CN104760983B - The improvement recovery of blowdown during a kind of PVC produces and method of comprehensive utilization - Google Patents
The improvement recovery of blowdown during a kind of PVC produces and method of comprehensive utilization Download PDFInfo
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Abstract
The present invention relates to improvement recovery and the method for comprehensive utilization of blowdown in a kind of PVC production, the carbide slurry of discharging in utilizing PVC to produce and carbon dioxide production regeneration calcium carbonate, composite regenerated calcium carbonate is made again with regeneration calcium carbonate, flotation coal dust and calcium carbide dust, be raw material production calcium carbide with composite calcium carbonate, simultaneously with regenerating calcium carbonate, coal dust, Calcium Fluoride (Fluorspan), iron powder or powdered iron ore as subsidiary material, make the generation that deslagging agent is used for controlling slag in furnace of calcium carbide, Fesi Furnace.Its advantage is: carbide slurry, calcium carbide dust, carbonic acid gas and the coalwashing plant coal slime of PVC factory being discharged are carried out improvement and reclaimed and comprehensive utilization; produce composite calcium carbonate; as a kind of novel material producing calcium carbide; substitute lime, coke production calcium carbide completely; to eliminate the blowdown of PVC factory, exploitation renewable resource, to preserve the ecological environment, and eliminate two kinds of knotty problems of furnace bottom rising and three-phase electrode material inequality completely.
Description
Technical field
The present invention relates to improvement recovery and the method for comprehensive utilization of blowdown in a kind of PVC production, belong to chemical spent material regeneration and field of comprehensive utilization.
Background technology
China is that PVC maximum in the world produces country, produces several ten million tons per year, blowdown incredible amount.Example: produce 100 ten thousand tons of polyvinyl chloride producer year discharge carbide slurry 1,124 ten thousand tons per year for one, need 1,800,000 tons of calcium carbides every year, newly-increased more than 100 mu of soil is deposited, and nearly ten million ton of sewage endangers groundwater resource.Produce 1,800,000 tons of calcium carbides, need 1,080,000 tons, coke, discharge carbonic acid gas 1,240,000 tons, discharge calcium carbide dust 100,000 tons, needs raw ore lime stone 5,400,000 tons, produces lime 2,700,000 tons, discharges atmospheric dust 100,000 tons simultaneously, discharge carbonic acid gas 1,730,000 tons; Produce lime and need 300,000 tons, coke, abandoned mine ground-slag lime 1,000,000 tons, produce lime, production calcium carbide discharges carbonic acid gas 2,970,000 tons every year altogether.Produce in calcium carbide, ferrosilicon in mineral hot furnace at present, because having the objectionable impuritiess such as a small amount of sulphur, phosphorus, silicon-dioxide, magnesium oxide, aluminium sesquioxide in natural mineral resources, two kinds of knotty problems of serious harm quality product are difficult to get rid of.As: (1) furnace bottom slag goes up.(2) three-phase electrode material is uneven, occur strong, in, weak phenomenon, and periodically stove repaiied by stopping production prepurging, seriously constrains the situation of high and stable yields.
Summary of the invention
The object of this invention is to provide improvement recovery and the method for comprehensive utilization of blowdown in a kind of PVC production; the carbide slurry that PVC factory is discharged by the present invention, calcium carbide dust, carbonic acid gas and coalwashing plant coal slime are carried out improvement and are reclaimed and comprehensive utilization; produce composite calcium carbonate; as a kind of novel material producing calcium carbide; substitute lime, coke production calcium carbide completely; to eliminate the blowdown of PVC factory, exploitation renewable resource, to preserve the ecological environment, and eliminate two kinds of knotty problems of furnace bottom rising and three-phase electrode material inequality completely.
Thinking of the present invention is:
The carbide slurry of discharging in utilizing PVC to produce and carbon dioxide production regeneration calcium carbonate, composite regenerated calcium carbonate is made again with regeneration calcium carbonate, flotation coal dust and calcium carbide dust, be raw material production calcium carbide with composite calcium carbonate, add Calcium Fluoride (Fluorspan), iron powder or powdered iron ore as subsidiary material with regeneration calcium carbonate, coal dust simultaneously, make the generation that deslagging agent is used for controlling slag in furnace of calcium carbide, Fesi Furnace.
