothermal reduction method
The reduction rate of salt is higher, and up to 99% or more, chromium oxide product qualities are higher, and object is mutually uniform, narrower particle size distribution, and purity is reachable
99.6% or more, reach the standard of pigment-level chromium oxide；The method is easy to operate, and cost is relatively low, and by-product is Ke Xunhuanliyong,
Non-pollutant discharge, environmental protection and energy saving, clean manufacturing have significant economic benefit.
The Applicant declares that the present invention illustrates the process method of the present invention through the above embodiments, but the present invention not office
It is limited to above-mentioned process, that is, does not mean that the present invention must rely on above-mentioned process and could implement.Technical field
Technical staff is it will be clearly understood that any improvement in the present invention, the equivalence replacement and auxiliary to raw material, operation selected by the present invention are former
Material, the addition operated, the selection etc. of concrete mode, all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of preparation method of chromium oxide, which is characterized in that the described method comprises the following steps:
(1) sexavalence chromium salt solution is added in reaction unit, is passed through closed heating after protective gas, is held after reaching target temperature
It is continuous to be passed through reducibility gas and react, obtain mixed slurry；
(2) mixed slurry for obtaining step (1) is separated by solid-liquid separation, and obtains chromium oxyhydroxide powder；
(3) the chromium oxyhydroxide powder for obtaining step (2) carries out calcination processing, obtains chromium oxide.
2. preparation method according to claim 1, which is characterized in that step (1) the sexavalence chromic salts include chromate and/
Or bichromate；
Preferably, the chromate includes the alkali metal salt of chromic acid, preferably sodium chromate and/or potassium chromate；
Preferably, the bichromate includes the alkali metal salt of dichromic acid, preferably sodium dichromate and/or potassium bichromate；
Preferably, in step (1) the sexavalence chromium salt solution chromium ion concentration be 0.18~4.5mol/L, preferably 0.61~
3.7mol/L。
3. preparation method according to claim 1 or 2, which is characterized in that step (1) described reaction unit includes vertical anti-
Answer any one in kettle, horizontal reacting kettle or bubble tower, preferably bubble tower；
Preferably, step (1) described protective gas includes any one in nitrogen, helium, neon or argon gas or at least two
Combination；
Preferably, step (1) described reducibility gas includes hydrogen.
4. preparation method according to claim 1-3, which is characterized in that the temperature of step (1) described reaction is
180~350 DEG C, preferably 200~350 DEG C, further preferably 200~250 DEG C；
Preferably, step (1) target temperature is reaction temperature；
Preferably, the time of step (1) described reaction is 0.5~10h, preferably 1~6h, further preferably 2~4h；
Preferably, the pressure of step (1) described reaction be 4~16MPa, preferably 4~13MPa, further preferably 6~
11MPa；
Preferably, in step (1) described reaction process, the pressure of reducibility gas maintains 1~15MPa, preferably 1~8MPa,
Further preferably 1~5MPa.
5. preparation method according to claim 1-4, which is characterized in that step (1) reaction is in stirring bar
It is carried out under part；
Preferably, the stirring rate be 80~500r/min, preferably 100~400r/min, further preferably 200~
350r/min；
Preferably, step (1) is described is quickly cooled down cooling after reaction；
Preferably, the type of cooling is water cooling；
Preferably, the rate that cools is 1~20 DEG C/min, preferably 5~10 DEG C/min.
6. preparation method according to claim 1-5, which is characterized in that step (2) it is described separation of solid and liquid include
Filtering；
Preferably, described that chromium oxyhydroxide and filtrate is obtained by filtration；
Preferably, the filtrate includes sodium hydroxide and/or potassium hydroxide；
Preferably, the filtrate is used for the preparation of step (1) sexavalence chromium salt solution.
7. preparation method according to claim 1-6, which is characterized in that after step (2) described separation of solid and liquid, also
It is washed, it is dry, obtain chromium oxyhydroxide powder；
Preferably, the drying mode includes any one in vacuum drying, forced air drying or freeze-drying, and preferably freezing is dry
It is dry；
Preferably, the partial size of chromium oxyhydroxide powder obtained by step (2) is 45~120nm.
8. preparation method according to claim 1-7, which is characterized in that the temperature of step (3) described calcination processing
Degree is 550~1250 DEG C, preferably 800~1000 DEG C；
Preferably, the time of step (3) described calcination processing is 0.3~6h, preferably 0.5~2h.
