CN101367779B - Production apparatus and method for joint production of white carbon black from epoxypropane with chlorohydrination - Google Patents
Production apparatus and method for joint production of white carbon black from epoxypropane with chlorohydrination Download PDFInfo
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- CN101367779B CN101367779B CN2008100135944A CN200810013594A CN101367779B CN 101367779 B CN101367779 B CN 101367779B CN 2008100135944 A CN2008100135944 A CN 2008100135944A CN 200810013594 A CN200810013594 A CN 200810013594A CN 101367779 B CN101367779 B CN 101367779B
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 143
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 79
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000006229 carbon black Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 64
- 238000007127 saponification reaction Methods 0.000 claims abstract description 124
- 239000007788 liquid Substances 0.000 claims abstract description 123
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 73
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 62
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 47
- 239000000159 acid neutralizing agent Substances 0.000 claims abstract description 44
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 35
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 34
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 30
- 239000007791 liquid phase Substances 0.000 claims abstract description 28
- VZIQXGLTRZLBEX-UHFFFAOYSA-N 2-chloro-1-propanol Chemical compound CC(Cl)CO VZIQXGLTRZLBEX-UHFFFAOYSA-N 0.000 claims abstract description 23
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000460 chlorine Substances 0.000 claims abstract description 21
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 21
- 239000012071 phase Substances 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 14
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 230000004927 fusion Effects 0.000 claims abstract description 7
- 239000011780 sodium chloride Substances 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 273
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 91
- 239000002699 waste material Substances 0.000 claims description 36
- 238000003763 carbonization Methods 0.000 claims description 30
- 238000002844 melting Methods 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000012267 brine Substances 0.000 claims description 20
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 20
- 239000006200 vaporizer Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 18
- 239000007790 solid phase Substances 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 12
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 12
- 239000006004 Quartz sand Substances 0.000 claims description 11
- 239000004115 Sodium Silicate Substances 0.000 claims description 10
- 238000010790 dilution Methods 0.000 claims description 10
- 239000012895 dilution Substances 0.000 claims description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 6
- 235000011089 carbon dioxide Nutrition 0.000 claims description 3
- 238000006298 dechlorination reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 abstract description 13
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 4
- 235000011941 Tilia x europaea Nutrition 0.000 abstract description 4
- 239000004571 lime Substances 0.000 abstract description 4
- 239000000920 calcium hydroxide Substances 0.000 abstract description 2
- 235000011116 calcium hydroxide Nutrition 0.000 abstract description 2
- RZWHKKIXMPLQEM-UHFFFAOYSA-N 1-chloropropan-1-ol Chemical compound CCC(O)Cl RZWHKKIXMPLQEM-UHFFFAOYSA-N 0.000 abstract 1
- 235000019738 Limestone Nutrition 0.000 abstract 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 abstract 1
- 239000006028 limestone Substances 0.000 abstract 1
- 239000008267 milk Substances 0.000 abstract 1
- 210000004080 milk Anatomy 0.000 abstract 1
- 235000013336 milk Nutrition 0.000 abstract 1
- 238000004886 process control Methods 0.000 abstract 1
- 235000019795 sodium metasilicate Nutrition 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Abstract
The present invention relates to a production device for chlorine alcoholizated epoxy propane and white carbon black. The production device comprises an electrolysis production device, a white carbon black production device and a chlorine alcoholizated epoxy propane production device. The production device for chlorine alcoholizated epoxy propane and white carbon black is characterized in that the electrolysis production device is connected with the white carbon black production device through the connection between liquid alkaline output pipe mounted through an electrolytic cell and an alkali fusion reactor; the electrolysis production device is connected with the chlorine alcoholizated epoxy propane production device through the connection between a saponified liquid alkaline output pipe mounted through an electrolytic cell with a saponification column; and the chlorine alcoholizated epoxy propane production device is connected with the white carbon black production device through the connection between a gas phase output pipe mounted through a pre-neutralization column and arranged at the top of the pre-neutralization column and a carbon dioxide collector and the connection between the liquid phase output pipe of a separator and a pre-neutralization agent storage tank. The production method adopts the key points of process control: sodium carbonate aqueous solution produced in the production process of the white carbon black is used as a pre-neutralization agent instead of limestone to neutralize hydrochloric acid in propylene chlorohydrin solution, liquid alkaline can be produced with the aqueous solution containing NaCl through electrolysis in the electrolysis production device, the produced CO2 returns to the reacting system and reacts with Na2SiO3 to produce Na2CO3, and the Na2CO3 is then pre-neutralized and repeatedly recycled. At the same time, the liquid alkaline used in the process for producing and saponifying epoxy propane is used as the saponifier taking the place of lime milk (Ca(OH)2) to take saponification with chloropropanol so as to generate epoxy propane while the liquid alkaline produced with the generated NaCl solution after concentration through electrolysis in the electrolysis production device can be used for producing the white carbon black. The production device for chlorine alcoholizated epoxy propane and white carbon black provided by the present invention has the advantages that the whole production process forms a closed cycle and realizes zero emission and circular economy, and is an environmentally friendly production method.
