CN101327939A - Method for solid caustic soda production by ionic membrane method - Google Patents

Method for solid caustic soda production by ionic membrane method Download PDF

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Publication number
CN101327939A
CN101327939A CNA2007100577108A CN200710057710A CN101327939A CN 101327939 A CN101327939 A CN 101327939A CN A2007100577108 A CNA2007100577108 A CN A2007100577108A CN 200710057710 A CN200710057710 A CN 200710057710A CN 101327939 A CN101327939 A CN 101327939A
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China
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caustic soda
gas
thickener
interchanger
ionic membrane
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CNA2007100577108A
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Chinese (zh)
Inventor
许增现
陈平生
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Tianjin Zhizhen Chemical Technology & Development Co Ltd
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Tianjin Zhizhen Chemical Technology & Development Co Ltd
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Priority to CNA2007100577108A priority Critical patent/CN101327939A/en
Publication of CN101327939A publication Critical patent/CN101327939A/en
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Abstract

The invention relates to a method of solid caustic soda production by ion-exchange membrane process belonging to the technology of flue gas heating and falling film countercurrent distillation, which comprises: transporting the hydrous caustic soda material into a final concentrator which is heated by the flue gas generated by a combustion furnace after the preorder countercurrent distillation, transporting the condensed hydrous product into a gas-liquid separator and separating the product into steam and anhydrous product caustic soda, wherein the distilled steam is employed to heat a double-effect heat exchanger, the transported anhydrous product caustic soda is treated again by a packed system or a postorder processing operation. The method of the invention has advantages of continuous production, low investment, small land occupation, simple operation and technology with a thermal efficiency more than 87%. The equipment of the invention adopts soda-corrosion resistant domestic materials. The technology of the invention can use all the fuel in China at present as well as satisfying the requirement of environment protection. All the production processes adopts automatical control.

Description

A kind of method that is applicable to the ionic membrane method solid caustic soda production
Affiliated technical field
The present invention relates to a kind of method that is applicable to the ionic membrane method solid caustic soda production, is a kind of caustic soda (sodium hydroxide) aqueous solution that is used for low concentration, and earlier by preorder falling liquid film countercurrent evaporation, then reconcentration is handled the method for solid caustic soda production.
Background technology
At present, domestic chlor-alkali plant solid caustic soda production technology, promptly the concentration technology of caustic soda soln mainly contains two kinds, and a kind of is the cooking stove method.This production method production technique is simple, and the initial stage drops into little, simple to operate.But labour intensity is big, and potential safety hazard is many, unstable product quality, and energy consumption height.Another kind is a molten-salt growth method, is imported technology.Adopting fused inorganic salt and water vapour is heating source, is that major equipment is produced with the exotic materials.This production line automation degree height, but continuous production, constant product quality, still, the initial stage has high input, the production cost height, the quality requirements height to heating source needs 8kg/cm 2The water vapour of pressure and Sweet natural gas heating.
Summary of the invention
Purpose of the present invention just provides a kind of method and specific equipment that is applicable to the ionic membrane method solid caustic soda production, and to solve the energy consumption height that existing cooking stove method exists, stove thermal efficiency is low, operation easier and randomness are all very big, quality is very unstable, and is periodical operation, produces unstable; And the import equipment investment is big, to the quality requirements height of heating energy source, the problem that working cost is very high.
Technical scheme of the present invention is:
A kind of method that is applicable to the ionic membrane method solid caustic soda production, the caustic soda raw material that will contain moisture through the preorder countercurrent evaporation after, import in the final thickener; The stack gas heating that this final thickener is produced by roasting kiln, the aqueous product input vapour liquid separator after concentrating separates; Isolate water vapor and water-free product caustic soda through vapour liquid separator, the water vapor of evaporation is used for II is imitated the interchanger heating; The water-free product caustic soda of output is again through packaging system or postorder manufacturing procedure.
