CN102649554B - Method for CO gas oxidative dehydrogenation - Google Patents
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- CN102649554B CN102649554B CN201110045204.3A CN201110045204A CN102649554B CN 102649554 B CN102649554 B CN 102649554B CN 201110045204 A CN201110045204 A CN 201110045204A CN 102649554 B CN102649554 B CN 102649554B
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Abstract
The invention relates to a method for CO gas oxidative dehydrogenation and mainly solves the technical problems of low hydrogen desorbing rate and high CO loss rate in a CO gas raw material oxidative dehydrogenation reaction process in the prior art. In the invention, by adopting mixture gas containing carbon monoxide and hydrogen as raw materials, and under the conditions that a catalyst takes platinum or palladium as an active constituent, the reaction temperature is 80 to 260 DEG C, the volume space velocity is 100 to 10,000 hours<-1>, the molar ratio of oxygen/hydrogen is (0.5-10): 1, and the reaction pressure ranges from 0.08 below zero to 5.0 MPa, the raw materials are in contact with a catalyst in a reactor to generate an effluent containing water. The method is characterized is that reactor is a sub-zone heat exchange tubular reactor, and the problems are well solved, and the method can be used for industrial production of CO gas oxidative dehydrogenation.
Description
Technical field
The present invention relates to a kind of method of CO (carbon monoxide converter) gas feed oxygen fluidized dehydrogenation, particularly, about adopting subregion heat exchanging pipe reactor to carry out the method for CO (carbon monoxide converter) gas feed oxygen fluidized dehydrogenation, be practically applicable in CO (carbon monoxide converter) gas feed oxygen fluidized 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 carbon monoxide 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 carbon monoxide coupling catalysts 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, carbon monoxide Mo/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 ℃ 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 to exist for CO (carbon monoxide converter) gas oxidative dehydrogenation process in previous literature technology, exist hydrogen decreasing ratio low, the technical problem that carbon monoxide rate of loss is high, provides a kind of method of new CO (carbon monoxide converter) gas oxydehydrogenation.The method, for CO (carbon monoxide converter) gas raw material oxidative dehydrogenation process, has hydrogen decreasing ratio high, the advantage that carbon monoxide 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 (carbon monoxide converter) gas oxydehydrogenation, take the gas mixture containing carbon monoxide and hydrogen as raw material, catalyzer is take platinum or palladium as active ingredient, be 80～260 ℃ in temperature of reaction, volume space velocity is 100～10000 hours
-1, oxygen/hydrogen mol ratio is 0.5～10: 1, and under the condition that reaction pressure is-0.08～5.0MPa, raw material contacts with catalyst reactor, generates the effluent that contains water, it is characterized in that, and described reactor is the shell-and-tube reactor of subregion heat exchange.
In technique scheme, reaction conditions is preferably: 130～240 ℃ of temperature of reaction, volume space velocity is 1000～8000 hours
-1, oxygen/hydrogen mol ratio is 0.6～8: 1, reaction pressure is 0～3.0MPa.Catalyst weight umber meter, platinum or palladium simple substance consumption preferable range are 0.003～1 part; Support of the catalyst is preferably selected from aluminum oxide, and consumption preferable range is 99～99.997 parts
In technique scheme, the reactor of inventive method is mainly made up of feed(raw material)inlet (1), porous gas sparger (2), gas distribution chamber (24), bundle of reaction tubes (5), catalyst bed (7), collection chamber (13), porous gas collection plate (11) and product outlet (12), it is characterized in that catalyst bed (7) is divided into the first heat exchange block (22), the second heat exchange block (19) and the 3rd heat exchange block (16) according to the mobile direction order of reaction gas; The first heat exchange block (22) is connected with first district's heat transferring medium entrance (21) with first district's heat transferring medium outlet (23), the second heat exchange block (19) is connected with Second Region heat transferring medium outlet (20) with Second Region heat transferring medium entrance (8), is connected with the 3rd heat exchange block (16) Yu tri-district's heat transferring medium entrance (15) He tri-district's heat transferring medium outlets (17).Porous gas sparger (2) is positioned at gas distribution chamber (24), and be connected with feed(raw material)inlet (1), porous gas collection plate (11) is positioned at collection chamber (13), and is connected with product outlet (12).Catalyst bed (7) is positioned at bundle of reaction tubes (5), and bundle of reaction tubes (5) is outer is heat transferring medium.Between the first heat exchange block (22) and the second heat exchange block (19), separate by the first subregion dividing plate (6), between the second heat exchange block (19) and the 3rd heat exchange block (16), separate by the second subregion dividing plate (9).The first subregion dividing plate (6) is lower apart from reactor upper tubesheet (4) is 1/8～1/3 of reactor length; Second subregion dividing plate (9) distance the first subregion dividing plate (6) is lower is 1/8～1/3 of reactor length.
