CN109160493B - SO 2 Device and process for preparing sulfur by smelting flue gas two-stage boiling reduction - Google Patents
SO 2 Device and process for preparing sulfur by smelting flue gas two-stage boiling reduction Download PDFInfo
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- CN109160493B CN109160493B CN201811320066.3A CN201811320066A CN109160493B CN 109160493 B CN109160493 B CN 109160493B CN 201811320066 A CN201811320066 A CN 201811320066A CN 109160493 B CN109160493 B CN 109160493B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0473—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide
- C01B17/0482—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide with carbon or solid carbonaceous materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0473—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide
- C01B17/0491—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide with hydrogen or hydrogen-containing mixtures, e.g. synthesis gas
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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
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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Abstract
The invention provides an SO 2 Device and method for preparing sulfur by smelting flue gas two-stage boiling reductionWherein the device comprises: a reduction furnace for converting SO 2 Preparing sulfur from smelting flue gas by adopting two-stage boiling reduction; the cyclone dust collector is connected with the reduction furnace through a pipeline and is used for removing dust from flue gas generated by the reduction furnace; the waste heat boiler is connected with the cyclone dust collector through a pipeline and is used for cooling the flue gas generated by the reduction furnace; the filter cartridge dust remover is connected with the waste heat boiler through a pipeline and is used for removing fine particles of flue gas generated by the reduction furnace; and the sulfur condenser is connected with the filter cartridge dust remover through a pipeline and is used for condensing flue gas generated by the reduction furnace to generate liquid sulfur. SO (SO) 2 The smelting flue gas sequentially passes through a reduction furnace, a cyclone dust collector, a waste heat boiler, a filter cartridge dust collector and a sulfur condenser to prepare sulfur. The SO 2 The device and the method for preparing sulfur by smelting flue gas two-stage boiling reduction do not generate coal tar in the reaction process to influence the product quality.
Description
Technical Field
The invention relates to the technical field of sulfur preparation, in particular to an SO 2 A device and a process for preparing sulfur by smelting flue gas two-stage boiling reduction.
Background
In the nonferrous smelting process, a great amount of SO is generated in the pyrometallurgy process of the metal sulfide mineral 2 The gas is generally recovered by adopting a method for preparing sulfuric acid from flue gas: after the smelting flue gas is purified and dried, SO in the flue gas 2 Reacts with oxygen in the fixed bed catalyst layer to generate SO 3 Then SO in a sulfuric acid absorption tower 3 Form sulfuric acid product with water. The technology has mature process, reliable equipment and high conversion rate, and becomes the process selection of most nonferrous smelting enterprises in China. However, the production of sulfuric acid from sulfur dioxide flue gas is not suitable for remote and local smelting plants without markets due to the limitations of production, storage, transportation and the like. Because sulfur is easier to store and transport than sulfuric acid and has a certain added value, the preparation of sulfur from high-concentration sulfur dioxide flue gas is a better choice in factories in some special areas.
The existing Claus process reduces part of sulfur dioxide into hydrogen sulfide through hydrogenation reduction, and the hydrogen sulfide enters a Claus furnace to react with the rest of sulfur dioxide to generate sulfur. However, the hydrogen source of the common smeltery is limited, and the hydrogen source does not have hydrogenation conditions. The adoption of the smelting common fuel as the reducing agent is more reasonable.
Chinese patent CN104045062 for preparing elemental sulfur by reducing methodMethods and systems for reducing SO with activated carbon at 600-850 DEG C 2 The technology adopts the active carbon with higher price as the reducing agent, the high cost limits the technical application of the technology, and if the conventional fuel coal with low price in smelting industry is used as the reducing agent, coal tar can be condensed together with elemental sulfur in the flue gas cooling process at the reaction temperature, thereby influencing the quality of sulfur products.
Chinese patent CN106467293 discloses a method for preparing sulfur and a system device for preparing sulfur, which uses carbonaceous reducing agent (coal, coke, active carbon, petroleum coke, natural gas and coal gas) to treat SO 2 Reduction of high concentration SO at high temperature 2 The main problem of the process is that (1) the difference between coal and other reducing agents is ignored, the other reducing agents belong to secondary energy sources which are purer, the coal belongs to primary energy sources, coal tar is inevitably generated at the reaction temperature described by the process when the coal is used as the reducing agent, and the coal tar and sulfur vapor are condensed together, so that the quality of sulfur products is seriously affected. The patent does not mention how to avoid the problem of coal tar generation when coal is used as a reducing agent; (2) due to conversion rate with SO in reduction reaction 2 The concentration is increased and decreased, and the concentration of SO is high 2 Under the condition, no effective measures are provided for ensuring the ideal sulfur recovery rate.
Disclosure of Invention
The present invention aims to solve the above problems in the prior art and provide an SO 2 The device and the method for preparing sulfur by smelting flue gas two-stage boiling reduction do not generate coal tar in the reaction process to influence the product quality.
The embodiment of the invention provides an SO 2 The device for preparing sulfur by smelting flue gas two-stage boiling reduction comprises:
a reduction furnace for converting SO 2 Preparing sulfur from smelting flue gas by adopting two-stage boiling reduction;
the cyclone dust collector is connected with the reduction furnace through a pipeline and is used for removing dust from flue gas generated by the reduction furnace;
the waste heat boiler is connected with the cyclone dust collector through a pipeline and is used for cooling the flue gas generated by the reduction furnace;
the filter cartridge dust remover is connected with the waste heat boiler through a pipeline and is used for removing fine particles of flue gas generated by the reduction furnace;
and the sulfur condenser is connected with the filter cartridge dust remover through a pipeline and is used for condensing flue gas generated by the reduction furnace to generate liquid sulfur.