Method of the present invention is as follows:
1) in PVC production, the improvement of blowdown is reclaimed:
Regenerate calcium carbonate to produce: the carbide slurry of discharging with acetylene generating station, for raw material, enters deposit arrangement pond and adjusts stand-by;
Adopt reverse inflation collisional mixing formula reaction mechanism, carbonic acid gas in reaction tower from bottom to top, carbide slurry is by the spraying type landing from top to bottom of reaction tower top, and in the pressurization of reaction tower bottom, carbonic acid gas mixing of seethe with excitement in carbide slurry is fully reacted, Calcium hydrogen carbonate can be produced for preventing carbonic acid gas surplus, take two kinds of mutual reverse convection hybrid reactions of material, the reaction of carbide slurry limit generates calcium carbonate limit and flows to settling tank, precipitation limit, limit is discharged by screw discharger, sends into forming machine and carry out kneading and compacting after thickner thickening; Water returns acetylene generating station to be continued to use; Its reaction formula is as follows:
Calcium hydroxide+carbonic acid gas → calcium carbonate+water
Ca(OH)
2+CO
2→CaCO
3+H
2O
Concentrated: regeneration calcium carbonate is discharged by screw discharger after settling tank precipitation, enters thickner and concentrates, the moisture content < 10wt% of the regeneration calcium carbonate after concentrated;
2) fully utilize:
I) the composite regenerated calcium carbonate of production calcium carbide is made:
To regenerate calcium carbonate, flotation coal dust for raw material, kneading and compacting is that granularity is at 20 millimeters ~ 40 millimeters spheroids, drying and dewatering to moisture content < 0.5wt%, the calculating of proportioning raw materials: the proportioning of regeneration calcium carbonate, flotation coal dust is calculated by the carbon balance gauge of butt in regeneration calcium carbonate and coal dust reaction process;
Described regeneration calcium carbonate can replace by calcium carbide dust part;
Described calcium carbide dust is not for landing dust;
The granularity of described flotation coal dust is 80 order ~ 200 orders;
Described flotation coal dust is pulverized anthracite or has bituminous coal powder;
1. in pulverized anthracite, fixed carbon > 81wt%, ash < 6wt%, fugitive constituent < 13wt%, moisture content < 10wt%, sulphur and phosphorus < 3wt ‰;
2. have in bituminous coal powder, fixed carbon > 55wt%, ash < 6wt%, fugitive constituent < 35wt%, moisture content < 10wt%, sulphur and phosphorus < 3wt ‰;
II) the special deslagging agent of furnace of calcium carbide is made:
To regenerate calcium carbonate, flotation coal dust, subsidiary material for raw material, kneading and compacting is that granularity is at 20 millimeters ~ 40 millimeters spheroids, drying and dewatering is to moisture content < 0.5wt%, subsidiary material are Calcium Fluoride (Fluorspan), iron powder or powdered iron ore, and proportioning raw materials is: regeneration calcium carbonate 40 ± 3wt%, coal dust 30 ± 2wt%, Calcium Fluoride (Fluorspan) 10 ± 1wt%, iron powder or powdered iron ore 20wt%;
Described powdered iron ore requires ferric oxide content > 55wt%;
III) the special deslagging agent of Fesi Furnace is made:
To regenerate calcium carbonate, flotation coal dust, subsidiary material for raw material, kneading and compacting is that granularity is at 20 millimeters ~ 40 millimeters spheroids, drying and dewatering is to moisture content < 0.5wt%, subsidiary material are Calcium Fluoride (Fluorspan), iron powder or powdered iron ore, and proportioning raw materials is: regeneration calcium carbonate 50 ± 3wt%, coal dust 10 ± 2wt%, Calcium Fluoride (Fluorspan) 30 ± 1wt%, iron powder or powdered iron ore 10wt%;
Described powdered iron ore requires ferric oxide content > 55wt%.