Description
Technical field
The present invention relates to a kind of production equipment and production method of Chemicals, what be specifically related to is the production equipment and the method for the white carbon black of chlorohydrination method propylene oxide coproduction.
Background technology
The required less investment of producing propylene oxide by chlorohydrination method production line, flow process is short, technical maturity, and production is safer, is to produce one of main method of propylene oxide at present in the world.In the producing propylene oxide by chlorohydrination method process, the manufacturer who has adopts lime masonry pre-neutralization agent, and saponification is then made saponifying agent with milk of lime, produces a large amount of waste residues and contains CaCl
2Waste water brings very big harm to environment.
Carborization among the production method of white carbon black produces a large amount of waste liquids, waste residue in process of production, serious environment pollution not only, and bring difficulty to aftertreatment.
The aforementioned production method of these two kinds of products has not met national industrial policies.
Summary of the invention
One of purpose of the present invention provides the production equipment of the white carbon black of a kind of chlorohydrination method propylene oxide coproduction.
Another object of the present invention provides the production method of the white carbon black of a kind of chlorohydrination method propylene oxide coproduction.
The technical scheme that adopts is:
The production equipment of the white carbon black of chlorohydrination method propylene oxide coproduction, comprise electrolysis production device, white carbon black production device, chlorohydrination method production of propylene oxide device, it is characterized in that: being connected between electrolysis production device and the white carbon black production device is to be connected realization with alkali-melting vessel by the liquid caustic soda output tube that electrolyzer is installed; Being connected between electrolysis production device and the chlorohydrination method production of propylene oxide device is to be connected realization with saponification column by the saponification liquid caustic soda output tube that electrolyzer is installed; Being connected between chlorohydrination method production of propylene oxide device and the white carbon black production device is the pre-neutralization top of tower gas phase output tube installed by the pre-neutralization tower with the carbon dioxide collection device be connected and separator liquid phase output tube that separator is installed and pre-neutralization agent storage tank be connected realization.
Above-mentioned electrolysis production device comprises electrolyzer, and electrolyzer is equipped with chlorine output tube, hydrogen output tube, strong brine input tube, liquid caustic soda output tube and saponification liquid caustic soda output tube;
Above-mentioned white carbon black production device comprises alkali-melting vessel, the carbonization still, separator, moisture eliminator, the carbon dioxide collection device, alkali-melting vessel is connected with the carbonization still by the alkali-melting vessel output tube, the carbonization still is connected with separator by carbonization still output tube, the carbonization still is connected with the carbon dioxide collection device by the feed carbon dioxide pipe, separator is connected with moisture eliminator by separator solid phase output tube, the carbon dioxide collection device is equipped with the pre-neutralization top of tower gas phase output tube from chlorohydrination method production of propylene oxide device, and separator is equipped with the separator liquid phase output tube that is connected with the pre-neutralization agent storage tank of chlorohydrination method production of propylene oxide device;
Above-mentioned chlorohydrination method production of propylene oxide device, comprise chlorohydrination reactor, pre-neutralization agent storage tank, the pre-neutralization tower, saponification column, rectifying tower, the saponification waste liquid storage tank, vaporizer, chlorohydrination reactor is equipped with the chlorine input tube, propylene input tube and clear water input tube, chlorohydrination reactor is connected with the pre-neutralization tower by propylene chlorohydrin solution output tube, pre-neutralization agent storage tank is equipped with the separator liquid phase output tube from the white carbon black production device, pre-neutralization agent storage tank is connected with the pre-neutralization tower by pre-neutralization agent output tube, the pre-neutralization tower is connected with saponification column by pre-neutralization tower liquid phase output tube, saponification column is connected with rectifying tower by the crude propene oxide output tube, rectifying tower is equipped with the propylene oxide output tube, saponification column is connected with the saponification waste liquid storage tank by saponification column waste liquid output tube, the saponification waste liquid storage tank is connected with vaporizer by saponification waste liquid storage tank output tube, vaporizer is equipped with the strong brine output tube that is connected with the electrolyzer of electrolysis production device, saponification column is equipped with the saponification liquid caustic soda output tube from the electrolysis production device, dispose dilution clear water pipe on the saponification liquid caustic soda output tube, the pre-neutralization tower is equipped with the pre-neutralization top of tower gas phase output tube that is connected with the carbon dioxide collection device;
