CN102320661B - Three-phase catalytic oxidation preparation technology of soluble chromate - Google Patents

Three-phase catalytic oxidation preparation technology of soluble chromate Download PDF

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CN102320661B
CN102320661B CN2011102617479A CN201110261747A CN102320661B CN 102320661 B CN102320661 B CN 102320661B CN 2011102617479 A CN2011102617479 A CN 2011102617479A CN 201110261747 A CN201110261747 A CN 201110261747A CN 102320661 B CN102320661 B CN 102320661B
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chromate
reactor
sodium
catalytic oxidation
reaction
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CN102320661A (en
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袁代建
王增祥
余冰
谢继云
高波
曾尚平
杨菲
张杨
王海红
刘光华
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Chongqing Minfeng Chemical Co Ltd
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Abstract

The invention relates to a preparation technology of chromate, specifically to a three-phase catalytic oxidation preparation technology of soluble chromate. The technology comprises the following steps of: heating alkali liquor with concentration of 20-60% to 50-300 DEG C, then, mixing chromite or carbon ferrochrome with the alkali liquor according to mass ratio of Cr2O3 : alkali liquor = 1 : 1.5-10 to form suspending liquid, and introducing the suspending liquid into a reactor; continuously inputting the air or the oxygen heated to 50-300 DEG C to the bottom of the reactor through a pipeline; setting a catalyst in the reactor according to the mass ratio of catalyst : Cr2O3 = 0.1-1.5 : 100, maintaining the temperature of the suspending liquid in the reactor at 50-300 DEG C, executing gas-liquid-solid three-phase bubbling reaction for 0.5-6 hours to generate soluble chromate raw products and chromium residues; removing impurities through filtering and crystallization to obtain the chromate. With the three-phase catalytic oxidation preparation technology of the soluble chromate, Cr2O3 conversion rate is high, reaction speed is fast, energy consumption is low, residue quantity is low, environment pollution is less, equipment investment is low and corrosion is low.