Advantage of the present invention is: the carbide slurry utilizing PVC factory to discharge, calcium carbide dust, carbonic acid gas and coalwashing plant coal slime are to produce composite regenerated calcium carbonate, as a kind of novel material producing calcium carbide, produce calcium carbide to produce 1800000 tons of PVC factory per year, year reduce carbide slurry and discharge 1,124 ten thousand tons, year can reduce Carbon emission total amount 2,970,000 tons, 100,000 tons, sulphur phosphorus; Reduce abandoned mine slag, whitewash ash, calcium carbide dust totally 120 ten thousand tons, save 5,400,000 tons, mineral resources Wingdale, save 1,380,000 tons, coke.Water Sproading recycles, economize on water 8,000,000 tons, regeneration calcium carbonate does not have the hazardous substances such as silicon-dioxide, aluminium sesquioxide, magnesium oxide, sulphur phosphorus, but also have a small amount of objectionable impurities in coal dust, therefore prepare the special deslagging agent of furnace of calcium carbide and the special deslagging agent of Fesi Furnace solves, completely eliminate two kinds of knotty problems of furnace bottom rising and three-phase electrode material inequality.Application of the present invention can make PVC factory reclaim blowdown recycling, becomes without blowdown modern plant.Regeneration calcium carbonate is that inexhaustible infinite loop re-uses, and can substitute lime, coke production calcium carbide completely, can administer blowdown and save the energy not only but also preserve the ecological environment.
Accompanying drawing explanation
Fig. 1 is composite regenerated calcium carbonate production technological process of the present invention.
Embodiment
The Production Flow Chart of regeneration calcium carbonate:
One, it is stand-by that the carbide slurry that acetylene generating station discharges enters deposit arrangement pond adjustment:
Raw material standard: calcium hydroxide 50wt%, moisture content 50wt%.
Regeneration calcium carbonate production reaction principle: reverse inflation collisional mixing formula: carbonic acid gas in reaction tower from bottom to top, carbide slurry (calcium hydroxide) is by the spraying type landing from top to bottom of reaction tower top, in order to abundant contact reacts, the pressurization of tower bottom makes carbonic acid gas mixing of seethe with excitement in carbide slurry fully react.Calcium hydrogen carbonate can be produced for preventing carbonic acid gas surplus; take two kinds of mutual reverse convection hybrid reactions of material; the reaction of carbide slurry limit generates calcium carbonate limit and flows to settling tank; precipitation limit, limit is discharged by screw discharger; after thickner thickening, send into forming machine carry out kneading and compacting, water returns acetylene generating station to be continued to use.
Calcium hydroxide+carbonic acid gas → calcium carbonate+water
Ca(OH)
2+CO
2→CaCO
3+H
2O
Molecular weight 746410018
1000kg595kg1351kg244kg
Be example by use per hour 200 tons of carbide slurry, need carbonic acid gas 59.5 tons, pure carbon dioxide per ton is 5100 cubic metres.
Two, concentrated: regeneration calcium carbonate is discharged by screw discharger after settling tank precipitation, enters thickner and concentrates, the moisture content < 10wt% of regeneration calcium carbonate after concentrated.
Three, the calcium carbide ingredient requirement of composite regenerated calcium carbonate:
1, calcium carbonate moisture content < 10wt% is regenerated;
2, flotation coal dust: pulverized anthracite or have bituminous coal powder (80 order ~ 200 order);
1. pulverized anthracite: < 13wt%, the moisture content < 10wt% of fixed carbon > 81wt%, ash < 6wt%, fugitive constituent, sulphur phosphorus < 3wt ‰.
2. bituminous coal powder is had: < 35wt%, the moisture content < 10wt% of fixed carbon > 55wt%, ash < 6wt%, fugitive constituent, sulphur phosphorus < 3wt ‰.
3, calcium carbide dust, requires not land dust.