The production method of the white carbon black of producing propylene oxide by chlorohydrination method coproduction, comprise electrolysis production process, carbon white production process, chlorohydrination method propylene oxide production process, it is characterized in that: the liquid caustic soda that the electrolysis production device is produced reacts with quartz sand through the alkali-melting vessel of liquid caustic soda output tube input white carbon black production device; From the carbonic acid gas of the pre-neutralization tower of chlorohydrination method production of propylene oxide device through pre-neutralization top of tower gas phase output tube input carbon dioxide collection device, and then the sodium silicate aqueous solution reaction interior and from alkali-melting vessel of input carbonization still generates white carbon black mixed solution, this white carbon black mixed solution is isolated solid phase through separator, this solid phase drying device drying is produced white carbon black product; The liquid caustic soda that the electrolysis production device is produced dilutes with clear water after the saponification column of saponification liquid caustic soda output tube input chlorohydrination method production of propylene oxide device, generate crude propene oxide with carry out saponification reaction from the propylene chlorohydrin in the pre-neutralization tower, crude propene oxide makes product propylene through rectifying tower rectifying; Import pre-neutralization agent storage tank by the isolated sodium carbonate solution of the separator of white carbon black production device through the separator liquid phase output tube;
Above-mentioned electrolysis production process, comprise that strong brine is through strong brine input tube input electrolyzer, produce chlorine, hydrogen and liquid caustic soda through electrolysis, chlorine and hydrogen is dechlorination hydrogen treatment process respectively, part liquid caustic soda is transported to the alkali-melting vessel of white carbon black production device through the liquid caustic soda output tube, another part liquid caustic soda is diluted to the saponification column of saponification liquid caustic soda through saponification liquid caustic soda output tube input chlorohydrination method production of propylene oxide device with clear water, it is 24-27wt% that strong brine contains NaCl, liquid caustic soda is the aqueous solution of NaOH, and containing NaOH is 9-11wt%;
Above-mentioned carbon white production process comprises alkali fusion and carbonization two portions; Alkali fusion is about to liquid caustic soda and quartz sand and adds in the alkali-melting vessel, and temperature of reaction is 170-190 ℃, reaction pressure is 0.7-0.8Mpa, the ratio of liquid caustic soda and quartz sand is 0.4-0.6:1wt%, makes sodium silicate aqueous solution, and the purified sodium silicate aqueous solution is conveyed into the carbonization still through the alkali-melting vessel output tube; Carbonization, promptly in the carbonization still, feed carbon dioxide by the carbon dioxide collection device through the feed carbon dioxide pipe, temperature of reaction is 85-95 ℃, reaction makes white carbon black and sodium carbonate solution, sends into separator and separates, and solid phase is conveyed into the moisture eliminator drying through separator solid phase output tube, temperature is controlled at 200-250 ℃ in the moisture eliminator, temperature out 100-110 ℃, make the white carbon black product, liquid phase is conveyed into pre-neutralization agent storage tank through the separator liquid phase output tube.
Above-mentioned chlorohydrination method propylene oxide production process, comprise that chlorine, propylene and water react generation propylene chlorohydrin solution in chlorohydrination reactor, propylene chlorohydrin solution is transported in the pre-neutralization tower through propylene chlorohydrin solution output tube, carry out pre-neutralization with mixing from the pre-neutralization agent in the pre-neutralization agent storage tank, PH in the pre-neutralization tower＜4 contain yellow soda ash (Na in the pre-neutralization agent
2CO
3) be 8-20wt%, the ratio of pre-neutralization agent and propylene chlorohydrin is 0.08-0.3:1wt%, gas phase is delivered to the carbon dioxide collection device through pre-neutralization top of tower gas phase output tube then, liquid phase is removed saponification column by the pre-neutralization tower through pre-neutralization tower liquid phase output tube, in saponification column, carry out saponification reaction with saponification liquid caustic soda through the output of saponification liquid caustic soda output tube, the dilution that the saponification liquid caustic soda is installed by saponification liquid caustic soda output tube adds the clear water dilution with the clear water pipe and generates, saponification column charging saponification liquor alkali concn is controlled at 4-10wt%, the crude propene oxide that generates after the saponification reaction goes rectifying tower rectifying to make product propylene, saponification waste liquid is transported to the saponification waste liquid storage tank through saponification column waste liquid output tube, the saponification waste liquid of saponification waste liquid storage tank is transported to vaporizer through saponification waste liquid storage tank output tube, evaporator temperature remains on 55-65 ℃, vacuum tightness is 55-95Kpa, after in vaporizer, concentrating, be transported to electrolysis in the electrolyzer by the strong brine output tube, evaporator outlet strong brine concentration is 24-27wt%, and temperature is 60 ± 5 ℃.
The present invention utilizes the aqueous sodium carbonate replacing lime masonry that produces in the white carbon black production process in the pre-neutralization agent and the hydrochloric acid in the propylene chlorohydrin solution, and the NaCl solution of generation can go the electrolyzer electrolysis to generate the NaOH aqueous solution, the CO of generation again
2Turn back to reaction system, with the sodium silicate aqueous solution reaction, generate sodium carbonate solution once more, go pre-neutralization again, reciprocation cycle.Simultaneously, production of propylene oxide saponifying process liquid caustic soda replacing lime breast (Ca (OH)
2) carry out saponification reaction as saponifying agent and propylene chlorohydrin, generate propylene oxide, meanwhile the NaCl aqueous solution of Sheng Chenging removes the electrolysis production device after concentrating, and the liquid caustic soda that electrolysis generates is used to produce white carbon black.
Advantage of the present invention is: whole process of production forms closed cycle, realizes zero release, is a kind of recycling economy, eco-friendly production method.
Description of drawings
Fig. 1 is the apparatus structure synoptic diagram of a kind of embodiment of the present invention
Specific embodiment
Embodiment one
The production equipment of the white carbon black of chlorohydrination method propylene oxide coproduction, comprise electrolysis production device 30, white carbon black production device 28, chlorohydrination method production of propylene oxide device 29, it is characterized in that: being connected between electrolysis production device 30 and the white carbon black production device 28 is to be connected realization with alkali-melting vessel 1 by the liquid caustic soda output tube 23 that electrolyzer 11 is installed; Being connected between electrolysis production device 30 and the chlorohydrination method production of propylene oxide device 29 is to be connected realization with saponification column 8 by the saponification liquid caustic soda output tube 31 that electrolyzer 11 is installed; Being connected between chlorohydrination method production of propylene oxide device 29 and the white carbon black production device 28 is by the realization that is connected with pre-neutralization agent storage tank 5 of pre-neutralization tower 6 pre-neutralization top of tower gas phase output tube of installing 18 and the separator liquid phase output tube of installing with separator 3 being connected of carbon dioxide collection device 7 16.
Above-mentioned electrolysis production device 30 comprises electrolyzer 11, and electrolyzer 11 is equipped with chlorine output tube, hydrogen output tube, concentrated solution input tube 22, liquid caustic soda output tube 23 and saponification liquid caustic soda output tube 31;
Above-mentioned white carbon black production device 28 comprises alkali-melting vessel 1, carbonization still 2, separator 3, moisture eliminator 4, carbon dioxide collection device 7, alkali-melting vessel 1 is connected with carbonization still 2 by alkali-melting vessel output tube 13, carbonization still 2 is connected with separator 3 by carbonization still output tube 15, is connected with carbon dioxide collection device 7 by feed carbon dioxide pipe 14; Separator 3 is connected with moisture eliminator 4 by separator solid phase output tube 24, carbon dioxide collection device 7 is equipped with the pre-neutralization top of tower gas phase output tube 18 from chlorohydrination method production of propylene oxide device 29, and separator 3 is equipped with the separator liquid phase output tube 16 that is connected with chlorohydrination method production of propylene oxide device 29 pre-neutralization agent storage tanks 5;
Above-mentioned chlorohydrination method production of propylene oxide device 29, comprise chlorohydrination reactor 26, pre-neutralization agent storage tank 5, pre-neutralization tower 6, saponification column 8, rectifying tower 12, saponification waste liquid storage tank 9, vaporizer 10, chlorohydrination reactor 26 is equipped with the chlorine input tube, propylene input tube and clear water input tube, chlorohydrination reactor 26 is connected with pre-neutralization tower 6 by propylene chlorohydrin solution output tube 27, pre-neutralization agent storage tank 5 is equipped with the separator liquid phase output tube 16 from white carbon black production device 28, pre-neutralization agent storage tank 5 is connected with pre-neutralization tower 6 by pre-neutralization agent output tube 17, pre-neutralization tower 6 is connected with saponification column 8 by pre-neutralization tower liquid phase output tube 19, saponification column 8 is connected with rectifying tower 12 by crude propene oxide output tube 25, rectifying tower 12 is equipped with the propylene oxide output tube, saponification column 8 is connected with saponification waste liquid storage tank 9 by saponification column waste liquid output tube 20, saponification waste liquid storage tank 9 is connected with vaporizer 10 by saponification waste liquid storage tank output tube 21, vaporizer 10 is equipped with the strong brine output tube 22 that is connected with the electrolyzer 11 of electrolysis production device 30, saponification column 8 is equipped with the saponification liquid caustic soda output tube 31 from electrolysis production device 30, dispose dilution clear water pipe on the saponification liquid caustic soda output tube 31, pre-neutralization tower 6 is equipped with the pre-neutralization top of tower gas phase output tube 18 that is connected with carbon dioxide collection device 7;
The production method of the white carbon black of chlorohydrination method propylene oxide coproduction, comprise electrolysis production process, carbon white production process, chlorohydrination method propylene oxide production process, it is characterized in that: the liquid caustic soda that electrolysis production device 30 is produced reacts with quartz sand through the alkali-melting vessel 1 of liquid caustic soda output tube 23 input white carbon black production devices 28; From the carbonic acid gas of the pre-neutralization tower 6 of chlorohydrination method production of propylene oxide device 29 through pre-neutralization top of tower gas phase output tube 18 input carbon dioxide collection devices 7, and then the 2 sodium silicate aqueous solution reactions interior and from alkali-melting vessel 1 of input carbonization still generate white carbon black mixed solution, this white carbon black mixed solution is isolated solid phase through separator 3, these solid phase drying device 4 dryings are produced white carbon black product; The liquid caustic soda that electrolysis production device 30 is produced is through the saponification column 8 of saponification liquid caustic soda output tube 31 input chlorohydrination method production of propylene oxide devices 29, before entering saponification column 8, this liquid caustic soda adds clear water dilution through the dilution of saponification liquid caustic soda output tube 31 with the clear water pipe by liquid caustic soda and forms the saponification liquid caustic soda, the saponification liquid caustic soda with carry out saponification from the propylene chlorohydrin in the pre-neutralization tower 6, the crude propene oxide of generation makes product propylene through rectifying tower 12 rectifying; Separator 3 isolated sodium carbonate solutions by white carbon black production device 28 are imported pre-neutralization agent storage tanks 5 through separator liquid phase output tube 16;
Above-mentioned electrolysis production process, comprise that concentrated solution is through concentrated solution input tube 22 input electrolyzers 11, produce chlorine, hydrogen and liquid caustic soda through electrolysis, chlorine and hydrogen is dechlorination hydrogen treatment process respectively, part liquid caustic soda is transported to the alkali-melting vessel 1 of white carbon black production device 28 through liquid caustic soda output tube 23, another part liquid caustic soda is diluted to the saponification column 8 of saponification liquid caustic soda through saponification liquid caustic soda output tube 31 input chlorohydrination method production of propylene oxide devices 29 with clear water, before entering saponification column 8, the dilution that this liquid caustic soda is installed by saponification liquid caustic soda output tube 31 adds clear water with the clear water pipe and is diluted to the saponification liquid caustic soda; Concentrated solution also claims strong brine, and containing NaCl is 26wt%; Liquid caustic soda is the aqueous solution of NaOH, and containing NaOH is 9wt%;
Carbon white production process comprises alkali fusion and carbonization two portions; Alkali fusion is about to liquid caustic soda and quartz sand and adds in the alkali-melting vessel 1, and the ratio of liquid caustic soda and quartz sand is 0.55:1wt%, temperature of reaction is 180 ℃, reaction pressure is 0.75Mpa, makes sodium silicate aqueous solution, and the purified sodium silicate aqueous solution is conveyed into carbonization still 2 through alkali-melting vessel output tube 13; Carbonization, promptly in carbonization still 2, feed carbon dioxide by carbon dioxide collection device 7 through feed carbon dioxide pipe 14, temperature of reaction is 90 ℃, reaction makes white carbon black and sodium carbonate solution, sends into separator 3 and separates, and solid phase is conveyed into moisture eliminator 4 dryings through separator solid phase output tube 24, temperature is controlled at 220 ℃ in the moisture eliminator 4,100 ℃ of temperature outs make the white carbon black product, and liquid phase is conveyed into pre-neutralization agent storage tank 5 through separator liquid phase output tube 16.
Above-mentioned chlorohydrination method propylene oxide production process, comprise chlorine, propylene and water react in chlorohydrination reactor 26 and generate propylene chlorohydrin solution, propylene chlorohydrin solution is transported in the pre-neutralization tower 6 through propylene chlorohydrin solution output tube 27, carry out pre-neutralization with mixing from the pre-neutralization agent in the pre-neutralization agent storage tank 5, PH is 3.5 in the pre-neutralization tower 6, concentration of sodium carbonate is controlled at 18wt% in the pre-neutralization agent, pre-neutralization agent and propylene chlorohydrin ratio are 0.12:1wt%, gas phase is delivered to carbon dioxide collection device 7 through pre-neutralization top of tower gas phase output tube 18 then, liquid phase is removed saponification column 8 by pre-neutralization tower 6 through pre-neutralization tower liquid phase output tube 19, in saponification column 8, carry out saponification reaction with saponification liquid caustic soda from the output of saponification liquid caustic soda output tube, saponification column 8 charging saponification liquor alkali concns are controlled at 9wt%, the crude propene oxide that generates after the saponification reaction makes product propylene through rectifying tower 12 rectifying, saponification waste liquid is transported to saponification waste liquid storage tank 9 through saponification column waste liquid output tube 20, the saponification waste liquid of saponification waste liquid storage tank 9 is transported to vaporizer 10 through saponification waste liquid storage tank output tube 21, vaporizer 10 temperature remain on 60 ℃, vacuum tightness is 85Kpa, in vaporizer 10, be condensed into strong brine, be transported to electrolysis in the electrolyzer 11 by strong brine output tube 22, evaporator outlet strong brine concentration is 24.5wt%, and temperature is 58 ℃;
Embodiment two
Embodiment two and embodiment one are basic identical, and difference is: liquid caustic soda concentration is 10wt%; Alkali-melting vessel 1 interior reaction temperature is 185 ℃, and pressure is 0.76Mpa, and the ratio of liquid caustic soda and quartz sand is 0.5:1wt%; Carbonization still 2 interior reaction temperatures are 89 ℃; Moisture eliminator 4 interior reaction temperatures are 230 ℃, and temperature out is controlled at 105 ℃; PH is 3 in the pre-neutralization tower 6, and concentration of sodium carbonate is controlled at 15wt% in the pre-neutralization agent, and pre-neutralization agent and propylene chlorohydrin ratio are 0.14:1wt%; Vaporizer 10 outlet strong brine concentration are 25.5wt%, and temperature is 60 ℃;
Embodiment three
Embodiment three and embodiment one are basic identical, and difference is: liquid caustic soda concentration is 11wt%; Alkali-melting vessel 1 interior reaction temperature is 188 ℃, and pressure is 0.79Mpa, and the ratio of liquid caustic soda and quartz sand is 0.6:1wt%; Carbonization still 2 interior reaction temperatures are 87 ℃; Moisture eliminator 4 interior reaction temperatures are 240 ℃, and temperature out is controlled at 107 ℃; PH is 2.8 in the pre-neutralization tower 6, and concentration of sodium carbonate is controlled at 19wt% in the pre-neutralization agent, and pre-neutralization agent and propylene chlorohydrin ratio are 0.16:1wt%; Vaporizer 10 outlet strong brine concentration are 26wt%, and temperature is 62 ℃.
Claims (8)
1. the production equipment of the white carbon black of chlorohydrination method propylene oxide coproduction, comprise electrolysis production device (30), white carbon black production equipment (28), chlorohydrination method production of propylene oxide device (29), it is characterized in that: being connected between electrolysis production device (30) and the white carbon black production equipment (28) is to be connected realization with alkali-melting vessel (1) by the liquid caustic soda output tube (23) that electrolyzer (11) is installed; Being connected between electrolysis production device (30) and the chlorohydrination method production of propylene oxide device (29) is to be connected realization with saponification column (8) by the saponification liquid caustic soda output tube (31) that electrolyzer (11) is installed; Being connected between chlorohydrination method production of propylene oxide device (29) and the white carbon black production equipment (28) is the pre-neutralization top of tower gas phase output tube (18) installed by pre-neutralization tower (6) with carbon dioxide collection device (7) be connected and separator liquid phase output tube (16) that separator (3) is installed and pre-neutralization agent storage tank (5) be connected realization.
2. the production equipment of the white carbon black of chlorohydrination method propylene oxide coproduction according to claim 1, it is characterized in that: described electrolysis production device (30) comprises electrolyzer (11), and electrolyzer (11) is equipped with chlorine output tube, hydrogen output tube, strong brine input tube (22), liquid caustic soda output tube (23) and saponification liquid caustic soda output tube (31).
3. the production equipment of the white carbon black of chlorohydrination method propylene oxide coproduction according to claim 1, it is characterized in that: described white carbon black production equipment (28) comprises alkali-melting vessel (1), carbonization still (2), separator (3), moisture eliminator (4), carbon dioxide collection device (7), alkali-melting vessel (1) is connected with carbonization still (2) by alkali-melting vessel output tube (13), carbonization still (2) is connected with separator (3) by carbonization still output tube (15), is connected with carbon dioxide collection device (7) by feed carbon dioxide pipe (14); Separator (3) is connected with moisture eliminator (4) by separator solid phase output tube (24), carbon dioxide collection device (7) is equipped with the pre-neutralization top of tower gas phase output tube (18) from chlorohydrination method production of propylene oxide device (29), and separator (3) is equipped with the separator liquid phase output tube (16) that is connected with the pre-neutralization agent storage tank (5) of chlorohydrination method production of propylene oxide device (29).
4. the production equipment of the white carbon black of chlorohydrination method propylene oxide coproduction according to claim 1, it is characterized in that: described chlorohydrination method production of propylene oxide device (29), comprise chlorohydrination reactor (26), pre-neutralization agent storage tank (5), pre-neutralization tower (6), saponification column (8), rectifying tower (12), saponification waste liquid storage tank (9), vaporizer (10), chlorohydrination reactor (26) is equipped with the chlorine input tube, propylene input tube and clear water input tube, chlorohydrination reactor (26) is connected with pre-neutralization tower (6) by propylene chlorohydrin solution output tube (27), pre-neutralization agent storage tank (5) is equipped with the separator liquid phase output tube (16) of the carbon black production equipment (28) of making clear one's meaning and position, pre-neutralization agent storage tank (5) is connected with pre-neutralization tower (6) by pre-neutralization agent output tube (17), pre-neutralization tower (6) is connected with saponification column (8) by pre-neutralization tower liquid phase output tube (19), saponification column (8) is connected with rectifying tower (12) by crude propene oxide output tube (25), rectifying tower (12) is equipped with the propylene oxide output tube, saponification column (8) is connected with saponification waste liquid storage tank (9) by saponification column waste liquid output tube (20), saponification waste liquid storage tank (9) is connected with vaporizer (10) by saponification waste liquid storage tank output tube (21), vaporizer (10) is equipped with the strong brine output tube (22) that is connected with the electrolyzer (11) of electrolysis production device (30), saponification column (8) is equipped with the saponification liquid caustic soda output tube (31) from electrolysis production device (30), saponification liquid caustic soda output tube (31) disposes dilution clear water pipe, and pre-neutralization tower (6) is equipped with the pre-neutralization top of tower gas phase output tube (18) that is connected with carbon dioxide collection device (7).
5. the production method of the white carbon black of chlorohydrination method propylene oxide coproduction, comprise electrolysis production process, white carbon black production process, chlorohydrination method propylene oxide production process, it is characterized in that: the liquid caustic soda that electrolysis production device (30) is produced reacts with quartz sand through the alkali-melting vessel (1) of liquid caustic soda output tube (23) the white carbon black production equipment of input (28); From the carbonic acid gas of the pre-neutralization tower (6) of chlorohydrination method production of propylene oxide device (29) through pre-neutralization top of tower gas phase output tube (18) input carbon dioxide collection device (7), and then input carbonization still (2) sodium silicate aqueous solution reaction interior and from alkali-melting vessel (1) generates white carbon black mixed solution, this white carbon black mixed solution is isolated solid phase through separator (3), this solid phase drying device (4) drying is produced white carbon black product; The saponification liquid caustic soda that electrolysis production device (30) is produced is through the saponification column (8) of saponification liquid caustic soda output tube (31) input chlorohydrination method production of propylene oxide device (29), before entering saponification column 8, the dilution that this liquid caustic soda is installed by saponification liquid caustic soda output tube (31) adds clear water with the clear water pipe and is diluted to the saponification liquid caustic soda, with carry out saponification from the propylene chlorohydrin in the pre-neutralization tower (6), the crude propene oxide of generation makes product propylene through rectifying tower (12) rectifying; The isolated sodium carbonate solution of separator (3) by white carbon black production equipment (28) is imported pre-neutralization agent storage tank (5) through separator liquid phase output tube (16).
6. the production method of the white carbon black of chlorohydrination method propylene oxide coproduction according to claim 5, it is characterized in that: described electrolysis production process, comprise that strong brine is through strong brine input tube (22) input electrolyzer (11), produce chlorine through electrolysis, hydrogen and liquid caustic soda, chlorine and hydrogen is dechlorination hydrogen treatment process respectively, part liquid caustic soda is transported to the alkali-melting vessel (1) of white carbon black production equipment (28) through liquid caustic soda output tube (23), another part liquid caustic soda is through the saponification column (8) of saponification liquid caustic soda output tube (31) input chlorohydrination method production of propylene oxide device (29), saponification column (8) is preceding entering, and the dilution that this liquid caustic soda is installed by saponification liquid caustic soda output tube (31) adds clear water with the clear water pipe and is diluted to the saponification liquid caustic soda; Strong brine also claims concentrated solution, and containing NaCl is 24～27wt%; Liquid caustic soda is the aqueous solution of NaOH, and containing NaOH is 9-11wt%.
7. the production method of the white carbon black of chlorohydrination method propylene oxide coproduction according to claim 5 is characterized in that: described white carbon black production process comprises alkali fusion and carbonization two portions; Alkali fusion, being about to liquid caustic soda solution and quartz sand adds in the alkali-melting vessel (1), temperature of reaction is 170～190 ℃, reaction pressure is 0.7～0.8Mpa, the ratio of liquid caustic soda and quartz sand is 0.4～0.6: 1wt%, make sodium silicate aqueous solution, the purified sodium silicate aqueous solution is conveyed into carbonization still (2) through alkali-melting vessel output tube (13); Carbonization, promptly in carbonization still (2), feed carbon dioxide by carbon dioxide collection device (7) through feed carbon dioxide pipe (14), temperature of reaction is 85～95 ℃, reaction makes white carbon black and sodium carbonate solution, sending into separator (3) separates, solid phase is conveyed into moisture eliminator (4) drying through separator solid phase output tube (24), the interior temperature of moisture eliminator (4) is controlled at 200～250 ℃, 100～110 ℃ of temperature outs, make white carbon black product, liquid phase is conveyed into pre-neutralization agent storage tank (5) through separator liquid phase output tube (16).
8. the production method of the white carbon black of chlorohydrination method propylene oxide coproduction according to claim 5, it is characterized in that: described chlorohydrination method propylene oxide production process, comprise chlorine, propylene and water react in chlorohydrination reactor (26) and generate propylene chlorohydrin solution, propylene chlorohydrin solution is transported in the pre-neutralization tower (6) through propylene chlorohydrin solution output tube (27), carry out pre-neutralization with mixing from the pre-neutralization agent in the pre-neutralization agent storage tank (5), the interior PH of pre-neutralization tower (6)＜4, the pre-neutralization agent concentration is controlled at 8-20wt%, the ratio of pre-neutralization agent and propylene chlorohydrin is 0.08-0.3: 1wt%, gas phase is delivered to carbon dioxide collection device (7) through pre-neutralization top of tower gas phase output tube (18) then, liquid phase is removed saponification column (8) by pre-neutralization tower (6) through pre-neutralization tower liquid phase output tube (19), in saponification column (8), carry out saponification reaction with the saponification liquid caustic soda of exporting by electrolysis production device (30) from saponification liquid caustic soda output tube (31), saponification column (8) charging saponification liquor alkali concn is controlled at 4-10wt%, the crude propene oxide that generates after the saponification reaction goes rectifying tower (12) rectifying to make product propylene through crude propene oxide output tube (25), saponification waste liquid is transported to saponification waste liquid storage tank (9) through saponification column waste liquid output tube (20), the saponification waste liquid of saponification waste liquid storage tank (9) is transported to vaporizer (10) through saponification waste liquid storage tank output tube (21), vaporizer (10) temperature remains on 60 ℃, vacuum tightness is 55-95Kpa, after in vaporizer (10), concentrating, be transported to electrolysis in the electrolyzer (11) by concentrated solution output tube (22), evaporator outlet strong brine concentration is 24～27wt%, and temperature is 60 ± 5 ℃.
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