Description

Triphase catalytic oxidation prepares the technique of dissolubility chromate
Technical field
The present invention relates to a kind of technique for preparing chromic salt, be specifically related to the technique that a kind of triphase catalytic oxidation prepares dissolubility chromate.
Background technology
Sodium chromate and potassiumchromate are common dissolubility chromates, it is also the basic material in Chrome Salt Industry, wherein Sodium chromate is the important source material for preparing sodium dichromate 99, potassiumchromate is the important source material of preparation potassium bichromate, sodium dichromate 99, be purposes the most extensively, chromium compounds product that output is maximum, the total class of world consumption commodity 10% relevant with the chromium series product, say that in a sense chromium salt production has certain strategic position.China is the production and consumption country of sodium dichromate 99 maximum in the world, accounts for 30% of global production capacity.At present, China's sodium dichromate 99 throughput is 370,000 t/a, and 2009 annual production are 270,000 t.
The technique of China's sodium dichromate 99 still be take at present has the calcium roasting method as main, accounts for 69 % of domestic aggregated capacity.Have the sodium dichromate 99 power consumption of calcium baked for producing high, contain that the chromium pollutant difficulty of governance is large, cost is high, large to environmental influence, contaminate environment is serious, is the root of Chrome Salt Industry highly energy-consuming, high pollution.Therefore by Environmental Protection Department, classified as high pollution, high environmental risk product, receive the concern of government and media, country has put into effect a lot of laws, rules and the behavior of industry policy standard industry.So the new technology that a series of Sodium chromates are produced under national policy guiding and CSR promotion comprises: Sodium chromate, the inferior fused salt liquid phase oxidation style of potassium system, calcium-free roasting technology are produced in ferrochrome alkali dissolved oxygen Sodium chromate processed, the tower Continuous Liquid Phase oxidation of Pneumatic fluidized.In its practical application, still exist separately certain problem.
1, calcium-free roasting technology: calcium-free roasting technique is not added the calcic auxiliary material in process of production with respect to there being the calcium roasting method to refer to, make its chromium slag physical property and have calcium chromium slag totally different, and then making the physical property of slag be improved greatly, non-cement compound matter in slag, without containing sexavalent chrome (Cr 6+) the sosoloid composition, be easy to efficiently embathe, in slag, do not contain the carcinogens yellow ultramarine, without calcium chromium slag, can smelt the croloy steel, realize the zero release of chromium slag, realize the production that cleans of chromic salts.Though the industrialization of this method, larger but the chromium slag produces slag, the quantity of slag is 0.7-0.8 ton/ton, and energy consumption is higher, and ten thousand yuan of output value comprehensive energy consumption signature coals are 1.52t.
2, the inferior fused salt liquid phase oxidation style of potassium system: take chromite and potash is that potassiumchromate and downstream oxidation chrome green product are produced in the stock liquid phase oxidation.Use inferior fused salt non-conventional media reaction system, the inferior fused salt of setting up efficient-clean conversion chromite resources is intended homogeneous phase atomic economy reaction/separate new process, novel method, replace conventional high-temperature kiln gas-solid sinter process, the main reaction temperature is down to 300 ℃, chromium recovery ratio raising 20% by 1200 ℃ of old techniques, and energy consumption descends 20%.The chromoxide green production cost is compared 10% left and right that descends with traditional technology, eliminated the chromium slag, contained chromium powder dirt exhaust emission from beginning of production.But the method can only the green product of manufacture order chromous oxide, and take sodium dichromate 99 as a series of chromium cpd products such as the chromic trioxide of raw material production, chromium powder tanning agent can not adopt this method manufacture, can not meet the needs that the chromic salts Enterprise Diversification is produced.
3, ferrochrome alkali dissolved oxygen Sodium chromate processed: give up ferrochrome (ferrochrome powder) and liquid sodium hydroxide of the metallurgical industry of take is that raw material adopts the pure oxygen oxidation, in hydrothermal system, realize the alkaline stripping of chromium, produce chromic salt by-product ferrochrome series pigments, process can have been utilized autothermal reaction, the method is raw materials used comparatively single, and need the high temperature of 280 ℃, the hyperbaric environment of 6MPa high pressure.
4, Sodium chromate is produced in the tower Continuous Liquid Phase oxidation of Pneumatic fluidized: take chromite ore fine and caustic soda (sodium hydroxide) is raw material, utilize the pressurization of patent equipment Pneumatic fluidized tower to produce, this method only be take chromite ore fine and is raw material, air is oxygenant, owing to there is no catalysts, temperature of reaction pressure is relatively high, and speed is slower.
Summary of the invention
