CN105152141A - Thermal technology for making acid from gypsum as well as device - Google Patents
Thermal technology for making acid from gypsum as well as device Download PDFInfo
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- CN105152141A CN105152141A CN201510480985.7A CN201510480985A CN105152141A CN 105152141 A CN105152141 A CN 105152141A CN 201510480985 A CN201510480985 A CN 201510480985A CN 105152141 A CN105152141 A CN 105152141A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
- Y02P40/121—Energy efficiency measures, e.g. improving or optimising the production methods
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Abstract
The invention discloses a thermal technology for making acid from gypsum. According to the thermal technology, a raw gypsum material which does not contain a reducing agent is dried and dehydrated by a dehydration furnace firstly, the raw material after drying and dehydration is preheated by a multi-level preheater, at least part of the preheated raw material is fed into a prereduction furnace, and the residual part is fed into a rotary kiln; the prereduction furnace reduces 20%-35% calcium sulfate into calcium sulfide, a hot raw material discharged from the prereduction furnace is fed into the rotary kiln, calcium sulfide and calcium sulfate react in the rotary kiln to generate sulfur dioxide and calcium oxide, sulfur dioxide enters an acid making procedure along with flue gas exhausted from the rotary kiln, calcium oxide and other components in the raw gypsum material are calcined into cement clinker in the rotary kiln and then discharged from the kiln, and the cement clinker is cooled and output. The invention further discloses a device for applying the thermal technology. Heat consumption of a gypsum acid-making system is reduced, the use amount of the reducing agent is reduced, the quality of clinker is improved, and the concentration of sulfur dioxide in the acid-making flue gas is increased, so that the investment and operation costs of a flue gas acid-making system are reduced.
Description
Technical field
The invention belongs to gypsum Sulphuric acid jointly producing cement technical field, particularly a kind of gypsum relieving haperacidity thermal technology and device.
Background technology
At present, China's phosphogypsum annual emissions more than 5,000 ten thousand tons (accumulative heap is high-volume more than 2.5 hundred million tons), desulfurated plaster annual emissions has reached 3,000 ten thousand tons, bunt gypsum annual emissions is more than 500 ten thousand tons, and the development along with phosphorus compound fertilizer, electric power, sea salt industry continues to increase by these industrial gypsums.Industrial gypsum is generally containing objectionable impurities, and long-term stacking not only takies a large amount of soil, and easily causes environmental pollution, and its comprehensive utilization is extremely urgent.Gypsum Sulphuric acid jointly producing cement technology not only can dispose the industrial residues such as phosphogypsum, desulfurated plaster, bunt gypsum in a large number, and the exploitation of sulphur ore deposit and limestone mine can be reduced, reducing Carbon emission, is a resource comprehensive utilization technology with popularizing application prospect.
Gypsum Sulphuric acid jointly producing cement technology is that fritz invents during the World War I, and has built the device of a daily output 40 tons of sulfuric acid in Germany at that time.And be that the development research of raw material Sulphuric acid and cement starts from the sixties in last century with phosphogypsum, Linz, AUT chemical company has built up in nineteen sixty-eight the factory that first hand utilizes phosphogypsum Sulphuric acid jointly producing cement, daily output 350 tons, sulfuric acid.In order to improve the thermo-efficiency of process, Lin Ci company takes to install counterflow heat exchanger additional at the pneumatic outlet of rotary kiln, and the hear rate of process is decreased.But gypsum legal system cement energy consumption index still produces cement far above limestone-based process.Within 1986, German Lu Qi company develops circulating fluidized bed energy saving type phosphorus gypsum thermal decomposition method Sulphuric acid jointly producing cement technology, and carried out pilot scale, by the mode of production that past phosphogypsum dehydration, decomposition and cement burning carry out in a long kiln, change over and carry out phosphogypsum dehydration Sum decomposition in circulating fluidized bed, in rotary furnace, carry out cement burning, but have no industrial applications always.
