CN102649554A - Method for CO gas oxidative dehydrogenation - Google Patents
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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 gas feed oxygen fluidized dehydrogenation, particularly, be useful in the CO gas feed oxygen fluidized dehydrogenation reaction process about adopting subregion heat exchanging pipe reactor drum to carry out the method for CO gas feed oxygen fluidized dehydrogenation.
Background technology
Barkite is important Organic Chemicals, is used for fine chemistry industry in a large number and produces various dyestuffs, medicine, important solvent, extraction agent and various midbody.Get into 21 century, barkite receives international extensively attention as degradable environment-friendly engineering plastics monomer.In addition, the barkite ordinary-pressure hydrolysis can get oxalic acid, and normal pressure ammonia is separated and can be got high-quality slow chemical fertilizer oxamyl.Barkite can also be used as solvent, produces medicine and dyestuff intermediate etc., for example carries out various condensation reactions with fatty ester, hexamethylene phenyl methyl ketone, amido alcohol and many heterogeneous ring compounds.It can also synthesize at the chest acyl alkali that pharmaceutically is used as hormone.In addition, the barkite low-voltage hydrogenation can prepare crucial industrial chemicals terepthaloyl moietie, and terepthaloyl moietie mainly relies on petroleum path to prepare at present, and cost is higher, and China needs a large amount of import terepthaloyl moietie every year, and import volume was nearly 4,800,000 tons in 2007.
The production route of tradition barkite utilizes oxalic acid to prepare with alcohol generation esterification, and the production technique cost is high, and energy consumption is big, and is seriously polluted, and prepared using is unreasonable.And adopt the carbon monoxide coupling technology to produce the focus that barkite has become domestic and international research.
As everyone knows; Carbon monoxide can be from the various gas mixtures that contain carbon monoxide separation and Extraction, the virgin gas that can be used for separating carbon monoxide in the industry comprises: the tail gas of synthetic gas, water-gas, semi-water gas and Iron And Steel Plant, calcium carbide factory and yellow phosphorus factory that Sweet natural gas and oil transform etc.It is pressure swing adsorption process that existing carbon monoxide separates the main method of purifying; China has many companies to develop transformation fractionation by adsorption carbon monoxide new technology; Especially the high-efficiency adsorbent of developing; Carbon monoxide there are high loading capacity and selectivity, can solve a difficult problem of from the high virgin gas of nitrogen or methane content, isolating high-purity carbon monooxide, can design and build up large-scale carbon monoxide tripping device.However, by this technology isolated carbon monoxide from synthetic gas, under the prerequisite of taking into account the carbon monoxide yield, generally the content of its hydrogen can reach more than 1%.And research shows that the existence of hydrogen can cause the active reduction of follow-up carbon monoxide coupling reaction catalyst, can't carry out until reaction, and therefore, the exploitation carbon monoxide selects the 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, the dehydrogenating agent based on the manganese series metal oxide is also arranged, but generally being used for the dehydrogenation of non-reducing gas such as high purity nitrogen, high purity oxygen and carbonic acid gas, these catalyzer or dehydrogenating agent purify.And exist down for the CO reducing gas, catalyzer is low to the decreasing ratio of hydrogen, and the rate of loss of CO is high.As adopt the method and the catalyzer of the disclosed catalytic oxidative dehydrogenation of document CN97191805.8, and be raw material at the CO mixed gas that is used for hydrogen content 10%, 220 ℃ of temperature of reaction, volume space velocity 3000 hours
-1, oxygen/hydrogen mol ratio is 0.6: 1, and reaction pressure is under the condition of 0.5MPa, and the rate of loss of CO is up to 1.5%, and the content of hydrogen is up to 1000ppm in the reaction effluent.
The subject matter that the related technology of above-mentioned document exists is that technology and catalyzer are unreasonable, causes the 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 in the technical literature to be used for CO gas oxidative dehydrogenation process in the past; Exist the hydrogen decreasing ratio low; The technical problem that the carbon monoxide rate of loss is high provides a kind of method of new CO gas oxydehydrogenation.This method is used for CO gas raw material oxidative dehydrogenation process, has hydrogen decreasing ratio height, the advantage that the carbon monoxide rate of loss is low.
In order to solve the problems of the technologies described above; The technical scheme that the present invention adopts is following: a kind of method of CO gas oxydehydrogenation; With the gas mixture that contains carbon monoxide and hydrogen is raw material; Catalyzer is an active ingredient with platinum or palladium, is 80～260 ℃ in temperature of reaction, and volume space velocity is 100～10000 hours
-1, oxygen/hydrogen mol ratio is 0.5～10: 1, and reaction pressure is under the condition of-0.08～5.0MPa, and raw material contacts with catalyst reactor, generates the elute that contains water, it is characterized in that said reactor drum is the shell-and-tube reactor of subregion heat exchange.