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, rear portion approaches balance with reaction, speed of response slows down, emit reaction heat also few, if the same before and after the temperature of refrigerant, if reduce like this coolant temperature, strengthen heat transfer temperature difference and move heat, reach the heat request that moves of top or anterior high speed of response 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 utility model is for this fundamental contradiction, break through the existing refrigerant with same temperature, and adopt the different sections of reactor to adopt differing temps refrigerant to solve, make the size that in reaction, heat exchange is shifted out by reaction heat need design, multiple districts before and after specifically can being divided into by reaction gas flow direction order in catalyst layer, carry out indirect heat exchange by refrigerant by heat transfer tube, thereby realize the equiblibrium mass distribution of full bed temperature, 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.
CO gas raw material oxidative dehydrogenation reactor of the present invention is for CO gas raw material oxidative dehydrogenation, use Fig. 1 shown device, adopt subregion heat exchange, accurately control temperature, adopting precious metal palladium or platinum Supported alumina is catalyzer, be 80～260 ℃ in reaction temperature in, 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 noble metal catalyst, and the 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 rate of loss that the decreasing ratio of hydrogen can reach 100%, CO can be less than 0.5%, has obtained good technique effect.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the CO gas raw material oxidative dehydrogenation reactor of the inventive method employing.
In Fig. 1,1 is feed(raw material)inlet, the 2nd, porous gas sparger, the 3rd, reactor upper cover, the 4th, upper tubesheet, the 5th, bundle of reaction tubes, 6 is first subregion dividing plates, the 7th, catalyst bed, the 8th, reactor tank body, 9 is second subregion dividing plates, the 10th, lower tubesheet, the 11st, porous gas collection plate, the 12nd, product outlet, the 13rd, collection chamber, the 14th, reactor lower cover, 15 Shi tri-district's heat transferring medium entrances, 16 is the 3rd heat exchange blocks, 17 Shi 3rd district heat transferring medium outlets, the 18th, Second Region heat transferring medium entrance, 19 is second heat exchange blocks, the 20th, the outlet of Second Region heat transferring medium, 21 is first district's heat transferring medium entrances, 22 is first heat exchange blocks, 23 is the heat transferring medium outlets of the firstth district, the 24th, gas distribution chamber,
Fig. 1 Raw is introduced by feed(raw material)inlet 1, after distributing, porous gas sparger 2 enters gas distribution chamber 24, enter afterwards in bundle of reaction tubes 5 and catalyst bed 7 contact reactss, the heat producing in reaction process is taken away by the heat transferring medium outside bundle of reaction tubes 5, reacted gas enters collection chamber 13, then by entering follow-up system through product outlet 12 after porous gas collection plate 11.In reaction raw materials gas enters bundle of reaction tubes 5 and in catalyst bed 7 contact reacts processes, successively through the first heat exchange block (22), the second heat exchange block (19) and the 3rd heat exchange block (16), the temperature of each heat exchange block can be by entering temperature and the control of flow philosophy of heat transferring medium of each heat exchange block, thereby reach the effect that temperature all walks.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Ironic oxalate is dissolved in water, is heated to 70 ℃, it is 50 meters that vacuum rotating is immersed in specific surface agent
2/ gram Al
2o
3on bead, be then dried 6 hours in 120 ℃.By SnCl
2, magnesium nitrate and Palladous nitrate be dissolved in the water respectively, making its pH value with HCl regulator solution is 4 left and right, then this solution is heated to 80 ℃, again be immersed on carrier, then in 140 ℃ dry 8 hours, then roasting 4 hours in 450 ℃ of air atmospheres, reductase 12 hour in 400 ℃ of hydrogen atmospheres, obtain catalyst A, it consists of as table 1:
The catalyst A that takes above-mentioned preparation packs in the reactor of accompanying drawing 1 shown device, first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thereby the control of realization response device catalyst bed temperature, with the Co mixed gas of hydrogen content 10% be raw material, 220 ℃ 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, reaction result is: the rate of loss of carbon monoxide is 0.31%, and in reaction effluent, the content of hydrogen is 2ppm.
