CN102491285A - Waste sulphuric acid concentrating and recycling equipment - Google Patents
Waste sulphuric acid concentrating and recycling equipment Download PDFInfo
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- CN102491285A CN102491285A CN2011103970415A CN201110397041A CN102491285A CN 102491285 A CN102491285 A CN 102491285A CN 2011103970415 A CN2011103970415 A CN 2011103970415A CN 201110397041 A CN201110397041 A CN 201110397041A CN 102491285 A CN102491285 A CN 102491285A
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Abstract
The invention relates to equipment for dehydrating and refining waste sulphuric acid aqueous solution with the concentration of 40%-90% into sulphuric acid with the concentration of higher than 95%. The equipment is characterized in that a steel barrel which is horizontally arranged or slightly inclined is taken as a main body, more than two pairs of external riding wheels are taken as supports, the equipment is driven to rotate by virtue of a big gear ring and an accessory device, which are arranged outside the barrel, continuous charging and discharging and a vacuum state are realized at the two ends of the barrel by adopting filler or mechanical seal, and the equipment adopts an external heating method for heating and adopts an internal component for enhancing heat transfer and mass transfer. The equipment has low manufacturing cost, high efficiency and low energy consumption. A figure on the right side in the specification shows that the equipment comprises the following components: a heat preservation hearth 1, a chimney 2, a concentrated kiln body 3, a vacuum air outlet 4, a waste acid feeding hole 5, riding wheel 6, a big gear ring 7, a hearth support 8, a hearth support 9, a hearth support 10, a coal-fired furnace 11, a riding wheel 12, a discharge hole 13, a material receiver 14 and an indoor compartment clapboard 15.
Description
Technical field
The present invention relates to a kind of sulfur waste acid and concentrate recovery system, is a kind of rotary type vaporizer, is similar to rotary kiln, is used for the dilute sulphuric acid of dry hydrogen chloride gas during PVC is produced or the sulfur waste acid that is used for washup is produced in mining industry concentrating the equipment that reclaims.
Background technology
In the chemical industry production process, there are a lot of fields will use sulfuric acid, such as in producing the PVC process; A large amount of hydrogen chloride gas all needs drying; These hydrogen chloride gas of current drying mainly usefulness all be the vitriol oil, these vitriol oils just become dilute sulphuric acid after suction, content is between 50%-90%; The general producer of these dilute sulphuric acids does not all have oneself to handle, but is sold to producer or the discharging that needs dilute sulphuric acid.In the washup process that in the exploitation of mineral products such as manganese ore, copper mine, relates to; Need wash materials such as the iron in the copper mine, zinc with purifying ore deposit article off; In this process, also can produce the sulfur waste acid of 50% a large amount of content, contain a large amount of sulphate of iron in these sulfuric acid; General industrial enterprise all can be discharged into these spent acid in the underground pit, and this causes the pollution of environment and the waste of resource to a certain extent.
Because sulfuric acid low price; In only 400 yuan/ton of most of periods, simultaneously the vitriolic boiling point is up to 338 ℃, very corrosive; It is often relatively more difficult to reclaim these spent acid; The expense that reclaims has simultaneously often surpassed the value of sulfuric acid itself, and therefore, inventing a kind of reasonable and economic mode reclaim(ed) sulfuric acid becomes a valuable problem.
For many years, the most of production firms of China use traditional interrupter method cast iron cauldron to concentrate the method for diluted acid, this equipment have build easily, cost is low, practical.But have that labor strength is big, severe operational environment, thermo-efficiency is low, energy consumption is high, problem such as seriously polluted, and device can not realize serialization, it is with high costs that final body reclaims now.