A kind of equipment that is applicable to the ionic membrane method solid caustic soda production, it is the equipment of elder generation through falling liquid film countercurrent evaporation, reconcentration processing then, whole device is made of double-countercurrent evaporation system, final thickener, stack gas and steam generating system and postorder system of processing; Final thickener adopts the stack gas heating; The stack gas generation systems is made up of roasting kiln, recirculation blower, coal-gas producer, gas blower, the air of gas blower links to each other with the inlet mouth of roasting kiln on the one hand, link to each other with the inlet mouth of recirculation blower on the other hand, the air outlet of roasting kiln is connected with the inlet mouth of final thickener; Steam in this equipment flowsheet all adopts self-produced steam.I is provided with steam generating system in the middle of imitating interchanger and final thickener, be connected with vapour generator through a part of stack gas after the final thickener heat release, vapour generator is communicated with chimney on the one hand, be communicated with gas bag on the other hand, the hot water outlet of gas bag is connected with the water-in of vapour generator more again, makes the hot water circulation utilization; The hot water storage tank is connected with gas bag by pump, and the pneumatic outlet of gas bag is connected with the inlet mouth that I is imitated interchanger; The centre that II is imitated interchanger and surface condenser is provided with the hot water storage tank, and the cooling water outlet that II is imitated interchanger, surface condenser, jacketed pipe heat exchanger links to each other with hot water storage tank's water-in respectively; Jacketed pipe heat exchanger and I are provided with the water of condensation storage tank in the middle of imitating interchanger.
As improvement of the present invention, the double-countercurrent evaporation in the device can be replaced by the three-effect counter flow vapo(u)rization system, promptly is provided with squirt pump in the middle of vapour liquid separator and gas bag, and the pneumatic outlet of this squirt pump links to each other with the gas feed that I is imitated interchanger.
As another improvement of the present invention, the internal structure of final thickener can have two kinds, one adds the good medium of thermal conductivity in the middle of the good heating muff of the corrosive of anti-caustic soda film-type evaporation pipe and thermal conductivity, fin is installed on heating muff, the fin spiral distributes, be welded on the outer wall of heating muff, realize the transmission of heat by convection of stack gas generating tube; It two adds the good medium of thermal conductivity in the middle of the good heating muff of the corrosive of anti-caustic soda film-type evaporation pipe and thermal conductivity, fin is installed on heating muff, fin spiral welding is connected on the outer wall of heating muff, and the outside of heating muff is to produce photothermal radiator tube, passes through radiative transfer.
When the present invention was further improved again, the structure of the process furnace of final thickener also can have two kinds, and a kind of is to be provided with the flow-disturbing parts in stove inside, added to produce radiating material (as silicon carbide) simultaneously in the stove inwall; Another kind is a not scrambling stream unit, and the same employing of stove inwall can produce the radiating material.
Advantage of the present invention is: the production method that is a kind of novel solid caustic soda invented at the existing national conditions of China.But its tangible characteristics are continuous production, and quality also can reach world's best level, and it is little to have cooking stove method investment simultaneously, take up an area of few, operation and advantage of simple technology, hot effect can reach more than 87%.Equipment adopts the corrosive of anti-caustic soda home made materials, by scientific and reasonable design, makes it possess the arts demand of satisfying.All fuel (coal gas, Sweet natural gas, fuel oil etc.) that this technology can use present China to have are produced, and can satisfy environmental requirement again simultaneously.All production processes all adopt automatic control.This technology self-produced steam can be with more than the 32% solution countercurrent evaporation to 99%, and energy consumption is saved more than 50% at least than common cooking stove, and wherein the energy consumption of three effect systems can be saved more than 60%, and more saves coal.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is the overall structure synoptic diagram of an embodiment of present device;
Fig. 2 is the overall structure synoptic diagram of second embodiment of present device;
Fig. 3 is the overall structure synoptic diagram of the 3rd embodiment of present device;
Fig. 4 is the overall structure synoptic diagram of the 4th embodiment of present device;
Fig. 5 is the cut-away view of thickener in the present device example;
Fig. 6 is the another kind of cut-away view of thickener in the present device example;
Fig. 7 is the structure iron of the process furnace of thickener in the present device example;
Fig. 8 is the another kind of structure iron of the process furnace of thickener in the present device example;
Fig. 9 is a kind of overall construction drawing of thickener among the present device embodiment.