[embodiment 2]
Iron nitrate is dissolved in water, is heated to 80 ℃, vacuum rotating impregnating ratio surface agent is 80 meters
2/ gram Al
2o
3on bead, be then dried 4 hours in 120 ℃.Repone K and ammonium palladic chloride are dissolved in the water respectively, making its pH value with HCl regulator solution is 4 left and right, then this solution is heated to 80 ℃, again be immersed on carrier, then in 140 ℃ dry 4 hours, then roasting 4 hours in 450 ℃ of air atmospheres, reductase 12 hour in 400 ℃ of hydrogen atmospheres, obtain catalyst B, it consists of as table 1.
The catalyst B that takes above-mentioned preparation packs in the reactor of accompanying drawing 1 shown device, first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thereby the control of realization response device catalyst bed temperature, with the Co mixed gas of hydrogen content 8% be raw material, 180 ℃ of temperature of reaction, volume space velocity 1000 hours
-1, oxygen/hydrogen mol ratio is 0.7: 1, and under the condition that reaction pressure is 0.2MPa, reaction result is: the rate of loss of carbon monoxide is 0.21%, and in reaction effluent, the content of hydrogen is 5ppm.
[embodiment 3]
Zinc nitrate, nitric acid niobium, rubidium nitrate are dissolved in the water respectively, and it is 30 meters that vacuum rotating is immersed in specific surface agent
2/ gram Al
2o
3on bead, 140 ℃ are dried 4 hours.Ammonium chloroplatinate is dissolved in ethanolic soln, is again immersed on carrier, 140 ℃ are dried 4 hours, then roasting 4 hours in 450 ℃ of air atmospheres is reduced 4 hours in 300 ℃ of hydrogen atmospheres, then in nitrogen atmosphere, is cooled to room temperature, obtain catalyzer C, composition is in table 1.
The catalyzer C that takes above-mentioned preparation packs in the reactor of accompanying drawing 1 shown device, first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thereby the control of realization response device catalyst bed temperature, with the Co mixed gas of hydrogen content 0.5% be raw material, 200 ℃ of temperature of reaction, volume space velocity 3000 hours
-1, oxygen/hydrogen mol ratio is 1: 1, reaction pressure is-condition of 0.05MPa under, reaction result is: the rate of loss of carbon monoxide is 0.33%, in reaction effluent, the content of hydrogen is 0.
[embodiment 4]
Manganous nitrate, saltpetre are dissolved in the water respectively, and it is 150 meters that vacuum rotating is immersed in specific surface agent
2/ gram Al
2o
3on bead, 140 ℃ are dried 4 hours.Sub-chlorine palladium acid is dissolved in ethanolic soln, is again immersed on carrier, 140 ℃ are dried 4 hours, then roasting 4 hours in 450 ℃ of air atmospheres is reduced 4 hours in 450 ℃ of hydrogen atmospheres, then in nitrogen atmosphere, is cooled to room temperature, obtain catalyzer D, composition is in table 1.
The catalyzer D that takes above-mentioned preparation packs in the reactor of accompanying drawing 1 shown device, first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thereby the control of realization response device catalyst bed temperature 350 ℃ of reduction 4 hours, is then raw material with the Co mixed gas of hydrogen content 1% with hydrogen, 130 ℃ of temperature of reaction, volume space velocity 800 hours
-1, oxygen/hydrogen mol ratio is 8: 1, and under the condition that reaction pressure is 5.0MPa, reaction result is: the rate of loss of carbon monoxide is 0.15%, and in reaction effluent, the content of hydrogen is 0.
[embodiment 5]
Iron nitrate, nitrate of baryta are dissolved in the water respectively, and it is 200 meters that vacuum rotating is immersed in specific surface agent
2/ gram Al
2o
3on bead, 140 ℃ are dried 4 hours.Ammonium palladic chloride is dissolved in ethanolic soln, is again immersed on carrier, 140 ℃ are dried 4 hours, then 450 ℃ of roastings 4 hours, in 350 ℃ of hydrogen atmospheres, reduce 4 hours, then in nitrogen atmosphere, are cooled to room temperature, obtain catalyzer E, and composition is in table 1.
The catalyzer E that takes above-mentioned preparation packs in the reactor of accompanying drawing 1 shown device, first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thereby the control of realization response device catalyst bed temperature 350 ℃ of reduction 4 hours, is then raw material with the Co mixed gas of hydrogen content 0.5% with hydrogen, 100 ℃ of temperature of reaction, volume space velocity 500 hours
-1, oxygen/hydrogen mol ratio is 5: 1, and under the condition that reaction pressure is 4.0MPa, reaction result is: the rate of loss of carbon monoxide is 0.12%, and in reaction effluent, the content of hydrogen is 0.