The sulfur waste acid method of enrichment of Japan Kimura-Datong District's chemical machinery company is to combine with glass lining pipe climbing-film evaporation and segmentation vacuum-evaporation, with H in the sulfur waste acid
2SO
4Massfraction be concentrated to 95% from 10%～40%, its technology can be divided into 3 sections, preceding two sections employing Resbon tube heater vaporizes concentrate, back one section is adopted the glass lining pipe climbing-film evaporator to concentrate, H in each section
2SO
4Massfraction raises gradually, reaches 60%, 80% and 95% respectively.Heat-processed adopts the elevated temperature heat carrier, and temperature is 150～220 ℃, can change organism into insoluble substance, removes by filter then, and this technology is carried out pilot scale with the scale of 2t/h, and 5 years ran well.This technology adaptive faculty is very strong, can be used for containing the useless vitriolic processing of multiple organic impurity.This technology uses the elevated temperature heat carrier to heat; And the energy must through 2 times heat passage, improved virtually for this extremely cheap product energy consumption of sulfuric acid, its equipment is more complicated also; This technology can only could be used when not too haggling over cost, and its cost is difficult to reach a standard in China.
Domestic scientist has invented another kind of method and has been called the non-volatile solution concentration method of vapor-liquid separation type (being called for short the WCG method).WCG ratio juris and technology are following: the dilute sulphuric acid that will give up is squeezed into the circulation upgrading tower by storage tank with acid and is concentrated; After the interchanger heating, getting into mist device and scatterer then forces atomizing and further forces vaporization; Gas after the separation gets into gas purifier after the height demist, purify the back discharging.Acid solution after the separation is got back to the circulation upgrading tower once again, after circulation repeatedly concentrates distillation, reaches concentration requirement, squeezes into vitriol oil storage tank with pump.The vitriol oil can be used as raw materials for production and utilizes.WCG method concentrating unit mainly is made up of interchanger, circulation upgrading tower and induced draft fan.The interchanger material is a graphite, and the upgrading tower material is a composite polypropylene, and pump and induced draft fan are acid-resistant system.This method is compared with the high temperature method of enrichment, vaporization temperature low (50～60 ℃), and steam consumption is few, expense low (expense that concentrates dilute sulphuric acid power consumption per ton and steam is about 30～60 yuan).Dying of Shanghai five factories produce the dilute sulphuric acid (the H2SO4 massfraction is 20%) that DISPERSE NAVY BLUE EXSF 300& BLUE 56 100 H-GL produces, and the dilute sulphuric acid that Hua Bachang, Wuhan Dyestuff Plant, the generation of dye house, Jining production dyestuff intermediate are dyed in Shanghai adopts the WCG method to concentrate, and has all obtained obvious effects.With the WCG method concentrate dilute sulphuric acid should note following some: (1) if there is solids to separate out, can influence separating of heat-transfer effect and spent acid in concentration process; (2) this installs non-airtightly, if volatile matter is arranged, can influence Working environment in the spent acid; (3) the device main body material is a composite polypropylene, and working temperature receives the restriction of material of main part, can not be above 80 ℃; (4) this method is only applicable to the H2SO4 massfraction less than 60% dilute sulphuric acid.
Fushun Petrochemical Company has been developed treatment technology of producing sulfuric acid from alkylated spent sulfuric acid through high temperature decomposition, has been applied to production practice for many years.Through repeatedly technological transformation; Made spent acid handle that to burn that sulphur etc. becomes be raw material with sulfur waste acid merely by joining; Produce high-concentration sulfuric acid, return alkyl plant and recycle, not only make resource obtain recycle; And solved environmental pollution problems, have remarkable economic efficiency, environmental benefit and social benefit.This arts demand burns about 1000 ℃ with sulfuric acid, and energy consumption is also than higher.
The relative merits of comprehensive the whole bag of tricks, a kind of equipment provided by the present invention is applicable to that content reclaims problem at the useless concentration of sulfuric acid 40% or more, and device structure is simple, control is simply.Also can well handle to solid particulate in the spent acid and volatile matter, little of hundreds of ton, all there is economic and practical device to use to up to ten thousand tons spent acid greatly.
Summary of the invention
This equipment is that the metal cylinder of an oval type adds accessory support and rotation Drive Structure; Added inner member in barrel and avoided back mixing and enhanced heat exchange, added at the two ends of equipment practical charging/discharging device be beneficial to be back to back liquid material with keep vacuum.