The method that is applicable to the ionic membrane method solid caustic soda production of the present invention (with reference to figure 1~Fig. 8): the caustic soda raw material that will contain moisture through the preorder countercurrent evaporation after, import in the final thickener 6; The stack gas heating that this final thickener 6 is produced by roasting kiln 91, the aqueous product input vapour liquid separator 7 after concentrating separates; Isolate water vapor and water-free product caustic soda through vapour liquid separator 7, the water vapor of evaporation is used for II is imitated interchanger 31 heating; The water-free product caustic soda of output is again through packaging system or postorder manufacturing procedure.
Referring to Fig. 1, one of specific equipment embodiment of the present invention, it is earlier through falling liquid film countercurrent evaporation, the equipment then managed behind the reconcentration, whole device is made of double-countercurrent evaporation system, final thickener, stack gas generation systems and postorder system of processing, and the steam in the flow process all adopts self-produced steam.Imitate interchanger 31, II single-effect evaporator 32, I effect interchanger 41 and I single-effect evaporator 42 by II and constitute the double-countercurrent evaporation system, the discharge port that II is imitated interchanger 31 links to each other with the opening for feed of II single-effect evaporator 32, the vapour outlet of II single-effect evaporator 32 links to each other with the inlet mouth of surface condenser 33, the discharge port of II single-effect evaporator 32 links to each other with jacketed pipe heat exchanger 36 by pump 22, jacketed pipe heat exchanger links to each other with the opening for feed that I is imitated interchanger 41, and the discharge port that I is imitated interchanger 41 is connected with the opening for feed of I single-effect evaporator 42; The discharge port of I single-effect evaporator 42 is connected with the opening for feed of final thickener 6, and inhibiter surge tank 53 links to each other with final thickener 6, and to reduce the corrosion of final thickener 6, the discharge port of final thickener 6 links to each other with the opening for feed of vapour liquid separator 7; The stack gas generation systems is made up of roasting kiln 91, recirculation blower 92, coal-gas producer 93, gas blower 94, the air of gas blower 94 links to each other with the inlet mouth of roasting kiln 91 on the one hand, inlet mouth with recirculation blower 92 links to each other on the other hand, and the air outlet of roasting kiln 91 is connected with the inlet mouth of final thickener 6; The postorder system of processing is made of flake alkali processing machine 10, solid caustic soda packing 11, grain washing tower (for removing CO2) 12, and the liquid exit of vapour liquid separator 7 links to each other with above-mentioned three devices respectively.
I is provided with steam generating system in the middle of imitating interchanger 41 and final thickener 6; Be connected with vapour generator 81 through a part of stack gas after final thickener 6 heat releases, vapour generator 81 is communicated with chimney 83 on the one hand, be communicated with gas bag 82 on the other hand, the hot water outlet of gas bag 82 is connected with the water-in of vapour generator 81 more again, makes the hot water circulation utilization; Hot water storage tank 34 is connected with gas bag 82 by pump 5, and the pneumatic outlet of gas bag 82 is connected with the inlet mouth that I is imitated interchanger 41.The pneumatic outlet of final thickener 6 is connected with the inlet mouth of recirculation blower 91, makes through the portion of air after final thickener 6 heat releases and reenters roasting kiln 91 comprehensive utilizations.
The centre of imitating interchanger 31 and surface condenser 33 at II is provided with hot water storage tank 34, and the cold water that II effect interchanger 31, surface condenser 33, jacketed pipe heat exchanger 35 produce respectively re-enters hot water storage tank 34.
Imitate interchanger 41 middle being provided with in the water of condensation storage tank 36 at jacketed pipe heat exchanger 35 and I.
Shown in Figure 2 is the overall structure of second embodiment of present device, and what this embodiment was different with previous embodiment is to adopt the three-effect counter flow evaporation technique, i.e. newly-increased squirt pump 71 in the middle of vapour liquid separator 7 and gas bag 82.The pneumatic outlet of gas bag 82 links to each other with the high-pressure inlet of squirt pump 71, the vapour outlet of vapour liquid separator 7 links to each other with the low-pressure gas import of squirt pump 71, the inlet mouth that the medium pressure gas outlet and the I of this squirt pump 71 are imitated interchanger 41 is communicated with, be used for imitating interchanger 41 heating, thereby realize the triple effect operation to I.
