CN102616825B - Purification process of desulfurization gypsum and gypsum raw materials purified through process - Google Patents
Purification process of desulfurization gypsum and gypsum raw materials purified through process Download PDFInfo
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Abstract
The invention discloses a purification process of desulfurization gypsum and gypsum raw materials purified through the process, which solve the problems that the existing purification process of desulfurization gypsum has large energy consumption and complex process, and the purified product has low purity. The purification process of the desulfurization gypsum comprises the following steps of material extracting, grinding and screening, primary ball-milling, scouring, flotation, clarification, and secondary ball-milling; and integrates physics, chemistry, mineral separation, powder preparation and other processing technologies into a whole. The product prepared by the process has high quality, and has the whiteness reaching to 93-95 percent. The purification process of the desulfurization gypsum and the gypsum raw materials purified through the process have the advantages that the process is simple, the practicability is strong, the energy consumption is low, the impurities extracted from the gypsum are fewer, and the granularity of the product is more uniform.
Description
Technical field
The present invention relates to a kind of desulfurated plaster purifying technique, the energy consumption that relates in particular to a kind of purifying technique that has solved existing desulfurated plaster is large, the purifying technique of the desulfurated plaster of the low problem of purity of the product of complex process, purification and the gypsum raw material of purifying out thereof.
Background technology
Desulfurated plaster is the by product that comes from the industry flue gas desulfurizations such as electric power, iron and steel.In Limestone-gypsum Wet Flue Gas Desulfurization Process process, 1 ton of sulfurous gas of every absorption will produce 2.7 tons of desulfurated plasters; Within 2010, China has the coal fired power generation unit of 7.0 hundred million kilowatts that flue gas desulfurization (FGD) unit has been installed, and produces the byproduct of nearly hundred million tons of wet desulphurizations---desulfurated plaster.Desulfurated plaster discharge enormous amount, piles up seriously contaminate environment.The recycling of desulfurated plaster is very necessary.
Desulfurated plaster and plaster of paris chemical constitution are basic identical, so by gradually for material of construction such as cement, plasterboard, baking-free building blocks.But because quality of desulphurization gypsum in actual production is subject to many factors (as flying dust in Wingdale quality, exhaust gas volumn, ature of coal, desulfuration efficiency, flue gas is sneaked into degree, daily production management etc.), be difficult to guarantee the stable of quality of desulphurization gypsum, different desulfurated plasters discharge producer, same desulfurated plaster discharges the desulfurated plaster of producer's different times discharge, its quality is all different, especially equal difference to some extent such as content of the content of calcium sulfate, dopant species and content, water in desulfurated plaster.This has affected the application in high-quality plastering of desulfurated plaster.
Purification to desulfurated plaster at present, in US Patent No. P5215672 and USP5500197, taked respectively multi-stage water power swirler technique and fine particle stage trapping technique to carry out the purification of gypsum slurries, adopt physical means to purify completely, its principle, equipment form and technical characterstic still belongs to traditional " hydrocyclone+vacuum band-type filter machine " technique, and the quality of the product that desulfurated plaster is purified is lower.In Chinese patent CN 101397148A, employing roughly selects, the reverse floatation process of selected and dark choosing, in simple ore dressing mode, desulfurated plaster is purified, need multistage flotation, part CaCO3 is separated with impurity, has reduced available CaSO4 content, and the CaCO3 that is positioned at desulfurated plaster powder core is difficult to remove, product purity after purification is lower, can not be guaranteed of quality.In patent CN 101870494A, adopt chemical process to purify to desulfurated plaster, i.e. pickling post-heating, solid-liquid separation is removed impurity while hot, by liquid phase cooling recrystallization, solid-liquid separation again under lesser temps, by filter cake washing, dry.This patent need to be heated to 80-100 ℃ to mother liquor, be cooled to 10-30 ℃, and to realize the dissolution-crystallization of gypsum, energy consumption is larger, complex process.Therefore, be badly in need of at present wanting the purifying technique of the desulfurated plaster that a kind of energy consumption purity low, the product after proposing is high and the gypsum raw material of purifying out thereof.
Summary of the invention
The object of the invention is to overcome deficiency of the prior art and provide that a kind of energy consumption is low, the purifying technique of technique is simple, the purity of the product of purifying is high desulfurated plaster and the gypsum raw material of purifying out thereof.