Preferably, the reduction furnace includes:
the air chamber is arranged at the bottom of the reduction furnace, is provided with a steam inlet and a flue gas inlet, and is provided with a furnace bottom blower at the flue gas inlet;
the gas distribution device is arranged in the reduction furnace and is positioned above the air chamber;
the water-cooling jacket clamp or the cooling bypass pipe is arranged outside the reduction furnace and is positioned above the gas distribution device;
the primary reaction zone is arranged in the reduction furnace and positioned above the gas distribution device, and is provided with a secondary gas inlet, a return device, a slag discharge port and a coal feed port, wherein the return device is connected with the cyclone dust collector;
the secondary reaction zone is arranged in the reduction furnace and is positioned above the primary reaction zone;
the furnace top is arranged at the top of the reduction furnace and is provided with a reduction furnace flue gas outlet;
and the steam drum is connected with the steam inlet and the water-cooling jacket or the cooling side pipe and is used for generating steam.
Preferably, the apparatus further comprises:
the filtering device is connected with the sulfur condenser through a pipeline and is used for removing impurities in liquid sulfur;
and the cooling packaging machine is connected with the filtering device through a pipeline and is used for cooling and packaging the liquid sulfur into sulfur granule products.
Preferably, the apparatus further comprises:
the normal-temperature hydrolysis device is connected with the sulfur condenser through a pipeline and is used for hydrolyzing the flue gas passing through the sulfur condenser to generate H 2 S；
The ionic liquid absorption tower is connected with the normal-temperature hydrolysis device through a pipeline and is used for absorbing H in the flue gas from the hydrolysis device 2 S and SO 2 ；
The analysis tower is connected with the reduction furnace through a pipeline and is used for converting H in the ionic liquid 2 S and SO 2 Releasing and conveying the waste into a reduction furnace;
and the ionic liquid circulating pump and the ionic liquid analysis circulating pump are respectively connected with the ionic liquid absorption tower and the analysis tower and are used for circulating the ionic liquid.
Preferably, the cyclone dust collector includes:
a base;
the cyclone dust collector main body is arranged at the top end of the base, and the base and the cyclone dust collector main body are of an integrated structure; an air inlet pipeline is arranged on one side of the cyclone main body, two support columns are arranged at the top end of the cyclone main body, the two support columns and the cyclone main body are of an integrated structure, a connecting pipe is arranged at the top end of the cyclone main body and is positioned between the two support columns, and a secondary purifying device is arranged at the top ends of the support columns;
the sound insulation material layer is arranged in the cylinder wall of the cyclone dust collector main body;
the water pipe is arranged above the sound insulation material layer;
the spray head is connected with the water pipe;
the inside of second grade purifier is provided with hollow dish, hollow dish passes through connecting pipe fixed connection with the cyclone main part, be provided with four arced pipes on the hollow dish, and hollow dish and arced pipe structure as an organic whole, one side that hollow dish was kept away from to the arced pipe is provided with small-size cyclone air intake, and arced pipe and small-size cyclone air intake pass through bolt fixed connection, be provided with small-size cyclone main part on the small-size cyclone air intake, and small-size cyclone main part and small-size cyclone air intake structure as an organic whole, small-size cyclone air outlet has been seted up on the top of small-size cyclone main part, the bottom of small-size cyclone main part is provided with small-size cyclone ash bucket, and small-size cyclone main part and small-size cyclone ash bucket structure as an organic whole, one side of small-size cyclone main part is provided with the dead lever, and connecting pipe and small-size cyclone main part pass through dead lever fixed connection, the top of second grade device is provided with air outlet pipeline, and second grade purifier structure as an organic whole.
Preferably, the waste heat boiler comprises:
a housing; the shell is provided with an air inlet, an air outlet, a water inlet and a water outlet;
the air inlet chamber is arranged at one end inside the shell and is connected with the air inlet;
the air outlet chamber is arranged at the other end of the inside of the shell and is connected with the air outlet;
the water tank is arranged in the shell and positioned at the middle part and is connected with the water inlet and the water outlet;
the air inlet chamber and the air outlet chamber are connected through a plurality of spiral pipelines, and the spiral pipelines are uniformly distributed in the water tank.