Shown in Figure 3 is the overall structure of the 3rd embodiment of present device, and this embodiment is different with the mode that the stack gas of first embodiment takes place.This embodiment adopts the heat-accumulation combustion mode.This type of heating belongs to routine techniques, and the efficient of cooking stove can reach more than 80%.The air outlet of coal-gas producer 133 and gas blower 134 links to each other with the inlet mouth of recuperative heater 131, the inlet mouth of recuperative heater 131 links to each other with the air outlet of final thickener 6, air outlet through final thickener 6 is connected with the inlet mouth of recuperative heater (81) again, and the waste gas that recuperative heater 131 produces is through pump 132 emptyings.I is imitated interchanger 41 and is adopted the self-produced steam heating.
Shown in Figure 4 is the overall structure of the 4th embodiment of present device, and what this embodiment was different with the 3rd embodiment is to adopt the three-effect counter flow evaporation technique, promptly is being added with squirt pumps 71 in the middle of vapour liquid separator 7 and I are imitated interchanger 41.The vapour outlet of vapour liquid separator 7 links to each other with the low-pressure gas import of squirt pump 71, self-produced steam links to each other with the high pressure gas import of squirt pump 71, the inlet mouth that the medium pressure gas outlet and the I of this squirt pump 71 are imitated interchanger 41 is communicated with, and is used for imitating interchanger 41 heating to I, thereby realizes the triple effect operation.
Referring to Fig. 5, the internal structure of described final thickener comprises film forming device 61, heating muff 62, fin 63, generating tube 64, heat-conducting medium 65 etc.In the middle of the good heating muff 62 of the corrosive of anti-caustic soda film-type evaporation pipe 64 and thermal conductivity, add the good medium 65 of thermal conductivity, fin 63 is installed on heating muff 62, fin 63 spirals distribute, be welded on the outer wall of heating muff 62, increase heat-conducting area on the one hand, change the heat transfer direction on the other hand, thereby realize the transmission of heat by convection of stack gas generating tube.
That shown in Figure 6 is another embodiment of internal structure of the final thickener of present device.A same embodiment of this embodiment is different be fin 63 spiral weldings be connected on heating muff 62 ' outer wall, heating muff 62 ' the outside be can produce photothermal radiator tube 66 ', pass through radiative transfer.
That shown in Figure 7 is an embodiment of the process furnace of present device.Process furnace comprises air outlet 66, thermal-radiating material 67, mould material 68, inlet mouth 69.This embodiment is provided with flow-disturbing parts 610 in stove inside, adds to produce radiating material (as silicon carbide) 67 simultaneously in the stove inwall.
That shown in Figure 8 is another embodiment of the process furnace of present device.What a same embodiment of this embodiment was different is its not scrambling stream unit 610, the same employing of stove inwall can produce radiating material 67 '.
Shown in Figure 9 is an overall construction drawing of the thickener of present device.Thickener internal structure and process furnace combination can generate four kinds of thickener overall structure.The overall construction drawing of this thickener is wherein a kind of just.
The principle of work of present device (is example with the double-countercurrent evaporation pattern) is summarized as follows: concentration is fed to II single-effect evaporator 32 at 32% caustic soda soln, the product side is operated under vacuum, II imitate interchanger 31 be by I single-effect evaporator 41 and final thickener 6 produce steam-heated.The steam that II single-effect evaporator 32 produces is condensed in water-cooled surface condenser 33, and the steam condensate of generation is collected in hot water storage tank 34 together with the water of condensation that II single-effect evaporator 32 shell sides produce.Alkali lye after imitate being concentrated by II is delivered to I single-effect evaporator 42 by jacketed pipe heat exchanger 35, produces brilliant side alkali lye and is concentrated into finite concentration.In the process by final thickener (6), alkali lye is concentrated into more than 99%, and the alkali lye after concentrating is through vapour liquid separator 7, and the liquid after the separation is again through packaging system or postorder manufacturing procedure, and isolated water vapour is sent to II and imitates interchanger 31.