[embodiment 6]
Getting 200 grams is 250 meters in specific surface agent
2/ gram Al
2o
3bead, be immersed in the 200 ml water solution containing 8.0 grams of Platinic chlorides, 14 grams of magnesium nitrates, 15 milliliters of hydrochloric acid, after taking-up, dry 4 hours at 140 ℃, then roasting 2 hours in 450 ℃ of air atmospheres, in 350 ℃ of hydrogen atmospheres, reduce 4 hours, then in nitrogen atmosphere, be cooled to room temperature, obtain catalyzer F, composition is in table 1.
The catalyzer F that takes above-mentioned preparation packs in the reactor of accompanying drawing 1 shown device, first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thereby the control of realization response device catalyst bed temperature 350 ℃ of reduction 4 hours, is then raw material with the Co mixed gas of hydrogen content 0.5% with hydrogen, 250 ℃ of temperature of reaction, volume space velocity 8000 hours
-1, oxygen/hydrogen mol ratio is 0.7: 1, and under the condition that reaction pressure is 0.2MPa, reaction result is: the rate of loss of carbon monoxide is 0.20%, and in reaction effluent, the content of hydrogen is 0.
[embodiment 7]
Cerous nitrate, zirconium nitrate, iron nitrate are dissolved in the water respectively, and it is 120 meters that vacuum rotating is immersed in specific surface agent
2/ gram Al
2o
3on bead, 140 ℃ are dried 4 hours.Ammonium palladic chloride is dissolved in ethanolic soln, is again immersed on carrier, 140 ℃ are dried 4 hours, then roasting 2 hours in 450 ℃ of air atmospheres is reduced 4 hours in 300 ℃ of hydrogen atmospheres, then in nitrogen atmosphere, is cooled to room temperature, obtain catalyzer G, composition is in table 1.
The catalyzer G that takes above-mentioned preparation packs in the reactor of accompanying drawing 1 shown device, first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thereby the control of realization response device catalyst bed temperature 350 ℃ of reduction 4 hours, is then raw material with the Co mixed gas of hydrogen content 5% with hydrogen, 190 ℃ of temperature of reaction, volume space velocity 5000 hours
-1, oxygen/hydrogen mol ratio is 2: 1, and under the condition that reaction pressure is 2.0MPa, reaction result is: the rate of loss of carbon monoxide is 0.38%, and in reaction effluent, the content of hydrogen is 0.
[embodiment 8]
Cupric nitrate, lanthanum nitrate, nickelous nitrate are dissolved in the water respectively, and it is 180 meters that vacuum rotating is immersed in specific surface agent
2/ gram Al
2o
3on bead, 140 ℃ are dried 4 hours.Ammonium palladic chloride is dissolved in ethanolic soln, is again immersed on carrier, 140 ℃ are dried 4 hours, then roasting 4 hours in 450 ℃ of air atmospheres is reduced 4 hours in 300 ℃ of hydrogen atmospheres, then in nitrogen atmosphere, is cooled to room temperature, obtain catalyzer H, composition is in table 1.
The catalyzer H that takes above-mentioned preparation packs in the reactor of accompanying drawing 1 shown device, first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thereby the control of realization response device catalyst bed temperature 350 ℃ of reduction 4 hours, is then raw material with the Co mixed gas of hydrogen content 1% with hydrogen, 90 ℃ of temperature of reaction, volume space velocity 200 hours
-1, oxygen/hydrogen mol ratio is 1: 1, and under the condition that reaction pressure is 1.0MPa, reaction result is: the rate of loss of carbon monoxide is 0.58%, and in reaction effluent, the content of hydrogen is 0.
[comparative example 1]
Adopt identical catalyzer, raw material and the condition of embodiment 1, just adopt the fixed-bed reactor of one section of heat exchange, reaction result is: the rate of loss of carbon monoxide is 1.2%, and in reaction effluent, the content of hydrogen is 12ppm.
[comparative example 2]
Adopt identical catalyzer, raw material and the condition of embodiment 2,, just adopt the fixed-bed reactor of one section of heat exchange, reaction result is: the rate of loss of carbon monoxide is 1.1%, in reaction effluent, the content of hydrogen is 18ppm.
Obviously the inventive method, for the selective oxidation of CO mixed gas except H-H reaction, has higher hydrogen decreasing ratio and lower CO rate of loss.