The invention also provides an SO 2 The two-stage boiling reduction process of preparing sulfur with smelting fume includes the following steps:
SO 2 smelting flue gas is blown into the air chamber from the flue gas inlet through the furnace bottom blower, water vapor enters the air chamber from the steam inlet, coal enters the primary reaction zone in the reduction furnace from the coal feed inlet to carry out high-temperature boiling reaction, and part of SO in the flue gas 2 Reducing under the high temperature of coal particles and water vapor to generate sulfur vapor and other gas byproducts H 2 S、COS、CS 2 、CO、H 2 Coal slag is discharged from a slag discharge port; the water-cooling jacket or the cooling bypass pipe is used for generating low-pressure steam and then entering the air chamber from the steam inlet;
the flue gas generated in the primary reaction zone enters the secondary reaction zone through the expansion section, and the residual SO in the flue gas in the secondary reaction zone 2 With newly generated reducing gas H 2 S、CO、H 2 The secondary reduction reaction is carried out to convert intoSulfur steam, and then the flue gas is discharged from a flue gas outlet of the reduction furnace at the furnace top;
the flue gas of the reduction furnace is subjected to centrifugal dust collection through a cyclone dust collector, the temperature of a waste heat boiler is reduced to 600 ℃, and the flue gas is purified through a filter cartridge dust collector, and the coal particles trapped by the centrifugal dust collection are returned to a primary reaction zone of the reduction furnace through a material returning device;
condensing the purified flue gas to 120-140 ℃ in a sulfur condenser, condensing elemental sulfur to produce liquid sulfur, filtering the liquid sulfur to remove impurities, producing sulfur particle products by a cooling packaging machine, evaporating softened water in the sulfur condenser to produce low-pressure steam, and entering an air chamber through a steam inlet;
the condensed flue gas enters a normal temperature hydrolysis device to hydrolyze COS and CS in the flue gas 2 Reacting at 60-80 ℃ under the action of normal temperature hydrolysis catalyst to generate H 2 S, sending the flue gas to an ionic liquid absorption tower;
when the flue gas enters the ion liquid absorption tower, residual SO in the flue gas is removed 2 、H 2 S is absorbed by ionic liquid, the absorbed flue gas is discharged after reaching the standard, and the saturated ionic liquid is sent to an analytical tower to produce high-concentration SO 2 The mixed gas contains H 2 S returns to the secondary gas inlet of the primary reaction zone of the reduction furnace.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims thereof as well as the appended drawings.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 shows an SO in an embodiment of the invention 2 Schematic diagram of a device for preparing sulfur by two-stage boiling reduction of smelting flue gas;
FIG. 2 shows another SO in an embodiment of the invention 2 Schematic diagram of device for preparing sulfur by smelting flue gas two-stage boiling reduction
FIG. 3 shows an SO in an embodiment of the invention 2 A principle flow chart of a method for preparing sulfur by smelting flue gas two-stage boiling reduction;
FIG. 4 is a schematic view of a cyclone separator according to an embodiment of the present invention;
FIG. 5 is a schematic view of a waste heat boiler according to an embodiment of the present invention;
FIG. 6 is a schematic view of a condenser according to an embodiment of the present invention;
fig. 7 is a schematic diagram of a liquid outlet device according to an embodiment of the invention.
Detailed Description
The preferred embodiments of the present invention will be described below with reference to the accompanying drawings, it being understood that the preferred embodiments described herein are for illustration and explanation of the present invention only, and are not intended to limit the present invention.
The embodiment of the invention provides an SO 2 The device for preparing sulfur by smelting flue gas two-stage boiling reduction is shown in figure 1, and comprises:
a reduction furnace 1 for converting SO 2 Preparing sulfur from smelting flue gas by adopting two-stage boiling reduction;
the cyclone dust collector 5 is connected with the reduction furnace 1 through a pipeline and is used for removing dust from flue gas generated by the reduction furnace;
the waste heat boiler 6 is connected with the cyclone dust collector 5 through a pipeline and is used for cooling the flue gas generated by the reduction furnace;
the filter cartridge dust remover 7 is connected with the waste heat boiler 6 through a pipeline and is used for removing fine particles of flue gas generated by the reduction furnace;
and the sulfur condenser 8 is connected with the filter cartridge dust remover 7 through a pipeline and is used for condensing flue gas generated by the reduction furnace to generate liquid sulfur.
SO 2 The smelting flue gas sequentially passes through a reduction furnace 1, a cyclone dust collector 5, a waste heat boiler 6, a filter cartridge dust collector 7 and a sulfur condenser 8 to prepare sulfur.
To achieve in realNow SO 2 The smelting flue gas is subjected to two-stage boiling reduction to prepare sulfur, and preferably, as shown in fig. 2, the reduction furnace comprises:
the gas chamber 1-1 is arranged at the bottom of the inside of the reduction furnace 1 and is provided with a steam inlet 1-2 and a flue gas inlet 1-3, and a furnace bottom blower 2 is arranged at the flue gas inlet 1-3;
the gas distribution device 1-4 is arranged in the reduction furnace 1 and is positioned above the gas chamber 1-1;
a water-cooling jacket or a cooling bypass pipe 1-5 which is arranged outside the reduction furnace 1 and above the gas distribution device 1-4;
the primary reaction zone 1-6 is arranged in the reduction furnace 1 and positioned above the gas distribution device 1-4, and is provided with a secondary gas inlet 1-10, a material returning device 1-11, a slag discharging port 1-12 and a coal feeding port 1-14, wherein the material returning device 1-11 is connected with the cyclone dust collector 5; the granular coal is conveyed to the coal feeding port 1-14 through the coal feeder 3, and the reacted coal ash slag is discharged into the coal slag cooler 4 through the slag discharging port 1-12. The coal feeder 3 includes a conveyor belt.
The secondary reaction zone 1-8 is arranged in the reduction furnace 1 and positioned above the primary reaction zone 1-6;
the furnace top 1-9 is arranged at the top of the reduction furnace 1 and is provided with a reduction furnace flue gas outlet;
and the steam drum 1-13 is connected with the steam inlet 1-2 and the water-cooling jacket or the cooling side pipe 1-5 and is used for generating water steam.
