CN104030247B - HCl oxidation reaction process and system with fluidized bed and adiabatic fixed bed connected in series - Google Patents
HCl oxidation reaction process and system with fluidized bed and adiabatic fixed bed connected in series Download PDFInfo
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- CN104030247B CN104030247B CN201410246874.5A CN201410246874A CN104030247B CN 104030247 B CN104030247 B CN 104030247B CN 201410246874 A CN201410246874 A CN 201410246874A CN 104030247 B CN104030247 B CN 104030247B
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 25
- 230000008569 process Effects 0.000 title abstract description 8
- 238000009413 insulation Methods 0.000 claims abstract description 143
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 134
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 126
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 126
- 238000006243 chemical reaction Methods 0.000 claims abstract description 110
- 239000007789 gas Substances 0.000 claims abstract description 106
- 239000001301 oxygen Substances 0.000 claims abstract description 55
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 55
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000011541 reaction mixture Substances 0.000 claims description 81
- 230000003647 oxidation Effects 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 8
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 description 70
- 230000009466 transformation Effects 0.000 description 38
- 239000000460 chlorine Substances 0.000 description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 21
- 229910052801 chlorine Inorganic materials 0.000 description 21
- 238000011068 loading method Methods 0.000 description 15
- 238000010523 cascade reaction Methods 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 230000035939 shock Effects 0.000 description 7
- 238000005660 chlorination reaction Methods 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- -1 phenyl aldehyde Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an HCl oxidation reaction process and system with a fluidized bed and a heat insulation fixed bed connected in series, wherein the reaction process comprises the following steps: the method comprises the following steps of uniformly mixing hydrogen chloride and oxygen, allowing the mixture to enter a fluidized bed reactor for oxidation reaction, allowing reaction mixed gas to leave the fluidized bed reactor, reducing the temperature of the reaction mixed gas to 350-410 ℃ through heat exchange, and allowing the reaction mixed gas to enter an adiabatic fixed bed reactor connected with a fluidized bed in series for further oxidation reaction. Wherein, the conversion rate of the hydrogen chloride in the fluidized bed reactor is 30-70%, the reaction mixed gas after the reaction of the fluidized bed reactor enters the fixed bed reactor for adiabatic reaction, and the maximum conversion rate of the hydrogen chloride can be up to 92.1% finally.
Description
Technical field
The present invention relates to a kind of reaction process and system of catalytic oxidation of hydrogen chloride for preparing chlorine gas, be specifically related to the reaction process carrying out being oxidized chlorine processed in the system that a kind of hydrogenchloride connects with insulation fix bed reactor at fluidized-bed reactor.
Background technology
Relate to during chlorine products produces urethane intermediates (MDI, TDI etc.), fluorine material intermediate, phenyl aldehyde, Repone K etc. are large, because by-product hydrogen chloride is difficult to process even contaminate environment, become the bottleneck problem that further develops of restriction relevant enterprise.And by the method for catalyzed oxidation, chlorine is made in by-product hydrogen chloride oxidation, realize the recycle of chlorine resource, be expected to become and relate to the technological approaches that chlorine Industrial Resources utilizes by-product hydrogen chloride.
Method by-product hydrogen chloride being transformed into chlorine mainly contains two kinds, and one is the method adopting electrolysis hydrochloric acid, as patent CN201010528518.4 set forth by the method for rare waste hydrochloric acid electrolytic preparation chlorine and hydrogen; Patent CN98812166.2 adopts oxygen-consuming cathodes electrolysis hydrochloric acid, and obtain chlorine and hydrogen, the purity of chlorine can reach more than 99%.The method of electrolysis hydrochloric acid prepares chlorine to consume a large amount of electric energy for cost, and the current consumption of ton chlorine is more than 1700kWh, and the production cost of chlorine is higher.
Another kind of method hydrogenchloride being transformed into chlorine is gas-solid catalysis oxidation style, and reaction formula is as follows.
In gas-solid catalysis oxidation style, the reactor of chlorine is become by chloration hydro-oxidation to mainly contain fixed bed and fluidized-bed two kinds.The method of oxidizing reaction is carried out in fixed-bed reactor, as patent CN201010567038.9 report take cupric chloride as main active component, take molecular sieve as carrier, with the addition of boron, basic metal, rare earth metal and alkaline-earth metal, and adopt the method for two step dippings to prepare heavy oil hydrogenating treatment catalyst, be 0.1 ~ 0.6MPa in reaction pressure, temperature of reaction is 320 ~ 460 DEG C, and hydrogenchloride mass space velocity is 0.1 ~ 2.5h
-1time, the transformation efficiency of hydrogenchloride can reach more than 85%.Patent 200810196433.3 discloses a kind of employing with REY molecular sieve for carrier, and with cupric chloride, rare earth nitrate and an alkali metal salt for active precursor power obtains heavy oil hydrogenating treatment catalyst, at 300 ~ 360 DEG C, hydrogenchloride is with 0.2 ~ 0.6Nm
3under the condition of the feeding rate of/h/kg, the transformation efficiency of hydrogenchloride is about 85%.Except the chloration hydro-oxidation method of carrying out in separate unit fixed-bed reactor, patent CN200710023245.6 then adopts the method for multiple stage fixed-bed reactor cascade reaction-dewatering coupling, by intersegmental condensation, the water that reaction generates is removed from reaction system, break the restriction of chemical reaction equilibrium, improve the transformation efficiency of hydrogenchloride.But in order to condensation dehydration, the temperature of reactant gases needs to be down to less than 100 DEG C from 430 DEG C, is elevated to about 400 DEG C again, the energy that this process need consumption is a large amount of before entering next reactor, be disadvantageous economically, and the hydrochloric acid that condensation produces is to intersegmental condensing equipment seriously corroded.
The hydrogen chloride oxidation reaction technique of carrying out in fluidized-bed is as document [Mortensen, etal.Chem.Eng.Sci.1996,51 (10): 2031-2039] report, in the fluidized-bed reactor of two series connection, hydrogenchloride is through chemisorption, then carry out oxidizing reaction and deviate from chlorine, the transformation efficiency of hydrogenchloride almost can reach 100%.But due to catalyzer cyclic conveying in the fluidized-bed of two series connection, very serious to the wearing and tearing of catalyzer and conversion unit, require extremely harsh to the material of catalyst physical performance and equipment, be unfavorable for suitability for industrialized production.