The object of the present invention is achieved like this:
A purifying technique for desulfurated plaster, its purifying technique comprises the steps:
Step 1, feeding: manually choose desulfurated plaster;
Step 2, crush and screen: the desulfurated plaster that step 1 is chosen is sent into crusher and pulverized, and with 200 orders and 500 order vibratory screening apparatuss, sieves, and the sieve time of shaking is 10～30min;
Step 3, a ball milling: step 2 is crushed and screened to the particle diameter obtaining and be mixed with slurry between 200～500 object desulfurated plasters, the solid-liquid weight ratio of controlling slurry is 1:3～1:6, sends in ball mill, then in slurry, adds grinding aid, add-on is 500～3000g/t, ball milling 5～30min;
Step 4, pickling: first the solid-liquid weight ratio of the slurry obtaining in ball milling of step 3 is adjusted into 1:6～1:10, then be placed in the water-bath of 20～40 ℃, first add sulfuric acid, stir 5～30min, add again hydrochloric acid, stir 5～30min, the sulfuric acid quality wherein adding is that 5～30 % of butt desulfurated plaster quality, the hydrochloric acid quality adding are 3～10% of butt desulfurated plaster quality again;
Step 5, flotation: the slurry after step 4 pickling is sent in flotation machine, and adding mass concentration is that 5% whipping agent, add-on are 1～5ml/L, then to add resultant magnetization hydrocarbon ils, add-on be 1.0～10ml/L, flotation 3～15min;
Step 6, clarification: by the slurry clarification 5～30min obtaining in step 5 flotation, to slurry layering;
Step 7, secondary ball milling: the top clear liquor of the slurry obtaining in step 6 clarification is removed, the solid-liquid weight ratio of adjusting bottom slurry is 1:1～1:3, then send into ball milling in ball mill, drum's speed of rotation 200～500r/min, Ball-milling Time 60～300min, complete the purification of desulfurated plaster, make gypsum raw material.
Described vibratory screening apparatus is the top formula of the hitting sieve that shakes.
Described grinding aid is at least one in ammonium chloride, EDTA, oxalic acid, citric acid, Trisodium Citrate, stearic acid, sodium stearate.
Ball mill in ball milling of described step 3 is colloidal mill.
Ball mill in described step 7 secondary ball milling is high energy ball mill, and this high energy ball mill is provided with the liner of tetrafluoroethylene, and abrading-ball is zirconium ball or agate ball.
The gypsum slurry obtaining after described step 7 secondary ball milling is directly used in Chemical Manufacture, or in 40 ℃, is dried to constant weight, encapsulation after centrifuge dehydration.
The whiteness of utilizing the gypsum raw material that the purifying technique of described desulfurated plaster purifies out is 93～95%, size is even, obtains in accordance with the following steps:
Step 1, feeding: manually choose desulfurated plaster;
Step 2, crush and screen: the desulfurated plaster that step 1 is chosen is sent into crusher and pulverized, and with 200 orders and 500 order vibratory screening apparatuss, sieves, and the sieve time of shaking is 10～30min;
Step 3, a ball milling: step 2 is crushed and screened to the particle diameter obtaining and be mixed with slurry between 200～500 object desulfurated plasters, the solid-liquid weight ratio of controlling slurry is 1:3～1:6, sends in ball mill, then in slurry, adds grinding aid, add-on is 500～3000g/t, ball milling 5～30min;
Step 4, pickling: first the solid-liquid weight ratio of the slurry obtaining in ball milling of step 3 is adjusted into 1:6～1:10, then be placed in the water-bath of 20～40 ℃, first add sulfuric acid, stir 5～30min, add again hydrochloric acid, stir 5～30min, the sulfuric acid quality wherein adding is that 5～30 % of butt desulfurated plaster quality, the hydrochloric acid quality adding are 3～10% of butt desulfurated plaster quality again;
Step 5, flotation: the slurry after step 4 pickling is sent in flotation machine, and adding mass concentration is that 5% whipping agent, add-on are 1～5ml/L, then to add resultant magnetization hydrocarbon ils, add-on be 1.0～10ml/L, flotation 3～15min;
Step 6, clarification: by the slurry clarification 5～30min obtaining in step 5 flotation, to slurry layering;
Step 7, secondary ball milling: the top clear liquor of the slurry obtaining in step 6 clarification is removed, the solid-liquid weight ratio of adjusting bottom slurry is 1:1～1:3, then send into ball milling in ball mill, drum's speed of rotation 200～500r/min, Ball-milling Time 60～300min, complete the purification of desulfurated plaster, make gypsum raw material.
Described butt desulfurated plaster is moisture free desulfurated plaster.
The present invention compared with prior art has following advantage:
Technique of the present invention comprises feeding, crushes and screens, the step of ball milling, pickling, flotation, clarification, secondary ball milling, technique is simple, convenient operation and realization, and the processing parameter of each step is simple, workable, the treatment technologies such as this process synthesis physics, chemistry, ore dressing, powder preparation are in one, energy consumption is low, utilizes the quality of the product that this technique purifies out high, and whiteness can reach 93～95%.