4, composite regenerated calcium carbonate proportioning raw materials: regeneration calcium carbonate (butt), coal dust (butt) calculate by fixed carbon, and calcium carbide dust is pressed calcium carbonate and calculated, whole proportioning is by producing the 300 liters of calculating of per kilogram calcium carbide gas forming amount.
Four, composite regenerated calcium carbonate kneading and compacting: granularity requirements: 20 millimeters ~ 40 millimeters ball-types;
Five, drying and dewatering: composite regenerated calcium carbonate ball-type sends into drying plant by transfer equipment, carries out drying and dewatering.
1, drying plant, box drying and dewatering, reverse production, the carbonic acid gas and waste heat of discharging is produced, from box drying plant bottom, from bottom to top with furnace of calcium carbide, composite regenerated calcium carbonate spheroid from drying baker from top to bottom, 4 to 6 hours drying and dewaterings at 200 DEG C to 300 DEG C, above add lower row's continuous seepage, and the carbon dioxide that top is discharged sends into reaction tower again by roots blower.
2, requiring pressure-fired in drying baker during drying and dewatering, forbid negative pressure to be produced, in case negative pressure enters oxygen combustion carbon, causing composite regenerated calcium carbonate defective because lacking carbon.
Produce calcium carbide working method just the same with the operation of calcium oxide coke production calcium carbide.
Calcium carbide produces reaction formula:
By the pure calcium carbonate=1000/64 × 100=1562.5kg required for the pure calcium carbide of 1000kg;
By the pure carbon=1000/64 × 36=563kg required for the pure calcium carbide of 1000kg;
By the pure carbon of 1000kg pure calcium carbonate charge composition=563/1562.5 × 100=360.32kg;
Pulverized anthracite fixed carbon 81wt% is example, and 1000kg calcium carbonate needs carbon 360.32kg × 100/81=444.84kg pulverized anthracite;
Have bituminous coal powder fixed carbon 55wt% to be example, 1000kg calcium carbonate needs carbon 360.32kg × 100/55=655.13kg to have bituminous coal powder.
Composite regenerated calcium carbonate produce calcium carbide and calcium oxide coke production calcium carbide different, composite regenerated calcium carbonate ratio resistance is greater than calcium oxide coke compound ratio resistance, so stove inter potential is also different, therefore the voltage produced required for calcium carbide uses also different, need reasonable voltage be adjusted, adjust three electrode center of circle distance of round simultaneously.Circle=primary electrode diameter × 2.7, three electrode centers of circle, now adjust electrode diameter × 2.8.
Mineral hot furnace produces calcium carbide, ferrosilicon, has the objectionable impuritiess such as a small amount of silicon-dioxide, aluminium sesquioxide, magnesium oxide, also can cause furnace bottom rising in the course of time, also can affect calcium carbide, ferrosilicon output and power consumption in carbon raw material.For avoiding this phenomenon, carrying out except Slag treatment simultaneously, adding furnace of calcium carbide special deslagging agent Fesi Furnace deslagging agent and controlling furnace bottom rising.In stove, slag generates rise never, creates a better working condition to furnace of calcium carbide, Fesi Furnace.
Make the special deslagging agent of furnace of calcium carbide:
Proportioning raw materials: regeneration calcium carbonate 40 ± 3wt%, coal dust 30 ± 2wt%, Calcium Fluoride (Fluorspan) 10 ± 1wt%, iron powder 20wt%, moisture content < 0.5wt%.
Kneading and compacting be granularity at 20 millimeters ~ 40 millimeters ball-types, drying and dewatering is to moisture content < 0.5wt%.
The slagging-off principle of the special deslagging agent of furnace of calcium carbide: in furnace of calcium carbide, slag main component is silicon carbide, aluminium sesquioxide, magnesium oxide, it is not tolerant to form high temperature, and sink to furnace bottom, increase gradually, cover with burner hearth, stove is repaiied in blowing out of being forced to stop production.In deslagging agent, calcium fluoride melting point is low, can dissolve high-melting-point substances aluminium sesquioxide, magnesium oxide etc. under the high temperature conditions, fusing point is reduced and has mobility.Simultaneously ferric oxide and carbon are reduced into iron, and iron reacts with slag major components silicon carbide generation affinity in stove and generates ferrosilicon, ferrosilicon and have the aluminium sesquioxide of mobility, magnesium oxide simultaneously to flow out outside stove, have reached the object of discharge slag.
The using method of the special deslagging agent of furnace of calcium carbide:
Usage: remove the gred weekly once, directly drops into the special deslagging agent of furnace of calcium carbide in furnace of calcium carbide, the same with normal production operation, 3 ~ 5 hours treatment times.(slagging-off does not affect normal production, produces slagging-off and carries out simultaneously.), consumption: determine according to calcium-carbide furnace transformer capacity day output.
Make the special deslagging agent of Fesi Furnace:
Proportioning raw materials: regeneration calcium carbonate 50 ± 3wt%, coal dust 10 ± 2wt%, Calcium Fluoride (Fluorspan) 30 ± 1wt%, iron powder 10wt%, moisture content < 0.5wt%.
Kneading and compacting be granularity at 20 millimeters ~ 40 millimeters ball-types, drying and dewatering is to moisture content < 0.5wt%.
Make the slagging-off principle of the special deslagging agent of Fesi Furnace: the materials such as Fesi Furnace slag main component aluminium sesquioxide, magnesium oxide generate high temperature silicon hydrochlorate, fusing point is high, high temperature 3000 DEG C is non-fusible, but Calcium Fluoride (Fluorspan) is its jinx, special for Fesi Furnace deslagging agent is added in stove and makes aluminium sesquioxide, magnesium oxide reduce fusing point to 1300 DEG C fast there is mobility, the ferrosilicon that same iron, carbon, silicon dioxde reaction generate flows out outside stove together, has reached the object that removing slag reduces furnace bottom.
The using method of the special deslagging agent of Fesi Furnace:
Usage: determine slagging-off number of times according to situation in stove, the same normal production of working method, but stop throwing ferrosilicon raw materials for production, change into and drop into the special deslagging agent of Fesi Furnace, with the use of material-tilting machine overturning dead angle place, electric current is the same with normal production and application, two hours row's primary slags, within 8 hours treatment times, after slagging-off, can normally drop into ferrosilicon raw materials for production, identical with charge level height during firm blow-on in space for collecting ashes in a stove; Also can scarfing cinder half a year once, Special Circumstances advanced processing.
Consumption: determine consumption according to Fesi Furnace transformer capacity size.
Producing calcium carbide with composite regenerated calcium carbonate in method of the present invention is a kind of New Regenerated raw material, calcium carbide is produced more superior than calcium oxide, and can infinite loop use, mine resources can be saved, can save coke raw material again, composite regenerated calcium carbonate can do the raw materials for production such as silicocalcium, cement, ironmaking again.
Why produced calcium carbide in the past and used calcium oxide without raw ore calcium carbonate? because the little quality of calcium oxide density is light, active good.The large poor activity of raw ore calcium carbonate density.Have in calcium oxide when calcium carbide is in the past produced the raw burn lime (calcium carbonate) of 5% to 20% sometimes even raw burn lime all can generate calcium carbide more than 30%, but the more power consumptions of raw burn lime are higher.And composite regenerated calcium carbonate changes its structure, be intimately combined with carbon dust with small particle, the less quality of density ratio calcium oxide is lighter, change its character simultaneously, the rapid reaction condition created, the faster energy saving of speed of response, produces calcium carbide economize on electricity 10 ~ 15% than calcium oxide in the past.
Composite regenerated calcium carbonate objectionable impurities is few, and furnace bottom rising is slow, the production environment created; Composite regenerated calcium carbonate can be produced without the high-quality super calcium carbide of sulphur phosphorus.
