CN102649564B - Method for dehydrogenating CO-containing mixed gas raw material by means of catalytic oxidation reaction - Google Patents
Method for dehydrogenating CO-containing mixed gas raw material by means of catalytic oxidation reaction Download PDFInfo
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- CN102649564B CN102649564B CN201110045662.7A CN201110045662A CN102649564B CN 102649564 B CN102649564 B CN 102649564B CN 201110045662 A CN201110045662 A CN 201110045662A CN 102649564 B CN102649564 B CN 102649564B
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Abstract
The invention relates to a method for dehydrogenating a CO-containing mixed gas raw material by means of a catalytic oxidation reaction. According to the method, the technical problems of difficulty in temperature control, low hydrogen gas removing rate and high CO loss rate in the dehydrogenation process of the CO-containing mixed gas raw material by means of the catalytic oxidation reaction in the prior art are mainly solved. The technical scheme adopted by the invention is that the method is realized by the step that with gases containing hydrogen gas and CO as raw materials and under the conditions that the reaction temperature is 80-260DEG C, the volume space velocity is 100-10000 hour<-1>, the mole ratio of oxygen gas to hydrogen gas is (0.5-10):1 and the reaction pressure is -0.08MPa to 5.0MPa, the raw materials are sequentially contacted with noble metal catalysts in an upper heat-insulated catalyst bed, a heat exchange catalyst bed and a lower heat-insulated catalyst bed of an enhanced heat exchange combined reactor in a hot spot distribution area and the hydrogen gas in the raw materials is oxidized into water. According to the technical scheme, the problems are better solved. The method can be used for the industrial production of the dehydrogenation of the CO-containing mixed gas raw material by means of the catalytic oxidation reaction.
Description
Technical field
The present invention relates to a kind of method of CO mixed gas feed by catalytic oxidation dehydrogenation that contain, particularly about adopting hotspot's distribution region enhanced heat exchange combined reactor, realize the reaction of CO mixed gas feed catalytic oxidative dehydrogenation, be practically applicable to containing in CO mixed gas feed catalytic oxidative dehydrogenation reaction process.
Background technology
Barkite is important Organic Chemicals, in a large number produces various dyestuffs, medicine, important solvent, extraction agent and various intermediate for fine chemistry industry.Enter 21 century, barkite is subject to international extensively attention as degradable environment-friendly engineering plastics monomer.In addition, barkite ordinary-pressure hydrolysis can obtain oxalic acid, and normal pressure ammonia solution can obtain high-quality slow chemical fertilizer oxamyl.Barkite can also be used as solvent, produces medicine and dyestuff intermediate etc., for example, carry out various condensation reactions with fatty acid ester, hexamethylene phenyl methyl ketone, amido alcohol and many heterogeneous ring compounds.It can also synthesize at the chest acyl alkali that is pharmaceutically used as hormone.In addition, barkite low-voltage hydrogenation can be prepared very important industrial chemicals ethylene glycol, and ethylene glycol mainly relies on petroleum path to prepare at present, and cost is higher, and China needs a large amount of import ethylene glycol every year, 2007 years nearly 4,800,000 tons of import volumes.
The production line of tradition barkite utilizes oxalic acid to prepare with alcohol generation esterification, and production technique cost is high, and energy consumption is large, seriously polluted, and prepared using is unreasonable.Become the focus of domestic and international research and adopt carbon monoxide coupling technology to produce barkite.
As everyone knows, carbon monoxide can be from various containing separation and Extraction the gas mixture of carbon monoxide, and the industrial unstripped gas that can be used for separating carbon monoxide comprises: the tail gas of synthetic gas, water-gas, semi-water gas and Steel Plant, calcium carbide factory and Yellow Phosphorous Plant that Sweet natural gas and oil transform etc.The main method of existing CO separating-purifying is pressure swing adsorption process, You Duo company of China has developed pressure-variable adsorption and has separated carbon monoxide new technology, especially the high-efficiency adsorbent of exploitation, carbon monoxide is had to high loading capacity and selectivity, can solve a difficult problem of isolating high-purity carbon monooxide from nitrogen or the high unstripped gas of methane content, can design and build up large-scale carbon monoxide tripping device.However, by this technology isolated carbon monoxide from synthetic gas, taking into account under the prerequisite of carbon monoxide yield, the content of its hydrogen can reach more than 1% under normal circumstances.And research shows that the existence of hydrogen can cause follow-up CO coupling reaction catalyst activity decreased, until reaction cannot be carried out, therefore, exploitation carbon monoxide selects dehydrogenation technical meaning great.
