CN104445132A - Method for preparing chromium phosphate by utilizing diene chrome waste liquid - Google Patents
Method for preparing chromium phosphate by utilizing diene chrome waste liquid Download PDFInfo
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- CN104445132A CN104445132A CN201410694956.6A CN201410694956A CN104445132A CN 104445132 A CN104445132 A CN 104445132A CN 201410694956 A CN201410694956 A CN 201410694956A CN 104445132 A CN104445132 A CN 104445132A
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Abstract
The invention discloses a method for preparing chromium phosphate by utilizing a diene chrome waste liquid, and in particular relates to utilization of a chrome waste liquid and preparation of the chromium phosphate. The method comprises the following steps: adding phosphoric acid and methanal in diene alcohol ketone acetate chrome waste liquid, stirring the phosphoric acid, the methanol and the diene alcohol ketone acetate chrome waste liquid, heating to the temperature of 80 to 110 DEG C, keeping the temperature for 30 to 60 minutes, stopping heating, cooling to the temperature which is equal to 80 DEG C or below, and performing filtration to obtain a green crude product of dihydrate chromium phosphate; calcining the crude product at the temperature of 850 to 950 DEG C for 2 to 4 hours, and obtaining brown anhydrous chromium phosphate; washing and purifying the crude product of dihydrate chromium phosphate by acetic acid many times so as to obtain a pure product of dihydrate chromium phosphate. Brown anhydrous chromium phosphate can be obtained by calcining the pure product of dihydrate chromium phosphate. The method utilized to prepare the chromium phosphate is convenient and has the advantages of good selectivity, low cost of raw materials, high additional values of products and good quality, and the requirements of industrialized production can be satisfied.
Description
Technical field
The present invention relates to a kind of preparation method of Plessy's green, particularly a kind of method utilizing diene chrome waste liquid to prepare Plessy's green.
Background technology
Plessy's green is a kind of excellent rust-stabilising pigment; be mainly used in wash primer and singly pack priming paint; in polyvinyl butyral acetal, vinyl resins and alcohol acid primer, rust-proof effect is good; to the strong adhesion of steel, aluminium, magnesium and most of coating; for the protection of boats and ships, aircraft, automobile, rail vehicle, bridge, also can be used for dyestuff, ceramic industry.Anhydrous phosphoric acid chromium to thermoae be stable, fusing point, up to 1800 DEG C, does not decompose during melting, can be used as the joint compound of refractory materials.Plessy's green colloid is also used for the treatment of the diseases such as cancer.
The preparation of current Plessy's green is reacted with chromium chloride and sodium phosphate usually.Because chromium chloride, sodium phosphate price are higher, and the product more complicated obtained, generate six water Plessy's greens, three water Plessy's greens, four water Plessy's greens, phosphate dihydrate chromium and acid phosphate chromium etc., need heat treated in diacetyl oxide just can obtain the single phosphate dihydrate chromium of product, therefore preparation cost is also high.A kind of new preparation method that Zhang Fuqiang designs is the ratio stirring heating of 1:0.5 ~ 0.6:0.2 ~ 0.5:15 with mol ratio by phosphoric acid, chromic oxide, initiator, water, obtain product is single, purity is high Plessy's green (Zhang Fuqiang. a kind of preparation method of Plessy's green. [P] patent: C01B25/37,2013-05-13).But do not solve the problem of high cost.Simultaneously because the preparation cost of Plessy's green is high, price, limits the use of Plessy's green.
The waste liquid produced after production of saponin diene contains chromium acetate, chromium trioxide, sodium acetate, acetic acid and other relevant organic oxygen compound etc., and after concentrated, chromium acetate exists with amorphous crystalline state, and the content of total chromium is (with Cr
2o
3meter) be about 10%, but containing a large amount of organic oxygen compound impurity, therefore can not directly apply, be also difficult to be separated.Because the current comprehensive utilization technique to this waste liquid is less, most enterprise is concentrated by this waste liquid, calcining, then sells steel mill's steel-making.This treatment process, on the one hand concentrating and having a large amount of pollution gas to discharge in calcination process, causes environmental pollution; On the other hand, the resources such as the sodium acetate in waste liquid, acetic acid are not recycled, and being one wastes greatly, concerning being also one to lose greatly enterprise.