Experimental results show that, utilize impurity in the gypsum that technique of the present invention proposes still less, the granularity of product is more even, activity is higher, can meet the demand of novel gypsum material to high-quality gypsum raw material, for example, the desulfurated plaster after utilizing the present invention to purify, can replace the high-quality plaster of paris completely for the preparation of calcium sulfate crystal whiskers.Specific experiment data are in Table 1 and table 2:
Table 1, desulfurated plaster raw material and product composition analysis/massfraction
| Sample classification | CaO | SO 3 | Al 2O 3 | SiO 2 | Fe 2O 3 | MgO | TiO 2 | K 2O | Na 2O |
| A sample | 33.23 | 37.23 | 2.86 | 5.18 | 0.64 | 1.24 | 0.10 | 0.21 | 0.01 |
| B sample | 35.84 | 39.32 | 2.49 | 5.56 | 0.46 | 0.92 | 0.31 | 0.20 | 0.01 |
| Embodiment 1 | 31.02 | 43.98 | 1.06 | 2.48 | 0.32 | 0.15 | 0.05 | 0.00 | 0.00 |
| Embodiment 2 | 32.34 | 46.08 | 0.86 | 2.01 | 0.21 | 0.01 | 0.00 | 0.00 | 0.00 |
| Embodiment 3 | 31.46 | 44.95 | 0.98 | 2.16 | 0.28 | 0.01 | 0.00 | 0.00 | 0.00 |
| Embodiment 4 | 30.62 | 43.33 | 1.20 | 2.65 | 0.36 | 0.02 | 0.05 | 0.01 | 0.01 |
Table 2, desulfurated plaster raw material and product granularity analysis
| Sample classification | D10 | D25 | D50 | D75 | D90 |
| A sample/% | 9.65 | 21.17 | 32.99 | 48.61 | 67.55 |
| B sample/% | 7.27 | 16.02 | 32.00 | 55.21 | 82.31 |
| Embodiment 1/ % | 1.12 | 1.45 | 1.72 | 2.03 | 2.28 |
| Embodiment 2/ % | 1.79 | 1.86 | 1.93 | 1.99 | 2.03 |
| Embodiment 3/ % | 1.78 | 1.86 | 1.94 | 2.01 | 2.06 |
| Embodiment 4/ % | 0.95 | 1.26 | 1.6 | 1.94 | 2.41 |
The product that the present invention purifies out can substitute the plaster of paris for industries high to gypsum raw material quality requirements such as chemical industry, gypsum decorative materials, effectively alleviated the pressure of the plaster of paris, have in Sustainable development, for desulfurated plaster discharge enormous amount, pile up the problems such as serious, contaminate environment a practicable way is provided.
Accompanying drawing explanation
The SEM photo of desulfurated plaster raw material before Fig. 1 art breading of the present invention.
The SEM photo of gypsum raw material after Fig. 2 art breading of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further illustrated.
Embodiment 1
A purifying technique for desulfurated plaster, its purifying technique comprises the steps:
Step 1, feeding: manually choose the desulfurated plaster of coal-burning power plant as A sample;
Step 2, crush and screen: the A sample that step 1 is chosen is sent into crusher and pulverized, and with 200 orders and 500 order vibratory screening apparatuss, sieves, and the sieve time of shaking is 10min;
Step 3, a ball milling: get step 2 and crush and screen the particle diameter that obtains between 200～500 object desulfurated plaster powder 200g, be hybridly prepared into 600 g water the slurry that solid-liquid weight ratio is 1 ﹕ 3, send in ball mill, then in slurry, add 0.4g grinding aid, ball milling 10min;
Step 4, pickling: first the solid-liquid weight ratio of the slurry obtaining in ball milling of step 3 is adjusted into 1:6, then be placed in the water-bath of 30 ℃, first add 15ml sulfuric acid, stir 5min, then add 6ml hydrochloric acid, stirring 30min, control mixing speed is 300r/min;
Step 5, flotation: the slurry after step 4 pickling is sent in flotation machine, and adding mass concentration is 5% whipping agent 5ml/L, then to add resultant magnetization hydrocarbon ils, add-on be 10ml/L, flotation 10min;
Step 6, clarification: by the slurry clarification 10min obtaining in step 5 flotation, to slurry layering;
Step 7, secondary ball milling: the top clear liquor of the slurry obtaining in step 6 clarification is removed, and the solid-liquid weight ratio of adjusting bottom slurry is 1:3, then sends into ball milling in ball mill, drum's speed of rotation 200r/min, Ball-milling Time 300min, completes the purification of desulfurated plaster, makes gypsum raw material.