The composition of table 1 catalyzer
| Catalyzer numbering | Catalyst weight composition (in metal) |
| A | 0.17％Pd+0.28％Sn+0.23％Mg+0.12％Fe/Al 2O 3 |
| B | 0.45％Pd+0.40％K+0.22％Fe/Al 2O 3 |
| C | 0.01％Pt+1％Nb+0.2％Rb/Al 2O 3 |
| D | 0.34％Pd+1.0％K+0.46％Mn/Al 2O 3 |
| E | 0.11％Pd+0.6％Ba+0.2％Fe/Al 2O 3 |
| F | 0.6％Pt+1.1％Mg/Al 2O 3 |
| G | 0.8％Pd+10％Ce+0.003％Zr+0.0507％Fe/Al 2O 3 |
| H | 0.005％Pd+0.015％La+5％Cu+0.2％Ni/Al 2O 3 |
Claims (1)
1. a method for CO (carbon monoxide converter) gas oxydehydrogenation, is dissolved in the water iron nitrate, nitrate of baryta respectively, and it is 200 meters that vacuum rotating is immersed in specific surface agent
2/ gram Al
2o
3on bead, 140 ℃ are dried 4 hours; Ammonium palladic chloride is dissolved in ethanolic soln, again be immersed on carrier, 140 ℃ are dried 4 hours, then 450 ℃ of roastings 4 hours, in 350 ℃ of hydrogen atmospheres, reduce 4 hours, then in nitrogen atmosphere, be cooled to room temperature, in metal, obtain weight and consist of 0.11%Pd+0.6%Ba+0.2%Fe/Al
2o
3catalyzer E;
Take in the catalyzer E reactor of above-mentioned preparation, first, second and third heat transferring medium all adopts saturation steam, just adopt the difference of pressure, realize the difference of temperature, thereby the control of realization response device catalyst bed temperature 350 ℃ of reduction 4 hours, is then raw material with the Co mixed gas of hydrogen content 0.5% with hydrogen, 100 ℃ of temperature of reaction, volume space velocity 500 hours
-1, oxygen/hydrogen mol ratio is 5: 1, and under the condition that reaction pressure is 4.0MPa, reaction result is: the rate of loss of carbon monoxide is 0.12%, and in reaction effluent, the content of hydrogen is 0;
Wherein, described reactor is the shell-and-tube reactor of subregion heat exchange, mainly formed by feed(raw material)inlet (1), porous gas sparger (2), gas distribution chamber (24), bundle of reaction tubes (5), catalyst bed (7), collection chamber (13), porous gas collection plate (11) and product outlet (12), it is characterized in that catalyst bed (7) is divided into the first heat exchange block (22), the second heat exchange block (19) and the 3rd heat exchange block (16) according to the mobile direction order of reaction gas; The first heat exchange block (22) is connected with first district's heat transferring medium entrance (21) with first district's heat transferring medium outlet (23), the second heat exchange block (19) is connected with Second Region heat transferring medium outlet (20) with Second Region heat transferring medium entrance (8), is connected with the 3rd heat exchange block (16) Yu tri-district's heat transferring medium entrance (15) He tri-district's heat transferring medium outlets (17); Porous gas sparger (2) is positioned at gas distribution chamber (24), and be connected with feed(raw material)inlet (1), porous gas collection plate (11) is positioned at collection chamber (13), and is connected with product outlet (12); Catalyst bed (7) is positioned at bundle of reaction tubes (5), and bundle of reaction tubes (5) is outer is heat transferring medium; Between the first heat exchange block (22) and the second heat exchange block (19), separate by the first subregion dividing plate (6), between the second heat exchange block (19) and the 3rd heat exchange block (16), separate by the second subregion dividing plate (9); The first subregion dividing plate (6) is lower apart from reactor upper tubesheet (4) is 1/8～1/3 of reactor length; Second subregion dividing plate (9) distance the first subregion dividing plate (6) is lower is 1/8～1/3 of reactor length.
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| CN103223339A (en) * | 2013-04-09 | 2013-07-31 | 中国科学院福建物质结构研究所 | Method for preparing supported Pd-based catalysts |
| CN106215956A (en) * | 2016-07-05 | 2016-12-14 | 中国科学院福建物质结构研究所 | A kind of activity plane defect type palladium chloride catalyst and its preparation method and application |
| CN109433192B (en) * | 2018-12-07 | 2021-06-01 | 东北大学 | Noble metal monoatomic dispersion type purification catalyst and preparation method thereof |
| CN112827437A (en) * | 2019-11-25 | 2021-05-25 | 江苏氢电新能源有限公司 | Self-heating dehydrogenation reaction device |
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| CN1988950A (en) * | 2004-05-28 | 2007-06-27 | 住友化学株式会社 | Heat exchange type reactor |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1988950A (en) * | 2004-05-28 | 2007-06-27 | 住友化学株式会社 | Heat exchange type reactor |
| 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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