Reaction conditions is preferably in the technique scheme: 130～240 ℃ of temperature of reaction, volume space velocity are 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 the consumption preferable range is 99～99.997 parts
The reactor drum of inventive method mainly is 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) in the technique scheme, 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) in proper order according to the mobile direction of reaction gas; The first heat exchange block (22) links to each other with first district's heat transferring medium inlet (21) with first district's heat transferring medium outlet (23); The second heat exchange block (19) links to each other with second district's heat transferring medium outlet (20) with second district's heat transferring medium inlet (8), links to each other with the 3rd district's heat transferring medium outlet (17) with the 3rd district's heat transferring medium inlet (15) with the 3rd heat exchange block (16).Porous gas sparger (2) is positioned at gas distribution chamber (24), and is connected with feed(raw material)inlet (1), and 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 to be heat transferring medium.Separate through the first subregion dividing plate (6) between the first heat exchange block (22) and the second heat exchange block (19), separate through the second subregion dividing plate (9) between the second heat exchange block (19) and the 3rd heat exchange block (16).The first subregion dividing plate (6) is following apart from reactor drum upper tubesheet (4) to be 1/8～1/3 of reactor length; The second subregion dividing plate (9) distance, the first subregion dividing plate (6) is 1/8～1/3 of reactor length down.
As everyone knows, the reaction of hydrogen and oxygen is high-intensity thermopositive reaction, and the hydrogen in the presence of CO removes reaction, requires very high to temperature controlling.If temperature control is improper, may cause because of temperature drift and cause CO and oxygen reaction, this not only can cause thermal discharge further to strengthen; Temperature further raises; And the loss of CO also can sharply increase, and it is most important through the oxidative dehydrogenation process to containing the CO gaseous mixture therefore to control the reaction bed uniformity of temperature profile, and the temperature distribution of beds is even more; The selection of hydrogen just removes control more easily, and keeps lower CO rate of loss easily.For the fixed-bed reactor of routine, because catalyzed reaction is carried out on catalyzer and not according to front and back phase uniform velocity, general reactor drum is anterior from balanced remote; Speed of response is fast, and it is also many to emit reaction heat, the rear portion with reaction near balance; Speed of response slows down, and emits reaction heat and also lacks, if the same before and after the temperature of refrigerant; If reduce coolant temperature like this, 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; Then reactor lower part or rear portion reaction heat reduce; Move heat and cause temperature of reaction to descend, speed of response is further slowed down below catalyst activity with regard to stopped reaction, therefore be difficult to the way that makes the best of both worlds of accomplishing that the front and rear part reaction is all carried out under optimal reaction temperature greater than reaction heat.The utility model is broken through existing refrigerant with same temperature to this fundamental contradiction, and adopts the different sections of reactor drum to adopt the differing temps refrigerant to solve; Make the size that heat exchange is shifted out by reaction heat in the reaction need design; A plurality of districts before and after specifically can being divided in proper order by reaction gas flow direction in catalyst layer come indirect heat exchange by refrigerant through heat transfer tube, thereby realize the equiblibrium mass distribution of full bed temperature; This is for the efficient of maximized performance catalyzer; Farthest reduce the loss of CO, and remove the hydrogen in the raw material comparatively up hill and dale, useful effect is provided.
CO gas raw material oxidative dehydrogenation reactor of the present invention is used for CO gas raw material oxidative dehydrogenation; Use device shown in Figure 1; Adopt the subregion heat exchange, accurate controlled temperature, adopting precious metal palladium or platinum load aluminum oxide is catalyzer; In the reaction temperature in is 80～260 ℃, and 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 contacts with noble metal catalyst, and the hydrogen in the raw material is oxidized to water, in containing the gas raw material of CO; The volumn concentration of hydrogen is greater than under 0～15% the condition; The decreasing ratio of hydrogen can reach 100%, and the rate of loss of CO can obtain better technical effect less than 0.5%.
Description of drawings
Fig. 1 is the synoptic diagram of the CO gas raw material oxidative dehydrogenation reactor of the inventive method employing.