Described vibratory screening apparatus is the top formula of the hitting sieve that shakes.
Described grinding aid is at least one in ammonium chloride, EDTA, oxalic acid, citric acid, Trisodium Citrate, stearic acid, sodium stearate.
Ball mill in ball milling of described step 3 is colloidal mill.
Ball mill in described step 7 secondary ball milling is high energy ball mill, and this high energy ball mill is provided with the liner of tetrafluoroethylene, and abrading-ball is zirconium ball or agate ball.
The gypsum slurry obtaining after described step 7 secondary ball milling is directly used in Chemical Manufacture, or in 40 ℃, is dried to constant weight, encapsulation after centrifuge dehydration.
The whiteness of utilizing the gypsum raw material that the purifying technique of described desulfurated plaster purifies out is 93.8%, size is even, obtains in accordance with the following steps:
Step 1, feeding: manually choose the desulfurated plaster of coal-burning power plant as A sample;
Step 2, crush and screen: the A sample that step 1 is chosen is sent into crusher and pulverized, and with 200 orders and 500 order vibratory screening apparatuss, sieves, and the sieve time of shaking is 10min;
Step 3, a ball milling: get step 2 and crush and screen the particle diameter that obtains between 200～500 object desulfurated plaster powder 200g, be hybridly prepared into 600 g water the slurry that solid-liquid weight ratio is 1 ﹕ 3, send in ball mill, then in slurry, add 0.4g grinding aid, ball milling 10min;
Step 4, pickling: first the solid-liquid weight ratio of the slurry obtaining in ball milling of step 3 is adjusted into 1:6, then be placed in the water-bath of 30 ℃, first add 15ml sulfuric acid, stir 5min, then add 6ml hydrochloric acid, stirring 30min, control mixing speed is 300r/min;
Step 5, flotation: the slurry after step 4 pickling is sent in flotation machine, and adding mass concentration is 5% whipping agent 5ml/L, then to add resultant magnetization hydrocarbon ils, add-on be 10ml/L, flotation 10min;
Step 6, clarification: by the slurry clarification 10min obtaining in step 5 flotation, to slurry layering;
Step 7, secondary ball milling: the top clear liquor of the slurry obtaining in step 6 clarification is removed, and the solid-liquid weight ratio of adjusting bottom slurry is 1:3, then sends into ball milling in ball mill, drum's speed of rotation 200r/min, Ball-milling Time 300min, completes the purification of desulfurated plaster, makes gypsum raw material.
Described butt desulfurated plaster is moisture free desulfurated plaster.
Experiment records, the whiteness 42.2% before desulfurated plaster is purified, and after purification processes, whiteness 93.8%, and raw material and product composition are in Table 3, and raw material and product cut size distribute in Table 4.
Embodiment 2
A purifying technique for desulfurated plaster, its purifying technique comprises the steps:
Step 1, feeding: manually choose the desulfurated plaster of coal-burning power plant as A sample;
Step 2, crush and screen: the A sample that step 1 is chosen is sent into crusher and pulverized, and with 200 orders and 500 order vibratory screening apparatuss, sieves, and the sieve time of shaking is 20min;
Step 3, a ball milling: get step 2 and crush and screen the particle diameter that obtains between 200～500 object desulfurated plaster powder 200g, be hybridly prepared into 800 g water the slurry that solid-liquid weight ratio is 1 ﹕ 4, send in ball mill, then in slurry, add 0.1 g grinding aid, ball milling 15min;
Step 4, pickling: first the solid-liquid weight ratio of the slurry obtaining in ball milling of step 3 is adjusted into 1:8, then be placed in the water-bath of 40 ℃, first add 35ml sulfuric acid, stir 10min, then add 5ml hydrochloric acid, stirring 20min, control mixing speed is 300r/min;
Step 5, flotation: the slurry after step 4 pickling is sent in flotation machine, and adding mass concentration is 5% whipping agent 3ml/L, then to add resultant magnetization hydrocarbon ils, add-on be 5ml/L, flotation 10min;
Step 6, clarification: by the slurry clarification 20min obtaining in step 5 flotation, to slurry layering;
Step 7, secondary ball milling: the top clear liquor of the slurry obtaining in step 6 clarification is removed, and the solid-liquid weight ratio of adjusting bottom slurry is 1:2, then sends into ball milling in ball mill, drum's speed of rotation 250r/min, Ball-milling Time 200min, completes the purification of desulfurated plaster, makes gypsum raw material.
Described vibratory screening apparatus is the top formula of the hitting sieve that shakes.
Described grinding aid is at least one in ammonium chloride, EDTA, oxalic acid, citric acid, Trisodium Citrate, stearic acid, sodium stearate.
Ball mill in ball milling of described step 3 is colloidal mill.
Ball mill in described step 7 secondary ball milling is high energy ball mill, and this high energy ball mill is provided with the liner of tetrafluoroethylene, and abrading-ball is zirconium ball or agate ball.
The gypsum slurry obtaining after described step 7 secondary ball milling is directly used in Chemical Manufacture, or in 40 ℃, is dried to constant weight, encapsulation after centrifuge dehydration.
The whiteness of utilizing the gypsum raw material that the purifying technique of described desulfurated plaster purifies out is 94.6%, size is even, obtains as follows:
Step 1, feeding: manually choose the desulfurated plaster of coal-burning power plant as A sample;
Step 2, crush and screen: the A sample that step 1 is chosen is sent into crusher and pulverized, and with 200 orders and 500 order vibratory screening apparatuss, sieves, and the sieve time of shaking is 20min;
Step 3, a ball milling: get step 2 and crush and screen the particle diameter that obtains between 200～500 object desulfurated plaster powder 200g, be hybridly prepared into 800 g water the slurry that solid-liquid weight ratio is 1 ﹕ 4, send in ball mill, then in slurry, add 0.1 g grinding aid, ball milling 15min;
Step 4, pickling: first the solid-liquid weight ratio of the slurry obtaining in ball milling of step 3 is adjusted into 1:8, then be placed in the water-bath of 40 ℃, first add 35ml sulfuric acid, stir 10min, then add 5ml hydrochloric acid, stirring 20min, control mixing speed is 300r/min;
Step 5, flotation: the slurry after step 4 pickling is sent in flotation machine, and adding mass concentration is 5% whipping agent 3ml/L, then to add resultant magnetization hydrocarbon ils, add-on be 5ml/L, flotation 10min;
Step 6, clarification: by the slurry clarification 20min obtaining in step 5 flotation, to slurry layering;
Step 7, secondary ball milling: the top clear liquor of the slurry obtaining in step 6 clarification is removed, and the solid-liquid weight ratio of adjusting bottom slurry is 1:2, then sends into ball milling in ball mill, drum's speed of rotation 250r/min, Ball-milling Time 200min, completes the purification of desulfurated plaster, makes gypsum raw material.
Described butt desulfurated plaster is moisture free desulfurated plaster.
Experiment records, the whiteness 42.2% before desulfurated plaster is purified, and after purification processes, whiteness 94.6%, and raw material and product composition are in Table 3, and raw material and product cut size distribute in Table 4.
Embodiment 3
A purifying technique for desulfurated plaster, its purifying technique comprises the steps:
Step 1, feeding: manually choose the desulfurated plaster of coal-burning power plant as B sample;
Step 2, crush and screen: the B sample that step 1 is chosen is sent into crusher and pulverized, and with 200 orders and 500 order vibratory screening apparatuss, sieves, and the sieve time of shaking is 30min;
Step 3, a ball milling: get step 2 and crush and screen the particle diameter that obtains between 200～500 object desulfurated plaster powder 200g, be hybridly prepared into 1000 g water the slurry that solid-liquid weight ratio is 1 ﹕ 5, send in ball mill, then in slurry, add 0.6g grinding aid, ball milling 20min;
Step 4, pickling: first the solid-liquid weight ratio of the slurry obtaining in ball milling of step 3 is adjusted into 1:10, then be placed in the water-bath of 20 ℃, first add 20ml sulfuric acid, stir 30min, then add 10ml hydrochloric acid, stirring 5min, control mixing speed is 300r/min;
Step 5, flotation: the slurry after step 4 pickling is sent in flotation machine, and adding mass concentration is 5% whipping agent 1ml/L, then to add resultant magnetization hydrocarbon ils, add-on be 4ml/L, flotation 15min;
Step 6, clarification: by the slurry clarification 30min obtaining in step 5 flotation, to slurry layering;
Step 7, secondary ball milling: the top clear liquor of the slurry obtaining in step 6 clarification is removed, and the solid-liquid weight ratio of adjusting bottom slurry is 1:1, then sends into ball milling in ball mill, drum's speed of rotation 500r/min, Ball-milling Time 60min, completes the purification of desulfurated plaster, makes gypsum raw material.
Described vibratory screening apparatus is the top formula of the hitting sieve that shakes.
Described grinding aid is at least one in ammonium chloride, EDTA, oxalic acid, citric acid, Trisodium Citrate, stearic acid, sodium stearate.
Ball mill in ball milling of described step 3 is colloidal mill.
Ball mill in described step 7 secondary ball milling is high energy ball mill, and this high energy ball mill is provided with the liner of tetrafluoroethylene, and abrading-ball is zirconium ball or agate ball.
The gypsum slurry obtaining after described step 7 secondary ball milling is directly used in Chemical Manufacture, or in 40 ℃, is dried to constant weight, encapsulation after centrifuge dehydration.
The whiteness of utilizing the gypsum raw material that the purifying technique of described desulfurated plaster purifies out is 93.5%, size is even, obtains as follows:
Step 1, feeding: manually choose the desulfurated plaster of coal-burning power plant as B sample;
Step 2, crush and screen: the B sample that step 1 is chosen is sent into crusher and pulverized, and with 200 orders and 500 order vibratory screening apparatuss, sieves, and the sieve time of shaking is 30min;
Step 3, a ball milling: get step 2 and crush and screen the particle diameter that obtains between 200～500 object desulfurated plaster powder 200g, be hybridly prepared into 1000 g water the slurry that solid-liquid weight ratio is 1 ﹕ 5, send in ball mill, then in slurry, add 0.6g grinding aid, ball milling 20min;
Step 4, pickling: first the solid-liquid weight ratio of the slurry obtaining in ball milling of step 3 is adjusted into 1:10, then be placed in the water-bath of 20 ℃, first add 20ml sulfuric acid, stir 30min, then add 10ml hydrochloric acid, stirring 5min, control mixing speed is 300r/min;
Step 5, flotation: the slurry after step 4 pickling is sent in flotation machine, and adding mass concentration is 5% whipping agent 1ml/L, then to add resultant magnetization hydrocarbon ils, add-on be 4ml/L, flotation 15min;
Step 6, clarification: by the slurry clarification 30min obtaining in step 5 flotation, to slurry layering;
Step 7, secondary ball milling: the top clear liquor of the slurry obtaining in step 6 clarification is removed, and the solid-liquid weight ratio of adjusting bottom slurry is 1:1, then sends into ball milling in ball mill, drum's speed of rotation 500r/min, Ball-milling Time 60min, completes the purification of desulfurated plaster, makes gypsum raw material.
Described butt desulfurated plaster is moisture free desulfurated plaster.
Experiment records, the whiteness 42.2% before desulfurated plaster is purified, and after purification processes, whiteness 93.5%, and raw material and product composition are in Table 3, and raw material and product cut size distribute in Table 4.
Embodiment 4
A purifying technique for desulfurated plaster, its purifying technique comprises the steps:
Step 1, feeding: manually choose the desulfurated plaster of coal-burning power plant as B sample;
Step 2, crush and screen: the B sample that step 1 is chosen is sent into crusher and pulverized, and with 200 orders and 500 order vibratory screening apparatuss, sieves, and the sieve time of shaking is 30min;
Step 3, a ball milling: get step 2 and crush and screen the particle diameter that obtains between 200～500 object desulfurated plaster powder 200g, be hybridly prepared into 600 g water the slurry that solid-liquid weight ratio is 1 ﹕ 3, send in ball mill, then in slurry, add 0.3g grinding aid, ball milling 30min;
Step 4, pickling: first the solid-liquid weight ratio of the slurry obtaining in ball milling of step 3 is adjusted into 1:5, then be placed in the water-bath of 40 ℃, first add 20ml sulfuric acid, stir 5min, then add 8ml hydrochloric acid, stirring 10min, control mixing speed is 300r/min;
Step 5, flotation: the slurry after step 4 pickling is sent in flotation machine, and adding mass concentration is 5% whipping agent 3ml/L, then to add resultant magnetization hydrocarbon ils, add-on be 1ml/L, flotation 15min;
Step 6, clarification: by the slurry clarification 30min obtaining in step 5 flotation, to slurry layering;
Step 7, secondary ball milling: the top clear liquor of the slurry obtaining in step 6 clarification is removed, and the solid-liquid weight ratio of adjusting bottom slurry is 1:2, then sends into ball milling in ball mill, drum's speed of rotation 400r/min, Ball-milling Time 240min, completes the purification of desulfurated plaster, makes gypsum raw material.
Described vibratory screening apparatus is the top formula of the hitting sieve that shakes.
Described grinding aid is at least one in ammonium chloride, EDTA, oxalic acid, citric acid, Trisodium Citrate, stearic acid, sodium stearate.
Ball mill in ball milling of described step 3 is colloidal mill.
Ball mill in described step 7 secondary ball milling is high energy ball mill, and this high energy ball mill is provided with the liner of tetrafluoroethylene, and abrading-ball is zirconium ball or agate ball.
The gypsum slurry obtaining after described step 7 secondary ball milling is directly used in Chemical Manufacture, or in 40 ℃, is dried to constant weight, encapsulation after centrifuge dehydration.
The whiteness of utilizing the gypsum raw material that the purifying technique of described desulfurated plaster purifies out is 93.5%, size is even, obtains in accordance with the following steps:
Step 1, feeding: manually choose the desulfurated plaster of coal-burning power plant as B sample;
Step 2, crush and screen: the B sample that step 1 is chosen is sent into crusher and pulverized, and with 200 orders and 500 order vibratory screening apparatuss, sieves, and the sieve time of shaking is 30min;
Step 3, a ball milling: get step 2 and crush and screen the particle diameter that obtains between 200～500 object desulfurated plaster powder 200g, be hybridly prepared into 600 g water the slurry that solid-liquid weight ratio is 1 ﹕ 3, send in ball mill, then in slurry, add 0.3g grinding aid, ball milling 30min;
Step 4, pickling: first the solid-liquid weight ratio of the slurry obtaining in ball milling of step 3 is adjusted into 1:5, then be placed in the water-bath of 40 ℃, first add 20ml sulfuric acid, stir 5min, then add 8ml hydrochloric acid, stirring 10min, control mixing speed is 300r/min;
Step 5, flotation: the slurry after step 4 pickling is sent in flotation machine, and adding mass concentration is 5% whipping agent 3ml/L, then to add resultant magnetization hydrocarbon ils, add-on be 1ml/L, flotation 15min;
Step 6, clarification: by the slurry clarification 30min obtaining in step 5 flotation, to slurry layering;
Step 7, secondary ball milling: the top clear liquor of the slurry obtaining in step 6 clarification is removed, and the solid-liquid weight ratio of adjusting bottom slurry is 1:2, then sends into ball milling in ball mill, drum's speed of rotation 400r/min, Ball-milling Time 240min, completes the purification of desulfurated plaster, makes gypsum raw material.
Described butt desulfurated plaster is moisture free desulfurated plaster.
Experiment records, the whiteness 40.8% before desulfurated plaster is purified, and after purification processes, whiteness 93.2%, and raw material and product composition are in Table 3, and raw material and product cut size distribute in Table 4.
Table 3, desulfurated plaster raw material and product composition analysis/massfraction
| Sample classification | CaO | SO 3 | Al 2O 3 | SiO 2 | Fe 2O 3 | MgO | TiO 2 | K 2O | Na 2O |
| A sample | 33.23 | 37.23 | 2.86 | 5.18 | 0.64 | 1.24 | 0.10 | 0.21 | 0.01 |
| B sample | 35.84 | 39.32 | 2.49 | 5.56 | 0.46 | 0.92 | 0.31 | 0.20 | 0.01 |
| Embodiment 1 | 31.02 | 43.98 | 1.06 | 2.48 | 0.32 | 0.15 | 0.05 | 0.00 | 0.00 |
| Embodiment 2 | 32.34 | 46.08 | 0.86 | 2.01 | 0.21 | 0.01 | 0.00 | 0.00 | 0.00 |
| Embodiment 3 | 31.46 | 44.95 | 0.98 | 2.16 | 0.28 | 0.01 | 0.00 | 0.00 | 0.00 |
| Embodiment 4 | 30.62 | 43.33 | 1.20 | 2.65 | 0.36 | 0.02 | 0.05 | 0.01 | 0.01 |
Table 4, desulfurated plaster raw material and product granularity analysis
| Sample classification | D10 | D25 | D50 | D75 | D90 |
| A sample/% | 9.65 | 21.17 | 32.99 | 48.61 | 67.55 |
| B sample/% | 7.27 | 16.02 | 32.00 | 55.21 | 82.31 |
| Embodiment 1/ % | 1.12 | 1.45 | 1.72 | 2.03 | 2.28 |
| Embodiment 2/ % | 1.79 | 1.86 | 1.93 | 1.99 | 2.03 |
| Embodiment 3/ % | 1.78 | 1.86 | 1.94 | 2.01 | 2.06 |
| Embodiment 4/ % | 0.95 | 1.26 | 1.6 | 1.94 | 2.41 |
Technique of the present invention comprises feeding, crushes and screens, the step of ball milling, pickling, flotation, clarification, secondary ball milling, technique is simple, convenient operation and realization, and the processing parameter of each step is simple, workable, the treatment technologies such as this process synthesis physics, chemistry, ore dressing, powder preparation are in one, energy consumption is low, utilizes the quality of the product that this technique purifies out high.By table 3 and table 4, can be found out, utilize impurity in the gypsum that technique of the present invention proposes still less, the granularity of product is more even.
With scanning electronic microscope to art breading of the present invention before desulfurated plaster raw material to amplify 50 times of scannings to obtain SEM photo be Fig. 1, gypsum raw material after art breading of the present invention is amplified to the SEM photo that 125 times of scannings obtain be Fig. 2, from picture, can find out that the particle diameter of gypsum raw material after art breading of the present invention is significantly less than the particle diameter of desulfurated plaster raw material before art breading of the present invention, after art breading of the present invention, the particle diameter uniformity coefficient of gypsum raw material is obviously greater than the particle diameter uniformity coefficient of desulfurated plaster raw material before art breading of the present invention.
Claims (6)
1. a purifying technique for desulfurated plaster, is characterized in that: its purifying technique comprises the steps:
Step 1, feeding: manually choose desulfurated plaster;
Step 2, crush and screen: the desulfurated plaster that step 1 is chosen is sent into crusher and pulverized, and with 200 orders and 500 order vibratory screening apparatuss, sieves, and the sieve time of shaking is 10～30min;
Step 3, a ball milling: step 2 is crushed and screened to the particle diameter obtaining and be mixed with slurry between 200～500 object desulfurated plasters, the solid-liquid weight ratio of controlling slurry is 1:3～1:6, sends in ball mill, then in slurry, adds grinding aid, add-on is 500～3000g/t, ball milling 5～30min;
Step 4, pickling: first the solid-liquid weight ratio of the slurry obtaining in ball milling of step 3 is adjusted into 1:6～1:10, then be placed in the water-bath of 20～40 ℃, first add sulfuric acid, stir 5～30min, add again hydrochloric acid, stir 5～30min, control mixing speed is 300r/min, and the sulfuric acid quality wherein adding is that 5～30 % of butt desulfurated plaster quality, the hydrochloric acid quality adding are 3～10% of butt desulfurated plaster quality;
Step 5, flotation: the slurry after step 4 pickling is sent in flotation machine, and adding mass concentration is that 5% whipping agent, add-on are 1～5mL/L, then to add resultant magnetization hydrocarbon ils, add-on be 1.0～10mL/L, flotation 5～15min;
Step 6, clarification: by the slurry clarification 5～30min obtaining in step 5 flotation, to slurry layering;
Step 7, secondary ball milling: the top clear liquor of the slurry obtaining in step 6 clarification is removed, the solid-liquid weight ratio of adjusting bottom slurry is 1:1～1:3, then send into ball milling in ball mill, drum's speed of rotation 200～500r/min, Ball-milling Time 60～300min, complete the purification of desulfurated plaster, make gypsum raw material.
2. the purifying technique of desulfurated plaster as claimed in claim 1, is characterized in that: described vibratory screening apparatus is the top formula of the hitting sieve that shakes.
3. the purifying technique of desulfurated plaster as claimed in claim 1, is characterized in that: described grinding aid is at least one in ammonium chloride, EDTA, oxalic acid, citric acid, Trisodium Citrate, stearic acid, sodium stearate.
4. the purifying technique of desulfurated plaster as claimed in claim 1, is characterized in that: the ball mill in ball milling of described step 3 is colloidal mill.
5. the purifying technique of desulfurated plaster as claimed in claim 1, is characterized in that: the ball mill in described step 7 secondary ball milling is high energy ball mill, and this high energy ball mill is provided with the liner of tetrafluoroethylene, and abrading-ball is zirconium ball or agate ball.
6. the purifying technique of desulfurated plaster as claimed in claim 1, is characterized in that: the gypsum slurry obtaining after described step 7 secondary ball milling is directly used in Chemical Manufacture, or in 40 ℃, is dried to constant weight, encapsulation after centrifuge dehydration.
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| CN105290012A (en) * | 2015-11-13 | 2016-02-03 | 山东先罗输送机械有限公司 | Gypsum cleaning device and technology |
| CN105442047B (en) * | 2015-12-25 | 2018-02-16 | 华东理工大学 | A kind of method that fluorine element is extracted from industrial gypsum |
| CN106186030A (en) * | 2016-07-11 | 2016-12-07 | 山东胜伟园林科技有限公司 | The preparation method of a kind of desulfurated plaster and in the application of saline-alkali land vegetation plantation |
| CN109574060A (en) * | 2018-12-19 | 2019-04-05 | 天津渤化永利化工股份有限公司 | A kind of method of desulfurized gypsum removal of impurities decoloration |
| CN110304852B (en) * | 2019-08-14 | 2020-10-09 | 江苏一夫科技股份有限公司 | Method for whitening desulfurized gypsum, gypsum obtained by method and application of gypsum |
| CN112266007B (en) * | 2020-11-04 | 2022-08-19 | 湖南振亚新材料科技有限公司 | Preparation method of high-purity high-whiteness calcium sulfate |
| CN114247556B (en) * | 2021-12-23 | 2023-06-09 | 四川轻化工大学 | Phase-change purification method for industrial byproduct gypsum and phase-change purified gypsum |
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