China as far back as last century the fifties just start the research of gypsum Sulphuric acid jointly producing cement technology.Last century the eighties, State Scientific and Technological Commission has organized the tackling key problem of " phosphogypsum Sulphuric acid jointly producing cement " to test, carry out after production test obtains success in Wudi, Shandong vitriol works, the engineering project of newly-built 7 cover annual outputs 40000 tons of sulfuric acid, 60,000 tons of cement in the whole nation, but operation situation is not good mostly, even stops production, changes products.Late nineteen nineties in last century, northern Shandong chemical industry was under the support of country, build up and produced 150000 tons of phosphorus ammoniums, by-product phosphogypsum system 200,000 tons of producing sulfuric acid and jointlies 300,000 tons of cement large-scale plants per year, become the combination preparing device that in world's gypsum Sulphuric acid history, technology is most advanced, largest.
But, even the gypsum Sulphuric acid jointly producing cement technology also following problem of ubiquity of existing advanced person: 1) gypsum with coke or coal for reductive agent, theoretical charcoal sulphur mol ratio is 0.5, but consider that a part of reductive agent can fall by combustion loss in firing system, therefore during actual batching, charcoal sulphur mol ratio will bring up to 0.65 ~ 0.8, and the excessive coke allocated into or coal cause cost to increase.2) in order to prevent reductive agent combustion loss cause Coating clogging in pre-heating system, strictly to control the temperature of material in pre-heating system lower than 650 DEG C, therefore the preheater progression of gypsum relieving haperacidity production line at most only level Four, often by three grades of operations, cause preheater flue gas temperature high, system hear rate is large.3) decomposition of gypsum and the sintering of grog coexist in rotary kiln and complete, and gypsum decomposes and needs reducing atmosphere, and clinkersintering needs oxidizing atmosphere, kiln atmosphere is difficult to coordinate, the weak oxide atmosphere of compromising can only be taked, be both unfavorable for improving gypsum rate of decomposition, and be also unfavorable for improving clinker quality.4) hear rate of gypsum dehydration Sum decomposition is large, causes combustion product gases amount large, and the exhaust gas volumn that produces of superfluous reductive agent burning and reductive agent and gypsum react the CO generated
2all enter in relieving haperacidity flue gas, make the SO in relieving haperacidity flue gas
2concentration is low, adds investment and the running cost of flue gas acid preparing system.
Summary of the invention
The present invention provides a kind of gypsum relieving haperacidity thermal technology and device for solving in known technology the technical problem that exists, and this technique and device are convenient to manipulation, can reduce reductive agent consumption, reduce hear rate, reduce costs, improve clinker quality.
The technical scheme that the present invention takes for the technical problem existed in solution known technology is: a kind of gypsum relieving haperacidity thermal technology, comprises the following steps: a) adopt dehydration furnace to carry out drying and dewatering to the gypsum raw material not containing reductive agent; B) raw material after drying and dewatering feed the abundant preheating of multistage preheater after gas solid separation; C) raw material after preheating have part feeding pre-reducing furnace at least, remainder feeding rotary kiln; In pre-reducing furnace, using carbon monoxide as reductive agent, the calcium sulfate accounting for calcium sulfate total amount 20 ~ 35% in gypsum raw material is reduced to sulfurated lime, the flue gas going out pre-reducing furnace enters dehydration furnace, and the hot raw material going out pre-reducing furnace feed rotary kiln after gas solid separation; D) in rotary kiln, sulfurated lime and calcium sulfate react, generate sulfurous gas and calcium oxide, described sulfurous gas enters towerman's sequence with the flue gas going out rotary kiln after multistage preheater cooling, described calcium oxide is sintered into cement clinker kiln discharge with other composition in gypsum raw material in rotary kiln, and exports after cooler cooling.
The carbon monoxide that pre-reducing furnace adopts is produced by coal dust incomplete combustion in stove, or is inputted by outside.
The external input sources of carbon monoxide is any one in water-gas, blast furnace gas, calcium carbide stove exhaust and yellow phosphoric tail gas.
The hot blast from cooler or ambient air is introduced respectively in the bottom of pre-reducing furnace and top.