At present, the dehydrogenation catalyst of report mainly contains Pd/Al both at home and abroad
2o
3, CoMo/Al
2o
3deng, also there is the dehydrogenating agent based on manganese series metal oxide, but being generally used for the dehydrogenation of the non-reducing gas such as High Purity Nitrogen, high purity oxygen and carbonic acid gas, these catalyzer or dehydrogenating agent purify.And under existing for CO reducing gas, catalyzer is low to the decreasing ratio of hydrogen, the rate of loss of CO is high.As adopt method and the catalyzer of the disclosed catalytic oxidative dehydrogenation of document CN97191805.8, and be raw material at the CO mixed gas for hydrogen content 10%, 220 DEG C of temperature of reaction, volume space velocity 3000 hours
-1, oxygen/hydrogen mol ratio is 0.6: 1, and under the condition that reaction pressure is 0.5MPa, the rate of loss of CO is up to 1.5%, and in reaction effluent, the content of hydrogen is up to 1000ppm.
The subject matter that the related technology of above-mentioned document exists is that technique and catalyzer are unreasonable, causes carbon monoxide rate of loss high, and hydrogen removes not thorough.
Summary of the invention
Technical problem to be solved by this invention is for containing CO mixed gas feed by catalytic oxidation dehydrogenation reaction process in previous literature technology, temperature control difficulty, exist hydrogen decreasing ratio low, the technical problem that CO rate of loss is high, provides a kind of new method by catalytic oxidation dehydrogenation containing CO mixed gas feed.Should be used for containing CO mixed gas feed catalytic oxidative dehydrogenation process by catalytic oxidation dehydrogenation containing CO mixed gas feed, temperature control is even, has hydrogen decreasing ratio high, the advantage that CO rate of loss is low.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of CO mixed gas feed by catalytic oxidation dehydrogenation that contain, taking the gas of hydrogen and CO as raw material, be 80～260 DEG C in temperature of reaction, volume space velocity is 100～10000 hours
-1, oxygen/hydrogen mol ratio is 0.5～10: 1, reaction pressure is under the condition of-0.08～5.0MPa, raw material successively with hotspot's distribution region enhanced heat exchange combined reactor in upper adiabatic catalyst beds, heat exchange catalyst bed contacts with the noble metal catalyst in lower adiabatic catalyst beds, hydrogen in raw material is oxidized to water, wherein enhanced heat exchange combined reactor in hotspot's distribution region is substantially by feed(raw material)inlet (1), porous gas grid distributor (3), gas distribution chamber (4), upper adiabatic catalyst beds (5), heat exchange catalyst bed (6), lower adiabatic catalyst beds (7), heat transfer tube (13), collection chamber (8) and porous gas collection plate (9) form, be primarily characterized in that heat exchange catalyst bed (6) is positioned at the bottom of adiabatic catalyst beds (5), the top of lower adiabatic catalyst beds (7), and heat transfer tube (13) is set in heat exchange catalyst bed (6).
In technique scheme, porous gas collection plate (9) is positioned at collection chamber (8), and is connected with pneumatic outlet (10).Porous gas grid distributor (3) is positioned at gas distribution chamber (4), and is connected with feed(raw material)inlet (1).Upper adiabatic catalyst beds (5) top is 1/30～1/6 of reactor length apart from the length of porous gas grid distributor (3) bottom; The bottom of lower adiabatic catalyst beds (7) is 1/30～1/6 of height for reactor apart from the vertical height on porous gas collection plate (9) top.The height of upper adiabatic catalyst beds (5) is 1/6～3/2 of heat exchange catalyst bed (6) height, and lower adiabatic catalyst beds (7) is 1/6～1/1 of heat exchange catalyst bed (6) height.