Summary of the invention
The object of the invention is for above problem, a kind of method utilizing diene chrome waste liquid to prepare Plessy's green is provided, its simple process, cost are low, product selectivity good, added value is high.Utilization for diene chrome waste liquid provides the method for another kind of high performance-price ratio.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is, provide a kind of method utilizing diene chrome waste liquid to prepare Plessy's green, concrete steps are:
1) in diene alcohol ketone acetic ester chrome waste liquid, add formaldehyde saturated aqueous solution and phosphoric acid, be heated with stirring to 80 ~ 110 DEG C, keep 30 ~ 60 minutes, sexavalent chrome (VI) is reduced into trivalent chromium (III), and obtains green precipitate; Wherein in the add-on of every formaldehyde and waste liquid, the ratio of the amount of sexavalent chrome (VI) is 1 ~ 2:1, and the add-on of phosphoric acid counts 0.95 ~ 1.1 times of chromium from waste chromium content with amount of substance;
2) material in step 1) is cooled to less than 80 DEG C and filters to obtain green phosphate dihydrate chromium crude product; Being washed by green phosphate dihydrate chromium crude product acetic acid, is colourless to washings, the dry phosphate dihydrate chromium sterling obtaining content more than 98.5%;
3) by green phosphate dihydrate chromium crude product or green phosphate dihydrate chromium sterling 850 ~ 950 DEG C of calcinings 2 ~ 4 hours, the brown anhydrous phosphoric acid chromium of content more than 98.3%.
The rate of recovery of chromium reaches more than 95%.
Containing impurity such as organic oxygen compound, acetic acid, phosphoric acid, SODIUM PHOSPHATE, MONOBASIC, phosphoric acid hydrogen chromium in thick product, owing to having containing acetic acid in waste liquid, also acetic acid is produced after chromium acetate and phosphatase reaction, the polarity of acetic acid is comparatively large simultaneously, and organism, inorganics have certain solubleness in acetic acid, and the concentration of acetic acid is larger, washing effect is better, reclaim also Vietnamese side just, more energy-conservation, therefore use the acetic acid eccysis impurity of more than 60%.
According to reaction principle, chromium ion is 1:1 with the ratio of the amount of phosphoric acid, when phosphoric acid amount is not enough, reaction is complete not, can reduce the rate of recovery of chromium, excessive too many time likely produce water miscible acid phosphate chromium, the rate of recovery of chromium can be made equally to reduce, therefore, select the scope 0.95 ~ 1.1 that floating, can guarantee that the recovery of chromium ion reaches more than 95%.
In described diene alcohol ketone acetic ester chrome waste liquid, total Cr(is in Cr) content 10 ~ 500g/L, Cr
6+content be 10 ~ 500mg/L.This waste liquid is the waste liquid after concentrating, and different according to concentrated degree, the content of Cr is larger.
In described step 1), phosphoric acid and formaldehyde saturated aqueous solution are joined in chrome waste liquid simultaneously; Commercially available formaldehyde has two kinds of forms: the saturated aqueous solution of polyoxymethylene and formaldehyde, and polyoxymethylene is solid, needs depolymerization during use, can produce formaldehyde gas and volatilize, and selects formaldehyde saturated aqueous solution more for convenience, and cost-saving.
Described step 2) described in each consumption of acetic acid and the volume ratio of original solution in step 1) be 0.5 ~ 1:1; The consumption of washing composition is relevant with by the volume that washs solid, first will ensure that washing composition can immersion solid thing completely, fully could contact with impurity, and by impurities dissolves in washing composition.Dosage of scour is too much, and when can cause recovery, energy consumption is too high.According to the output of Plessy's green, determine that the consumption of acetic acid and the volume ratio of former waste liquid are 0.5 ~ 1:1.
