CN104562179A - Method for preparing multi-purpose calcium sulfate whisker from alkali production liquid waste and waste sulfuric acid - Google Patents
Method for preparing multi-purpose calcium sulfate whisker from alkali production liquid waste and waste sulfuric acid Download PDFInfo
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- CN104562179A CN104562179A CN201410836956.5A CN201410836956A CN104562179A CN 104562179 A CN104562179 A CN 104562179A CN 201410836956 A CN201410836956 A CN 201410836956A CN 104562179 A CN104562179 A CN 104562179A
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- sulfuric acid
- calcium sulfate
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Abstract
The invention relates to a method for preparing multi-purpose calcium sulfate whisker from alkali production liquid waste and waste sulfuric acid. The method comprises specific steps as follows: (1), hydrochloric acid and a morphology control agent are added to a reactor, are stirred and heated to 50-150 DEG C; (2), the alkali production liquid waste, namely a calcium chloride solution, and the waste sulfuric acid are preheated to 50-150 DEG C and added to the reactor; (3), a stirring paddle rotating speed is adjusted, and mass transfer and heat transfer are enhanced; (4), constant reaction temperature is kept until the reaction is finished; (5); filtering, washing and drying are performed, and a product is obtained. According to requirements of different application fields, the length-diameter ratio and the length of the calcium sulfate whisker are manually regulated and controlled, the calcium sulfate whisker with the high length-diameter ratio can be produced and used as a reinforcing component, and the long calcium sulfate whisker with regular morphology can further be produced and used for paper making.
Description
[technical field]
The present invention relates to calcium sulfate crystal whiskers technical field, specifically, is a kind of method utilizing solvay liquor and Waste Sulfuric Acid multi-usage calcium sulfate crystal whiskers.
[background technology]
Soda ash is a kind of important industrial raw material, and China is also the production and consumption big country of soda ash.According to the data that Chinese soda industry association issues, China's soda ash annual production in 2010 ~ 2012 years is all more than 2,000 ten thousand tons.The process of solvay liquor is a great problem of our times soda industry, according to measuring and calculating, often produces 1 ton of soda ash, by generation about 10 tons of solvay liquors, if arbitrarily discharged by solvay liquor, not only pollutes the environment, affect the eubiosis, and be the significant wastage of resource.Solvay liquor is rich in calcium chloride, although some enterprises carry out process to solvay liquor and obtain industrial calcium chloride at present, its economic worth is low, lacks economic benefit.
Sulfuric acid is extensive in the sector application such as chemical industry, metallurgy, in the production process of these industries, will discharge a large amount of spent acid solution every year, as in the comprehensive development and utilization project of Qinghai Salt Lake Group Company Sweet natural gas and salt lake resources, inevitably produce Waste Sulfuric Acid.In addition, in China's titanium white powder manufacturer, most employing sulfuric acid process, according to the difference of mineral resources and the height of yield, often producing 1 ton of titanium dioxide, is the Waste Sulfuric Acid of 20% by by-product 7 ~ 11 tons of massfractions.In order to avoid to the pollution of environment and the waste of resource, comprehensive treating process and utilization must be carried out to industrial waste sulfuric acid.
With solvay liquor and Waste Sulfuric Acid Sulphuric acid calcium pyroborate, it is the new paragon of comprehensive utilization solvay liquor and Waste Sulfuric Acid.Whisker is that its diameter is very little with a kind of fiber that single crystal form grows under manual control condition, so that the defect being contained in normal appearance in macrocrystal hard to tolerate, and its atom high is orderly, and thus intensity is close to the theoretical value of perfect crystal.Crystal whisker materials is mainly divided into organic crystalline palpus and inorganic crystal whisker two class, inorganic crystal whisker material mainly comprises ceramic whiskers, inorganic carbon sources and metal whisker, inorganic crystal whisker has good physical strength, electrical insulating property, there is the characteristics such as high temperature resistant, wear-resisting, corrosion-resistant, due to its good physics, chemistry and mechanical property, be widely used in the fields such as chemical industry, national defence, machinery, the energy and environmental protection.
Calcium sulfate crystal whiskers, as a kind of inorganic crystal whisker material, not only possesses the physical and chemical performance of inorganic crystal whisker material high, and compared to other crystal whisker materials, its price is very cheap, has obvious superiority of effectiveness.Calcium sulfate crystal whiskers can be used for the fields such as reinforcing component, papermaking, environmental engineering, friction materials, asphalt modification, coating, current calcium sulfate crystal whiskers is used for reinforcing component and papermaking receives much concern, calcium sulfate crystal whiskers is used as the reinforcing component of the materials such as plastics, rubber, urethane, can significantly improve the tensile strength of goods, modulus in flexure, dimensional stability and thermal distoftion temperature; Calcium sulfate crystal whiskers is for papermaking, and alternative vegetable fibre, improves paper smoothness, gives paper better bulk, effectively improves the tensile property of paper, broken tensile energy etc.For for reinforcing component, general whisker length-to-diameter ratio is larger, increases effect better, and the preparation of high length-diameter ratio calcium sulfate crystal whiskers is focus and the target of research always.For papermaking, require that whisker has larger length, according to the calcium sulfate crystal whiskers technological standard that China Mining University formulates, calcium sulfate medium staple fibre meets the primary condition of Papermaking fibers, but calcium sulfate crystal whiskers obtained at present belongs to staple fibre category more, and quality portion is homogeneous, paper-making fibre cannot be substituted.