In technique scheme, reaction conditions is preferably: temperature of reaction is 120～240 DEG C, and volume space velocity is 500～6000 hours
-1, oxygen/hydrogen mol ratio is 0.5～4: 1, and reaction pressure is 0.01～2.0MPa, and noble metal catalyst active ingredient is preferably selected from palladium or platinum, and carrier is preferably selected from aluminum oxide.
As everyone knows, hydrogen is high-intensity thermopositive reaction with reacting of oxygen, and the hydrogen under CO exists removes reaction, requires very high to the control of temperature.If temperature control is improper, may cause and cause CO and oxygen reaction because of temperature drift, this not only can cause thermal discharge further to strengthen, temperature further raises, and the loss of CO also can sharply increase, therefore control reaction bed uniformity of temperature profile to most important by oxidative dehydrogenation process containing CO gaseous mixture, the temperature distribution of beds is more even, the selection of hydrogen just removes and more easily controls, and easily keeps lower CO rate of loss.For conventional fixed-bed reactor, because catalyzed reaction is carried out on catalyzer and not according to front and back phase uniform velocity, general reactor front portion is from balanced remote, speed of response is fast, emit reaction heat also many, show as anterior mid-way partially and easily occur significant hot spot region, and rear portion approaches balance with reaction, speed of response slows down, emit reaction heat also few, if adopt conventional shell-and-tube reactor, the same before and after the temperature of its refrigerant, if reduce like this coolant temperature, strengthen heat transfer temperature difference and move heat, reach the heat request that moves of the high speed of response of middle front part and strong reaction heat, reactor lower part or rear portion reaction heat reduce, move heat be greater than reaction heat cause temperature of reaction decline, speed of response is further slowed down until catalyst activity is following with regard to stopped reaction, therefore be difficult to accomplish that front and rear part reacts the way making the best of both worlds of all carrying out under optimal reaction temperature.The present invention is directed to this fundamental contradiction, and according to the characteristic exotherm reacting, at reactor middle part, heat transfer zone is set, and reactor two ends arrange adiabatic region, make hot spot region flattening, temperature distribution is more evenly rationally, this is for the efficiency of maximized performance catalyzer, farthest reduce the loss of CO, and remove comparatively up hill and dale the hydrogen in raw material, useful effect is provided.
The present invention's Fig. 1 shown device, hotspot's distribution region enhanced heat exchange combined reactor, accurately controls temperature, and adopting precious metal palladium or platinum Supported alumina is catalyzer, is 80～260 DEG C in temperature of reaction, and volume space velocity is 100～10000 hours
-1oxygen/hydrogen mol ratio is 0.5～10: 1, reaction pressure is under the condition of-0.08～5.0MPa, raw material contacts with the noble metal catalyst in upper adiabatic catalyst beds, heat exchange catalyst bed and lower adiabatic catalyst beds in the enhanced heat exchange combined reactor of hotspot's distribution region successively, hydrogen in raw material is oxidized to water, containing in the gas raw material of CO, the volumn concentration of hydrogen is to be greater than under 0～15% condition, the decreasing ratio of hydrogen can reach 100%, the rate of loss of CO can be less than 0.3%, has obtained good technique effect.
Brief description of the drawings
Fig. 1 is the hotspot's distribution region enhanced heat exchange combined reactor schematic diagram that the present invention adopts.
In Fig. 1,1 is feed(raw material)inlet, the 2nd, and manhole, the 3rd, porous gas grid distributor, the 4th, gas distribution chamber, the 5th, upper adiabatic catalyst beds, the 6th, heat exchange catalyst bed, the 7th, lower adiabatic catalyst beds, the 8th, collection chamber, the 9th, porous gas collection plate, the 10th, pneumatic outlet, the 11st, catalyzer unloads outlet, and the 12nd, heat transferring medium outlet, the 13rd, heat transfer tube, the 14th, heat transferring medium entrance, the 15th, reactor tank body.
Fig. 1 Raw is introduced by feed(raw material)inlet 1, gas enters the further mixed distribution of distributing chamber 4 after porous gas grid distributor 3 distributes, then enter adiabatic catalyst beds 5 and catalyzer contact reacts, there is the reaction effluent of certain temperature rise to enter again heat exchange catalyst bed 6, the heat discharging in reaction process carries out shifting out of heat by heat transfer tube 13, keep the temperature in heat exchange catalyst bed 6 even, effluent after most of raw material reaction finally enters after lower adiabatic catalyst beds 7 further reacts completely, effluent enters collection chamber 8, enter follow-up system by porous gas collection plate 9 through pneumatic outlet 10.Carry out shifting out and controlling of heat because hot(test)-spot temperature distributed areas adopt heat transfer tube, thereby reach the uniform effect of whole reactor catalyst bed tempertaure.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
With the hotspot's distribution region enhanced heat exchange combined reactor of Fig. 1, adopt the catalyzer in heat transfer tube heat exchanging catalyst bed to carry out heat exchange, wherein, the upper adiabatic catalyst beds top of reactor is 1/20 of reactor length apart from the length of porous gas grid distributor bottom; The bottom of lower adiabatic catalyst beds is 1/10 of height for reactor apart from the vertical height on porous gas collection plate top, the height of the upper adiabatic catalyst beds of reactor is 1/8 of heat exchange catalyst bed height, lower adiabatic catalyst beds is 1/4 of heat exchange catalyst bed height, the catalyzer of the palladium Supported alumina taking palladium content as 0.5% is as catalyzer, with the CO mixed gas of hydrogen content 10% be raw material, at 220 DEG C of reaction temperature ins, volume space velocity 3000 hours
-1, oxygen/hydrogen mol ratio is 0.6: 1, and under the condition that reaction pressure is 0.5MPa, reaction result is: the rate of loss of CO is 0.32%, and in reaction effluent, the content of hydrogen is 0ppm, and reactor catalyst bed temperature is poor is less than 10 DEG C.
[embodiment 2]
With the hotspot's distribution region enhanced heat exchange combined reactor of Fig. 1, adopt the catalyzer in heat transfer tube heat exchanging catalyst bed to carry out heat exchange, wherein, the upper adiabatic catalyst beds top of reactor is 1/10 of reactor length apart from the length of porous gas grid distributor bottom; The bottom of lower adiabatic catalyst beds is 1/20 of height for reactor apart from the vertical height on porous gas collection plate top, the height of the upper adiabatic catalyst beds of reactor is 1/3 of heat exchange catalyst bed height, lower adiabatic catalyst beds is 1/4 of heat exchange catalyst bed height, the catalyzer of the palladium Supported alumina taking palladium content as 0.2% is as catalyzer, with the CO mixed gas of hydrogen content 5% be raw material, at 200 DEG C of reaction temperature ins, volume space velocity 1000 hours
-1, oxygen/hydrogen mol ratio is 0.7: 1, and under the condition that reaction pressure is 0.1MPa, reaction result is: the rate of loss of CO is 0.15%, and in reaction effluent, the content of hydrogen is 3ppm, and reactor catalyst bed temperature is poor is less than 8 DEG C.
[embodiment 3]
With the hotspot's distribution region enhanced heat exchange combined reactor of Fig. 1, adopt the catalyzer in heat transfer tube heat exchanging catalyst bed to carry out heat exchange, wherein, the upper adiabatic catalyst beds top of reactor is 1/8 of reactor length apart from the length of porous gas grid distributor bottom; The bottom of lower adiabatic catalyst beds is 1/5 of height for reactor apart from the vertical height on porous gas collection plate top, the height of the upper adiabatic catalyst beds of reactor is 1/3 of heat exchange catalyst bed height, lower adiabatic catalyst beds is 1/6 of heat exchange catalyst bed height, the catalyzer of the palladium Supported alumina taking palladium content as 0.3% is as catalyzer, with the CO mixed gas of hydrogen content 1% be raw material, at 180 DEG C of reaction temperature ins, volume space velocity 5000 hours
-1, oxygen/hydrogen mol ratio is 0.8: 1, and under the condition that reaction pressure is 2.5MPa, reaction result is: the rate of loss of CO is 0.15%, and in reaction effluent, the content of hydrogen is 3ppm, and reactor catalyst bed temperature is poor is less than 6 DEG C.
[embodiment 4]
With the hotspot's distribution region enhanced heat exchange combined reactor of Fig. 1, adopt the catalyzer in heat transfer tube heat exchanging catalyst bed to carry out heat exchange, wherein, the upper adiabatic catalyst beds top of reactor is 1/15 of reactor length apart from the length of porous gas grid distributor bottom; The bottom of lower adiabatic catalyst beds is 1/20 of height for reactor apart from the vertical height on porous gas collection plate top, the height of the upper adiabatic catalyst beds of reactor is 1/3 of heat exchange catalyst bed height, lower adiabatic catalyst beds is 1/4 of heat exchange catalyst bed height, the catalyzer of the palladium Supported alumina taking palladium content as 0.2% is as catalyzer, with the CO mixed gas of hydrogen content 0.5% be raw material, at 180 DEG C of reaction temperature ins, volume space velocity 4000 hours
-1, oxygen/hydrogen mol ratio is 0.6: 1, reaction pressure is-condition of 0.05MPa under, reaction result is: the rate of loss of CO is 0.11%, in reaction effluent, the content of hydrogen is 1ppm, reactor catalyst bed temperature is poor is less than 5 DEG C.
[embodiment 5]
With the hotspot's distribution region enhanced heat exchange combined reactor of Fig. 1, adopt the catalyzer in heat transfer tube heat exchanging catalyst bed to carry out heat exchange, wherein, the upper adiabatic catalyst beds top of reactor is 1/8 of reactor length apart from the length of porous gas grid distributor bottom; The bottom of lower adiabatic catalyst beds is 1/20 of height for reactor apart from the vertical height on porous gas collection plate top, the height of the upper adiabatic catalyst beds of reactor is 1/2 of heat exchange catalyst bed height, lower adiabatic catalyst beds is 1/3 of heat exchange catalyst bed height, the catalyzer of the platinum Supported alumina taking platinum content as 0.1% is as catalyzer, with the CO mixed gas of hydrogen content 0.8% be raw material, at 260 DEG C of reaction temperature ins, volume space velocity 500 hours
-1, oxygen/hydrogen mol ratio is 0.7: 1, and under the condition that reaction pressure is 0.01MPa, reaction result is: the rate of loss of CO is 0.16%, and in reaction effluent, the content of hydrogen is 3ppm, and reactor catalyst bed temperature is poor is less than 5 DEG C.
[comparative example 1]
With reference to each step and the reaction conditions of embodiment 1, just adopt insulation fix bed reactor containing CO mixed gas feed catalytic oxidative dehydrogenation reactor, reaction result is: the rate of loss of CO is 3.2%, and in reaction effluent, the content of hydrogen is 160ppm, and reactor catalyst bed temperature is poor is 18 DEG C.
[comparative example 2]
With reference to each step and the reaction conditions of embodiment 2, just CO mixed gas feed catalytic oxidative dehydrogenation reactor adopts insulation fix bed reactor, reaction result is: the rate of loss of CO is 4.2%, and in reaction effluent, the content of hydrogen is 180ppm, and reactor catalyst bed temperature is poor is 12 DEG C.
Claims (4)
- Containing CO mixed gas feed by the method for catalytic oxidation dehydrogenation, taking the gas of hydrogen and CO as raw material, be 80～260 DEG C in temperature of reaction, volume space velocity is 100～10000 hours -1, oxygen/hydrogen mol ratio is 0.5～10: 1, reaction pressure is under the condition of-0.08～5.0MPa, raw material successively with hotspot's distribution region enhanced heat exchange combined reactor in upper adiabatic catalyst beds, heat exchange catalyst bed contacts with the noble metal catalyst in lower adiabatic catalyst beds, hydrogen in raw material is oxidized to water, wherein enhanced heat exchange combined reactor in hotspot's distribution region is substantially by feed(raw material)inlet (1), porous gas grid distributor (3), gas distribution chamber (4), upper adiabatic catalyst beds (5), heat exchange catalyst bed (6), lower adiabatic catalyst beds (7), heat transfer tube (13), collection chamber (8) and porous gas collection plate (9) form, be primarily characterized in that heat exchange catalyst bed (6) is positioned at the bottom of adiabatic catalyst beds (5), the top of lower adiabatic catalyst beds (7), and heat transfer tube (13) is set in heat exchange catalyst bed (6), wherein, upper adiabatic catalyst beds (5) top of described reactor is 1/30～1/6 of reactor length apart from the length of porous gas grid distributor (3) bottom, the bottom of lower adiabatic catalyst beds (7) is 1/30～1/6 of height for reactor apart from the vertical height on porous gas collection plate (9) top, the height of the upper adiabatic catalyst beds (5) of reactor is 1/6～3/2 of heat exchange catalyst bed (6) height, and lower adiabatic catalyst beds (7) is 1/6～1/1 of heat exchange catalyst bed (6) height.
- 2. contain according to claim 1 the method for CO mixed gas feed by catalytic oxidation dehydrogenation, the porous gas collection plate (9) that it is characterized in that reactor is positioned at collection chamber (8), and is connected with pneumatic outlet (10).
- 3. contain according to claim 1 the method for CO mixed gas feed by catalytic oxidation dehydrogenation, the porous gas grid distributor (3) that it is characterized in that reactor is positioned at gas distribution chamber (4), and is connected with feed(raw material)inlet (1).
- 4. contain according to claim 1 the method for CO mixed gas feed by catalytic oxidation dehydrogenation, it is characterized in that temperature of reaction is 120～240 DEG C, volume space velocity is 500～6000 hours -1, oxygen/hydrogen mol ratio is 0.5～4: 1, and reaction pressure is 0.01～2.0MPa, and noble metal catalyst active ingredient is selected from palladium or platinum, and carrier is selected from aluminum oxide.
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| WO2018096018A1 (en) * | 2016-11-24 | 2018-05-31 | Haldor Topsøe A/S | Multi bed reactor comprising an adiabatic and a heated catalyst bed |
| CN110841563B (en) * | 2019-11-27 | 2022-04-05 | 云南电网有限责任公司电力科学研究院 | Device and method for dehydrogenation by utilizing tail gas of thermomotor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003144924A (en) * | 2001-11-09 | 2003-05-20 | Mitsubishi Chemicals Corp | Selective oxidation catalyst for hydrogen, selective oxidation method for hydrogen and dehydrogenation method for hydrocarbon |
| CN2621805Y (en) * | 2003-06-03 | 2004-06-30 | 华东理工大学 | Shell external cooling-thermal insulating and combined fixed bed catalyst chember |
| CN101543776A (en) * | 2009-04-28 | 2009-09-30 | 华烁科技股份有限公司 | Dehydrogenation catalyst for feed gas containing carbon monoxide, preparation method and application method thereof |
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| JPS5688801A (en) * | 1979-10-27 | 1981-07-18 | Mitsubishi Gas Chem Co Inc | Separating and obtaining method of hydrogen and carbon monoxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003144924A (en) * | 2001-11-09 | 2003-05-20 | Mitsubishi Chemicals Corp | Selective oxidation catalyst for hydrogen, selective oxidation method for hydrogen and dehydrogenation method for hydrocarbon |
| CN2621805Y (en) * | 2003-06-03 | 2004-06-30 | 华东理工大学 | Shell external cooling-thermal insulating and combined fixed bed catalyst chember |
| CN101543776A (en) * | 2009-04-28 | 2009-09-30 | 华烁科技股份有限公司 | Dehydrogenation catalyst for feed gas containing carbon monoxide, preparation method and application method thereof |
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