Claims (8)
1. PVC produce in the improvement recovery of blowdown and a method of comprehensive utilization, it is characterized in that:
1) in PVC production, the improvement of blowdown is reclaimed:
Regenerate calcium carbonate to produce: the carbide slurry of discharging with acetylene generating station, for raw material, enters deposit arrangement pond and adjusts stand-by;
Adopt reverse inflation collisional mixing formula reaction mechanism, carbonic acid gas in reaction tower from bottom to top, carbide slurry is by the spraying type landing from top to bottom of reaction tower top, and in the pressurization of reaction tower bottom, carbonic acid gas mixing of seethe with excitement in carbide slurry is fully reacted, carbide slurry reaction generates carbonic acid calcium current and enters settling tank, is discharged, enter thickner and concentrate by screw discharger, the moisture content < 10wt% of the regeneration calcium carbonate after concentrated, water returns acetylene generating station to be continued to use;
2) fully utilize:
I) the composite regenerated calcium carbonate of production calcium carbide is made:
To regenerate calcium carbonate, flotation coal dust for raw material, kneading and compacting is that granularity is at 20 millimeters ~ 40 millimeters spheroids, drying and dewatering to moisture content < 0.5wt%, the calculating of proportioning raw materials: the proportioning of regeneration calcium carbonate, flotation coal dust is calculated by the carbon balance gauge of butt in regeneration calcium carbonate and coal dust reaction process;
II) the special deslagging agent of furnace of calcium carbide is made:
To regenerate calcium carbonate, flotation coal dust, subsidiary material for raw material, kneading and compacting is that granularity is at 20 millimeters ~ 40 millimeters spheroids, drying and dewatering is to moisture content < 0.5wt%, subsidiary material are Calcium Fluoride (Fluorspan), iron powder or powdered iron ore, and proportioning raw materials is: regeneration calcium carbonate 40 ± 3wt%, coal dust 30 ± 2wt%, Calcium Fluoride (Fluorspan) 10 ± 1wt%, iron powder or powdered iron ore 20wt%;
III) the special deslagging agent of Fesi Furnace is made:
To regenerate calcium carbonate, flotation coal dust, subsidiary material for raw material, kneading and compacting is that granularity is at 20 millimeters ~ 40 millimeters spheroids, drying and dewatering is to moisture content < 0.5wt%, subsidiary material are Calcium Fluoride (Fluorspan), iron powder or powdered iron ore, and proportioning raw materials is: regeneration calcium carbonate 50 ± 3wt%, coal dust 10 ± 2wt%, Calcium Fluoride (Fluorspan) 30 ± 1wt%, iron powder or powdered iron ore 10wt%.
2. PVC according to claim 1 produce in the improvement recovery of blowdown and method of comprehensive utilization, it is characterized in that: step 2) described in regeneration calcium carbonate can replace by calcium carbide dust part.
3. PVC according to claim 2 produce in the improvement recovery of blowdown and method of comprehensive utilization, it is characterized in that: described calcium carbide dust is not for landing dust.
4. PVC according to claim 1 produce in the improvement recovery of blowdown and method of comprehensive utilization, it is characterized in that: step 2) described in the granularity of flotation coal dust be 80 order ~ 200 orders.
5. PVC according to claim 4 produce in the improvement recovery of blowdown and method of comprehensive utilization, it is characterized in that: described flotation coal dust is pulverized anthracite or has bituminous coal powder.
6. PVC according to claim 5 produce in the improvement recovery of blowdown and method of comprehensive utilization, it is characterized in that: in pulverized anthracite, fixed carbon > 81wt%, ash < 6wt%, fugitive constituent < 13wt%, moisture content < 10wt%, sulphur and phosphorus < 3wt ‰.
7. PVC according to claim 5 produce in the improvement recovery of blowdown and method of comprehensive utilization, it is characterized in that: have in bituminous coal powder, fixed carbon > 55wt%, ash < 6wt%, fugitive constituent < 35wt%, moisture content < 10wt%, sulphur and phosphorus < 3wt ‰.
8. PVC according to claim 1 produce in the improvement recovery of blowdown and method of comprehensive utilization, it is characterized in that: step 2) described in powdered iron ore in ferric oxide content > 55wt%.
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