Background technology
Can produce a large amount of citric acid gypsums in the Hydrocerol A enterprise production process; Its main solid waste is terra alba, and the common practice that present most of enterprises adopt is temporary transient storage of expropriation of land or leased land or landfill, not only takies a large amount of arable lands; The waste resource; And fundamentally thoroughly solve useless admittedly pollution problem, and cause that useless admittedly pile up like a mountain, form a kind of novel white pollution or grey and pollute.Citric acid gypsum seems a kind of solid waste, is a kind of very valuable building resource actually, if can correctly utilize, comprehensive exploitation, will turn waste into wealth.
At present, mostly the terra alba on the market is with the plaster of paris to be that the raw material calcining forms, and is mainly used in fields such as plasterboard, gypsum lines, gypsum block.In recent years, along with the develop rapidly of building field, plaster of paris development of resources is serious, even has arrived deficient stage, and country has also put into effect relevant policies protection Mineral resources.Therefore, from application prospect, chemical gypsum will replace the plaster of paris, become a kind of novel material of construction.From the detected result to citric acid gypsum, its whiteness, grade are much better than phosphogypsum and desulfurated plaster, can match in excellence or beauty with the plaster of paris, and processability is good.Domestic comprehensive treating process to citric acid gypsum is at the early-stage with application, and slower development does not form the production of industriallization, mass-producing as yet.
At present, the technology that on the gypsum production line, generally adopts has two kinds, i.e. one-step technology and two-step process.Single stage method is to integrate treatment process dry, that calcine, and gypsum raw material is sent in the calcining furnace by feeder, under the effect of mechanical dispersion power and hot blast; Accomplish flash-evaporation dehydration along the rotation route; Discharged by discharge gate after reaching requirement moisture, residence time of material is short, belongs to quick burning.This technical process is succinct, and is more suitable to the lower plaster of paris of raw material moisture, desulfurated plaster, phosphogypsum, but as far as citric acid gypsum and be not suitable for; Treatment capacity is bigger first, and second moisture is higher, causes directly that investment is high, running cost is high; Load of dust remove is big, and technology is also unstable; In addition, citric acid gypsum is different from the plaster of paris, desulfurated plaster and phosphogypsum, and oven dry, one step of calcining accomplish, and are unfavorable for the improved performance of its finished product.
And drying mode mainly contains following several kinds: 1, airflow drying; Normally hot flue gas directly contacts with material, and thermo-efficiency is very high, and energy consumption is lower; But material pollutes to some extent; The citric acid gypsum one cover airflow drying device higher to moisture in addition, that treatment capacity is bigger can not meet the demands, and investment is high, and load of dust remove is big; 2, this moral drying machine, i.e. Rotatingandflashstreamingdrier is similar to the calcining furnace of single stage method, and high moisture material is not suitable for; 3, rotary kiln.Normally flue gas or thermal oil are as heating medium, and thermo-efficiency is general, and the moisture high material is used few, sticking easily barrel, and it is inhomogeneous to be heated; 4, tube bank dryer, the present higher a kind of drying plant of thermo-efficiency, but be not suitable for the gypsum material, knot tube wall phenomenon is serious; 5, paddle heater, thermal oil are as heating medium, and the part siccative returns throws the reduction material moisture, the material inequality of being heated, and water vapor is bigger, is not easy timely discharge, and influence calcining and dust-removal system are not suitable for the big material of moisture and handle.
Calcining manners mainly contains two kinds, i.e. quick burning and calcining at a slow speed, and the representative of quick burning is this moral calcining furnace, and material is portion's residence time weak point within it, and the calcining effect is bad, and burning is more, and half water-content is lower, and product performance are unstable; This shows that above-mentioned disclosed technology all can't well be applied in the recovery and production of citric acid gypsum.
Summary of the invention
To existing many weak points in the existing citric acid gypsum utilization; The invention provides a kind of process method of utilizing citric acid gypsum industriallization full automatic control to produce plaster of Paris, i.e. pre-treatment+oven dry+calcining+grinding four step rule technology, this technology is to the own characteristic of citric acid gypsum; Carry out comprehensive process optimization; Production process is stable, and level of automation is high, and quality product is high and stable, easy to control.The present invention is intended to that Hydrocerol A industry solid waste-citric acid gypsum is carried out comprehensive treating process and utilizes, reach turn waste into wealth, the purpose of energy-saving and emission-reduction.Simultaneously, the plaster of Paris excellent property of utilizing citric acid gypsum to produce can be used as a kind of New Building Materials, substitutes the plaster of paris, thereby protects national natural Mineral resources, has wide application and market outlook.
The concrete process step that the present invention adopts is following:
(1) the citric acid gypsum raw material is washed, and, made the pH value of raw materials treated be controlled at 4-10 to wherein adding alkaline matter;
(2) the pretreated citric acid gypsum of above-mentioned process is sent into the cylinder dryer, drying time is controlled at 15-30min, and bake out temperature is controlled at 450-550 ℃, attached water content weight fraction≤6% of oven dry back raw material;
(3) material after will drying is delivered to fluidized-bed kiln; The calcining temperature of calcining furnace is controlled at 150-190 ℃, calcination time 30-50min, crystal water content weight fraction≤5% in the material of after calcining, discharging;
(4) material after will calcining send into the ball mill grinding both product.
The citric acid gypsum raw material that the present invention adopted is the calcium sulfate slag that produces in the citric acid production process, and it is a fine particulate, and fineness is the 80-200 order, and color is a white, and whiteness is 85-92%, and grade is higher, reaches more than 95%.
This raw material is a kind of of chemical gypsum, and its performance is much better than desulfurated plaster, phosphogypsum, and is suitable basically with the plaster of paris, and the alternative plaster of paris uses.
Adopt above-mentioned technology, at first add alkaline matter regulating the pH value of whole gypsum raw material, thereby a good reaction environment is provided, and it is better under the environment of meta-alkalescence, to handle the plaster of Paris quality of gained for follow-up processing; In order to reach best effect; The alkaline matter that the present invention adopted is generally one or more in sodium hydroxide, quicklime, Youxiaolin, the Losantin etc.; After adding alkaline matter, the pH value of generally controlling raw material is at 4-10, the preferred 6.5-8.5 that is controlled at; Before regulating pH, need the citric acid gypsum raw material is washed, removing impurity and other solvend wherein, convenient follow-up processing, the number of times of general control washing is 1-3 time.
When drying through pretreated raw material, the contriver has contrasted existing various oven dry means, finds to adopt the cylinder dryer to dry and is suitable for raw material of the present invention most; Because the raw material that the present invention adopted is obtained in the production process; Staple calcium sulfate all is to occur with the form of terra alba, and moisture content is bigger, and the amount of raw material is big; Dry finally having confirmed employing cylinder dryer through contriver after the test of many times; And the concrete parameter when having confirmed oven dry is: drying time is controlled at 15-30min, and bake out temperature is controlled at 450-550 ℃
Through the raw material after the oven dry; Its attached water content is controlled at weight fraction≤6%, and the whiteness of raw material is able to keep, and meets the requirement of high-grade material industry for the gypsum whiteness; And the main attached water of removing of oven dry; Material adhesive water after the oven dry can not be too high, otherwise the calcination process load is excessive, and energy consumption will rise.And adopt roller dryer here; Can effectively handle the raw material that quantity is big, moisture is high; The calcining process that goes on foot for the back provides strong support; And in order further to reach purpose of energy saving, the thermal source of dryer can adopt warm air, and obtains in the waste gas that warm air generally can efflux from production process through the form of heat exchange.
Why adopt fluidized-bed kiln to calcine; Be because fluidized-bed kiln is an incinerating form at a slow speed, and it adopts thermal oil as heating medium, material within it portion's residence time long; The formation and the whole phase composite that help half crystalline distribute; Calcine evenly relatively, product performance are relatively stable, have intensity preferably.Than quick burning method commonly used now, the stability that can effectively enhance product performance, and the consumption of the reduction energy have reduced the cost of handling.This calcining furnace must with the above-mentioned supporting use of cylinder dryer, have only forward oven dry up to standard, the calcining of back could be carried out smoothly.In order to reach best effect, the parameter the when contriver controls calcining is: calcining temperature is controlled at 150-190 ℃, and calcination time 30-50min further is controlled at: temperature is controlled at 160-180 ℃, time 35-45min.
After calcining; Crystal water content≤5% in the material of discharging, the overwhelming majority is a semi-hydrated gypsum in the material of discharging like this, contains the dihydrate gypsum of a spot of dehydrated gyp-and trace simultaneously; Phase composite and distribution have rationally improved the quality and the stability of product greatly.
Directly sending into the ball mill grinding through the raw material after the above-mentioned processing and both got product, adopt grinding here, is that the material after the calcining is handled; Further promote its processability and product properties, resulting product, its presetting period 6-12min; Final setting time 10-25min, 2h folding strength 2.4-3.0MPa, whiteness is more than 90%; Meet " plaster of Paris " GB9776-2008 standard fully, can be used as qualified gypsum for building.
In sum, the production technique of the plaster of Paris that the present invention adopted adopts citric acid gypsum as raw material; Adopted four step rule technology, be fit to the comprehensive treating process of citric acid gypsum and other high moisture material, technology is advanced; Level of automation is high, and controllability is good, the products obtained therefrom excellent property.And whole production technology has realized the low pollution operation of less energy-consumption, and the equipment that is adopted is existing device, can be handling higher, and be suitable for relevant enterprise and on the prior art level, improve, have wide promotion prospect.
Embodiment
The water cut of mentioning among the following embodiment is weight fraction
Embodiment 1
A kind of four step rule technology of utilizing citric acid gypsum industriallization full automatic control to produce plaster of Paris, its step is following:
1, the citric acid gypsum raw material is washed pre-treatment, and to wherein adding micro-quicklime, the pH value of raw materials treated is 6.62;
2, the raw material of handling well is quantitatively sent into the cylinder dryer by conveying belt, drying time is 28min, and bake out temperature is controlled at 450 ℃, and oven dry postadhesion water-content is 3.42%;
3, the mass transport after will drying is to fluidized-bed kiln;
4, the calcining furnace calcining temperature is 180 ℃, and calcination time is 47min, and discharging crystal water content is 3.65%;
5, the plaster of Paris after will calcining is sent into the ball mill grinding;
6, the terra alba behind the grinding is sent into finished bin by delivery system;
7, terra alba is 7-9min through detecting the presetting period, final setting time 20-25min, and 2h folding strength 2.45-2.55MPa, whiteness 90.5-91.0% meets the requirement of " plaster of Paris " GB9776-2008.
Embodiment 2:
A kind of four step rule technology of utilizing citric acid gypsum industriallization full automatic control to produce plaster of Paris, its step is following:
1, the citric acid gypsum raw material is washed pre-treatment, and to wherein adding micro-Youxiaolin, the pH value of raw materials treated is 7.83;
2, the raw material of handling well is quantitatively sent into the cylinder dryer by conveying belt, drying time is 25min, and bake out temperature is controlled at 480 ℃, and oven dry postadhesion water-content is 5.67%;
3, the mass transport after will drying is to fluidized-bed kiln;
4, the calcining furnace calcining temperature is 170 ℃, and calcination time is 45min, and discharging crystal water content is 4.24%;
5, the plaster of Paris after will calcining is sent into the ball mill grinding;
6, the terra alba behind the grinding is sent into finished bin by delivery system;
7, terra alba is 6-8min through detecting the presetting period, final setting time 18-22min, and 2h folding strength 2.65-2.75MPa, whiteness 90.8-91.5% meets the requirement of " plaster of Paris " GB9776-2008.
Embodiment 3:
A kind of four step rule technology of utilizing citric acid gypsum industriallization full automatic control to produce plaster of Paris, its step is following:
1, the citric acid gypsum raw material is washed pre-treatment, and to wherein adding micro-sodium hydroxide and Losantin, the pH value of raw materials treated is 7.74;
2, the raw material of handling well is quantitatively sent into the cylinder dryer by conveying belt, drying time is 23min, and bake out temperature is controlled at 500 ℃, and oven dry postadhesion water-content is 2.58%;
3, the mass transport after will drying is to fluidized-bed kiln;
4, the calcining furnace calcining temperature is 175 ℃, and calcination time is 42min, and discharging crystal water content is 4.33%;
5, the plaster of Paris after will calcining is sent into the ball mill grinding;
6, the terra alba behind the grinding is sent into finished bin by delivery system;
7, terra alba is 6-9min through detecting the presetting period, final setting time 16-20min, and 2h folding strength 2.7-2.8MPa, whiteness 91.4-92.0% meets the requirement of " plaster of Paris " GB9776-2008.
Embodiment 4:
A kind of four step rule technology of utilizing citric acid gypsum industriallization full automatic control to produce plaster of Paris, its step is following:
1, the citric acid gypsum raw material is washed pre-treatment, and to the mixture that wherein adds micro-quicklime and Youxiaolin, the pH value of raw materials treated is 8.57;
2, the raw material of handling well is quantitatively sent into the cylinder dryer by conveying belt, drying time is 21min, and bake out temperature is controlled at 520 ℃, and oven dry postadhesion water-content is 1.62%;
3, the mass transport after will drying is to fluidized-bed kiln;
4, the calcining furnace calcining temperature is 165 ℃, and calcination time is 36min, and discharging crystal water content is 4.9%;
5, the plaster of Paris after will calcining is sent into the ball mill grinding;
6, the terra alba behind the grinding is sent into finished bin by delivery system;
7, terra alba is 7-10min through detecting the presetting period, final setting time 19-22min, and 2h folding strength 2.8-2.9MPa, whiteness 90.8-91.7% meets the requirement of " plaster of Paris " GB9776-2008.
Embodiment 5:
A kind of four step rule technology of utilizing citric acid gypsum industriallization full automatic control to produce plaster of Paris, its step is following:
1, the citric acid gypsum raw material is washed pre-treatment, and to the mixture that wherein adds micro-sodium hydroxide and Youxiaolin, the pH value of raw materials treated is 6.71;
2, the raw material of handling well is quantitatively sent into the cylinder dryer by conveying belt, drying time is 20min, and bake out temperature is controlled at 510 ℃, and oven dry postadhesion water-content is 1.4%;
3, the mass transport after will drying is to fluidized-bed kiln;
4, the calcining furnace calcining temperature is 160 ℃, and calcination time is 44min, and discharging crystal water content is 4.41%;
5, the plaster of Paris after will calcining is sent into the ball mill grinding;
6, the terra alba behind the grinding is sent into finished bin by delivery system;
7, terra alba is 8-11min through detecting the presetting period, final setting time 19-24min, and 2h folding strength 2.75-2.90MPa, whiteness 92.2-93.0% meets the requirement of " plaster of Paris " GB9776-2008.
Embodiment 6:
A kind of four step rule technology of utilizing citric acid gypsum industriallization full automatic control to produce plaster of Paris, its step is following:
1, the citric acid gypsum raw material is washed pre-treatment, and to the mixture that wherein adds micro-sodium hydroxide, quicklime and Youxiaolin, the pH value of raw materials treated is 9.25;
2, the raw material of handling well is quantitatively sent into the cylinder dryer by conveying belt, drying time is 18min, and bake out temperature is controlled at 550 ℃, and oven dry postadhesion water-content is 0.8%;
3, the mass transport after will drying is to fluidized-bed kiln;
4, the calcining furnace calcining temperature is 155 ℃, and calcination time is 49min, and discharging crystal water content is 4.77%;
5, the plaster of Paris after will calcining is sent into the ball mill grinding;
6, the terra alba behind the grinding is sent into finished bin by delivery system;
7, terra alba is 7-11min through detecting the presetting period, final setting time 20-24min, and 2h folding strength 2.7-2.8MPa, whiteness 91.1-92.2% meets the requirement of " plaster of Paris " GB9776-2008.