Rarer relatively sulfuric acid gets in the rotary type vaporizer through sealed structure from an end; Be introduced into first compartment, and whole rotary type vaporizer is divided into the dozens of compartment vertically by manual work, compartment can fully effectively separate the sulfuric acid that concentrates completion with the dilute sulphuric acid that just gets into avoids back-mixing; And sulfuric acid can flow to subordinate's compartment along with the rotational automatic of rotary type vaporizer; In flow process, heated gradually and heat up by the high-temperature flue gas in the cylindrical shell outside, and evaporate the high-temperature steam heat exchange that with tail end; Through after the evaporation of certain hour, wait the qualified back of moisture from terminal discharging.And with the heat exchange of low temperature sulfuric acid after saturation steam be drawn out of system from feed end, discharge wastewater reuse after the condensation.
Along with the raising of sulfuric acid concentration, if contain organism in the sulfur waste acid then dehydration carbonization that can be progressively, if contain inorganic salt then can progressively separate out, sulfuric acid has the ability of self-cleaning in spissated process, and under comparatively high temps, sulfuric acid can resolve into SO in this equipment
3And water vapor, and the SO that decomposites
3Can be absorbed by the dilute acid soln of front equipment end, thereby reduce the sulfuric acid loss.Organic carbonization residue and inorganic salt then can very simple centrifugal removing.Can in system, add a spot of vanadium catalyst when being necessary and oxygen is strengthened organic oxygenolysis, so that the impurity in the acid drops to is minimum.
This device under general condition only needs moisture in the sulfuric acid is deviate to get final product reuse, such as reaching 95% when acid concentration when above, but in particular cases also can the sulfuric acid direct evaporation be come out elevated temperature at some; Thereby obtain thorough purified sulfuric acid; Certain energy consumption at this moment can be higher a little, even like this, the sulfuric acid that reclaims 1 ton 50% also only needs about 50 yuan energy consumption; In most of the cases, the energy consumption of one ton of spent acid of processing only needs 20 yuan to 30 yuan.
Sulfuric acid dehydration is under high vacuum, to carry out in this equipment, therefore has lower vaporization temperature, and endures the sulfuric acid pot and compares and can reduce vaporization temperature significantly and improve equipment life.Evaporation equipment is under slew rope, to carry out, and hot face is a continuous renewal, has avoided enduring the unidirectional problem of being heated and damaging easily of sulfuric acid pot fully.The mode that equipment can adopt coal fuel directly to burn and heat; Hot blast flows along the opposite direction of feedstock direction; With the abundant heat exchange of low temperature sulfuric acid of continuous adding, equipment can be installed an amount of heat pipe or finned tube on cylindrical shell, strengthen the heat exchange between stack gas and the sulfuric acid liquid through heat pipe and finned tube; The air outlet temperature of stack gas can be reduced to below 300 degree, and energy utilization efficiency is very high.Device interior can be installed some orderly material delivering plate and fillers, can effectively make the superheated vapour of high density end and the cryogenic liquid of lower concentration end carry out effective heat exchange to improve efficiency of utilization.
According to the difference of concrete processing reclaim(ed) sulfuric acid, this device can adopt multiple material, such as stainless steel, high quality steel, high silicon cast iron, enamel equipment or the like.This device is easy to serialization production owing to simple in structure, and single cover processing power can reach tens thousand of tons, and invests little.
Description of drawings
Fig. 1 is the sectional view of this equipment.
As shown in Figure 1,1 insulation burner hearth, 2 chimneys, 3 concentrate cylindrical shell, 4 vacuum degassing mouths, 5 dilute sulphuric acid opening for feeds; 6 support rollers, 7 bull gears, 8 burner hearths support, and 9 burner hearths support, and 10 burner hearths support; 11 coal furnaces, 12 support rollers, 13 finished acid discharge ports, 14 receivers, 15 interior compartment dividing plates.
Claims (5)
1. a novel waste vitriolization equipment is a rotary type vaporizer, is used for that refining or direct evaporation becomes 95% above vitriolic equipment with the dehydration of the sulfur waste aqueous acid of 40%-90%.
2. the barrel according to the described rotary type vaporizer of claim one is designed with compartment; Utilize compartment to make separating that the acid solution of different concns can be orderly; The material of lower concentration and the direct back mixing of material of high density have been avoided, in artificial formation temperature of barrel and concentration gradient.
3. the barrel according to the described rotary type vaporizer of claim one has some orderly material delivering plate and fillers, can effectively make the superheated vapour of high density end and the cryogenic liquid of lower concentration end carry out effective heat exchange to improve efficiency of utilization.