The object of the present invention is to provide that a kind of raw material is wide, equipment investment is little, produce that the quantity of slag is few, environmental pollution is little and reduce the chromic salt preparation technology of energy consumption and equipment corrosion.
In order to address the above problem, the invention provides the technique that a kind of triphase catalytic oxidation prepares dissolubility chromate, include following steps:
A, the alkali lye that is 20～60% by concentration are heated to 50～300 ℃, then according to Cr 2O 3: the mass ratio mixing trivalent chromium compound of alkali lye=1:1.5～10 forms suspension, and suspension is passed in reactor;
B, will be heated to 50～300 ℃ of air or oxygens by the continuous input reactor of pipeline bottom;
C, reactor are according to catalyzer: Cr 2O 3The mass ratio of=0.1～15:100 arranges catalyzer, maintains reactor inner suspension liquid temp at 50～300 ℃, and the gas-liquid-solid three-phase blistering reaction generated dissolubility chromate crude product and chromium slag in 0.5～6 hour;
D, after filtration, crystallization obtains chromic salt.
Further, requirement according to actual production, limiting the alkali lye described in steps A is sodium hydroxide, sodium carbonate, potassium hydroxide or salt of wormwood, the corresponding dissolubility chromate generated is respectively Sodium chromate, Sodium chromate, potassiumchromate, potassiumchromate, and described trivalent chromium compound is chromite, carbon ferrochrome or contains the chromium waste.
Further, according to the present situation of business equipment, described reactor is the combination of reactor, reaction tower or a plurality of reaction towers.
As preferred version, consider that this technique can, in the situation that pressurization further improves speed of response, therefore, in step C, maintain the pressure of 0.1～0.8 MPa in reactor.
As preferred version, the effect of combined catalyst and cost, limit the one or more kinds of compositions in oxide compound, manganate and permanganate that catalyzer described in step C is ozone, persulfide, superoxide, ferrate, nitrate, manganese, Sodium chromate, sodium dichromate 99, chromic trioxide.
Take and prepare Sodium chromate and be example, the effective constituent of reactant chromite or carbon ferrochrome is FeOCr 2O 3, Cr wherein 2O 3Under the condition of high temperature, high pressure and catalyzer, carry out following the reaction with sodium hydroxide and oxidizing gas:
2FeOCr 2O 3+ 8NaOH+3.5O 2 Catalyzer 4Na 2CrO 4+ Fe 2O 3+ 4H 2O
After reaction, obtain containing sodium hydroxide, Na 2CrO 4With the solution of other water-soluble impurities and the solidliquid mixture of chromium slag.After filtering out the chromium slag, obtain containing sodium hydroxide, Na 2CrO 4Solution with other water-soluble impurities.Wherein the chromium slag can be sent to steelworks steel-making after washing, removing toxic substances.After filtrate adds sodium hydroxide to make saturated solution, through subsequent techniques such as pervaporation, crystallization and removal of impurities, finally obtain chromium acid sodium solution, Sodium chromate can be used for preparing sodium dichromate.
The technique that the triphase catalytic oxidation of employing technical solution of the present invention prepares dissolubility chromate has following advantage:
1, raw material is wide, and not only chromite ore fine is raw material, but also can the ferrochrome powder, nearly all chromium cpd (solvable, insoluble) that contains is raw material, with potassium hydroxide solution replace sodium hydroxide solution, can directly prepare potassium bichromate; With sodium carbonate, replace sodium hydroxide, can save and separate sodium hydroxide step, sodium carbonate direct reuse; By the oxygen replaces air, make oxygenant, not only reaction pressure can be reduced, speed is accelerated, also can avoid Carbon Dioxide in Air and sodium hydroxide (hydroxide) to generate sodium carbonate (salt of wormwood), reduce the carbonate difficult separation and recycling in the Sodium chromate sepn process, as use ozone, can use no or little catalyzer.Adopt sodium carbonate to prepare the reaction principle equation of Sodium chromate as follows:
2FeOCr 2O 3+ 4Na 2CO 3+ 3.5O 2 Catalyzer 4Na 2CrO 4+ Fe 2O 3+ 4CO 2
2, than calcium-free roasting, prepare the technique of Sodium chromate, it is under the prerequisite that guarantees higher reaction effect, and equipment investment is less, and it is less that it produces quantity of slag, also reduced Cr 6+Pollution to environment.
3, due to the technique that has adopted triphase catalytic oxidation, use by catalyzer, improved speed of reaction, reduced temperature of reaction and corrodibility, owing to without Sweet natural gas or coal dust, making fuel, reaction conversion ratio is high, but adopts 3.64 tons of this technology ton product reducing emission of carbon dioxide, reduces discharging 2.3 tons of chromium residues, reduce discharging 50 kilograms of pollutent sexavalent chromes, save 1.3 tons of standard coals.
The accompanying drawing explanation
The present invention is further detailed explanation below in conjunction with the drawings and specific embodiments:
Fig. 1 is the step block diagram that triphase catalytic oxidation of the present invention prepares the process example 1 of dissolubility chromate.
Embodiment
In following proposal, known concrete structure and characteristic are no longer set forth at this.
Embodiment 1
As shown in Figure 1, the invention provides the technique that a kind of triphase catalytic oxidation prepares dissolubility chromate, include following steps:
A, the sodium carbonate solution that is 20% by concentration are heated to 150 ℃, then according to Cr 2O 3: Na 2CO 3The mass ratio mixing chromite of=1:1.5 or carbon ferrochrome form suspension, and suspension is passed in reactor;
B, will be heated to 150 ℃ of air or oxygens and input continuously reactor bottom by pipeline;
In C, reactor according to catalyzer: Cr 2O 3The mass ratio of=0.1:100 arranges catalyzer, catalyzer is the mixture of oxide compound, manganate and the permanganate of ferrate, nitrate, manganese, maintain reactor inner upper pressure at 0.1 MPa, maintain reactor inner suspension liquid temp at 150 ℃, the gas-liquid-solid three-phase blistering reaction generated solubility chromic acid sodium crude product and chromium slag in 4 hours;
D, after filtration, crystallization obtains Sodium chromate.
In whole reaction, temperature has been controlled at 150 ℃, and pressure-controlling is at 0.1 MPa, and the reaction times is 4 hours, wherein Cr 2O 3Transformation efficiency be 95%, slag rate is 15%, visible technique of the present invention, under the prerequisite that guarantees high conversion and high reaction rate, has been saved energy consumption, has reduced equipment loss.
Embodiment 2
Concrete steps are substantially the same manner as Example 1, and distinctive points is the variation of reaction conditions and parameter:
A, the sodium hydroxide solution that is 60% by concentration are heated to 300 ℃, then according to Cr 2O 3: the mass ratio mixing carbon ferrochrome of NaOH=1:10 forms suspension, and suspension is passed in reactor;
B, will be heated to 300 ℃ of air or oxygens and input continuously reactor bottom by pipeline;
In C, reactor according to catalyzer: Cr 2O 3The mass ratio of=15:100 arranges catalyzer, catalyzer is the mixture of oxide compound, persulfide, superoxide and the ferrate of manganese, do not pressurize in reactor inside, maintain reactor inner suspension liquid temp at 300 ℃, the gas-liquid-solid three-phase blistering reaction generated solubility chromic acid sodium crude product and chromium slag in 0.5 hour;
D, after filtration, crystallization and washing obtain pure Sodium chromate.
In whole reaction, temperature has been controlled at 300 ℃, and the reaction times is 0.5 hour, wherein Cr 2O 3Transformation efficiency be 97%, slag rate is 5%.
Embodiment 3
Concrete steps are substantially the same manner as Example 1, and distinctive points is the variation of reaction conditions and parameter:
A, the sodium hydroxide solution that is 40% by concentration are heated to 50 ℃, then according to Cr 2O 3: the mass ratio mixing chromite of NaOH=1:5 forms suspension, and suspension is passed in reaction tower;
B, will be heated to 50 ℃ of air or oxygens and input continuously reaction tower bottom by pipeline;
In C, reaction tower according to catalyzer: Cr 2O 3The mass ratio of=8:100 arranges catalyzer, catalyzer is the mixture of superoxide, Sodium chromate and chromic trioxide, maintain reactor inner upper pressure at 0.5 MPa, maintain reactor inner suspension liquid temp at 50 ℃, the gas-liquid-solid three-phase blistering reaction generated solubility chromic acid sodium crude product and chromium slag in 6 hours;
D, after filtration, crystallization and washing obtain pure Sodium chromate.
In whole reaction, temperature has been controlled at 50 ℃, and pressure-controlling is at 0.5 MPa, and the reaction times is 6 hours, wherein Cr 2O 3Transformation efficiency be 97%, slag rate is 8%.
Embodiment 4
Provide a kind of triphase catalytic oxidation to prepare the technique of potassiumchromate, include following steps:
A, the potassium hydroxide solution that is 20% by concentration are heated to 200 ℃, then according to Cr 2O 3: the mass ratio mixing chromite of KOH=1:7 forms suspension, and suspension is passed in reaction tower;
B, will be heated to 200 ℃ of oxygen and input continuously reactor tower section by pipeline;
In C, reaction tower according to catalyzer: Cr 2O 3The mass ratio of=4:100 arranges catalyzer, catalyzer is the mixture of ozone, persulfide, superoxide, maintain reactor inner upper pressure at 0.8 MPa, maintain reaction tower inner suspension liquid temp at 200 ℃, the gas-liquid-solid three-phase blistering reaction generated solubility chromic acid potassium crude product and chromium slag in 5 hours;
D, after filtration, crystallization obtains potassiumchromate.
In whole reaction, temperature has been controlled at 200 ℃, and pressure-controlling is at 0.8 MPa, and the reaction times is 5 hours, wherein Cr 2O 3Transformation efficiency be 99%, slag rate is 10%, visible technique of the present invention, under the prerequisite that guarantees high conversion and high reaction rate, has been saved energy consumption, has reduced equipment loss.
Main innovate point of the present invention is the selection of catalyzer and the combination of catalyzer, by catalyzer is applied to phase reaction, thereby fast reaction speed, the energy consumption that reduces, reduces equipment loss, reduces chromium slag output.For other catalyzer and the combination thereof that limit and drop on the selection of reactant ratio in limited range, the selection of reaction conditions parameter, those of ordinary skills can, from above embodiment, inspiring and obtain basic result under the prerequisite without performing creative labour, repeat no more.
Above-described is only the preferred embodiment of the present invention; should be understood that; for a person skilled in the art; under the prerequisite that does not break away from technique of the present invention; can also make some improvement; these also should be considered as protection scope of the present invention, and these can not affect effect of the invention process and practical applicability.