The water-gas that produces through coal-gas producer 93 produces stack gas in roasting kiln 91, stack gas is sent in the final thickener 6 as heating member.In the part of the stack gas after final thickener 6 heat releases input vapour generator 81, then through chimney 83 emptyings; Another part enters roasting kiln 91 recycles once more by recirculation blower 92.
For the steam in this equipment flowsheet, except that adopting self-produced steam, also can adopt extraneous steam; Thickener internal structure in this equipment and process furnace combination can produce four kinds of thickener overall structure; Together with four kinds of ionic membrane solid caustic soda production technologies, all combined methods are all in this patent protection domain.This patent both had been fit to large-scale chlor-alkali plant and had been used to make solid caustic soda, and what also be fit to various places is the small-sized and individual solid caustic soda processing enterprise of fuel with coal gas, and the while also can be used for the evaporating and concentrating process that solid potassium hydroxide manufacturing etc. does not have crystal salt to separate out.

Claims (10)

1, a kind of method that is applicable to the ionic membrane method solid caustic soda production is characterized in that: the caustic soda raw material that will contain moisture through the preorder countercurrent evaporation after, import in the final thickener (6) and concentrate; This final thickener (6) is separated in the aqueous product input vapour liquid separator (7) after concentrating by the stack gas heating that roasting kiln (91) produces; Isolate water vapor and water-free product caustic soda through vapour liquid separator (7), the water vapor of evaporation is used for II is imitated interchanger (31) heating; The water-free product caustic soda of output is again through packaging system or postorder manufacturing procedure.
2, the described specific equipment that is applicable to the ionic membrane method solid caustic soda production of a kind of claim 1, it is the equipment of elder generation through falling liquid film countercurrent evaporation, reconcentration processing then, whole device is made of double-countercurrent evaporation system, final thickener, stack gas and steam generating system and postorder system of processing, it is characterized in that: described final thickener (6) adopts the stack gas heating; Described stack gas generation systems is made up of roasting kiln (91), recirculation blower (92), coal-gas producer (93), gas blower (94), the air of gas blower (94) links to each other with the inlet mouth of roasting kiln (91) on the one hand, inlet mouth with recirculation blower (92) links to each other on the other hand, and the air outlet of roasting kiln (91) is connected with the inlet mouth of final thickener (6).
3, the described specific equipment that is applicable to the ionic membrane method solid caustic soda production of a kind of claim 1, it is the equipment of elder generation through falling liquid film countercurrent evaporation, reconcentration processing then, whole device is made of three-effect counter flow vapo(u)rization system, stack gas and steam generating system and postorder system of processing, it is characterized in that: final thickener (6) wherein adopts the stack gas heating; Described stack gas generation systems is made up of roasting kiln (91), recirculation blower (92), coal-gas producer (93), gas blower (94), the air of gas blower (94) links to each other with the inlet mouth of roasting kiln (91) on the one hand, inlet mouth with recirculation blower (92) links to each other on the other hand, and the air outlet of roasting kiln (91) is connected with the inlet mouth of final thickener (6); Be provided with squirt pump (71) in the middle of vapour liquid separator (7) and gas bag (82), the pneumatic outlet of this squirt pump (71) links to each other with the gas feed that I is imitated interchanger (41).
4, according to claim 2 or the 3 described specific equipments that are applicable to the ionic membrane method solid caustic soda production, it is characterized in that: the internal structure of described final thickener (6) can have two kinds, one adds the good medium (65) of thermal conductivity in the middle of the good heating muff (62) of the corrosive of anti-caustic soda film-type evaporation pipe (64) and thermal conductivity, fin (63) is installed on heating muff (62), fin (63) spiral distributes, be welded on the outer wall of heating muff (62), realize the transmission of heat by convection of stack gas generating tube; It two adds the good medium (65 ') of thermal conductivity in the middle of the good heating muff (62 ') of the corrosive of anti-caustic soda film-type evaporation pipe (64 ') and thermal conductivity, fin (63 ') is installed on heating muff (62 '), fin (63 ') spiral welding is connected on the outer wall of heating muff (62 '), the outside of heating muff (62 ') is to produce photothermal radiator tube (66 '), passes through radiative transfer.