4. contact intensive ground according to the cylindrical shell outside of the described rotary type vaporizer of claim one with flue gas in high temperature section strengthening and heat transferring device can be installed; These devices comprise heat pipe, finned tube; Can be effectively with the heat of system orderly pass to device interior, improve the overall thermal utilization ratio.
5. from feed end vacuum pipe is installed according to the described rotary type vaporizer of claim one and is vacuumized, system is under the negative pressure state, can reduce vaporization temperature significantly, be able to equipment life prolong thereby make.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103970415A CN102491285A (en) | 2011-12-05 | 2011-12-05 | Waste sulphuric acid concentrating and recycling equipment |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103970415A CN102491285A (en) | 2011-12-05 | 2011-12-05 | Waste sulphuric acid concentrating and recycling equipment |
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| CN102491285A true CN102491285A (en) | 2012-06-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2011103970415A Pending CN102491285A (en) | 2011-12-05 | 2011-12-05 | Waste sulphuric acid concentrating and recycling equipment |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107777665A (en) * | 2017-09-19 | 2018-03-09 | 荆门市格林美新材料有限公司 | A kind of acid pickle retracting device |
| CN110040693A (en) * | 2019-04-24 | 2019-07-23 | 成都先进金属材料产业技术研究院有限公司 | Utilize the method for calcium monohydrogen phosphate processing waste sulfuric acid solution |
| CN110040696A (en) * | 2019-04-29 | 2019-07-23 | 成都先进金属材料产业技术研究院有限公司 | Utilize the method for manganese chloride processing titanium dioxide waste acid by sulfuric acid process |
| CN111362234A (en) * | 2020-04-16 | 2020-07-03 | 浙江嘉福新材料科技有限公司 | NMST byproduct sulfuric acid concentration equipment and process thereof |
| CN111362234B (en) * | 2020-04-16 | 2024-06-07 | 浙江嘉福新材料科技有限公司 | NMST byproduct sulfuric acid concentration equipment and process thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000274948A (en) * | 1999-03-19 | 2000-10-06 | Kawasaki Heavy Ind Ltd | External heating rotary kiln |
| CN101450794A (en) * | 2007-12-03 | 2009-06-10 | 灵宝市金源矿业有限责任公司 | Recovery and utilization method of waste sulfuric acid in wet smelting acid making system |
| CN102219191A (en) * | 2011-04-20 | 2011-10-19 | 江苏亚邦染料股份有限公司 | Recycling method for waste sulfuric acid of dye intermediate product |
-
2011
- 2011-12-05 CN CN2011103970415A patent/CN102491285A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000274948A (en) * | 1999-03-19 | 2000-10-06 | Kawasaki Heavy Ind Ltd | External heating rotary kiln |
| CN101450794A (en) * | 2007-12-03 | 2009-06-10 | 灵宝市金源矿业有限责任公司 | Recovery and utilization method of waste sulfuric acid in wet smelting acid making system |
| CN102219191A (en) * | 2011-04-20 | 2011-10-19 | 江苏亚邦染料股份有限公司 | Recycling method for waste sulfuric acid of dye intermediate product |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107777665A (en) * | 2017-09-19 | 2018-03-09 | 荆门市格林美新材料有限公司 | A kind of acid pickle retracting device |
| CN110040693A (en) * | 2019-04-24 | 2019-07-23 | 成都先进金属材料产业技术研究院有限公司 | Utilize the method for calcium monohydrogen phosphate processing waste sulfuric acid solution |
| CN110040696A (en) * | 2019-04-29 | 2019-07-23 | 成都先进金属材料产业技术研究院有限公司 | Utilize the method for manganese chloride processing titanium dioxide waste acid by sulfuric acid process |
| CN111362234A (en) * | 2020-04-16 | 2020-07-03 | 浙江嘉福新材料科技有限公司 | NMST byproduct sulfuric acid concentration equipment and process thereof |
| CN111362234B (en) * | 2020-04-16 | 2024-06-07 | 浙江嘉福新材料科技有限公司 | NMST byproduct sulfuric acid concentration equipment and process thereof |
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Application publication date: 20120613 |