Preferably, the furnace bottom is gradually enlarged from bottom to top in a conical shape, the primary reaction zone 1-6 and the secondary reaction zone 1-8 are cylindrical, and the middle is connected by an enlarging section 1-7.
To remove impurities from the sulfur product. Preferably, the apparatus further comprises:
the filtering device is connected with the sulfur condenser through a pipeline and is used for removing impurities in liquid sulfur;
and the cooling packaging machine is connected with the filtering device through a pipeline and is used for cooling and packaging the liquid sulfur into sulfur granule products.
In order to achieve the standard emission of the flue gas, preferably, as shown in fig. 2, the device further comprises:
the normal-temperature hydrolysis device 9 is connected with the sulfur condenser 8 through a pipeline and is used for hydrolyzing the flue gas passing through the sulfur condenser 8 to generate H 2 S；
An ion liquid absorption tower 10 connected with the normal temperature hydrolysis device 9 through a pipeline and used for absorbing H in the flue gas from the hydrolysis device 2 S and SO 2 ；
A resolving tower 11 connected with the reduction furnace 1 through a pipeline and used for resolving H in the ionic liquid 2 S and SO 2 Released and conveyed into the reduction furnace 1;
the ion liquid circulating pump 12, the ion liquid analysis circulating pump 13, the ion liquid absorption tower 10 and the analysis tower 11 are connected in series through pipelines and are used for ion liquid circulation.
Preferably, as shown in fig. 3, the cyclone dust collector includes:
a base 21;
a cyclone main body 24 disposed at a top end of the base 21, wherein the base 21 and the cyclone main body 24 are integrally formed; an air inlet pipeline 29 is arranged on one side of the cyclone main body 24, two support columns 25 are arranged at the top ends of the cyclone main body 24, the two support columns 25 and the cyclone main body 24 are of an integrated structure, a connecting pipe 28 is arranged at the top end of the cyclone main body 24, the connecting pipe 28 is positioned in the middle of the two support columns 25, and a secondary purifying device 26 is arranged at the top ends of the support columns 25;
a sound insulation material layer 22 disposed in a wall of the cyclone main body 24;
a water pipe 23 disposed above the sound insulation material layer 22;
a nozzle 30 connected to the water pipe 23;
the inside of second grade purifier is provided with hollow dish, hollow dish passes through connecting pipe fixed connection with the cyclone main part, be provided with four arced pipes on the hollow dish, and hollow dish and arced pipe structure as an organic whole, one side that hollow dish was kept away from to the arced pipe is provided with small-size cyclone air intake, and arced pipe and small-size cyclone air intake pass through bolt fixed connection, be provided with small-size cyclone main part on the small-size cyclone air intake, and small-size cyclone main part and small-size cyclone air intake formula structure as an organic whole, small-size cyclone air outlet has been seted up on the top of small-size cyclone main part, the bottom of small-size cyclone main part is provided with small-size cyclone ash bucket, and small-size cyclone main part and small-size cyclone ash bucket structure as an organic whole, one side of small-size cyclone main part is provided with the dead lever, and small-size cyclone main part passes through dead lever fixed connection, the top of second grade device is provided with air outlet pipeline, and second grade purifier and 27 formula structures as an organic whole.
In order to make the heat exchange between the flue gas and the water in the exhaust-heat boiler more sufficient, it is preferable that, as shown in fig. 4, the exhaust-heat boiler includes:
a housing 36; the shell 36 is provided with an air inlet 31, an air outlet 32, a water inlet 33 and a water outlet 34;
an intake chamber 37 provided at one end inside the housing 36 and connected to the intake port 31;
an air outlet chamber 38 provided at the other end inside the housing 36 and connected to the air outlet 32;
a water tank 39 disposed in the middle of the housing 36 and connected to the water inlet 33 and the water outlet 34;
the inlet chamber 37 and the outlet chamber 38 are connected by a plurality of spiral pipes 35, said spiral pipes 35 being uniformly distributed in the water tank 39.
The flue gas is fully contacted with water in the water tank through the spiral pipeline 35, so that the heat transfer efficiency is increased, and the flue gas waste heat is fully utilized.
The cartridge dust collector includes:
the cylinder body is a cylinder, and two ends of the cylinder body are respectively provided with an air inlet and an air outlet;
the filter screens are equal to the cylinder in size and are uniformly distributed in the cylinder;
a filter screen replacement window is arranged on the surface of the cylinder body corresponding to the filter screen.