Claims (4)

1. triphase catalytic oxidation prepares the technique of dissolubility chromate, it is characterized in that including following steps:
A, the alkali lye that is 20～60% by concentration are heated to 50～200 ℃, then according to Cr 2O 3: the mass ratio mixing trivalent chromium compound of alkali lye=1:1.5～10 forms suspension, and suspension is passed in reactor;
B, will be heated to 50～200 ℃ of air or oxygens by the continuous input reactor of pipeline bottom;
C, reactor are according to catalyzer: Cr 2O 3The mass ratio of=0.1～15:100 arranges catalyzer, maintains reactor inner suspension liquid temp at 50～200 ℃, and the gas-liquid-solid three-phase blistering reaction generated dissolubility chromate crude product and chromium slag in 0.5～6 hour;
D, after filtration, crystallization obtains chromic salt;
Catalyzer described in step C is at least a in persulfide, ferrate, Sodium chromate, sodium dichromate 99, chromic trioxide.
2. triphase catalytic oxidation according to claim 1 prepares the technique of dissolubility chromate, it is characterized in that: the alkali lye described in steps A is sodium hydroxide, sodium carbonate, potassium hydroxide or solution of potassium carbonate, the corresponding dissolubility chromate generated is respectively Sodium chromate, Sodium chromate, potassiumchromate, potassiumchromate, and described trivalent chromium compound is chromite, carbon ferrochrome or contains the chromium waste.
3. triphase catalytic oxidation according to claim 1 prepares the technique of dissolubility chromate, it is characterized in that: described reactor is the combination of reactor, reaction tower or a plurality of reaction towers.
4. triphase catalytic oxidation according to claim 1 prepares the technique of dissolubility chromate, it is characterized in that: in step C, in reactor, maintain the pressure of 0.1～0.8 MPa.
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CN104512928B (en) * 2013-09-30 2017-04-19 湖北振华化学股份有限公司 Bubbling tower three-phase reaction apparatus for liquid-phase oxidation leaching of chromite, and method thereof
CN104512930A (en) * 2013-09-30 2015-04-15 湖北振华化学股份有限公司 Method for producing chromate by liquid-phase catalytic oxidation of chromite
CN104512931B (en) * 2013-09-30 2017-10-10 湖北振华化学股份有限公司 Pressurization liquid phase oxidation chromite decomposition method and the device for liquid phase oxidation chromite decomposition of pressurizeing
CN104726689B (en) * 2013-12-24 2017-05-10 中国科学院过程工程研究所 Method for decomposing chromite by low-temperature atmospheric-pressure fluidization
CN104276604A (en) * 2014-04-29 2015-01-14 余华强 Method for preparing chromate through caustic soda solid oxidization of chromite ore
CN106745292B (en) * 2017-01-04 2018-03-09 萍乡市利升科技有限公司 A kind of Pneumatic fluidized tower of continuous production of potassium manganate and its application
CN107827156A (en) * 2017-11-13 2018-03-23 陕西省商南县东正化工有限责任公司 A kind of method that sodium chromate is prepared using chromic acid chromium
CN108358246B (en) * 2018-01-09 2019-12-10 中南大学 Preparation method and application of sodium ferrochrome material

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CN101481144A (en) * 2008-01-09 2009-07-15 中国科学院过程工程研究所 Clean production method for preparing potassium chromate from chromic iron
CN101659444A (en) * 2008-08-27 2010-03-03 中国科学院过程工程研究所 Clean production method for preparing sodium chromate from chromite

Patent Citations (3)

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CN101481144A (en) * 2008-01-09 2009-07-15 中国科学院过程工程研究所 Clean production method for preparing potassium chromate from chromic iron
CN101659444A (en) * 2008-08-27 2010-03-03 中国科学院过程工程研究所 Clean production method for preparing sodium chromate from chromite

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