9. preparation method according to claim 1-8, which is characterized in that the described method comprises the following steps:
(1) chromate and/or dichromate solution that the concentration of chromium ion is 0.18~4.5mol/L are added in reaction unit,
It is passed through closed heating after protective gas, reaches and is continually fed into hydrogen after target temperature and reacts, the reaction temperature is 180
~350 DEG C, the reaction time is 0.5~10h, and reaction pressure is 4~16MPa, and wherein hydrogen partial pressure is 1~15MPa, and reaction terminates
Quick water-cooled cooling afterwards, rate of temperature fall are 1~20 DEG C/min, obtain mixed slurry；
(2) mixed slurry that step (1) obtains successively is filtered, is washed, it is dry, obtain chromium oxyhydroxide powder and filter
Liquid, the partial size of gained chromium oxyhydroxide powder are 45~120nm；
(3) the chromium oxyhydroxide powder for obtaining step (2) carries out calcination processing, and the calcination processing temperature is 550~1250
DEG C, the calcination processing time is 0.3~6h, obtains chromium oxide.
10. a kind of chromium oxide being prepared using any one of the claim 1-9 preparation method, which is characterized in that described
Chromium oxide is pigment-level chromium oxide；
Preferably, the colorimetric parameter of the chromium oxide are as follows: L*=40~60, a*=-14~-21, b*=10~19.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811550247.5A CN109354068B (en) | 2018-12-18 | 2018-12-18 | Chromium oxide and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811550247.5A CN109354068B (en) | 2018-12-18 | 2018-12-18 | Chromium oxide and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109354068A true CN109354068A (en) | 2019-02-19 |
| CN109354068B CN109354068B (en) | 2021-02-05 |
Family
ID=65329050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811550247.5A Active CN109354068B (en) | 2018-12-18 | 2018-12-18 | Chromium oxide and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109354068B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110394138A (en) * | 2019-08-27 | 2019-11-01 | 青海省博鸿化工科技股份有限公司 | A kind of continuous reaction apparatus and application thereof |
| CN110407253A (en) * | 2019-07-08 | 2019-11-05 | 重庆理工大学 | A kind of method of barium chromate preparation chrome oxide green |
| CN112607739A (en) * | 2020-11-26 | 2021-04-06 | 安徽盈锐优材科技有限公司 | Preparation method of modified silicon carbide for thermal spraying |
| CN114436332A (en) * | 2022-01-30 | 2022-05-06 | 青海省博鸿化工科技股份有限公司 | Hydroxyl chromic oxide with bottom-center orthogonal structure and preparation method of chromic oxide |
| CN114436330A (en) * | 2022-01-30 | 2022-05-06 | 青海省博鸿化工科技股份有限公司 | Preparation method of alpha-hydroxyl chromium oxide |
| CN114715937A (en) * | 2021-01-06 | 2022-07-08 | 中国科学院青海盐湖研究所 | Three-dimensional layered monohydrate chromium hydroxide nanospheres and preparation method thereof |
| CN116425517A (en) * | 2023-04-25 | 2023-07-14 | 砺瓷(上海)新材料有限公司 | Chromium oxide powder and coating preparation method |
| CN114436330B (en) * | 2022-01-30 | 2024-05-14 | 青海省博鸿化工科技股份有限公司 | Preparation method of alpha-hydroxy chromium oxide |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3723611A (en) * | 1970-06-20 | 1973-03-27 | Bayer Ag | Production of chromium (iii) oxide of low sulfur content |
| CN1907865A (en) * | 2005-08-02 | 2007-02-07 | 中国科学院过程工程研究所 | Method of preparing chromium oxide by reducing chromate with gaseous reducing agent at low temperature |
| CN101475217A (en) * | 2008-01-04 | 2009-07-08 | 中国科学院过程工程研究所 | Method for preparing pigment grade chromium hemitrioxide green by using gaseous reducing agent low temperature reduction chromate salt |
| CN102010005A (en) * | 2010-11-02 | 2011-04-13 | 天津派森科技有限责任公司 | Method for preparing chromic oxide |
-
2018
- 2018-12-18 CN CN201811550247.5A patent/CN109354068B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3723611A (en) * | 1970-06-20 | 1973-03-27 | Bayer Ag | Production of chromium (iii) oxide of low sulfur content |
| CN1907865A (en) * | 2005-08-02 | 2007-02-07 | 中国科学院过程工程研究所 | Method of preparing chromium oxide by reducing chromate with gaseous reducing agent at low temperature |