The invention also provides an SO 2 The two-stage boiling reduction process of preparing sulfur with smelting fume includes the following steps: as shown in the figure 3 of the drawings,
SO 2 smelting flue gas is blown into the air chamber from the flue gas inlet through the furnace bottom blower, water vapor enters the air chamber from the steam inlet, coal enters the primary reaction zone in the reduction furnace from the coal feed inlet to carry out high-temperature boiling reaction, and part of SO in the flue gas 2 Reducing under the high temperature of coal particles and water vapor to generate sulfur vapor and other gas byproducts H 2 S、COS、CS 2 、CO、H 2 Coal slag is discharged from a slag discharge port; the water-cooling jacket or the cooling bypass pipe is used for generating low-pressure steam and then entering the air chamber from the steam inlet;
the flue gas generated in the primary reaction zone enters the secondary reaction zone through the expansion section, and the residual SO in the flue gas in the secondary reaction zone 2 With newly generated reducing gas H 2 S、CO、H 2 The secondary reduction reaction is carried out to convert the sulfur vapor, and then the flue gas is discharged from a flue gas outlet of the reduction furnace at the top of the furnace;
the flue gas of the reduction furnace is subjected to centrifugal dust collection through a cyclone dust collector, the temperature of a waste heat boiler is reduced to 600 ℃, and the flue gas is purified through a filter cartridge dust collector, and the coal particles trapped by the centrifugal dust collection are returned to a primary reaction zone of the reduction furnace through a material returning device;
condensing the purified flue gas to 120-140 ℃ in a sulfur condenser, condensing elemental sulfur to produce liquid sulfur, filtering the liquid sulfur to remove impurities, producing sulfur particle products by a cooling packaging machine, evaporating softened water in the sulfur condenser to produce low-pressure steam, and entering an air chamber through a steam inlet;
the condensed flue gas enters a normal temperature hydrolysis device to hydrolyze COS and CS in the flue gas 2 Reacting at 60-80 ℃ under the action of normal temperature hydrolysis catalyst to generate H 2 S, sending the flue gas to an ionic liquid absorption tower;
when the flue gas enters the ion liquid absorption tower, residual SO in the flue gas is removed 2 、H 2 S is absorbed by ionic liquid, the absorbed flue gas is discharged after reaching the standard, and the saturated ionic liquid is sent to an analytical tower to produce high-concentration SO 2 The mixed gas contains H 2 S returns to the reduction furnaceAnd a secondary gas inlet of the primary reaction zone.
Preferably, SO 2 Mixing smelting flue gas and steam to enter a primary reaction zone SO 2 The concentration is less than or equal to 30 percent, the granular coal is fed from a coal feeding hole, and the coal feeding quantity and SO 2 +O 2 The molar ratio is 1.2-2, the ratio of steam quantity to coal feeding quantity is 0.2-0.4, the steam pressure is more than or equal to 0.3MPa, the reaction temperature in the furnace is 950-1150 ℃, and coal tar and hot molten state coal ash are avoided;
preferably, the primary reaction zone is a gas-solid reaction zone, the main reducing agent is coal, and the granularity of the coal is below 5 mm; the secondary reaction zone is a gas-gas reaction zone, and the main reducing agent is CO and H generated by primary reaction 2 S、H 2 A reducing gas;
preferably, the flue gas of the reduction furnace returns larger particle coal trapped by inertial dust collection of the cyclone dust collector to the reduction furnace through the material returning device;
preferably, reducing furnace flue gas subjected to inertial dust collection enters a waste heat boiler to be cooled to 600 ℃;
preferably, the filter cartridge dust remover dust removing element is a ceramic filter cartridge;
preferably, residual COS and CS in the condensed flue gas 2 Reacting under the action of a hydrolysis catalyst at 60-80 ℃ to generate hydrogen sulfide, wherein the normal temperature hydrolysis catalyst mainly comprises gamma-Al 2O3;
preferably, the main components of the ionic liquid in the ionic liquid absorption tower are cationic methyl diethylamine alcohol (MDEA) and specific anions, and a small amount of activating agent and antioxidant are added at the same time, SO that the ionic liquid can cooperatively adsorb SO 2 And H is 2 S, adsorbing saturated ionic liquid, feeding the ionic liquid into an analysis tower, and analyzing high-concentration SO under steam heating 2 And H is 2 The mixed gas of S is used as a secondary raw material gas to return to a secondary gas inlet of a primary reaction zone of the reduction furnace;
the main reaction involved in the invention is as follows:
1. the reduction furnace has the following reactions:
1) The primary reaction zone mainly reacts
SO 2 +C→S+CO 2
H 2 O+C→H 2 +CO
2S+C→CS 2
S+CO→COS
COS+H 2 O→H 2 S+CO 2
2) The secondary reaction zone mainly reacts
SO 2 +2CO→S+2CO 2
SO 2 +H 2 →S+H 2 O
S+H 2 →H 2 S
2H 2 S+SO 2 →S+2H 2 O
2. COS hydrolysis reaction:
COS+H 2 O→H 2 S+CO 2 (catalysis)
CS 2 +2H 2 O→2H 2 S+CO 2 (catalysis)
3. Ionic liquid absorption-desorption:
desulfurization reaction: SO (SO) 2 +H 2 O+R→RH++HSO 3 -
H 2 S+R→RH++HS-
Analytical reaction (high temperature): RH++ HSO 3 -→SO 2 +H 2 O+R
RH++HS-→H 2 S+R
Compared with the existing sulfur-containing flue gas preparation technology, the method has the main advantages that:
the reducing agent adopts the common fuel coal of a smelting plant and a certain proportion of water vapor, a large amount of strong reducing gases such as hydrogen, hydrogen sulfide, carbon monoxide and the like are generated in the reaction process, and the gas reduction reaction is carried out in the secondary reaction zone, so that the sulfur recovery rate can be effectively improved;
unlike the preparation of water gas followed by reduction of SO 2 The process of the invention requires two reaction furnaces or reaction areas (complex structure) separated into two different atmospheres, and in the invention, one reduction furnace is divided into an upper reaction area and a lower reaction area by taking an expansion section as a limit, so that the structure is simple, and the failure rate is low;
the reaction temperature in the furnace is controlled to be 950-1150 ℃, so that on one hand, the problem that the production of coal tar below 800 ℃ affects the quality of liquid sulfur of products, and on the other hand, the problem that the melting of coal ash above 1200 ℃ is not beneficial to ash discharge is avoided;
the water-cooling jacket clamp and the sulfur condenser in the reducing furnace produce low-pressure steam which returns to the furnace bottom air inlet chamber, so that the waste heat is effectively utilized;
the normal temperature hydrolysis device, the ion liquid absorption tower and the analytic tower are used for selectively treating different sulfur-containing components in the flue gas and finally converting the flue gas into high-concentration SO 2 And H is 2 S mixed gas is used as secondary raw material gas to return to the reduction furnace for feeding, so that classification treatment of different sulfur-containing byproducts is realized, the comprehensive recovery effect is good, and the total recovery rate of sulfur is 96-99%.
In one embodiment, a sulfur condenser includes:
as shown in fig. 6, the device comprises a first header 61, a second header 62, a plurality of micro-channel condensation pipelines 63, a liquid outlet device 65 and a flat heat pipe 64, wherein the first header 61 and the second header 62 are arranged in parallel, the plurality of micro-channel condensation pipelines 63 are arranged in parallel, two ends of the plurality of micro-channel condensation pipelines 63 are respectively welded to the first header 61 and the second header 62, the plurality of micro-channel condensation pipelines 63, the first header 61 and the second header 62 are communicated, one end of the flat heat pipe 64 is arranged between two adjacent micro-channel condensation pipelines 63, and the contact area of the flat heat pipe 64 and the micro-channel condensation pipelines 63 is integrally bonded or welded;
the micro-channel condensation pipeline is in a serpentine bending arrangement, the micro-channel condensation pipeline comprises a plurality of sections of micro-channel condensation straight pipes which are arranged in parallel and a micro-channel condensation bent pipe which is connected with the adjacent micro-channel condensation straight pipes, one end of the flat heat pipe is arranged between the two adjacent sections of micro-channel condensation straight pipes, and the contact area of the flat heat pipe and the micro-channel condensation straight pipes is integrally bonded or welded;
at least two flat heat pipes are arranged between two adjacent micro-channel condensing straight pipes;
the flat heat pipe comprises a metal flat plate, at least one capillary structure and a heat transfer working medium, wherein the capillary structure is arranged in the metal flat plate, the capillary structure is a micro-groove or a capillary core, the length of the capillary structure is the same as that of the flat heat pipe, and the heat transfer working medium circularly flows in a cavity of the capillary structure to transfer heat;
the liquid outlet device is arranged at a micro-channel condensation bent pipe at a lower position, as shown in fig. 7, a liquid guide plate 72, a liquid passing channel 73 and a liquid sealing plate 74 are sequentially arranged in a liquid outlet channel of the liquid outlet device 71 from top to bottom, the front end of the liquid guide plate 72 is fixedly arranged on the inner wall of a first side of the liquid outlet device 71, and the tail end 75 of the liquid guide plate 72 extends to a second side opposite to the first side and is inclined downwards; the front end of the liquid sealing plate 74 is fixedly arranged on the inner wall of the second side of the liquid outlet device 71, and the tail end 77 of the liquid sealing plate 74 extends to the first side and inclines upwards; the liquid sealing plate 74 and the liquid guide plate 72 are arranged at intervals to form a liquid passing channel 73, the tail end 75 of the liquid guide plate 72 and the inner wall of the second side of the liquid outlet device 71 are arranged at intervals to form a first liquid passing port 76, and the first liquid passing port 76 is used as a water inlet of the liquid passing channel 73; the tail end 77 of the liquid sealing plate 74 and the inner wall of the first side of the liquid outlet device 71 are arranged at intervals to form a second liquid passing port 78, and the second liquid passing port 78 is used as a liquid outlet of the liquid passing channel 73; and, the end 77 of the liquid-sealing plate 74 is higher than the end 75 of the liquid-guiding plate 72.
The condensing pipeline is arranged in a snake shape, so that the contact area between the gas and the outside is increased, and the condensing effect is improved; the liquid outlet device is arranged, so that gas can be effectively prevented from overflowing when the condensate fills the liquid passing channel, and the outflow of liquid is not influenced.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (6)
1. SO (SO) device 2 The device for preparing sulfur by smelting flue gas two-stage boiling reduction is characterized by comprising:
a reduction furnace for converting SO 2 Preparing sulfur from smelting flue gas by adopting two-stage boiling reduction;
the cyclone dust collector is connected with the reduction furnace through a pipeline and is used for removing dust from flue gas generated by the reduction furnace;
the waste heat boiler is connected with the cyclone dust collector through a pipeline and is used for cooling the flue gas generated by the reduction furnace;
the filter cartridge dust remover is connected with the waste heat boiler through a pipeline and is used for removing fine particles of flue gas generated by the reduction furnace;
the sulfur condenser is connected with the filter cartridge dust remover through a pipeline and is used for condensing the flue gas generated by the reduction furnace to generate liquid sulfur;
the cyclone dust collector includes:
a base;
the cyclone dust collector main body is arranged at the top end of the base, and the base and the cyclone dust collector main body are of an integrated structure; an air inlet pipeline is arranged on one side of the cyclone main body, two support columns are arranged at the top end of the cyclone main body, the two support columns and the cyclone main body are of an integrated structure, a connecting pipe is arranged at the top end of the cyclone main body and is positioned between the two support columns, and a secondary purifying device is arranged at the top ends of the support columns;
the sound insulation material layer is arranged in the cylinder wall of the cyclone dust collector main body;
the water pipe is arranged above the sound insulation material layer;
the spray head is connected with the water pipe;
the inside of the secondary purification device is provided with a hollow disc, the hollow disc is fixedly connected with the cyclone main body through a connecting pipe, four arc-shaped pipes are arranged on the hollow disc, the hollow disc and the arc-shaped pipes are of an integrated structure, one side of the arc-shaped pipes, which is far away from the hollow disc, is provided with a small cyclone air inlet, the arc-shaped pipes are fixedly connected with the small cyclone air inlet through bolts, the small cyclone air inlet is provided with a small cyclone main body, the small cyclone main body and the small cyclone air inlet are of an integrated structure, the top end of the small cyclone main body is provided with a small cyclone air outlet, the bottom end of the small cyclone main body is provided with a small cyclone ash bucket, one side of the small cyclone main body is provided with a fixing rod, the connecting pipe is fixedly connected with the small cyclone main body through the fixing rod, the top end of the secondary purification device is provided with an air outlet pipeline, and the secondary purification device is of an integrated structure;
the reduction furnace includes:
the air chamber is arranged at the bottom of the reduction furnace, is provided with a steam inlet and a flue gas inlet, and is provided with a furnace bottom blower at the flue gas inlet;
the gas distribution device is arranged in the reduction furnace and is positioned above the air chamber;
the water-cooling jacket clamp or the cooling bypass pipe is arranged outside the reduction furnace and is positioned above the gas distribution device;
the primary reaction zone is arranged in the reduction furnace and positioned above the gas distribution device, and is provided with a secondary gas inlet, a return device, a slag discharge port and a coal feed port, wherein the return device is connected with the cyclone dust collector;
the secondary reaction zone is arranged in the reduction furnace and is positioned above the primary reaction zone;
the furnace top is arranged at the top of the reduction furnace and is provided with a reduction furnace flue gas outlet;
and the steam drum is connected with the steam inlet and the water-cooling jacket or the cooling side pipe and is used for generating steam.
2. The SO of claim 1 2 Device of smelting flue gas two-stage boiling reduction preparation sulphur, its characterized in that, the device still includes:
the filtering device is connected with the sulfur condenser through a pipeline and is used for removing impurities in liquid sulfur;
and the cooling packaging machine is connected with the filtering device through a pipeline and is used for cooling and packaging the liquid sulfur into sulfur granule products.
3. The SO of claim 1 2 A device for preparing sulfur by smelting flue gas two-stage boiling reduction,characterized in that the device further comprises:
the normal-temperature hydrolysis device is connected with the sulfur condenser through a pipeline and is used for hydrolyzing the flue gas passing through the sulfur condenser to generate H 2 S；
The ionic liquid absorption tower is connected with the normal-temperature hydrolysis device through a pipeline and is used for absorbing H in the flue gas from the hydrolysis device 2 S and SO 2 ；
The analysis tower is connected with the reduction furnace through a pipeline and is used for converting H in the ionic liquid 2 S and SO 2 Releasing and conveying the waste into a reduction furnace;
and the ionic liquid circulating pump and the ionic liquid analysis circulating pump are respectively connected with the ionic liquid absorption tower and the analysis tower and are used for circulating the ionic liquid.
4. The SO of claim 1 2 The device for preparing sulfur by smelting flue gas two-stage boiling reduction is characterized in that the waste heat boiler comprises:
a housing; the shell is provided with an air inlet, an air outlet, a water inlet and a water outlet;
the air inlet chamber is arranged at one end inside the shell and is connected with the air inlet;
the air outlet chamber is arranged at the other end of the inside of the shell and is connected with the air outlet;
the water tank is arranged in the shell and positioned at the middle part and is connected with the water inlet and the water outlet;
the air inlet chamber and the air outlet chamber are connected through a plurality of spiral pipelines, and the spiral pipelines are uniformly distributed in the water tank.
5. The SO of claim 1 2 The device for preparing sulfur by smelting flue gas two-stage boiling reduction is characterized in that the sulfur condenser comprises:
the device comprises a first header, a second header, a plurality of micro-channel condensation pipelines, a liquid outlet device and flat heat pipes, wherein the first header and the second header are arranged in parallel, the plurality of micro-channel condensation pipelines are arranged in parallel, two ends of the plurality of micro-channel condensation pipelines are respectively welded to the first header and the second header, the plurality of micro-channel condensation pipelines, the first header and the second header are communicated, one end of each flat heat pipe is arranged between two adjacent micro-channel condensation pipelines, and the contact areas of the flat heat pipes and the micro-channel condensation pipelines are integrally bonded or welded;
the micro-channel condensation pipeline is in a serpentine bending arrangement, the micro-channel condensation pipeline comprises a plurality of sections of micro-channel condensation straight pipes which are arranged in parallel and a micro-channel condensation bent pipe which is connected with the adjacent micro-channel condensation straight pipes, one end of the flat heat pipe is arranged between the two adjacent sections of micro-channel condensation straight pipes, and the contact area of the flat heat pipe and the micro-channel condensation straight pipes is integrally bonded or welded;
at least two flat heat pipes are arranged between two adjacent sections of the micro-channel condensation straight pipes;
the flat heat pipe comprises a metal flat plate, at least one capillary structure and a heat transfer working medium, wherein the capillary structure is arranged in the metal flat plate, the capillary structure is a micro-groove or a capillary core, the length of the capillary structure is the same as that of the flat heat pipe, and the heat transfer working medium circularly flows in a cavity of the capillary structure to transfer heat;
the liquid outlet device is arranged at a micro-channel condensation bent pipe positioned at the lower position, a liquid guide plate, a liquid passing channel and a liquid sealing plate are sequentially arranged in a liquid discharging channel of the liquid outlet device from top to bottom, the front end of the liquid guide plate is fixedly arranged on the inner wall of the first side of the liquid outlet device, and the tail end of the liquid guide plate extends to a second side opposite to the first side and inclines downwards; the front end of the liquid sealing plate is fixedly arranged on the inner wall of the second side of the liquid outlet device, and the tail end of the liquid sealing plate extends to the first side and inclines upwards; the liquid sealing plate and the liquid guide plate are arranged at intervals to form a liquid passing channel, the tail end of the liquid guide plate and the inner wall of the second side of the liquid outlet device are arranged at intervals to form a first liquid passing port, and the first liquid passing port is used as a water inlet of the liquid passing channel; the tail end of the liquid sealing plate and the inner wall of the first side of the liquid outlet device are arranged at intervals to form a second liquid passing port which is used as a liquid outlet of the liquid passing channel; and the tail end of the liquid sealing plate is higher than the tail end of the liquid guide plate.