[summary of the invention]
The object of the invention is to overcome the deficiencies in the prior art, a kind of method utilizing solvay liquor and Waste Sulfuric Acid multi-usage calcium sulfate crystal whiskers is provided.
The object of the invention is to be achieved through the following technical solutions:
Utilize a method for solvay liquor and Waste Sulfuric Acid multi-usage calcium sulfate crystal whiskers, its concrete steps are:
(1) hydrochloric acid and Morphological control agent are added in reactor, open and stir, add and be heated to 50 ~ 150 DEG C;
The massfraction of described hydrochloric acid is 0.5 ~ 30%.
Described Morphological control agent is stearic acid, sodium laurate, sodium oleate, myristic acid potassium, polyoxyethylene glycol, potassium palmitate, Dodecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, any one in cetyl trimethylammonium bromide.
The massfraction of described Morphological control agent is 0.05 ~ 20%.
(2) solvay liquor calcium chloride solution and Waste Sulfuric Acid are preheating to 50 ~ 150 DEG C respectively, join in reactor;
Described calcium chloride solution and the molar concentration rate of Waste Sulfuric Acid are 1: 3 ~ 3: 1.
Added hydrochloric acid, solvay liquor calcium chloride solution, the volume ratio of Waste Sulfuric Acid is 0.5 ~ 5: 1: 1.
(3) rotating speed of agitator is regulated, reinforcing mass transfer and heat transfer;
Described mixing speed is 0.1 ~ 10ms
-1.
(4) keep temperature of reaction constant, to reacting end;
The described reaction times is 10min ~ 12h.
(5) filter, washing, dry, obtain product.
Compared with prior art, positively effect of the present invention is:
(1) with solvay liquor and Waste Sulfuric Acid for raw material, turn waste into wealth, not only solve the process problem of solvay liquor and Waste Sulfuric Acid, effective decreasing pollution, and can produce high-quality calcium sulfate crystal whiskers, creation economic benefit;
(2) the present invention makes high-quality calcium sulfate crystal whiskers at ambient pressure, and technique is simple, with low cost, is easy to suitability for industrialized production;
(3) the present invention is directed to the requirement in different application field, achieve the artificial adjustment of calcium sulfate crystal whiskers length-to-diameter ratio, length, the calcium sulfate crystal whiskers of high length-diameter ratio can be produced, as reinforcing component, the calcium sulfate crystal whiskers of high length, regular appearance can also be produced, for papermaking.
[accompanying drawing explanation]
Fig. 1 is process flow sheet of the present invention.
Fig. 2 is the Stereo microscope figure of product in embodiments of the invention 2.
Fig. 3 is the opticmicroscope figure of product in embodiments of the invention 2.
Fig. 4 is the opticmicroscope figure of product in embodiments of the invention 3.
[embodiment]
The present invention is below provided a kind of embodiment utilizing the method for solvay liquor and Waste Sulfuric Acid multi-usage calcium sulfate crystal whiskers.
Embodiment 1
By massfraction be 5% hydrochloric acid and stearic acid add in reactor, stearic acid massfraction is 0.5%, open and stir, add and be heated to 60 ~ 80 DEG C, by preheated molar concentration rate be 1: 3 calcium chloride solution and Waste Sulfuric Acid join in reactor, the volume ratio of added hydrochloric acid, solvay liquor calcium chloride solution, Waste Sulfuric Acid is 0.5: 1: 1, and adjustment stir speed (S.S.) is 1.2ms
-1, keep homo(io)thermism 180min.After reaction terminates, filter, filter cake deionized water wash 5 times, at 80 DEG C of baking oven inner drying 12h.Gained calcium sulfate crystal whiskers mean diameter is 2.1 μm, and length-to-diameter ratio is 200.
Embodiment 2
By massfraction be 15% hydrochloric acid and sodium oleate add in reactor, sodium oleate massfraction is 1%, open and stir, add and be heated to 80 ~ 100 DEG C, by preheated molar concentration rate be 1: 1 calcium chloride solution and Waste Sulfuric Acid join in reactor, the volume ratio of added hydrochloric acid, solvay liquor calcium chloride solution, Waste Sulfuric Acid is 1.5: 1: 1, and adjustment stir speed (S.S.) is 0.5ms
-1, keep homo(io)thermism 30min.After reaction terminates, filter, filter cake deionized water wash 5 times, at 100 DEG C of baking oven inner drying 15h.Gained calcium sulfate crystal whiskers mean diameter is 3.6 μm, and length-to-diameter ratio is 230.