5, according to claim 2 or the 3 described specific equipments that are applicable to the ionic membrane method solid caustic soda production, it is characterized in that: the structure of the process furnace of described final thickener (6) also can have two kinds, a kind of is to be provided with flow-disturbing parts (610) in stove inside, adds to produce radiating material (as silicon carbide) (67) simultaneously in the stove inwall; Another kind is not scrambling stream unit (610), and the same employing of stove inwall can produce radiating material (67 ').
6, the specific equipment that is applicable to the ionic membrane method solid caustic soda production according to claim 2 is characterized in that: described I is provided with steam generating system in the middle of imitating interchanger (41) and final thickener (6); Be connected with vapour generator (81) through a part of stack gas after final thickener (6) heat release, vapour generator (81) is communicated with chimney (83) on the one hand, same on the other hand gas bag (82) is communicated with, the hot water outlet of gas bag (82) is connected with the water-in of vapour generator (81) more again, makes the hot water circulation utilization; Hot water storage tank (34) is connected with gas bag (82) by pump (5), and the pneumatic outlet of gas bag (82) is connected with the inlet mouth that I is imitated interchanger (41).
7, the specific equipment that is applicable to the ionic membrane method solid caustic soda production according to claim 3 is characterized in that: described I is provided with steam generating system in the middle of imitating interchanger (41) and final thickener (6); Be connected with vapour generator (81) through a part of stack gas after final thickener (6) heat release, vapour generator (81) is communicated with chimney (83) on the one hand, same on the other hand gas bag (82) is communicated with, the hot water outlet of gas bag (82) is connected with the water-in of vapour generator (81) more again, makes the hot water circulation utilization; Hot water storage tank (34) is connected with gas bag (82) by pump (5), the pneumatic outlet of gas bag (82) links to each other with the high-pressure inlet of squirt pump (71), the vapour outlet of vapour liquid separator (7) links to each other with the low-pressure gas import of squirt pump (71), and the inlet mouth that the medium pressure gas outlet and the I of this squirt pump (71) are imitated interchanger (41) is communicated with.
8, according to claim 2 or the 3 described specific equipments that are applicable to the ionic membrane method solid caustic soda production, it is characterized in that: the centre that described II is imitated interchanger (31) and surface condenser (33) is provided with hot water storage tank (34), and the cooling water outlet that II is imitated interchanger (31), surface condenser (33), jacketed pipe heat exchanger (35) links to each other with hot water storage tank's (34) water-in respectively; Described jacketed pipe heat exchanger (35) and I are provided with water of condensation storage tank (36) in the middle of imitating interchanger (41).
9, according to claim 2 or the 3 described specific equipments that are applicable to the ionic membrane method solid caustic soda production, it is characterized in that: the pneumatic outlet of described final thickener (6) is connected with the inlet mouth of recirculation blower (91).
10, according to claim 2 or the 3 described specific equipments that are applicable to the ionic membrane method solid caustic soda production, it is characterized in that:, except that adopting self-produced steam, also can adopt extraneous steam for the steam in this equipment flowsheet; Thickener internal structure in this equipment and process furnace combination can produce four kinds of thickener overall structure.
CNA2007100577108A 2007-06-22 2007-06-22 Method for solid caustic soda production by ionic membrane method Pending CN101327939A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102285670A (en) * 2011-06-16 2011-12-21 肖正群 Method and device for performing alkali concentration by utilizing synthesis waste heat of hydrogen chloride
CN102515202A (en) * 2011-12-13 2012-06-27 宜宾天原集团股份有限公司 Method for producing ionic membrane flake caustic by using fire coal falling film method
CN102583444A (en) * 2012-02-07 2012-07-18 张健 Alkali-manufacturing device and alkali-manufacturing method for manufacturing alkali in three-section falling film coal burning method

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102285670A (en) * 2011-06-16 2011-12-21 肖正群 Method and device for performing alkali concentration by utilizing synthesis waste heat of hydrogen chloride
CN102515202A (en) * 2011-12-13 2012-06-27 宜宾天原集团股份有限公司 Method for producing ionic membrane flake caustic by using fire coal falling film method
CN102583444A (en) * 2012-02-07 2012-07-18 张健 Alkali-manufacturing device and alkali-manufacturing method for manufacturing alkali in three-section falling film coal burning method

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