Another technical scheme that the present invention takes for the technical problem existed in solution known technology is: a kind of device applying above-mentioned technique, comprise dehydration furnace, cyclonic separator II, cyclonic separator I, multistage preheater, pre-reducing furnace, rotary kiln and cooler, the bottom of described dehydration furnace is connected with the air outlet of described cyclonic separator I, the top of described dehydration furnace is connected with the blast inlet of described cyclonic separator II, the discharge port of described cyclonic separator II is connected with the blast pipe of described multistage preheater by material distributing valve II, the blast inlet of the most next stage cyclone cylinder of multistage preheater is connected with described rotary kiln air outlet, the discharge port of the most next stage cyclone cylinder of multistage preheater is connected with described pre-reducing furnace and described rotary kiln respectively by material distributing valve I, the air outlet of described multistage preheater is connected with acid making system, the bottom of described pre-reducing furnace is provided with reductive agent entrance and fuel inlet, the outlet of described pre-reducing furnace is connected with the blast inlet of described cyclonic separator I, and the discharge port of described cyclonic separator I is connected with described rotary kiln opening for feed, the discharge port of described rotary kiln is connected with cooler.
The top of described pre-reducing furnace is connected with cooler by heating duct I, and described heating duct I is provided with cold blast valve, and the bottom of described pre-reducing furnace is connected with cooler by heating duct II.
Described multistage preheater is 3 ~ 6 grades of cyclone preheaters.
The air outlet of described cyclonic separator II is connected with the raw material grinding mill beyond this thermal apparatus.
The advantage that the present invention has and positively effect are:
1) gypsum raw material are not containing reductive agent, therefore there will not be reductive agent combustion loss cause the problems such as Coating clogging in pre-heating system, without the need to limiting the temperature of material in pre-heating system, preheater progression can design from energy-saving and cost-reducing angle, take away heat to reduce flue gas, reduce the calorific loss of system.
2) reductive agent directly adds in pre-reducing furnace, eliminates the loss in preheater, therefore can reduce the consumption of reductive agent, reduces production cost.
3) the first step redox reaction (namely generating the reaction of sulfurated lime) of gypsum is carried out in pre-reducing furnace, clinkersintering carries out in rotary kiln, thus the atmosphere of pre-reducing furnace and rotary kiln can be controlled as required respectively, be conducive to the reaction efficiency of raising gypsum and improve clinker quality, being convenient to manipulation.
4) flue gas that gypsum dehydration and the first step redox reaction produce does not mix mutually with the relieving haperacidity flue gas going out rotary kiln, and relieving haperacidity sulfur dioxide in flue gas concentration can significantly improve, and is conducive to the investment and the running cost that reduce flue gas acid preparing system.
Accompanying drawing explanation
Fig. 1 is the apparatus structure schematic diagram of a kind of gypsum relieving haperacidity of application the present invention thermal technology.
In figure: 1 is dehydration furnace, 2 is cyclonic separators II, and 3 is one cyclonic cylinders, 4 is secondary rotary air ducts, and 5 is three grades of cyclone cylinders, and 6 is Category Four cyclone cylinders, 7 is five-stage whirlwind cylinders, 8 is pre-reducing furnaces, and 9 is cyclonic separators I, and 10 is rotary kilns, 11 is coolers, 12-1 is material distributing valve I, 12-2 is material distributing valve II, and 13 is cold blast valves.
Embodiment
For summary of the invention of the present invention, Characteristic can be understood further, hereby exemplify following examples, and coordinate accompanying drawing to be described in detail as follows:
Refer to Fig. 1, a kind of gypsum relieving haperacidity thermal technology, comprises the following steps:
A) dehydration furnace 1 is adopted to carry out drying and dewatering to the gypsum raw material not containing reductive agent;
B) raw material after drying and dewatering feed the abundant preheating of multistage preheater after gas solid separation;
C) raw material after preheating have part feeding pre-reducing furnace 8 at least, remainder feeding rotary kiln 10; In pre-reducing furnace 8, using carbon monoxide as reductive agent, the calcium sulfate accounting for calcium sulfate total amount 20 ~ 35% in gypsum raw material is reduced to sulfurated lime.Pre-reducing furnace 8 adopts carbon monoxide as reductive agent, and by adding fuel combustion, make in-furnace temperature maintain 700 ~ 1000 DEG C, under reducing atmosphere the calcium sulfate accounting for calcium sulfate total amount 20 ~ 35% in gypsum raw material is reduced to sulfurated lime, its reaction formula is:
CaSO
4+4CO→CaS+4CO
2
The flue gas going out pre-reducing furnace 8 enters dehydration furnace 1, and the hot raw material going out pre-reducing furnace 8 feed rotary kiln 10 after gas solid separation;
D) in rotary kiln 10, sulfurated lime and calcium sulfate react, and generate sulfurous gas and calcium oxide, its reaction formula is:
3CaSO
4+CaS→4CaO+4SO
2
Described sulfurous gas enters towerman's sequence with the flue gas going out rotary kiln 10 after multistage preheater cooling, and described calcium oxide is sintered into cement clinker kiln discharge with other composition in gypsum raw material in rotary kiln 10, and exports after cooler 11 cools.
The flue gas that above-mentioned technique makes the first step decomposition reaction of gypsum (namely generating the reaction of sulfurated lime) produce is all for the oven dry of gypsum raw material, dehydration and part preheating, the flue gas that gypsum dehydration is produced enters peripherals, and do not enter in kiln discharge relieving haperacidity flue gas, kiln discharge relieving haperacidity flue gas enters towerman's sequence after multistage preheater cooling, do not go out kiln gas in kiln discharge relieving haperacidity flue gas to be mixed into, make the SO in kiln discharge relieving haperacidity flue gas
2concentration significantly increases, and can reduce investment and the running cost of flue gas acid preparing system.
In the present embodiment, the carbon monoxide that above-mentioned pre-reducing furnace 8 adopts is produced by coal dust incomplete combustion in stove or is inputted by outside.The external input sources of carbon monoxide is any one in water-gas, blast furnace gas, calcium carbide stove exhaust and yellow phosphoric tail gas.Introduce the hot blast from cooler 11 or ambient air on the top of pre-reducing furnace 8, CO burning remaining in pre-reducing furnace 8 can be become carbonic acid gas, the combustion heat release of carbon monoxide can be made full use of, the discharge of carbon monoxide can be avoided again to exceed standard; The hot blast from cooler 11 or ambient air is introduced, as combustion air in the bottom of pre-reducing furnace 8.
Apply the device of above-mentioned technique, comprise dehydration furnace 1, cyclonic separator II 2, cyclonic separator I 9, multistage preheater, pre-reducing furnace 8, rotary kiln 10 and cooler 11, the bottom of described dehydration furnace 1 is connected with the air outlet of described cyclonic separator I 9, and the top of described dehydration furnace is connected with the blast inlet of described cyclonic separator II 2; The discharge port of described cyclonic separator II 2 is connected with the blast pipe of described multistage preheater by material distributing valve II 12-2; The blast inlet of the most next stage cyclone cylinder of multistage preheater is connected with the air outlet of described rotary kiln 10, and the discharge port of the most next stage cyclone cylinder of multistage preheater is connected with described pre-reducing furnace 8 and rotary kiln 10 respectively by material distributing valve I 12-1; The air outlet of described multistage preheater is connected with acid making system; The bottom of described pre-reducing furnace 8 is provided with reductive agent entrance and fuel inlet; The outlet of described pre-reducing furnace 8 is connected with the blast inlet of described cyclonic separator I 9, and the discharge port of described cyclonic separator I 9 is connected with the opening for feed of described rotary kiln 10; The discharge port of described rotary kiln 10 is connected with cooler 11.
The flue gas that above-mentioned thermal apparatus can use pre-reducing furnace 8 all enters dehydration furnace 1, the flue gas of using dehydration furnace 1 enters peripherals, make kiln discharge relieving haperacidity flue gas enter towerman's sequence after multistage preheater cooling, do not go out kiln gas in kiln discharge relieving haperacidity flue gas and be mixed into, make the SO in kiln discharge relieving haperacidity flue gas
2concentration increases, and can reduce investment and the running cost of flue gas acid preparing system.
In the present embodiment, the air outlet of described cyclonic separator II 2 is connected with the raw material grinding mill beyond this thermal apparatus, waste gas is used for the oven dry of raw material.The top of described pre-reducing furnace 8 is connected with cooler 11 by heating duct I, and described heating duct I is provided with cold blast valve 13.Introduce the hot blast from cooler 11 on the top of pre-reducing furnace 8, make remaining CO burning in stove transfer carbonic acid gas to, both made full use of the combustion heat release of carbon monoxide, the discharge of carbon monoxide can be avoided again to exceed standard; The bottom of described pre-reducing furnace 8 is connected with cooler 11 by heating duct II, introduces in pre-reducing furnace 8 hot blast of cooler 11 as combustion-supporting warm air.
The progression of described multistage preheater can design from energy-saving and cost-reducing angle, takes away heat, reduce the calorific loss of system, with 3 ~ 6 grades of cyclone preheaters for preferred version to reduce flue gas.In the present embodiment, the progression of described multistage preheater is 5, there are 5 cyclone cylinders, be one cyclonic cylinder 3, secondary rotary air duct 4, three grades of cyclone cylinders 5, Category Four cyclone cylinder 6 and five-stage whirlwind cylinders 7 respectively, the discharge port of cyclonic separator 2 is connected with the blast pipe of one cyclonic cylinder 3, secondary rotary air duct 4 and three grades of cyclone cylinders 5 respectively by two material distributing valve 12-2.According to the difference of system operation situation, the point of the blanking feeding preheater of cyclonic separator 2 can be switched, thus changes the actual heat exchange progression between material, gas, control out the relieving haperacidity flue-gas temperature of one cyclonic cylinder 3.When guaranteeing flue-gas temperature higher than dew-point temperature, reduce the temperature of relieving haperacidity flue gas, to reduce the heat that flue gas is taken away as far as possible.
The most discharge port of next stage cyclone cylinder of described multistage preheater is connected by material distributing valve I 12-1 with the opening for feed of described pre-reducing furnace 8 with the opening for feed of described rotary kiln 10.When pre-reducing furnace 8 overhauls, material directly can be fed in rotary kiln 10, avoid stopping kiln.In addition, by being dispensed into stove and the amount entering kiln raw material, CaS and CaSO in kiln can also be made
4mol ratio at about 1:3.
In the present embodiment, described dehydration furnace 1 adopts riser stove, and in riser stove, hot blast and raw material carry out heat exchange with suspended state.Can several reducing be set in tube furnace, to form effect of spurting, the heat exchange between strengthening gas, material.
The present invention is conducive to reducing gypsum acid making system hear rate, reduces reductive agent consumption, improves clinker quality, improves relieving haperacidity sulfur dioxide in flue gas concentration thus the investment of reduction flue gas acid preparing system and running cost.
The present embodiment is only preferred embodiment of the present invention, and is not used to limit the present invention.Gypsum dehydration stove 1 involved in the present invention can, for the duct type dehydration furnace adopted in the present embodiment, can be also fluidization formula dehydration furnace, or other can realize the type of furnace of identical function.Cooler 11 involved in the present invention both can be grate cooler, also can be single cylinder cooling machine etc. other there is the cooler of high-temperature material refrigerating function.All according to technical spirit of the present invention to any simple modification made for any of the above embodiments, all still belong in the scope of technical solution of the present invention.
Claims (8)
1. a gypsum relieving haperacidity thermal technology, is characterized in that, comprises the following steps:
A) dehydration furnace is adopted to carry out drying and dewatering to the gypsum raw material not containing reductive agent;
B) raw material after drying and dewatering feed the abundant preheating of multistage preheater after gas solid separation;
C) raw material after preheating have part feeding pre-reducing furnace at least, remainder feeding rotary kiln; In pre-reducing furnace, using carbon monoxide as reductive agent, the calcium sulfate accounting for calcium sulfate total amount 20 ~ 35% in gypsum raw material is reduced to sulfurated lime, the flue gas going out pre-reducing furnace enters dehydration furnace, and the hot raw material going out pre-reducing furnace feed rotary kiln after gas solid separation;
D) in rotary kiln, sulfurated lime and calcium sulfate react, generate sulfurous gas and calcium oxide, described sulfurous gas enters towerman's sequence with the flue gas going out rotary kiln after multistage preheater cooling, described calcium oxide is sintered into cement clinker kiln discharge with other composition in gypsum raw material in rotary kiln, and exports after cooler cooling.
2. gypsum relieving haperacidity thermal technology according to claim 1, is characterized in that, the carbon monoxide that pre-reducing furnace adopts is produced by coal dust incomplete combustion in stove, or is inputted by outside.
3. gypsum relieving haperacidity thermal technology according to claim 2, is characterized in that, the external input sources of carbon monoxide is any one in water-gas, blast furnace gas, calcium carbide stove exhaust and yellow phosphoric tail gas.
4. gypsum relieving haperacidity thermal technology according to claim 1, is characterized in that, introduces the hot blast from cooler or ambient air in the bottom of pre-reducing furnace and top respectively.
5. apply the device of technique as claimed in claim 1 for one kind, it is characterized in that, comprise dehydration furnace, cyclonic separator II, cyclonic separator I, multistage preheater, pre-reducing furnace, rotary kiln and cooler, the bottom of described dehydration furnace is connected with the air outlet of described cyclonic separator I, the top of described dehydration furnace is connected with the blast inlet of described cyclonic separator II, the discharge port of described cyclonic separator II is connected with the blast pipe of described multistage preheater by material distributing valve II, the blast inlet of the most next stage cyclone cylinder of multistage preheater is connected with described rotary kiln air outlet, the discharge port of the most next stage cyclone cylinder of multistage preheater is connected with described pre-reducing furnace and described rotary kiln respectively by material distributing valve I, the air outlet of described multistage preheater is connected with acid making system, the bottom of described pre-reducing furnace is provided with reductive agent entrance and fuel inlet, the outlet of described pre-reducing furnace is connected with the blast inlet of described cyclonic separator I, and the discharge port of described cyclonic separator I is connected with described rotary kiln opening for feed, the discharge port of described rotary kiln is connected with cooler.
6. gypsum relieving haperacidity thermal apparatus according to claim 5, it is characterized in that, the top of described pre-reducing furnace is connected with cooler by heating duct I, and described heating duct I is provided with cold blast valve, and the bottom of described pre-reducing furnace is connected with cooler by heating duct II.
7. gypsum relieving haperacidity thermal apparatus according to claim 6, it is characterized in that, described multistage preheater is 3 ~ 6 grades of cyclone preheaters.
8. gypsum relieving haperacidity thermal apparatus according to claim 6, it is characterized in that, the air outlet of described cyclonic separator II is connected with the raw material grinding mill beyond this thermal apparatus.
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| CN112142350A (en) * | 2020-09-15 | 2020-12-29 | 长沙中硅环保科技有限公司 | Phosphogypsum desulfurization and calcination treatment system and treatment method |
| CN115259102A (en) * | 2022-07-28 | 2022-11-01 | 成都铭炬环保工程技术有限公司 | Process and equipment for preparing concentrated sulfur dioxide flue gas and silicate clinker by flue gas splitting |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110885064A (en) * | 2018-09-10 | 2020-03-17 | 云南创森环保科技有限公司 | System and method for producing cement clinker and sulfuric acid by using calcium sulfate |
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| CN115259102A (en) * | 2022-07-28 | 2022-11-01 | 成都铭炬环保工程技术有限公司 | Process and equipment for preparing concentrated sulfur dioxide flue gas and silicate clinker by flue gas splitting |
| CN115259102B (en) * | 2022-07-28 | 2023-11-28 | 成都铭炬环保工程技术有限公司 | Process and equipment for preparing sulfur dioxide concentrated flue gas and silicate clinker by flue gas diversion |
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