Embodiment 3
By massfraction be 5% hydrochloric acid and dodecyl dimethyl benzyl ammonium bromide add in reactor, dodecyl dimethyl benzyl ammonium bromide massfraction is 0.2%, open and stir, add and be heated to 80 ~ 100 DEG C, by preheated molar concentration rate be 1: 1 calcium chloride solution and Waste Sulfuric Acid join in reactor, the volume ratio of added hydrochloric acid, solvay liquor calcium chloride solution, Waste Sulfuric Acid is 2: 1: 1, and adjustment stir speed (S.S.) is 2.0ms
-1, keep homo(io)thermism 600min.After reaction terminates, filter, filter cake deionized water wash 5 times, at 100 DEG C of baking oven inner drying 10h.Gained calcium sulfate crystal whiskers mean length is 1600 μm, and length-to-diameter ratio is 120.
Embodiment 4
By massfraction be 20% hydrochloric acid and polyoxyethylene glycol add in reactor, polyoxyethylene glycol massfraction is 15%, open and stir, add and be heated to 100 ~ 120 DEG C, by preheated molar concentration rate be 2: 1 calcium chloride solution and Waste Sulfuric Acid join in reactor, the volume ratio of added hydrochloric acid, solvay liquor calcium chloride solution, Waste Sulfuric Acid is 1: 1: 1, and adjustment stir speed (S.S.) is 1.0ms
-1, keep homo(io)thermism 300min.After reaction terminates, suction filtration, filter cake deionized water wash 5 times, at 100 DEG C of baking oven inner drying 12h.Gained calcium sulfate crystal whiskers mean length is 1800 μm, and length-to-diameter ratio is 150.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (8)
1. utilize a method for solvay liquor and Waste Sulfuric Acid multi-usage calcium sulfate crystal whiskers, it is characterized in that, its concrete steps are:
(1) hydrochloric acid and Morphological control agent are added in reactor, open and stir, add and be heated to 50 ~ 150 DEG C;
(2) solvay liquor calcium chloride solution and Waste Sulfuric Acid are preheating to 50 ~ 150 DEG C respectively, join in reactor;
(3) rotating speed of agitator is regulated, reinforcing mass transfer and heat transfer;
(4) keep temperature of reaction constant, to reacting end;
(5) filter, washing, dry, obtain product.
2. a kind of method utilizing solvay liquor and Waste Sulfuric Acid multi-usage calcium sulfate crystal whiskers as claimed in claim 1, it is characterized in that, in described step (1), the massfraction of described hydrochloric acid is 0.5 ~ 30%.
3. a kind of method utilizing solvay liquor and Waste Sulfuric Acid multi-usage calcium sulfate crystal whiskers as claimed in claim 1, it is characterized in that, in described step (1), described Morphological control agent is stearic acid, sodium laurate, sodium oleate, myristic acid potassium, polyoxyethylene glycol, potassium palmitate, Dodecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, any one in cetyl trimethylammonium bromide.
4. a kind of method utilizing solvay liquor and Waste Sulfuric Acid multi-usage calcium sulfate crystal whiskers as claimed in claim 1, it is characterized in that, in described step (1), the massfraction of described Morphological control agent is 0.05 ~ 20%.
5. a kind of method utilizing solvay liquor and Waste Sulfuric Acid multi-usage calcium sulfate crystal whiskers as claimed in claim 1, it is characterized in that, in described step (2), described calcium chloride solution and the molar concentration rate of Waste Sulfuric Acid are 1: 3 ~ 3: 1.
6. a kind of method utilizing solvay liquor and Waste Sulfuric Acid multi-usage calcium sulfate crystal whiskers as claimed in claim 1, it is characterized in that, in described step (2), added hydrochloric acid, solvay liquor calcium chloride solution, the volume ratio of Waste Sulfuric Acid is 0.5 ~ 5: 1: 1.
7. a kind of method utilizing solvay liquor and Waste Sulfuric Acid multi-usage calcium sulfate crystal whiskers as claimed in claim 1, it is characterized in that, in described step (3), described mixing speed is 0.1 ~ 10ms
-1.
8. a kind of method utilizing solvay liquor and Waste Sulfuric Acid multi-usage calcium sulfate crystal whiskers as claimed in claim 1, it is characterized in that, in described step (4), the described reaction times is 10min ~ 12h.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105112989A (en) * | 2015-10-14 | 2015-12-02 | 科洋环境工程(上海)有限公司 | Preparation method of calcium sulfate whisker |
CN109179618A (en) * | 2018-10-09 | 2019-01-11 | 龙蟒佰利联集团股份有限公司 | A kind of processing method of titanium dioxide wastewater |
-
2014
- 2014-12-24 CN CN201410836956.5A patent/CN104562179A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105112989A (en) * | 2015-10-14 | 2015-12-02 | 科洋环境工程(上海)有限公司 | Preparation method of calcium sulfate whisker |
CN105112989B (en) * | 2015-10-14 | 2017-09-12 | 科洋环境工程(上海)有限公司 | A kind of preparation method of calcium sulfate crystal whiskers |
CN109179618A (en) * | 2018-10-09 | 2019-01-11 | 龙蟒佰利联集团股份有限公司 | A kind of processing method of titanium dioxide wastewater |
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