Calcining temperature in step 3) is 900 DEG C, and calcination time is 3 hours; Containing impurity such as organic oxygen compound, acetic acid, phosphoric acid, SODIUM PHOSPHATE, MONOBASIC in thick product.Organic oxygen compound is that incendivity becomes carbonic acid gas and water is removed at about 400 DEG C, the boiling point of acetic acid about 118 DEG C, the boiling point of phosphoric acid is 158 DEG C, the boiling point of SODIUM PHOSPHATE, MONOBASIC is about 100 DEG C, can vapor away in advance during calcining.Other inorganic salt impurities content are little, on the quality of Plessy's green without too large impact.The temperature that phosphate dihydrate chromium loses crystal water is 850 DEG C, in order to fully decompose dehydration, therefore temperature is selected in 850 ~ 950 DEG C.Temperature is low, and calcination time is long, and temperature height calcination time is just short, and according to analysis of experimental data, from the viewpoint of energy-conservation and quality two, optimum temps is 900 DEG C, and the time is 3 hours.
The mass concentration of the phosphoric acid described in step 1) is 50 ~ 85%.
In preferred scheme, the stirring velocity described in step 1) is 100 ~ 1000 revs/min; Can be regulated the granular size of Plessy's green by the control of rotating speed, rotating speed is fast, and particle is little, and the impurity of parcel is just few.Also can react if do not stirred, but easily lump, trouble is caused to the separation of impurity.
Also do not utilize this waste liquid to prepare the relevant report of Plessy's green at present, do not utilize chromium acetate to produce the relevant report of Plessy's green yet.
Reaction principle of the present invention is:
First, be that a small amount of sexavalent chrome is reduced into trivalent chromium by formaldehyde, trivalent chromium and phosphoric acid generate phosphate dihydrate chromium in case of heating; And original chromium acetate generates phosphate dihydrate chromium with phosphatase reaction in case of heating in waste liquid.
When usual employing chromium trichloride prepares Plessy's green, can generate six water Plessy's greens, three water Plessy's greens, four water Plessy's greens, phosphate dihydrate chromium and acid phosphate chromium etc., product is complicated, needs heat treated in diacetyl oxide just can obtain pure phosphate dihydrate chromium.And the present invention is different due to the waste liquid environment adopted, as contained organic oxygen compound, acetic acid, sodium acetate etc. in this waste liquid, only generates stable phosphate dihydrate chromium, having stronger selectivity.
The beneficial effect that the present invention has:
1) diene chrome waste liquid is low, the costly useful resources of a kind of price, effectively can be utilized the chromium resource in waste liquid by the method, and the Plessy's green added value of production is high, and the utilization for diene chrome waste liquid provides the method for another kind of high performance-price ratio.
The market price of current this waste liquid is 1100 ~ 1300 yuan/ton, and the price of amounting to into chromium acetate is 1430 ~ 1680 yuan/ton, and this price only has 1/10th of technical grade chromium acetate.Chromium acetate per ton can produce phosphate dihydrate chromium 0.95 ton (rate of recovery by 95%), add artificial water power, tax revenue etc., the cost of phosphate dihydrate chromium per ton is less than 10000 yuan, and the existing market valency of phosphate dihydrate chromium is between 30000 yuan ~ 38000 yuan/ton, often produce profitable more than 20000 yuan of one ton of phosphate dihydrate chromium, anhydrous phosphoric acid chromium price is higher.Therefore the added value of product that method provided by the invention is produced is high, good in economic efficiency.
2) adopt the method simple, easy to operate, be suitable for suitability for industrialized production, the utilization ratio of chromium is high, and the rate of recovery can reach more than 95%, can turn waste into wealth, and a new outlet is found in the utilization for diene chrome waste liquid.
3) method provided by the invention, its selectivity is good, only generates stable phosphate dihydrate chromium or anhydrous phosphoric acid chromium.Quality product meets the requirement of suitability for industrialized production.
Embodiment
Further illustrate the present invention below in conjunction with embodiment, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Sampling analysis: gathered diene waste liquid is analyzed, wherein the content of chromium is: total Cr(is in Cr) content 149.6g/L, Cr
6+content be 125.8mg/L, pH 1.09.
Example 1: get waste liquid 5L, adds 2mL formaldehyde saturated aqueous solution, 1.66kg85% phosphoric acid, stirs (rotating speed 100 revs/min) and is heated to 110 DEG C, keep 30 minutes, stop heating; Then be chilled to less than 80 DEG C, filter to obtain green phosphate dihydrate chromium crude product, wash 3 times with 2.5L70% acetic acid at every turn; Dry green phosphate dihydrate chromium, 2.61kg, content 98.7%.The rate of recovery 99.1%.
Example 2: get waste liquid 500mL, adds 0.2mL formaldehyde saturated aqueous solution, 0.27kg50% phosphoric acid, stirs (rotating speed 1000 revs/min) and is heated to 100 DEG C, keep 60 minutes, stop heating; Be chilled to less than 80 DEG C, filter to obtain green phosphate dihydrate chromium crude product, wash 4 times with 500mL glacial acetic acid at every turn; Dry green phosphate dihydrate chromium 0.26kg, content 99.0%.The rate of recovery 98.8%.
Example 3: get waste liquid 20L, adds 6.5mL formaldehyde saturated aqueous solution, 7.66kg70% phosphoric acid, stirs (rotating speed 200 revs/min) and is heated to 80 DEG C, keep 50 minutes, stop heating; Be chilled to less than 80 DEG C, filter to obtain green phosphate dihydrate chromium crude product, wash 4 times with 15L80% acetic acid at every turn; Dry green phosphate dihydrate chromium 10.01kg.Content 98.5%.The rate of recovery 95.1%.
Example 4: get waste liquid 1L, adds 0.3mL formaldehyde saturated aqueous solution, 0.32kg85% phosphoric acid, stirs (rotating speed 500 revs/min) and is heated to 100 DEG C, keep 40 minutes, stop heating.Be chilled to less than 80 DEG C, filter to obtain green phosphate dihydrate chromium crude product.By this green phosphate dihydrate chromium crude product in 950 DEG C of calcinings 2 hours, obtain brown anhydrous phosphoric acid chromium 0.42kg.Content 98.3%.The rate of recovery 96.7%.
Example 5: get waste liquid 3L, adds 1.5mL formaldehyde saturated aqueous solution, 1.41kg60% phosphoric acid, stirs (rotating speed 600 revs/min) and is heated to 80 DEG C, keep 60 minutes, stop heating.Be chilled to less than 80 DEG C, filter to obtain green phosphate dihydrate chromium crude product.By this green phosphate dihydrate chromium crude product in 850 DEG C of calcinings 4 hours, obtain brown anhydrous phosphoric acid chromium 1.25kg.Content 98.6%.The rate of recovery 98.5%.
Example 6: get waste liquid 2L, adds 0.8mL formaldehyde saturated aqueous solution, 0.64kg85% phosphoric acid, stirs (rotating speed 800 revs/min) and is heated to 110 DEG C, keep 30 minutes, stop heating.Be chilled to less than 80 DEG C, filter to obtain green phosphate dihydrate chromium crude product.By this green phosphate dihydrate chromium crude product in 900 DEG C of calcinings 3 hours, obtain brown anhydrous phosphoric acid chromium 0.81kg.Content 98.5%.The rate of recovery 95.8%.
Example 7: get waste liquid 10L, adds 3.5mL formaldehyde saturated aqueous solution, 6.20kg50% phosphoric acid, stirs (rotating speed 700 revs/min) and is heated to 90 DEG C, keep 50 minutes, stop heating.Be chilled to less than 80 DEG C, filter to obtain green phosphate dihydrate chromium crude product, wash 4 times with 5L60% acetic acid at every turn.Dry green phosphate dihydrate chromium.By this green phosphate dihydrate chromium in 930 DEG C of calcinings 3 hours, obtain brown anhydrous phosphoric acid chromium 4.12kg.Content 98.8%.The rate of recovery 97.4%.
Claims (7)
1. utilize diene chrome waste liquid to prepare a method for Plessy's green, it is characterized in that, concrete steps are:
1) in diene alcohol ketone acetic ester chrome waste liquid, add formaldehyde saturated aqueous solution and phosphoric acid, be heated with stirring to 80 ~ 110 DEG C, keep 30 ~ 60 minutes, sexavalent chrome (VI) is reduced into trivalent chromium (III), and obtains green precipitate; Wherein in the add-on of formaldehyde and waste liquid, the ratio of the amount of sexavalent chrome (VI) is 1 ~ 2:1, and the add-on of phosphoric acid counts 0.95 ~ 1.1 times of chromium from waste chromium content with amount of substance;
2) material in step 1) is cooled to less than 80 DEG C and filters to obtain green phosphate dihydrate chromium crude product; Being washed by green phosphate dihydrate chromium crude product acetic acid, is colourless to washings, the dry phosphate dihydrate chromium sterling obtaining content more than 98.5%;
3) by green phosphate dihydrate chromium crude product or green phosphate dihydrate chromium sterling 850 ~ 950 DEG C of calcinings 2 ~ 4 hours, the brown anhydrous phosphoric acid chromium of content more than 98.3%.
2. the method utilizing diene chrome waste liquid to prepare Plessy's green according to claim 1, is characterized in that: in described diene alcohol ketone acetic ester chrome waste liquid, total Cr(is in Cr) content 10 ~ 500g/L, Cr
6+content be 10 ~ 500mg/L.
3. the method utilizing diene chrome waste liquid to prepare Plessy's green according to claim 1, is characterized in that: in described step 1), phosphoric acid and formaldehyde saturated aqueous solution is joined in chrome waste liquid simultaneously.
4. the method utilizing diene chrome waste liquid to prepare Plessy's green according to claim 1, is characterized in that: described step 2) described in the concentration of acetic acid be 60 ~ 100%, the volume ratio of the original solution in each consumption and step 1) is: 0.5 ~ 1:1.
5. the method utilizing diene chrome waste liquid to prepare Plessy's green according to claim 1, it is characterized in that: the calcining temperature in step 3) is 900 DEG C, calcination time is 3 hours.
6. prepare the method for Plessy's green according to the diene chrome waste liquid that utilizes one of claim 1-5 Suo Shu, it is characterized in that: the mass concentration of the phosphoric acid described in step 1) is 50 ~ 85%.
7. prepare the method for Plessy's green according to the diene chrome waste liquid that utilizes one of claim 1-5 Suo Shu, it is characterized in that: the stirring velocity described in step 1) is 100 ~ 1000 revs/min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105061191A (en) * | 2015-08-18 | 2015-11-18 | 湖北竹溪人福药业有限责任公司 | Method of recycling acid wastewater generated during production of dehydropregnenolone acetate |
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| RU2190647C1 (en) * | 2001-04-03 | 2002-10-10 | Воронежская государственная технологическая академия | Method of synthesis of chrome phosphate-containing pigment |
| CN103274382A (en) * | 2013-05-13 | 2013-09-04 | 天津市化学试剂研究所 | Preparation method of chromium phosphate |
| CN104108754A (en) * | 2014-07-31 | 2014-10-22 | 三峡大学 | Method for preparing nano Cr2O3 by utilizing waste liquid containing chromium (Cr) |
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2014
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Patent Citations (4)
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| SU1404105A1 (en) * | 1987-01-09 | 1988-06-23 | Ленинградский Технологический Институт Им.Ленсовета | Catalyst for decomposition of sulfuric acid |
| RU2190647C1 (en) * | 2001-04-03 | 2002-10-10 | Воронежская государственная технологическая академия | Method of synthesis of chrome phosphate-containing pigment |
| CN103274382A (en) * | 2013-05-13 | 2013-09-04 | 天津市化学试剂研究所 | Preparation method of chromium phosphate |
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Non-Patent Citations (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061191A (en) * | 2015-08-18 | 2015-11-18 | 湖北竹溪人福药业有限责任公司 | Method of recycling acid wastewater generated during production of dehydropregnenolone acetate |
| CN105061191B (en) * | 2015-08-18 | 2016-08-24 | 湖北竹溪人福药业有限责任公司 | A kind of method that diene alcohol ketone acetic ester waste acid water recycles |
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