6. SO (SO) device 2 The method for preparing sulfur by smelting flue gas two-stage boiling reduction is characterized by comprising the following steps of:
SO 2 smelting flue gas is blown into the air chamber from the flue gas inlet through the furnace bottom blower, water vapor enters the air chamber from the steam inlet, coal enters the primary reaction zone in the reduction furnace from the coal feed inlet to carry out high-temperature boiling reaction, and part of SO in the flue gas 2 Reducing under the high temperature of coal particles and water vapor to generate sulfur vapor and other gas byproducts H 2 S、COS、CS 2 、CO、H 2 Coal slag is discharged from a slag discharge port; the water-cooling jacket or the cooling bypass pipe is used for generating low-pressure steam and then entering the air chamber from the steam inlet;
the flue gas generated in the primary reaction zone enters the secondary reaction zone through the expansion section, and the residual SO in the flue gas in the secondary reaction zone 2 With newly generated reducing gas H 2 S、CO、H 2 The secondary reduction reaction is carried out to convert the sulfur vapor, and then the flue gas is discharged from a flue gas outlet of the reduction furnace at the top of the furnace;
the flue gas of the reduction furnace is subjected to centrifugal dust collection through a cyclone dust collector, the temperature of a waste heat boiler is reduced to 600 ℃, and the flue gas is purified through a filter cartridge dust collector, and the coal particles trapped by the centrifugal dust collection are returned to a primary reaction zone of the reduction furnace through a material returning device;
the purified flue gas enters a sulfur condenser to be condensed to 120-140 ℃, elemental sulfur is condensed to produce liquid sulfur, impurities are removed after the liquid sulfur is filtered, a sulfur particle product is produced by a cooling packaging machine, softened water is evaporated in the sulfur condenser to produce low-pressure steam, and the low-pressure steam enters the air chamber through a steam inlet;
the condensed flue gas enters a normal temperature hydrolysis device to hydrolyze COS and CS in the flue gas 2 Reacting at 60-80 ℃ under the action of normal-temperature hydrolysis catalyst to generate H 2 S, sending the flue gas to an ionic liquid absorption tower;
when the flue gas enters the ion liquid absorption tower, residual SO in the flue gas is removed 2 、H 2 S is absorbed by ionic liquid, the absorbed flue gas is discharged after reaching the standard, and the saturated ionic liquid is sent to an analytical tower to produce high-concentration SO 2 The mixed gas contains H 2 S returns to the secondary gas inlet of the primary reaction zone of the reduction furnace.
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| CN201811320066.3A CN109160493B (en) | 2018-11-07 | 2018-11-07 | SO 2 Device and process for preparing sulfur by smelting flue gas two-stage boiling reduction |
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| CN206172976U (en) * | 2016-09-19 | 2017-05-17 | 江苏德义通环保科技有限公司 | Prepare system's device of sulphur |
| CN106745145A (en) * | 2017-01-11 | 2017-05-31 | 江苏德义通环保科技有限公司 | A kind of method and system device that calcium oxide and sulphur are produced from gypsum |
| CN108128757A (en) * | 2018-02-01 | 2018-06-08 | 长沙有色冶金设计研究院有限公司 | A kind of technique of flue gas during smelting sulphur |
| CN108479311A (en) * | 2018-04-17 | 2018-09-04 | 安徽华铂再生资源科技有限公司 | A kind of method of cyclic absorption secondary lead smelting and ring collection sulfur dioxide in flue gas |
| CN209226582U (en) * | 2018-11-07 | 2019-08-09 | 北京矿冶科技集团有限公司 | SO2The boiling reduction of flue gas during smelting two-part prepares the device of sulphur |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN206172976U (en) * | 2016-09-19 | 2017-05-17 | 江苏德义通环保科技有限公司 | Prepare system's device of sulphur |
| CN106745145A (en) * | 2017-01-11 | 2017-05-31 | 江苏德义通环保科技有限公司 | A kind of method and system device that calcium oxide and sulphur are produced from gypsum |
| CN108128757A (en) * | 2018-02-01 | 2018-06-08 | 长沙有色冶金设计研究院有限公司 | A kind of technique of flue gas during smelting sulphur |
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