Except above-mentioned two kinds of main reaction process, CN200880024532.1 discloses the method for carrying out chloration hydro-oxidation chlorine in the insulation fix bed reactor of at least 18 series connection, the temperature out of every platform adiabatic reactor catalyzer is 370 DEG C, and final HCl transformation efficiency can reach 88%.But it is too much to there is tandem reactor number of units in this method, and device fabrication cost is high, and process line is numerous and jumbled, operates too loaded down with trivial details, practical application difficulty.CN200980139740.0 then discloses 3 insulation fix bed methods of carrying out chloration hydro-oxidation oxidation chlorine processed of series connection, the wherein insulation fix bed middle catalyzer loading ruthenium base and uranium base two kinds of different activities respectively of every platform, after series connection adiabatic reaction, the transformation efficiency of hydrogenchloride can reach about 90%.Although tandem reactor number of units is few, its temperature out reaches 470 DEG C, and the temperature rise of separate unit reactor reaches more than 150 DEG C, harsh to the stability requirement of catalyzer, very easily burns out catalyzer because of overtemperature.
The reaction of preparing chlorine by oxidizing hydrogen chloride belongs to thermopositive reaction, when adopting fixed-bed reactor, there is significant focus, if misoperation, very likely occur temperature runaway and burn out catalyzer in beds.For shifting out reaction heat in time, usually adopt shell and tube reactor, but due to the severe corrosive of reaction system, make involving great expense of shell-and-tube reactor.Insulation fix bed reactor preparation is simple, cheap, convenient operation and control.But the thermal discharge (28.4kJ/molHCl) during hydrogen chloride oxidation reaction is comparatively large, when hydrogenchloride is 1/1 with the mol ratio of oxygen, thermal insulation warming will reach 453.1 DEG C, and it is impossible that use separate unit insulation fix bed reactor reaches higher conversion.
As everyone knows, fluidized-bed reactor moves good in thermal property, and device structure is simple, cheap, but owing to there is obvious air-teturning mixed phenomenon, the transformation efficiency of reactant is then relatively low compared with fixed bed.
Summary of the invention
Contriver is by experimental results demonstrate: by fluidized-bed and insulation fix bed reactor combined serial, lower at transformation efficiency, when reactant concn is higher, speed of response is very fast, utilize fluidized-bed good move thermal characteristics, remove most of reaction heat, then enter in the insulation fix bed reactor of follow-up series connection and react, transformation efficiency can be improved as far as possible.By the insulation fix bed combined serial of multiple stage, in the temperature of reaction in every platform insulation fix bed reactor is in scope that catalyzer can bear.By the mode of fluidized-bed reactor and multiple stage insulation fix bed reactor combined serial, not only significantly can reduce equipment manufacturing cost, reduce production cost, and the transformation efficiency of hydrogenchloride also can reach the requirement that industrialization runs.
Therefore, the object of this invention is to provide a kind of method of preparing chlorine by catalytic oxidation of hydrogen chloride, specifically chloration hydro-oxidation is transformed into the method for chlorine in the fluidized-bed reactor and insulation fix bed reactor of series connection.
Another object of the present invention is to provide the reactive system that this fluidized-bed reactor is connected with insulation fix bed reactor.
The object of the invention is to realize in the following manner:
A kind of method of catalytic oxidation of hydrogen chloride for preparing chlorine gas, the method comprises the following steps: by hydrogenchloride and oxygen mix even, enter fluidized-bed reactor and carry out oxidizing reaction, reaction mixture gas body leaves fluidized-bed reactor, through heat exchange, reaction mixture gas temperature being reduced to temperature is 350 ~ 410 DEG C, then to enter in the insulation fix bed reactor of connecting with fluidized-bed oxidizing reaction further.Oxygen of the present invention is the common name of " oxygen ", and it can be gaseous oxygen or liquid oxygen.
In aforesaid method, hydrogen chloride oxidation reaction carries out in the fluidized-bed reactor and insulation fix bed reactor of series connection, hydrogenchloride and oxygen mix even, first react in a fluidized bed reactor, reaction mixture gas, after heat exchange, enters in the insulation fix bed reactor of series connection and continues reaction generation chlorine.
In aforesaid method, fluidized-bed reactor number of units is 1, and the number of units of insulation fix bed reactor is 1 ~ 6, preferably 2 ~ 5.The loadings of catalyzer in insulation fix bed reactor, according to W
n-1/ W
nthe mode of=1.3 ~ 2.7 (2<N<6) is loaded, W
nbe loaded catalyst in the insulation fix bed reactor of N platform series connection, W
n-1it is the loadings of catalyzer in N-1 platform insulation fix bed reactor.When insulation fix bed reactor is multiple stage, between multiple stage insulation fix bed reactor, combine connection in a series arrangement; Arrange both interchanger or heat transfer space or interchanger and heat transfer space between multiple stage insulation fix bed reactor to be arranged alternately.
In aforesaid method, hydrogenchloride transformation efficiency is in a fluidized bed reactor 30% ~ 70%, preferably 40% ~ 60%.
In aforesaid method, reacted reaction mixture gas body in a fluidized bed reactor, after leaving fluidized-bed reactor, by the mode of indirect heat exchange, is reduced to 350 ~ 410 DEG C by the temperature of reaction mixture gas body.The mode of described indirect heat exchange, refer to that reaction mixture gas body is by metal wall, transfer heat to the heat-eliminating medium of metal wall opposite side, the heat that above-mentioned heat-eliminating medium obtains in indirect heat exchange process, for the preheating of hydrogenchloride and oxygen, also can be used for producing high pressure steam.Heat-eliminating medium of the present invention can be fused salt.The heat that fused salt obtains can be used for the preheating of hydrogenchloride and oxygen, also can be used for producing high pressure steam.
In aforesaid method, reacted reaction mixture gas body in a fluidized bed reactor, after leaving fluidized-bed reactor, also by the mode of direct heat exchange, is reduced to 350 ~ 410 DEG C by the temperature of reaction mixture gas body, preferably 360 ~ 380 DEG C.The mode of described direct heat exchange, refers to that reaction mixture gas body and heat-eliminating medium directly contact thus the temperature of reaction mixture gas body reduced.Heat-eliminating medium described herein refers to the mixed gas of hydrogenchloride and oxygen, gaseous oxygen or liquid oxygen, and preferred gaseous oxygen or liquid oxygen are as heat-eliminating medium, and more preferably liquid oxygen is as heat-eliminating medium.Direct heat exchange of the present invention refers to that the mixed gas of reaction mixture gas body and low temperature chlorination hydrogen and oxygen, gaseous oxygen or liquid oxygen directly contact and cools, and cooled reaction mixture gas temperature is reduced to 350 ~ 410 DEG C.
When the insulation fix bed reactor of connecting with fluidized-bed reactor is more than 2 or 2, connection is combined in a series arrangement between multiple stage insulation fix bed reactor, reaction mixture gas body between the insulation fix bed reactor of series connection, after indirect or direct heat exchange, temperature is reduced to 350 ~ 410 DEG C.
In aforesaid method, be specially reaction mixture gas body out from fluidized-bed reactor, enter after heat exchange in the insulation fix bed reactor of series connection and continue reaction.When the insulation fix bed reactor of connecting with fluidized-bed reactor is 2, reaction mixture gas body between the 1st insulation fix bed reactor, pass through indirect heat exchange, reaction mixture gas temperature is reduced to 350 ~ 410 DEG C, preferably 360 ~ 380 DEG C, after enter the 2nd insulation fix bed reactor of series connection; When series connection N platform (2<N<6) insulation fix bed reactor, from N-1 platform insulation fix bed reactor reaction mixture gas body out, pass through indirect heat exchange, reaction mixture gas temperature is reduced to 350 ~ 410 DEG C, preferably after 360 ~ 380 DEG C, enter the N platform insulation fix bed reactor of series connection, proceed reaction.At N platform insulation fix bed reactor reaction mixture gas body out, by the mode of indirect heat exchange, reaction mixture gas temperature is reduced to 120 ~ 200 DEG C, preferably 150 ~ 180 DEG C, enters follow-up workshop section.
In aforesaid method, reaction mixture gas body out from fluidized-bed reactor, enters after also caning be passed through heat exchange in the insulation fix bed reactor of series connection and continues reaction.When the insulation fix bed reactor of connecting with fluidized-bed reactor is 2, reaction mixture gas body between the 1st insulation fix bed reactor, by directly contacting with the gas mixture of low temperature chlorination hydrogen and oxygen, the heat-eliminating medium such as gaseous oxygen or liquid oxygen, after reaction mixture gas temperature is reduced to 350 ~ 410 DEG C, enter the 2nd insulation fix bed reactor of series connection; When series connection N platform (2<N<6) insulation fix bed reactor, from N-1 platform insulation fix bed reactor reaction mixture gas body out, by directly contacting with the gas mixture of low temperature chlorination hydrogen and oxygen, the heat-eliminating medium such as gaseous oxygen or liquid oxygen, enter the N platform insulation fix bed reactor of series connection after reaction mixture gas temperature is reduced to 350 ~ 410 DEG C, proceed reaction.At N platform insulation fix bed reactor reaction mixture gas body out, by the mode of indirect heat exchange, reaction mixture gas temperature is reduced to 150 ~ 200 DEG C, enters follow-up workshop section.
In aforesaid method, when entering fluidized-bed reactor, the mol ratio of oxygen and hydrogenchloride is 1/8 ~ 2/1, preferably 1/4 ~ 1/1; Be 1 ~ 10atm (absolute pressure) in the reaction pressure of fluidized-bed reactor, preferably 3 ~ 8atm (absolute pressure); Temperature of reaction is 380 ~ 430 DEG C.
In aforesaid method, the temperature of reaction of reaction mixture gas body in insulation fix bed reactor is 350 ~ 450 DEG C, preferably 380 ~ 430 DEG C, and reaction pressure is 1 ~ 10atm, preferably 3 ~ 8atm.
The catalyzer used in insulation fix bed reactor in the present invention can be noble metal catalyst, as commercial ruthenium catalyst, Au catalyst etc.; Also can be transition-metal catalyst, as copper catalyst, chrome catalysts etc.The shape of catalyzer can have any required shape, the particle of such as spherical, cylindric, ring-type, starriness, cloverleaf pattern or sheet.
Described hydrogenchloride is 0.75 ~ 7.5Nm by the feeding rate of fluidized-bed
3/ kg catalyzer/h.
For a system for the method for above-mentioned catalytic oxidation of hydrogen chloride for preparing chlorine gas, this system comprises fluidized-bed reactor and one or more insulation fix bed reactor, combines in a series arrangement and connect between fluidized-bed reactor with insulation fix bed reactor.When insulation fix bed reactor is multiple stage, between multiple stage insulation fix bed reactor, combine connection in a series arrangement; Arrange both interchanger or heat transfer space or interchanger and heat transfer space between multiple stage insulation fix bed reactor to be arranged alternately.
Advantage of the present invention is compared with the prior art: relative to fluidized-bed reactor and the calandria type fixed bed reactor of routine, the method of fluidized-bed reactor of the present invention and insulation fix bed reactor cascade reaction, its advantage is: 1. after the cascade reaction of fluidized-bed reactor and insulation fix bed reactor, utilize fluidized-bed good move thermal characteristics, partial reaction heat is shifted out reaction system, by the reacting weight of hydrogenchloride in control flow check fluidized bed reactor, just can control heat removable in a fluidized bed reactor, just can control the heat reacting generation in series connection insulation fix bed reactor simultaneously.Therefore, the temperature runaway phenomenon produced because of strong exothermic heat of reaction in calandria type fixed bed reactor can be avoided.2. be used alone compared with tubular heat exchange type fixed-bed reactor, the structure of fluidized-bed reactor and insulation fix bed reactor significantly simplifies, cheap, is simplified in the preparation of reactor and the amplification performance of technique.
Accompanying drawing explanation
Fig. 1 is the system of the catalytic oxidation of hydrogen chloride for preparing chlorine gas that fluidized-bed reactor of the present invention is connected with 4 adiabatic reactors.
Number in the figure is: 1-hydrogenchloride feeding line; 2-oxygen feeding pipeline; 3-fluidized-bed reactor; 4-reaction mixture gas body feed liquid pipeline; Reaction mixture gas body feed liquid pipeline after 5-heat exchange; 6-is through 4 insulation fix bed reactor reacted reaction mixture gas body discharging pipelines.AR1-the 1st insulation fix bed reactor, AR2-the 2nd insulation fix bed reactor, AR3-the 3rd insulation fix bed reactor, AR4-the 4th insulation fix bed reactor.E1-the 1st interchanger, E2-the 1st heat transfer space, E3-the 2nd heat transfer space, E4-the 3rd heat transfer space, E5-the 2nd interchanger.
In figure, the combined serial of fluidized-bed reactor and 4 insulation fix bed reactors of connecting, wherein between 4 insulation fix bed reactors of connecting, there is a direct heat exchange space, after can entering for cryogenic media, carry out thermal exchange with the pyroreaction mixed gas in last insulation fix bed reactor exit.
Before entering fluidized-bed reactor, hydrogenchloride and oxygen mix laggard enter in fluidized-bed reactor 3.Reaction mixture gas body after fluidized-bed reaction, after interchanger E1 heat exchange, obtains the reaction mixture gas body after heat exchange, and the heat-exchange method in E1 adopts indirect heat exchange, namely with fused salt, the reaction heat that fluidized reaction produces is shifted out reaction system.Reaction mixture gas body after heat exchange enters the 1st adiabatic reactor reactor A R1, pyroreaction mixed gas after adiabatic reaction carries out direct heat exchange with heat-eliminating medium in E2, namely the gas in E2 heat transfer space is entered, except high-temperature reacting gas, also have and enter AR1 there is the low temperature chlorination hydrogen of same composition and the mixed gas of oxygen.Heat-eliminating medium enters interchanger in every section of adiabatic reactor exit.Similarly, the reaction mixture gas body be mixed to get in E2, enter the 2nd adiabatic reactor AR2, the reaction mixture gas body after adiabatic reaction enters the 3rd adiabatic reactor AR3 carry out thermal exchange with the mixed gas entering low temperature chlorination hydrogen and oxygen that AR1 has same composition in E3 heat transfer space after.After adiabatic reaction, reaction mixture gas body is obtained in AR3, the 4th adiabatic reactor AR4 is entered carry out thermal exchange with the mixed gas entering low temperature chlorination hydrogen and oxygen that AR1 has same composition in E4 heat transfer space after, through four reacted reaction mixture gas bodies of insulation fix bed reactor in E5 after indirect heat exchange is by reaction heat discharge system, enter subsequent process flow.
Fig. 2 is the system of the catalytic oxidation of hydrogen chloride for preparing chlorine gas that fluidized-bed reactor of the present invention is connected with 3 adiabatic reactors.
Number in the figure is: 1-hydrogenchloride feeding line; 2-oxygen feeding pipeline; 3-fluidized-bed reactor; 4-reaction mixture gas body feed liquid pipeline; Reaction mixture gas body feed liquid pipeline after 5-heat exchange; 6-is through the 1st the reacted reaction mixture gas fluid line of insulation fix bed reactor; The reaction mixture gas fluid line of 7-through the 1st insulation fix bed reactor and after heat exchange; 8-is through the 2nd the reacted reaction mixture gas fluid line of insulation fix bed reactor; The reaction mixture gas fluid line of 9-through the 2nd insulation fix bed reactor and after heat exchange; 10-is through the 3rd the reacted reaction mixture gas fluid line of insulation fix bed reactor; The reaction mixture gas fluid line of 11-through the 3rd insulation fix bed reactor and after heat exchange.AR1-the 1st insulation fix bed reactor, AR2-the 2nd insulation fix bed reactor, AR3-the 3rd insulation fix bed reactor, E1 First interchanger, E2 second interchanger, E3 the 3rd interchanger, E4 the 4th interchanger.
In figure, fluidized-bed reactor and the combined serial of 3 insulation fix bed reactors of connecting, be provided with fused salt heat exchange system, remove reaction heat for indirect heat exchange between the insulation fix bed reactor of 3 series connection.Before entering fluidized-bed reactor, hydrogenchloride and oxygen mix laggard enter in fluidized-bed reactor 3.Reaction mixture gas body after fluidized-bed reaction is after First interchanger E1 indirect heat exchange, enter the 1st adiabatic reactor AR1, after reacted mixed gas carries out indirect heat exchange in second interchanger E2, enter the 2nd adiabatic reactor reactor A R2, after the reaction mixture gas body generated carries out indirect heat exchange in the 3rd interchanger E3, enter the 3rd adiabatic reactor reactor, after the reaction mixture gas body of generation carries out indirect heat exchange in the 4th interchanger E4, reaction heat is discharged system.The reaction mixture gas body be obtained by reacting enters subsequent process flow.
Embodiment
By the following examples explanation is further expalined to the present invention:
As shown in Fig. 1 ~ 2, a kind of system for catalytic oxidation of hydrogen chloride for preparing chlorine gas, this system comprises fluidized-bed reactor 3 and one or more insulation fix bed reactor AR1 ~ 6, combines in a series arrangement and connect between fluidized-bed reactor with insulation fix bed reactor.When insulation fix bed reactor is multiple stage, between multiple stage insulation fix bed reactor, combine connection in a series arrangement; Arrange both interchanger or heat transfer space or interchanger and heat transfer space between multiple stage insulation fix bed reactor to be arranged alternately.
Embodiment 1:
In embodiment 1, first pass through fluidized-bed reactor after hydrogenchloride and oxygen mix, after fluidized-bed reactor reaction, the reaction mixture gas body obtained, through interchanger heat exchange, then passes through 4 insulation fix bed reactors altogether.
Hydrogenchloride and oxygen are 2 enter fluidized-bed reactor with mol ratio, and the inlet pressure of fluidized-bed reactor is 10atm, and fluidized reaction temperature is 400 DEG C.Hydrogenchloride is with 6Nm
3the feeding rate of/kg catalyzer/h is by fluidized-bed, and the CeCuK/Y molecular sieve catalyst loadings in fluidized-bed is 1532kg, and after reaction, the transformation efficiency of fluidized-bed reactor exit hydrogenchloride is 30%.After indirect heat exchange, the reaction mixture gas temperature entering First insulation fix bed reactor is 350 DEG C, the insulation fix bed reactor of series connection is 4, the temperature in of every platform insulation fix bed reactor inner catalyst layer is 350 DEG C, temperature out is 430 DEG C, and the loadings of 1 ~ 4 insulation fix bed reactor inner catalyst is followed successively by 1185.7kg, 1797.3kg, 3118.1kg and 7280.4kg.Adopt indirect heat exchange between insulation fix bed reactor, namely reaction mixture gas body is contacted with low-temperature heat exchange medium by metal wall.Through fluidized-bed and 4 insulation fix bed reactor cascade reactions, the total mass air speed of hydrogenchloride reaches 1.0h
-1, reach 85.7% at the transformation efficiency of adiabatic hydrogenchloride.The out temperature of every section of insulation fix bed reactor, loaded catalyst and reaction result are as shown in table 1.
Table 1
| Adiabatic reactor reactor | 1st | 2nd | 3rd | 4th |
| Inlet temperature/DEG C | 350 | 350 | 350 | 350 |
| Temperature out/DEG C | 430 | 430 | 430 | 430 |
| Catalyst quality/kg | 1185.7 | 1797.3 | 3118.1 | 7280.4 |
| Every platform reactor outlet total conversion rate/% | 44.6 | 58.1 | 73.6 | 85.7 |
Embodiment 2:
In example 2, first pass through fluidized-bed reactor after hydrogenchloride and oxygen mix, after fluidized-bed reactor reaction, the reaction mixture gas body obtained, through interchanger heat exchange, then passes through 4 adiabatic catalytic reactors altogether.
Hydrogenchloride and oxygen are 1 enter fluidized-bed reactor with mol ratio, fluidized-bed reactor inlet pressure be 6atm, fluidized reaction temperature is 380 DEG C.Hydrogenchloride is with 6Nm
3the feeding rate of/kg catalyzer/h is by fluidized-bed, and the loaded catalyst in fluidized-bed is 1532kg, and after reaction, the transformation efficiency of fluidized-bed reactor exit hydrogenchloride is 36%.After indirect heat exchange, the reaction mixture gas temperature entering First adiabatic reactor reactor is 350 DEG C, the adiabatic reactor of series connection is 4, the temperature in of every platform adiabatic reactor inner catalyst layer is 350 DEG C, temperature out is 430 DEG C, and the loadings of 1 ~ 4 adiabatic reactor inner catalyst is followed successively by 994.0kg, 1781.0kg, 4656.0kg and 7722.5kg.Adopt indirect heat exchange between adiabatic reactor, namely reaction mixture gas body does not contact with low-temperature heat exchange medium.Through fluidized-bed and 4 insulation fix bed reactor cascade reactions, the total mass air speed of hydrogenchloride reaches 0.9h
-1, reach 88.3% at the transformation efficiency of adiabatic hydrogenchloride.The out temperature of every section of adiabatic reactor, loaded catalyst and reaction result are as shown in table 2.
Table 2
| Adiabatic reactor reactor | 1st | 2nd | 3rd | 4th |
| Inlet temperature/DEG C | 350 | 350 | 350 | 350 |
| Temperature out/DEG C | 430 | 430 | 430 | 374 |
| Catalyst quality/kg | 994.0 | 1781.0 | 4656.0 | 7722.5 |
| Every platform reactor outlet total conversion rate/% | 47.03 | 60.01 | 76.93 | 88.3 |
Example 3:
In embodiment 3, according to the schematic flow sheet shown in accompanying drawing 1, first pass through fluidized-bed reactor after hydrogenchloride and oxygen mix, after fluidized-bed reactor reaction, the reaction mixture gas body obtained, through interchanger heat exchange, then passes through 3 adiabatic reactors altogether.
Hydrogenchloride and oxygen are 1 enter fluidized-bed reactor with mol ratio, and the inlet pressure of fluidized-bed reactor is 3atm, and fluidized reaction temperature is 400 DEG C.Hydrogenchloride is with 2Nm
3the feeding rate of/kg catalyzer/h is by fluidized-bed, and the loaded catalyst in fluidized-bed is 3830.4kg, and after reaction, the transformation efficiency of fluidized-bed reactor exit hydrogenchloride is 60%.After indirect heat exchange, the reaction mixture gas temperature entering First adiabatic reactor reactor is 380 DEG C, the adiabatic reactor totally 3 of series connection, the inlet temperature of every platform adiabatic reactor inner catalyst layer is respectively 380 DEG C, 390 DEG C and 400 DEG C, temperature out is respectively 430 DEG C, 430 DEG C and 423.2 DEG C, and the loadings of 1 ~ 3 adiabatic reactor inner catalyst is followed successively by 1401.4kg, 2210.2kg and 3955.7kg.Through fluidized-bed and 3 insulation fix bed cascade reactions, the total mass air speed of hydrogenchloride is 1.1h
-1, the transformation efficiency of hydrogenchloride reaches 85.4%.The out temperature of every platform adiabatic reactor, loaded catalyst and reaction result are as shown in table 3.
Table 3
| Adiabatic reactor reactor | 1st | 2nd | 3rd |
| Inlet temperature/DEG C | 380 | 390 | 400 |
| Temperature out/DEG C | 430 | 430 | 423.2 |
| Catalyst quality/kg | 1401.4 | 2210.2 | 3955.7 |
| Every platform reactor outlet total conversion rate/% | 70.61 | 79.09 | 85.4 |
Example 4:
In example 4, first pass through fluidized-bed reactor after hydrogenchloride and oxygen mix, after fluidized-bed reactor reaction, the reaction mixture gas body obtained, through interchanger heat exchange, then passes through 5 insulation fix bed reactors altogether.
Hydrogenchloride and oxygen are 1 enter fluidized-bed reactor with mol ratio, and the inlet pressure of fluidized-bed reactor is 2atm, and fluidized reaction temperature is 430 DEG C.Hydrogenchloride is with 7.5Nm
3the feeding rate of/kg catalyzer/h is by fluidized-bed, and the loaded catalyst in fluidized-bed is 1225.7kg, and after reaction, the transformation efficiency of fluidized-bed reactor exit hydrogenchloride is 30%.After interchanger, the reaction mixture gas temperature entering First adiabatic reactor reactor is 380 DEG C, and the adiabatic reactor of series connection is 5, and the inlet temperature of every platform adiabatic reactor catalyst in reactor layer is 380 DEG C, and temperature out is 430 DEG C.The loadings of 1 ~ 5 section of catalyzer is followed successively by 376.3kg, 519.8kg, 781.2kg, 1357.8kg and 3340.6kg, and through fluidized-bed and 5 insulation fix bed reactor cascade reactions, the total mass air speed of hydrogenchloride is 3.5h
-1, the transformation efficiency of hydrogenchloride reaches 85.15%.Out temperature and every platform reaction inner catalyst loadings of every platform insulation fix bed reactor are as shown in table 4.
Table 4
| Adiabatic reactor reactor | 1st | 2nd | 3rd | 4th | 5th |
| Temperature in/DEG C | 380 | 380 | 380 | 380 | 380 |
| Temperature out/DEG C | 430 | 430 | 430 | 430 | 430 |
| Catalyst quality/kg | 376.3 | 519.8 | 781.2 | 1357.8 | 3340.6 |
| Every platform reactor outlet total conversion rate/% | 41.67 | 52.32 | 62.95 | 73.56 | 85.15 |
Example 5:
Example 5 is that a fluidized-bed reactor is connected an insulation fix bed reactor.Hydrogenchloride and oxygen are 1 enter fluidized-bed reactor with mol ratio, and the inlet pressure of fluidized-bed reactor is 8atm, and fluidized reaction temperature is 380 DEG C.Hydrogenchloride is with 1Nm
3the feeding rate of/kg catalyzer/h is by fluidized-bed, and the loaded catalyst in fluidized-bed is 8332kg, and after reaction, the transformation efficiency of fluidized-bed reactor exit hydrogenchloride is 70%.After interchanger, the reaction mixture gas temperature entering insulation fix bed reactor is 350 DEG C, and the insulation fix bed reactor temperature out of series connection is 420 DEG C, and loaded catalyst is 7129.7kg, and the total mass air speed of hydrogenchloride during cascade reaction is 0.9h
-1, the transformation efficiency of hydrogenchloride reaches 85.78%.Out temperature and the loaded catalyst of adiabatic reactor are as shown in table 5.
Table 5
| Adiabatic reactor inlet temperature/DEG C | 350 |
| Adiabatic reactor temperature out/DEG C | 420 |
| Catalyst quality/kg | 7129.7 |
| Every platform reactor outlet total conversion rate/% | 85.78 |
Embodiment 6:
Example 6 is that 1 fluidized-bed reactor is connected 5 insulation fix bed reactors.Hydrogenchloride and oxygen are 2 enter fluidized-bed reactor with mol ratio, and the inlet pressure of fluidized-bed reactor is 1atm, and fluidized reaction temperature is 410 DEG C.Hydrogenchloride is with 6Nm
3the feeding rate of/kg catalyzer/h is by fluidized-bed, and the loaded catalyst in fluidized-bed is 1838.6kg, and after reaction, the transformation efficiency of fluidized-bed reactor exit hydrogenchloride is 30%.After interchanger, the reaction mixture gas temperature entering First adiabatic reactor reactor is 400 DEG C, the adiabatic reactor of series connection is 5, the inlet temperature of every platform adiabatic reactor inner catalyst layer is 400 DEG C, temperature out is 430 DEG C, 1 ~ 5 insulation fix bed reactor inner catalyst loadings is followed successively by 246.2kg, 330.6kg, 481.1kg, 808.8kg and 2039.5kg, and through fluidized-bed and 5 insulation fix bed cascade reactions, the total mass air speed of hydrogenchloride is 4.8h
-1, the transformation efficiency of hydrogenchloride reaches 85.07%.The out temperature of every platform adiabatic reactor, loaded catalyst and reaction result are as shown in table 6.
Table 6
| Adiabatic reactor reactor | 1st | 2nd | 3rd | 4th | 5th |
| Inlet temperature/DEG C | 400 | 400 | 400 | 400 | 400 |
| Temperature out/DEG C | 430 | 430 | 430 | 430 | 430 |
| Catalyst quality/kg | 246.2 | 330.6 | 481.1 | 808.8 | 2039.5 |
| Every section of reactor outlet total conversion rate/% | 41.78 | 53.54 | 63.3 | 76.04 | 85.07 |
Embodiment 7:
Example 7 is that 1 fluidized-bed reactor is connected 5 insulation fix bed reactors.Hydrogenchloride and oxygen are 2 enter fluidized-bed reactor with mol ratio, and the inlet pressure of fluidized-bed reactor is 3atm, and fluidized reaction temperature is 410 DEG C.Hydrogenchloride is with 6Nm
3the feeding rate of/kg catalyzer/h is by fluidized-bed, and the loaded catalyst in fluidized-bed is 1838.6kg, and after reaction, the transformation efficiency of fluidized-bed reactor exit hydrogenchloride is 38%.After interchanger, the reaction mixture gas temperature entering First adiabatic reactor reactor is 390 DEG C, the adiabatic reactor of series connection is 5, the inlet temperature of every platform adiabatic reactor inner catalyst layer is 390 DEG C, 1 ~ 5 insulation fix bed reactor inner catalyst loadings is followed successively by 886.1kg, 1589.3kg, 3691.3kg, 6705.9kg and 8792.8kg, through fluidized-bed and 5 insulation fix bed cascade reactions, the total mass air speed of hydrogenchloride is 1.2h
-1, the transformation efficiency of hydrogenchloride reaches 87.3%.The out temperature of every platform adiabatic reactor, loaded catalyst and reaction result are as shown in table 7.
Table 7
| Adiabatic reactor reactor | 1st | 2nd | 3rd | 4th | 5th |
| Inlet temperature/DEG C | 390 | 390 | 390 | 390 | 390 |
| Temperature out/DEG C | 430 | 430 | 430 | 430 | 399.4 |
| Catalyst quality/kg | 886.1 | 1589.3 | 3691.3 | 6705.9 | 8792.8 |
| Every section of reactor outlet total conversion rate/% | 45.03 | 58.03 | 71.01 | 83.98 | 87.3 |
Embodiment 8:
Example 8 is that 1 fluidized-bed reactor is connected 5 insulation fix bed reactors.Hydrogenchloride and oxygen are 2 enter fluidized-bed reactor with mol ratio, and the inlet pressure of fluidized-bed reactor is 8atm, and fluidized reaction temperature is 430 DEG C.Hydrogenchloride is with 6Nm
3the feeding rate of/kg catalyzer/h is by fluidized-bed, and the loaded catalyst in fluidized-bed is 1838.6kg, and after reaction, the transformation efficiency of fluidized-bed reactor exit hydrogenchloride is 70%.After interchanger, the reaction mixture gas temperature entering First adiabatic reactor reactor is 390 DEG C, the adiabatic reactor of series connection is 2, the inlet temperature of every platform adiabatic reactor inner catalyst layer is 390 DEG C, 1 ~ 2 insulation fix bed reactor inner catalyst loadings is followed successively by 1967.3kg, 4213.7kg, through fluidized-bed and 2 insulation fix bed cascade reactions, the total mass air speed of hydrogenchloride is 2.2h
-1, the transformation efficiency of hydrogenchloride reaches 85.0%.The out temperature of every platform adiabatic reactor, loaded catalyst and reaction result are as shown in table 8.
Table 8
| Adiabatic reactor reactor | 1st | 2nd |
| Inlet temperature/DEG C | 390 | 390 |
| Temperature out/DEG C | 430 | 430 |
| Catalyst quality/kg | 1967.3 | 4213.7 |
| Every section of reactor outlet total conversion rate/% | 81.9 | 85.0 |
Embodiment 9:
In embodiment 9, first pass through fluidized-bed reactor after hydrogenchloride and oxygen mix, then by the adiabatic reactors of 4 series connection altogether.
Hydrogenchloride and oxygen are 4 enter fluidized-bed reactor with mol ratio, and the inlet pressure of fluidized-bed reactor is 8atm, and fluidized reaction temperature is 430 DEG C.Hydrogenchloride is with 0.75Nm
3the feeding rate of/kg catalyzer/h is by fluidized-bed, and the loaded catalyst in fluidized-bed is 12257.3kg, and after reaction, the transformation efficiency of fluidized-bed reactor exit hydrogenchloride is 45%.After interchanger, the reaction mixture gas temperature entering First insulation fix bed reactor is 350 DEG C, the insulation fix bed reactor of series connection is 4, catalyst layer inlet temperature in every platform reaction is 350 DEG C, beds temperature out in 1 ~ 4 reactor is 430 DEG C, the temperature out of the 4th catalyst in reactor bed is 383.5 DEG C, 1 ~ 4 catalyst in reactor loadings is followed successively by 3025kg, 5254kg, 12127kg and 18481kg, through fluidized-bed reactor and 4 insulation fix bed reactor cascade reactions, the total mass air speed of hydrogenchloride is 0.3h
-1, the transformation efficiency of hydrogenchloride reaches 85.94%.The out temperature of every platform insulation fix bed reactor, loaded catalyst and reaction result are as shown in table 9.
Table 9
| Adiabatic reactor reactor | 1st | 2nd | 3rd | 4th |
| Temperature in/DEG C | 350 | 350 | 350 | 350 |
| Temperature out/DEG C | 430 | 430 | 430 | 383.5 |
| Catalyst quality/kg | 3025 | 5254 | 12127 | 18481 |
| Every section of reactor outlet total conversion rate/% | 55.29 | 65.54 | 75.76 | 85.94 |
Embodiment 10:
In embodiment 10, first fluidized-bed reactor is passed through after hydrogenchloride and oxygen mix, then by 3 insulation fix bed reactors altogether, between two between insulation fix bed reactor by the mode of direct cold shock, make reaction mixture gas body be reduced to required temperature.
Hydrogenchloride and oxygen are 2 enter fluidized-bed reactor with mol ratio, and the inlet pressure of fluidized-bed reactor is 5atm, and fluidized reaction temperature is 420 DEG C.Hydrogenchloride is with 2Nm
3the feeding rate of/kg catalyzer/h is by fluidized-bed, and the loaded catalyst in fluidized-bed is 1838.6kg, and after reaction, the transformation efficiency of fluidized-bed reactor exit hydrogenchloride is 50%.The reaction mixture gas temperature exported at fluidized-bed reactor is 420 DEG C, this gas 772Nm
3the oxygen of/h carries out cold shock, makes its temperature be reduced to 371.5 DEG C, enters the 1st insulation fix bed reactor and reacts; In the outlet of the 1st insulation fix bed reactor, the temperature of reaction mixture gas body is 430 DEG C; This gas 907.9Nm
3the oxygen of/h carries out cold shock, makes its temperature be reduced to 378.9 DEG C, then enters the 2nd insulation fix bed reactor and reacts; In the outlet of the 2nd insulation fix bed reactor, the temperature of reaction mixture gas body is 430 DEG C; This gas 908.4Nm
3the oxygen of/h carries out cold shock, makes its temperature be reduced to 384.6 DEG C, then enters the 3rd insulation fix bed reactor and reacts; In the outlet of the 3rd insulation fix bed reactor, the temperature of reaction mixture gas body is 396.3 DEG C.
1st ~ 3 insulation fix bed reactor inner catalyst loadings are followed successively by 1962.3kg, 4059.2kg and 5674kg, and through fluidized-bed and 3 insulation fix bed cascade reactions, the total mass air speed of hydrogenchloride is 0.4h
-1, hydrogenchloride is 1/1.2 with the ratio of oxygen total mole number, and the transformation efficiency of hydrogenchloride reaches 92.1%.The out temperature of every section of insulation fix bed reactor, loaded catalyst and reaction result are as shown in table 10.
Table 10
| Adiabatic reactor reactor | 1st | 2nd | 3rd |
| Temperature in/DEG C | 371.5 | 378.9 | 384.6 |
| Temperature out/DEG C | 430 | 430 | 396.3 |
| Catalyst quality/kg | 1962.3 | 4059.2 | 5674 |
| Every section of reactor outlet total conversion rate/% | 67.42 | 81.97 | 92.1 |
Embodiment 11:
In embodiment 11, first pass through fluidized-bed reactor after hydrogenchloride and oxygen mix, then by the adiabatic reactors of 4 series connection altogether.
Hydrogenchloride and oxygen are 6 enter fluidized-bed reactor with mol ratio.Fluidized-bed reactor inlet pressure be 6atm, fluidized-bed reaction temperature is 430 DEG C.Hydrogenchloride is with 1Nm
3the feeding rate of/kg catalyzer/h is by fluidized-bed, and the loaded catalyst in fluidized-bed is 10455.2kg, and the transformation efficiency of fluidized-bed reactor exit hydrogenchloride is 30%.After interchanger, the reaction mixture gas temperature entering First insulation fix bed reactor is 350 DEG C.The insulation fix bed reactor of series connection is 4, catalyst layer inlet temperature in every platform reactor is 350 DEG C, beds temperature out in 1 ~ 3 reactor is 430 DEG C, the temperature out of the 4th catalyst in reactor bed is 430 DEG C, and 1 ~ 4 catalyst in reactor loadings is followed successively by 2186.3kg, 2997.5kg, 5168.3kg and 8234.6kg.Through fluidized-bed reactor and 4 insulation fix bed reactor cascade reactions, the total mass air speed of hydrogenchloride is 0.6h
-1, the transformation efficiency of hydrogenchloride reaches 67.3%.The out temperature of every platform insulation fix bed reactor, loaded catalyst and reaction result are as shown in table 11.
Table 11
| Adiabatic reactor reactor | 1st | 2nd | 3rd | 4th |
| Temperature in/DEG C | 350 | 350 | 350 | 350 |
| Temperature out/DEG C | 430 | 430 | 430 | 383.5 |
| Catalyst quality/kg | 2186.3 | 2997.5 | 5168.3 | 8234.6 |
| Every platform reactor outlet transformation efficiency/% | 40.3 | 49.8 | 60.2 | 67.3 |
Embodiment 12:
In embodiment 12, first pass through fluidized-bed reactor after hydrogenchloride and oxygen mix, then by the adiabatic reactors of 3 series connection altogether.
Hydrogenchloride and oxygen are 5.6 enter fluidized-bed reactor with mol ratio, and the inlet pressure of fluidized-bed reactor is 5atm, and fluidized-bed reaction temperature is 430 DEG C.Hydrogenchloride is with 1Nm
3the feeding rate of/kg catalyzer/h is by fluidized-bed, and the loaded catalyst in fluidized-bed is 11850kg, and the transformation efficiency of fluidized-bed reactor exit hydrogenchloride is 37.1%.Employing hydrogen chloride gas is quench gas, and the cold shock tolerance entering the 1st insulation fix bed reactor is 1789.5Nm
3/ h, after direct heat exchange, the reaction mixture gas temperature entering the 1st insulation fix bed reactor is 384 DEG C, and in the 1st insulation fix bed reactor, loaded catalyst is 2540kg; Be 430 DEG C from the 1st insulation fix bed reactor reaction mixture gas temperature out, use 1650.3Nm
3after the hydrogen chloride gas cold shock of/h, temperature is reduced to 391.6 DEG C and enters in the 2nd insulation fix bed reactor, and the loaded catalyst in the 2nd insulation fix bed reactor is 4240kg; Be 430 DEG C from the 2nd insulation fix bed reactor reaction mixture gas temperature out, use 1352.4Nm
3after the hydrogen chloride gas cold shock of/h, temperature is reduced to 400.8 DEG C, and enter in the 3rd insulation fix bed reactor, the loaded catalyst in the 3rd insulation fix bed reactor is 6056kg.Through fluidized-bed reactor and 3 insulation fix bed reactor cascade reactions, the total mass air speed of hydrogenchloride is 1.4h
-1, total mol ratio of hydrogenchloride and oxygen is 7.8, and the transformation efficiency of hydrogenchloride reaches 49.2%, and the transformation efficiency of oxygen reaches 96.0%.The out temperature of every platform insulation fix bed reactor, loaded catalyst and reaction result are as shown in table 9.
Table 12
| Adiabatic reactor reactor | 1st | 2nd | 3rd |
| Temperature in/DEG C | 384.1 | 391.6 | 400.8 |
| Temperature out/DEG C | 430 | 430 | 430 |
| Catalyst quality/kg | 2540 | 4240 | 6056 |
| Every platform adiabatic reactor outlet HCl transformation efficiency/% | 42.4 | 46.2 | 49.2 |
| Every platform adiabatic reactor outlet O 2Transformation efficiency/% | 80.1 | 89.0 | 96.0 |
Claims (3)
1. the method for a catalytic oxidation of hydrogen chloride for preparing chlorine gas, it is characterized in that the method comprises the following steps: by hydrogenchloride and oxygen mix even, enter fluidized-bed reactor and carry out oxidizing reaction, reaction mixture gas body leaves fluidized-bed reactor, through direct heat exchange, reaction mixture gas temperature being reduced to temperature is 350 ~ 410 DEG C, then to enter in the insulation fix bed reactor of connecting with fluidized-bed oxidizing reaction further; Insulation fix bed reactor is N platform, 2 < N < 6, connection is combined in a series arrangement between N platform insulation fix bed reactor, between N platform insulation fix bed reactor, interchanger or heat transfer space are set, from N-1 platform insulation fix bed reactor reaction mixture gas body out, by directly contacting with heat-eliminating medium, reaction mixture gas temperature is reduced to after 350 ~ 410 DEG C, after enter series connection N platform insulation fix bed reactor proceed reaction; The mode of described direct heat exchange, refer to that reaction mixture gas body and heat-eliminating medium directly contact thus the temperature of reaction mixture gas body reduced, described heat-eliminating medium is oxygen or hydrogen chloride gas; The range of reaction temperature of reaction mixture gas body in insulation fix bed reactor is 350 ~ 450 DEG C, and reaction pressure is 3 ~ 8atm.
2. method according to claim 1, is characterized in that, when entering fluidized-bed reactor, the mol ratio of oxygen and hydrogenchloride is 1/8 ~ 2/1; In a fluidized bed reactor, reaction pressure is 1 ~ 10atm, and temperature of reaction is 380 ~ 430 DEG C.
3. method according to claim 1, is characterized in that, hydrogenchloride is 0.75 ~ 7.5Nm by the feeding rate of fluidized-bed
3/ kg catalyzer/h.
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