| CN101475217A (en) * | 2008-01-04 | 2009-07-08 | 中国科学院过程工程研究所 | Method for preparing pigment grade chromium hemitrioxide green by using gaseous reducing agent low temperature reduction chromate salt |
| CN102010005A (en) * | 2010-11-02 | 2011-04-13 | 天津派森科技有限责任公司 | Method for preparing chromic oxide |
Non-Patent Citations (2)
| Title |
|---|
| BAI YULAN ET AL.: "Hydrogen Reduction: A Novel Method of Synthesizing Ultra-fine Chromic Oxide Powder", 《JOURNAL OF WUHAN UNIVERSITY OF TECHNOLOGY-MATER》 * |
| 李平等: "铬酸钠氢还原烧结法制备氧化铬绿颜料", 《化工学报》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110407253A (en) * | 2019-07-08 | 2019-11-05 | 重庆理工大学 | A kind of method of barium chromate preparation chrome oxide green |
| CN110394138A (en) * | 2019-08-27 | 2019-11-01 | 青海省博鸿化工科技股份有限公司 | A kind of continuous reaction apparatus and application thereof |
| CN112607739A (en) * | 2020-11-26 | 2021-04-06 | 安徽盈锐优材科技有限公司 | Preparation method of modified silicon carbide for thermal spraying |
| CN114715937A (en) * | 2021-01-06 | 2022-07-08 | 中国科学院青海盐湖研究所 | Three-dimensional layered monohydrate chromium hydroxide nanospheres and preparation method thereof |
| CN114436332A (en) * | 2022-01-30 | 2022-05-06 | 青海省博鸿化工科技股份有限公司 | Hydroxyl chromic oxide with bottom-center orthogonal structure and preparation method of chromic oxide |
| CN114436330A (en) * | 2022-01-30 | 2022-05-06 | 青海省博鸿化工科技股份有限公司 | Preparation method of alpha-hydroxyl chromium oxide |
| CN114436330B (en) * | 2022-01-30 | 2024-05-14 | 青海省博鸿化工科技股份有限公司 | Preparation method of alpha-hydroxy chromium oxide |
| CN116425517A (en) * | 2023-04-25 | 2023-07-14 | 砺瓷(上海)新材料有限公司 | Chromium oxide powder and coating preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109354068B (en) | 2021-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109354068A (en) | A kind of chromium oxide and preparation method thereof | |
| CN109368697A (en) | A kind of chromium oxide and preparation method thereof | |
| US9422167B2 (en) | Method for forming basic nickel carbonate | |
| CN107416872B (en) | Preparation method of magnesium-aluminum carbonate hydrotalcite | |
| CN106277053B (en) | A kind of preparation method of chromium oxide | |
| CN108862391B (en) | Low-Fischer tungsten oxide and preparation method thereof | |
| CN107399748B (en) | A kind of production method for extracting magnesium hydroxide and calcium carbonate from dolomite | |
| CN107555477B (en) | Method for preparing bismuth vanadate yellow pigment | |
| CN107954474A (en) | A kind of method that vanadium product and chromium sulfate basic are produced using vanadium chromium solution | |
| US9663383B2 (en) | Process for preparing chromium(III) oxide | |
| CN102910683A (en) | Production method for synthesizing nanoscale oxide iron red through full-wet method | |
| CN111484079B (en) | Method for preparing chromium oxide green from chromium-containing waste liquid in naphthoquinone production | |
| CN104386752B (en) | A kind of method that menadione gained raffinate is prepared chromium sulfate basic of producing of utilizing | |
| CN114436332A (en) | Hydroxyl chromic oxide with bottom-center orthogonal structure and preparation method of chromic oxide | |
| CN109650446A (en) | A kind of chromium oxide and preparation method thereof | |
| CN101993112B (en) | Clean method for preparing low-sulfur chromium oxide green | |
| CN115072749B (en) | Method for extracting lithium from spodumene without slag | |
| CN108084737B (en) | Environment-friendly yellow inorganic pigment and preparation method thereof | |
| CN102897838B (en) | One-step preparation method of sodium bichromate | |
| CN114436330B (en) | Preparation method of alpha-hydroxy chromium oxide | |
| CN102503415B (en) | Preparation method of compound zirconium oxide | |
| CN108328656A (en) | A method of bismuth vanadium pigments are synthesized by ammonium metavanadate | |
| CN114436330A (en) | Preparation method of alpha-hydroxyl chromium oxide | |
| CN110407253A (en) | A kind of method of barium chromate preparation chrome oxide green | |
| CN108217706A (en) | A kind of Fe2O3Low temperature preparation α-Al are co-doped with CuO2O3The method of powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |