CN102602891B - Method for preparing chlorine from hydrogen chloride - Google Patents
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- CN102602891B CN102602891B CN 201210021723 CN201210021723A CN102602891B CN 102602891 B CN102602891 B CN 102602891B CN 201210021723 CN201210021723 CN 201210021723 CN 201210021723 A CN201210021723 A CN 201210021723A CN 102602891 B CN102602891 B CN 102602891B
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 99
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910000041 hydrogen chloride Inorganic materials 0.000 title claims abstract description 95
- 239000000460 chlorine Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 54
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 52
- 239000007789 gas Substances 0.000 claims abstract description 46
- 230000008878 coupling Effects 0.000 claims abstract description 19
- 238000010168 coupling process Methods 0.000 claims abstract description 19
- 238000005859 coupling reaction Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 238000005336 cracking Methods 0.000 claims description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims description 2
- 238000010504 bond cleavage reaction Methods 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 230000007017 scission Effects 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 10
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 230000009466 transformation Effects 0.000 description 20
- 239000006227 byproduct Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 241000370738 Chlorion Species 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 206010009866 Cold sweat Diseases 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- -1 MDI Chemical class 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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Abstract
The invention discloses a method for preparing chorine from hydrogen chloride, wherein chlorine and hydrogen are prepared by the splitting decomposition of hydrogen chloride gas in a coupling environment of microwave or/and magnetic field with arc plasma. The device can operate stably by the method with relatively-low energy consumption, the conversion rate of hydrogen chloride in the embodiment can be up to 99.98%, the heat carried in the tail gas can be recycled in the form of superheated water steam, and the high-pressure steam in the production has great industrial application prospect.
Description
Technical field:
The present invention relates to a kind of method for preparing chlorine with hydrogenchloride.
Technical background:
Chlorine is a kind of important chemical material, and its main application fields is chemical industry synthetic materials (urethane, polyvinyl chloride, Resins, epoxy etc.) and organic synthesis intermediate (toluene(mono)chloride, Mono Chloro Acetic Acid etc.).Chlorine mainly makes by electrolytic saltwater, the caustic soda of coproduction simultaneously.When market during to chlorine and alkali demand fluctuation, will cause the uneven in development problem of chlorine industry, present " the long chlorine of alkali is short " or " the long alkali of chlorine is lacked ".In recent years, fast development along with organochlorine industry such as MDI, the year consumption of China's chlorine has reached 1,700 ten thousand tons, and these chlorine are almost all by the chlor-alkali device provisioning, chlorine energy consumption height processed not only, and the caustic soda of coproduction superfluous surpass 8,000,000 tons/year (above data source is from CNPC and chemical industry, 2010, (2): 20; " CNPC and chemical industry economic analysis ").It is very low that great majority relate in the production process of chlorine products the chlorine atom utilization, as with the phosgene being the reaction process (producing isocyanic ester such as MDI, TDI) of raw material, the chlorine atom is only as the carrier of reaction process, do not have fully in the target approach product, the chlorine atom utilization is 0, and final 100% is converted into hydrogenchloride.According to incompletely statistics, (this data source promotes conference, Nanjing from national oil and chemical industry energy-saving and emission-reduction to Chinese annual by-product hydrogen chloride more than 3,800,000 tons; 2008.10.29).
At present, a large amount of by-product hydrogen chlorides get nowhere and to consume chlorine industry chlorine under-supply, have become the general character difficult problem of a plurality of enterprises and relevant industries development.Patent and bibliographical information mainly contain with the method that hydrogenchloride prepares chlorine at present: inorganic reagent oxidation style and catalytic oxidation.
The inorganic reagent oxidation style mainly contains the Kel-Chlor method of Weldson method and the exploitation of Kellogg company.The Weldson method needs a large amount of expensive MnO
2, and can only reclaim 50% chlorine in theory.The Kel-Chlor method is used the mixture oxidation chlorination hydrogen of nitric acid and sulfuric acid, and material corrodibility is big, and reactor needs special material, and investment is high; And, this method reactions steps complexity, by product is many, has serious secondary pollution.DuPont once adopted this technology to build up the device of 200,000 tons/year in a cover in 1974, but had just closed down in the near future.
Catalytic oxidation is the focus of studying at present, is divided into ruthenium system, chromium system, Cu-series catalyst with catalyst active center's type.
SUMITOMO CHEMICAL KCC has developed with rutile TiO
2The load ruthenium oxide catalysts, aspect catalyzer application a large amount of patents, formed blockade on new techniques; The said firm has developed the complexes that utilize this catalyzer, but this catalyzer is expensive, the cost height.
Mitsui east presses KCC with amorphous Si O
2Load C rO
3For catalyst development MT-Chlor technology, temperature of reaction is at 350～430 ℃, the transformation efficiency of hydrogenchloride is 75～80%, and has built up 3～60,000 tons/year production equipment in 1986.But the catalyzer CrO that this process is used
3The catalytic active component chromium ion runs off easily, influences catalyst life, and environmental pollution is bigger; And this catalyzer is to the existence of Fe very responsive (to small amount of N i and Ti too), SiO
2Be lower than 1% with the Fe content of reactor wall, this device is closed down at present.
Cu-series catalyst is a class catalyzer of developing the earliest, and U.S. Shell Oil Company adopts SiO
2The load copper salt catalyst, and developed the technology that adopts this catalyzer, nineteen sixty-five has been built up 30,000 tons/year device in Holland and India respectively, but the seventies initial stage closes owing to economical efficiency.California, USA university is catalyzer with cupric oxide and cupric chloride, adopts two-section flowing bed technology to finish lab scale and pilot scale, but does not see industrialized report.After 2000, China begins the research that hydrogenchloride prepares chlorine, and main research institution is Nanjing University of Technology and Tsing-Hua University, has developed Al
2O
3Bead load copper salt catalyst.Find that in research process the active ingredient cupric ion at high temperature volatilizees easily and runs off, and influences the quality of catalyst life and chlorine, bring the burden of chlorine purification; Cause that simultaneously catalyzer " is clamminess ", this catalyzer is applied in the fixed-bed reactor may cause line clogging, and is applied in the fluidized-bed reactor, and catalyzer easily lumps influences fluid effect.
Catalytic oxidation prepares in the chlorine process hydrogen in the hydrogenchloride is combined with oxygen and becomes water, and hydrogen is not utilized effectively; And if control badly, the water vapor absorbing hydrogen chloride is easy to produce hydrochloric acid severe corrosion equipment and pipeline, threatens the stability of production process; This method equipment used and pipe material require very high, expensive, the apparatus cost height, and also in case corrosion is not well controlled, the equipment amortization cost is very high.
Though above-mentioned two kinds of methods also have industrialized unit, green chemical industry is the trend of contemporary chemical industry development, therefore, seeks a kind of economy, environmental protection, that the stable method of process control procedure changes into chlorine with hydrogenchloride is imperative.And laid-open U.S. Patents US5935390 in 1999 proposed electricity consumption perhaps inductive plasma cracking HCl gas prepare Cl
2, the transformation efficiency of HCl can reach more than 90% in the example, is a kind of novelty and feasible method.But this patent and imperfection, higher (every cracking 1L hydrogenchloride consumed power is about 12.4～18.9KWh), and HCl gas need be preheating to＞1300 ℃ HCl, Cl such as: energy consumption
2And their split product in hot environment very vivaciously almost can with any material generation chemical reaction, therefore can infer that device ratio of depreciation used in the patent will be very high, be difficult to industrialization promotion.
Summary of the invention:
The object of the invention is to provide a kind of and prepares the method for chlorine with hydrogenchloride, prepares Cl with electric capacity or inductive plasma cracking HCl gas
2Compare, energy consumption is lower in the transformation efficiency that improves HCl, and reclaims the heat that carries in the product gas by the form with the superheated water bleed steam, and by-product mesohigh steam is to cut down the consumption of energy.
For realizing above purpose, technical scheme of the present invention is as follows:
The invention provides and a kind ofly prepare the method for chlorine with hydrogenchloride, it is characterized in that, hydrogen chloride gas at microwave or/and under the environment of magnetic field and arc plasma coupling cracking make chlorine and hydrogen.
Utilize electric arc to make the hydrogen chloride gas volume ionization produce hydroperoxyl radical (H), chlorine radical (Cl) or hydrogen ion (H
+), chlorion (Cl
-); Combination produces hydrogen between the hydroperoxyl radical (or hydrogen ion), and in conjunction with producing chlorine, hydroperoxyl radical (or hydrogen ion) is hydrogenchloride still with chlorine radical (or chlorion) combination between the chlorine radical (or chlorion); H
2, the HCl dissociation energy is respectively: 4.48eV, 2.63eV, and in local high-energy environment, be more prone between the free radical (or ion) between the hydroperoxyl radical (or hydrogen ion) in conjunction with producing hydrogen, between the chlorine radical (or chlorion) in conjunction with producing chlorine.Microwave can change the energy density of plasma body, make plasma body can diffuse to more wide space, rather than only concentrate on a certain zone between the anode and cathode, magnetic field energy guiding ion (or free radical) is along Movement in Magnetic Field, therefore can improve its transformation efficiency with microwave or magnetic field and the arc plasma cracking HCl that is coupled.
The concrete implementation step of method of the present invention is as follows:
(1), working gas is led in elder generation in cracker, replaces the oxygen in the scission reaction system, makes the volume content of the oxygen of atmosphere in the reactive system be lower than 0.1%; The open plasma direct supply is regulated size of current and is produced arc plasma then;
(2), the arc plasma that produces of the first step stable after, open microwave or/and magnetic field power supply;
(3), regulate the working gas flow, feed hydrogenchloride in cracker, the volume flow ratio of regulating working gas and hydrogenchloride is: 1: 10～1: 1, and preferred 1: 5～1: 4, force value in the cracker is 10%～90% of hydrogenchloride feed pressure, preferred 40%～60%; The beginning microwave is or/and magnetic field coupling arc plasma cracking hydrogenchloride prepares chlorine; The input speed of hydrogenchloride is 0.59～1.08m/s, and the chlorine of generation absorbs with alkali lye, and hydrogen is collected afterfire and handled.
Described hydrogenchloride is substantially anhydrous hydrogenchloride, substantially anhydrously refer to water content in the hydrogenchloride less than 1% (massfraction), this hydrogenchloride can be the impure hydrogenchloride of by-product when producing C1, C2 hydrochloric ether, namely may contain in VCM, TDI, MDI, PCE, TCE, COCl2, HF and the Chlorofluorocarbons (CFCs) one or more in the hydrogenchloride.
Preferably, the 3rd) in the step, hydrogen chloride gas with working gas with volume flow ratio is earlier: 1: 10～1: 1, entered mixed pipe line in preferred 1: 5～1: 4, and enter in the cracker by two transfer lines respectively again after mixing through mixed pipe line.
Sampling analysis: absorb chlorine with saturated liquor kalii iodide, takes out the solution behind an amount of absorption chlorine, with the transformation efficiency size of iodometric titrationiodimetry titration analysis hydrogenchloride.
Wherein, the process for separating and purifying of chlorine, hydrogen and working gas can adopt the existing maturation process of chlorine industry, with the method for cooling compression chlorine is separated; With method the separating hydrogen and working gas of transformation absorption.
In the present invention, working gas on the other hand also as inert diluent, changes the limits of explosion of hydrogen and chlorine mixed gas, and reaction process is carried out under the condition of safety and stability.Therefore the volume ratio of preferred working gas and hydrogenchloride is 1: 5～1: 4 in the process of the test.
In the inventive method, the 1st) electric current of step ionic medium power supply output is 80～150A, preferred 125～140A.
In the inventive method, the 2nd) power that adds microwave in the step is: 0.1～2kW, preferred 0.8～1.2kW.
In the inventive method, the 2nd) in the step institute to add magneticstrength be 0.1～2A/m, preferred 1.0～1.2A/m.
In the inventive method, described working gas is rare gas elementes such as argon gas, krypton gas or neon.
In the inventive method, the working electrode of cracker: the anode material is copper or graphite, and the negative electrode material can be stainless steel, copper, molybdenum, tantalum, nickel, tungsten or their alloy, preferred nickel, tungsten, nickel-containing alloys, contains tungstenalloy.
The inventive method also comprises the 4th) step reclaims the heat that carries in electrolysate chlorine and the hydrogen with the form of superheated water bleed steam, production mesohigh steam.
Concrete implementation step is as follows:
(1) at first with METERING DIAPHRAGM PUMPS steam condensate or feedwater are transported in the external jacket pipe and header tank of product pipeline, steam condensate or the feedwater liquid level in header tank accounts for 10%～60% of header tank cumulative volume;
(2) force value of regulating in the header tank reaches 0.2MPa～3MPa, the heat that carries in the steam condensate absorption product gas and vaporizing, vapour-liquid is separated in header tank, and the mesohigh steam of by-product is discharged recovery through pneumatic pressure-regulating valve from header tank after reaching pressure set points.
Find in specific implementation process: the transformation efficiency that microwave and arc plasma coupling cracking hydrogenchloride prepares chlorine prepares the transformation efficiency height of chlorine than magnetic field and the arc plasma cracking hydrogenchloride that is coupled; The transformation efficiency that microwave and magnetic field and arc plasma coupling cracking hydrogenchloride prepare chlorine is the highest.
The present invention adopts microwave or/and magnetic field and arc plasma coupling cracking hydrogenchloride prepares chlorine has the following advantages:
(1) requirement of device material is low, and laid down cost is low; Without catalyzer, the problem of having avoided catalyzer to bring; Hydrogen in the cracking process in the hydrogenchloride is converted into hydrogen rather than is combined with oxygen and produces water, avoids producing in the production process hcl corrosion equipment and pipeline, hydrogen can be used as the clean energy utilization or purify after be applied in the chemical process such as hydrogenation.
(2) by the heat in the form recovery tail gas of using the superheated water bleed steam, by-product mesohigh steam, force value is up to more than the 0.8MPa, and by-product mesohigh steam can be used for pipeline companion heat, raw material preheating etc., can cut down the consumption of energy.
(3) under relatively low energy consumption, the device steady running can realize the transformation efficiency that HCl is higher, and bigger prospects for commercial application is arranged.We adopt microwave or magnetic field and arc plasma coupling cracking hydrogenchloride to prepare chlorine, and under relatively low energy consumption, HCl can enter directly at normal temperatures that cracking prepares Cl in the environment that microwave or magnetic field and arc plasma be coupled
2, transformation efficiency is the highest in the example also reaches 99.98%, and device running stable (in the example steady running 583h) has bigger industrialization promotion prospect.
Description of drawings:
Fig. 1 is the reaction unit synoptic diagram of microwave coupling arc plasma cracking hydrogenchloride and byproduct steam.
Fig. 2 is the reaction unit synoptic diagram of magnetic field coupling arc plasma cracking hydrogenchloride and byproduct steam.
Fig. 3 is the reaction unit synoptic diagram of magnetic field and microwave coupling arc plasma cracking hydrogenchloride and byproduct steam.
Embodiment
For a better understanding of the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
As shown in Fig. 1-2, cracker 8 cavitys are stainless steel (316L, Sch40, GB/T12495-90 (the Ia)) pipe of the DN200 of long 80cm, volume is about 25.91L, seal with tongued and grooved flanges (glass reinforced plastic material), plasma electrical source (110V) 15 is the WWL-LSG precision linear large power DC voltage stabilization and current stabilization power supply of Yangzhou Shuanghong Electronics Co., Ltd.'s production; Microwave power source 7 is the WB.2-MY200S microwave power source of Beijing Zhuo Chuan electronics technology company limited production.
As shown in Figure 1, be the reaction unit synoptic diagram of microwave coupling arc plasma cracking hydrogenchloride and byproduct steam.
Working gas pipeline 2 and hydrogenchloride pipeline 1 (316L,
Wall thickness is 1mm) the bifurcation road is passed the cracker tongued and grooved flanges respectively and is entered cracker 8 after mixed pipe line mixes working gas and hydrogenchloride, and and tongued and grooved flanges between seal with epoxy resin glue; Negative electrode union lever 5 passes the cracker tongued and grooved flanges and enters cracker 8, and seal with epoxy resin glue with tongued and grooved flanges, negative electrode union lever 5 inside have circulating water cooling system to be used for anticathode cooling, this circulating water cooling system comprises negative electrode cooling water inlet pipe 3 and negative electrode cooling water outlet pipe 4, negative electrode union lever 5 is threaded with negative electrode 6, and the cathode power line is drawn with the negative electrode of plasma electrical source 15 from negative electrode union lever 5 and is connected; Microwave power source 7 is fixedlyed connected with cracker 8, and its pistol head enters in the cracker 8, and relative with negative electrode 6; Anode union lever 13 passes the cracker tongued and grooved flanges and enters cracker 8, and and tongued and grooved flanges between seal with epoxy resin glue, anode 14 is arranged in cracker 8 and anode union lever 13 is threaded, and the plate supply line is drawn with the anode of plasma electrical source 15 from anode union lever 13 and is connected; Split product pipeline 9 is drawn from cracker 8, pipeline is the jacket pipe form, the one end opening is steam condensate or feedwater import, the other end opening links to each other with header tank 12 entrances, split product pipeline 9 also connects sampling line and alkali lye suction line by first pneumatic pressure-regulating valve 10, and first pneumatic pressure-regulating valve 10 is used for regulating the pressure in the cracker 8; Header tank 12 connects second pneumatic pressure-regulating valve, 12, the second pneumatic pressure-regulating valves 11 and is used for regulating the external jacket pipe of split product pipeline 9 and the pressure of header tank 12.
As shown in Figure 2, be the reaction unit synoptic diagram of magnetic field coupling arc plasma cracking hydrogenchloride and byproduct steam.
As shown in Figure 3, be the reaction unit synoptic diagram of magnetic field and microwave coupling arc plasma cracking hydrogenchloride and byproduct steam.
A microwave source and a Magnetic Field Source are set respectively in the cracker 8 among Fig. 3, and other structures are identical with Fig. 1.
Embodiment 1-6 and Comparative Examples 1-7 under the different experimental conditions are as shown in table 1:
Reaction unit is seen Fig. 1.Experiment condition is: anode 14 materials are copper, and negative electrode 6 materials are tungsten; The feed pressure of working gas and hydrogenchloride all is 0.4MPa; Selected working gas is argon gas, at first uses the oxygen in the argon replaces reactive system, makes that the volume content of oxygen is lower than 0.1% in the reactive system; The open plasma power supply 15 then, regulate plasma electrical source 15 electric currents, and size of current is set at 100A, 125A, 135A, 140A respectively; Set first pneumatic pressure-regulating valve 10 for regulating automatically, setting its pressure is 0.2MPa, is the force value in the cracker 8; After treating arc stability, open hydrogenchloride pipeline 1, regulate hydrogenchloride flow and argon flow amount; Open microwave power source 7, regulate the microwave power size; Beginning arc plasma or microwave and arc plasma coupling cracking hydrogenchloride prepare chlorine, and the chlorine of generation adopts alkali lye to absorb, and hydrogen collects burning disposal.The transformation efficiency size of sampling analysis hydrogenchloride, the transformation efficiency of the hydrogenchloride under the corresponding process parameters sees Table 1.With METERING DIAPHRAGM PUMPS the 0.2MPa steam condensate is transported in the header tank 12, liquid level is positioned at header tank cumulative volume 40% place; Second pneumatic pressure-regulating valve 11 is set at automatic adjusting, and force value is 0.8MPa, along with the carrying out of experiment, and beginning by-product 0.8MPa steam.At experiment condition be: plasma power supply 15 electric currents are 125A, and the power of microwave power source 7 is 1.2kW, and the flow of argon gas and hydrogenchloride is respectively 0.4L/min, 1.6L/min, and device has moved 583h continuously, has produced the 0.8MPa steam of about 178.4Kg altogether.Can estimate that if will install amplification, the efficient of byproduct steam will correspondingly improve; And, if the pressure set points when improving pneumatic pressure-regulating valve and regulating automatically can be produced the more steam of higher-grade (more high pressure).
Table 1
Q in the table
VAr/ Q
VHC1The volume flow ratio of expression argon gas and hydrogenchloride, down together.
Contrast by embodiment 1-6 and Comparative Examples 1-5 is as can be seen: under the condition of identical plasma current, working gas and hydrogenchloride volume ratio, the transformation efficiency of microwave coupling arc plasma cracking hydrogenchloride is higher than the transformation efficiency of single arc plasma cracking hydrogenchloride far away.Calculate energy consumption with the total electric energy that per hour consumes except the hydrogenchloride amount of cracking, average every cracking 1L hydrogenchloride, the electric energy of single arc plasma consumption is than the microwave electric energy height that arc plasma consumes that is coupled.
Embodiment 7-13 and Comparative Examples 6 under the different experimental conditions are as shown in table 2:
Reaction unit is seen Fig. 2.Experiment condition is: anode 14 materials are copper, and negative electrode 6 materials are tungsten; The feed pressure of working gas and hydrogenchloride all is 0.4MPa; Selected working gas is argon gas, at first uses the oxygen in the argon replaces reactive system, makes that the volume content of oxygen is lower than 0.1% in the reactive system; The open plasma power supply 15 then, regulate plasma electrical source 15 electric currents, and size of current is set at 100A, 125A, 150A respectively; Set first pneumatic pressure-regulating valve 10 for regulating automatically, setting its pressure is 0.2MPa, is the force value in the cracker 8; After treating arc stability, open hydrogenchloride pipeline 1, regulate hydrogenchloride flow and argon flow amount; Open magnetic field power supply, regulate magnitude of field intensity; Beginning arc plasma or magnetic field and arc plasma coupling cracking hydrogenchloride prepare chlorine, the transformation efficiency size of sampling analysis hydrogenchloride, and the transformation efficiency of the hydrogenchloride under the corresponding process parameters sees Table 2; With METERING DIAPHRAGM PUMPS feedwater is transported in the header tank, liquid level is 40%; Second pneumatic pressure-regulating valve 11 is set at automatic adjusting, and force value is 1.0MPa, along with the carrying out of experiment, and beginning by-product 1.0MPa steam.Calculate energy consumption with the total electric energy that per hour consumes except the hydrogenchloride amount of cracking.
Table 2
Contrast by embodiment 12 and Comparative Examples 6 is as can be seen: under the condition of identical plasma current, working gas and hydrogenchloride volume ratio, the transformation efficiency of magnetic field coupling arc plasma cracking hydrogenchloride is higher than the transformation efficiency of single arc plasma cracking hydrogenchloride far away.Calculate energy consumption with the total electric energy that per hour consumes except the hydrogenchloride amount of cracking, average every cracking 1L hydrogenchloride, the electric energy of single arc plasma consumption is than the magnetic field electric energy height that arc plasma consumes that is coupled.
Embodiment 14-19 under the different experimental conditions is as shown in table 3:
Reaction unit is seen Fig. 3.Experiment condition is: experiment condition is: anode 14 materials are copper, and negative electrode 6 materials are tungsten; The feed pressure of working gas and hydrogenchloride all is 0.4MPa; Selected working gas is argon gas, at first uses the oxygen in the argon replaces reactive system, makes that the volume content of oxygen is lower than 0.1% in the reactive system; The open plasma power supply 15 then, regulate plasma electrical source 15 size of current; Set first pneumatic pressure-regulating valve 10 for regulating automatically, setting its pressure is 0.2MPa; Open microwave power source 7, regulate the watt level of microwave power source; Open magnetic field power supply, regulate magnitude of field intensity, regulate the flow size of argon gas and hydrogenchloride, beginning microwave, magnetic field and arc plasma coupling cracking hydrogenchloride prepare chlorine, and the transformation efficiency size of the hydrogenchloride under the corresponding process parameters sees Table 3.With METERING DIAPHRAGM PUMPS the 0.2MPa steam condensate is transported in the header tank, liquid level is 40%; Second pneumatic pressure-regulating valve 11 is set at automatic adjusting, and force value is 1.5MPa, along with the carrying out of experiment, and beginning by-product 1.5MPa steam.Calculate energy consumption with the total electric energy that per hour consumes except the hydrogenchloride amount of cracking.
Table 3
Claims (11)
1. a hydrogenchloride prepares the method for chlorine, it is characterized in that this method is carried out according to following steps:
(1), working gas is led in elder generation in cracker, replaces the oxygen in the scission reaction system, makes the volume content of the oxygen of atmosphere in the reactive system be lower than 0.1%; The open plasma direct supply is regulated size of current and is produced arc plasma then;
(2), the arc plasma that produces of the first step stable after, open microwave or/and magnetic field power supply produces microwave or/and magnetic field in cracker;
(3), regulate the working gas flow, in cracker, feed hydrogenchloride, the volume flow ratio of regulating working gas and hydrogenchloride is: 1: 10～1: 1, the force value in the cracker was 10%～90% of hydrogenchloride feed pressure; The beginning microwave is or/and magnetic field coupling arc plasma cracking hydrogenchloride prepares chlorine, and the input speed of hydrogenchloride is 0.59～1.08m/s.
2. the method for claim 1 is characterized in that, the volume flow ratio of working gas and hydrogenchloride is: 1: 5～1: 4, the force value in the cracker was 40%～60% of hydrogenchloride feed pressure.
3. the method for claim 1 is characterized in that, the 1st) electric current of step ionic medium power supply output is 80～150A.
4. method as claimed in claim 3 is characterized in that, the 1st) electric current of step ionic medium power supply output is 125～140A.
5. the method for claim 1 is characterized in that, the 2nd) power that adds microwave in the step is: 0.1～2kW.
6. method as claimed in claim 5 is characterized in that, the 2nd) power that adds microwave in the step is: 0.8～1.2kW.
7. the method for claim 1 is characterized in that, the 2nd) in the step institute to add magneticstrength be 0.1～2A/m.
8. method as claimed in claim 7 is characterized in that, the 2nd) in the step institute to add magneticstrength be 1.0～1.2A/m.
9. as each described method among the claim 1-8, it is characterized in that the working gas described in this method is rare gas element.
10. as each described method among the claim 1-8, it is characterized in that the working electrode of the cracker of this method: the anode material is copper or graphite, and the negative electrode material is stainless steel, copper, molybdenum, tantalum, nickel, tungsten or their alloy.
11. according to each described method in the claim 1 to 8, it is characterized in that this method also comprises the 4th) step reclaims the heat that carries in electrolysate chlorine and the hydrogen with the form of superheated water bleed steam, production mesohigh steam.
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| CN106335878A (en) * | 2016-08-12 | 2017-01-18 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Method for preparing chlorine gas from hydrochloric acid |
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| US5935390A (en) * | 1996-02-29 | 1999-08-10 | E. I. Du Pont De Nemours And Company | Producing chlorine and hydrogen from hydrogen chloride by plasma process |
| CN1720195A (en) * | 2002-12-06 | 2006-01-11 | Mks仪器股份有限公司 | Method and apparatus for fluorine generation and recirculation |
| CN101862674A (en) * | 2010-05-24 | 2010-10-20 | 清华大学 | Monolithic catalyst for use in preparation of chloride by using hydrogen chloride and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5935390A (en) * | 1996-02-29 | 1999-08-10 | E. I. Du Pont De Nemours And Company | Producing chlorine and hydrogen from hydrogen chloride by plasma process |
| CN1720195A (en) * | 2002-12-06 | 2006-01-11 | Mks仪器股份有限公司 | Method and apparatus for fluorine generation and recirculation |
| CN101862674A (en) * | 2010-05-24 | 2010-10-20 | 清华大学 | Monolithic catalyst for use in preparation of chloride by using hydrogen chloride and preparation method thereof |
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