1 is the feed(raw material)inlet among Fig. 1, the 2nd, and porous gas sparger, the 3rd, reactor drum upper cover, the 4th, upper tubesheet, the 5th, bundle of reaction tubes; 6 is first subregion dividing plates, the 7th, and catalyst bed, the 8th, the reactor drum 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, the reactor drum lower cover, 15 is the 3rd district's heat transferring medium inlets, and 16 is the 3rd heat exchange blocks, and 17 is the heat transferring medium outlets of the 3rd district; 18 is second district's heat transferring medium inlets, and 19 is second heat exchange blocks, and 20 is the heat transferring medium outlets of second district, and 21 is first district's heat transferring medium inlets; 22 is first heat exchange blocks, and 23 is the heat transferring medium outlets of first district, the 24th, and the gas distribution chamber
Raw material is introduced by feed(raw material)inlet 1 among Fig. 1;, porous gas sparger 2 gets into gas distribution chamber 24 after distributing; Get in the bundle of reaction tubes 5 afterwards and catalyst bed 7 contact reactss; The heat that produces in the reaction process is taken away through bundle of reaction tubes 5 outer heat transferring mediums, and reacted gas gets into collection chamber 13, gets into follow-up systems through porous gas collection plate 11 after product exports 12 then.In reaction raw materials gas gets into bundle of reaction tubes 5 and in the 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 through getting into each heat exchange block the controls respectively such as temperature and flow of heat transferring medium, thereby reach the effect that temperature all goes on foot.
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
Ironic oxalate is dissolved in the water, is heated to 70 ℃, the vacuum rotary dipping is 50 meters in the specific surface agent
2The Al of/gram
2O
3On the bead, then in 120 ℃ of dryings 6 hours.With SnCl
2, magnesium nitrate and Palladous nitrate be dissolved in the water respectively, using the HCl regulator solution to make its pH value is about 4, then this solution is heated to 80 ℃; Be immersed on the carrier once more; Then in 140 ℃ of dryings 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 like table 1:
The catalyst A that takes by weighing above-mentioned preparation is packed in the reactor drum of accompanying drawing 1 shown device; First, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure, realizes the difference of temperature; Thereby the control of realization response device catalyst bed temperature; Use the Co mixed gas of hydrogen content 10% to be raw material, 220 ℃ of temperature of reaction, volume space velocity 3000 hours
-1, oxygen/hydrogen mol ratio is 0.6: 1, and reaction pressure is under the condition of 0.5MPa, and reaction result is: the rate of loss of carbon monoxide is 0.31%, and the content of hydrogen is 2ppm in the reaction effluent.
[embodiment 2]
Iron nitrate is dissolved in the water, is heated to 80 ℃, the agent of vacuum rotary dipping specific surface is 80 meters
2The Al of/gram
2O
3On the bead, then in 120 ℃ of dryings 4 hours.Repone K and ammonium palladic chloride are dissolved in the water respectively, and using the HCl regulator solution to make its pH value is about 4, then this solution is heated to 80 ℃; Be immersed on the carrier once more; Then in 140 ℃ of dryings 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 like table 1.
The catalyst B that takes by weighing above-mentioned preparation is packed in the reactor drum of accompanying drawing 1 shown device; First, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure, realizes the difference of temperature; Thereby the control of realization response device catalyst bed temperature; Use the Co mixed gas of hydrogen content 8% to be raw material, 180 ℃ of temperature of reaction, volume space velocity 1000 hours
-1, oxygen/hydrogen mol ratio is 0.7: 1, and reaction pressure is under the condition of 0.2MPa, and reaction result is: the rate of loss of carbon monoxide is 0.21%, and the content of hydrogen is 5ppm in the reaction effluent.
[embodiment 3]
Zinc nitrate, nitric acid niobium, rubidium nitrate are dissolved in the water respectively, and the vacuum rotary dipping is 30 meters in the specific surface agent
2The Al of/gram
2O
3On the bead, 140 ℃ of dryings 4 hours.Ammonium chloroplatinate is dissolved in the ethanolic soln, is immersed in once more on the carrier, 140 ℃ of dryings 4 hours; Then roasting 4 hours in 450 ℃ of air atmospheres, reduction is 4 hours in 300 ℃ of hydrogen atmospheres, then in nitrogen atmosphere, is cooled to room temperature; Obtain catalyzer C, form and see table 1.
The catalyzer C that takes by weighing above-mentioned preparation packs in the reactor drum of accompanying drawing 1 shown device; First, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure, realizes the difference of temperature; Thereby the control of realization response device catalyst bed temperature; Use the Co mixed gas of hydrogen content 0.5% to 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%, the content of hydrogen is 0 in the reaction effluent.
[embodiment 4]
Manganous nitrate, saltpetre are dissolved in the water respectively, and the vacuum rotary dipping is 150 meters in the specific surface agent
2The Al of/gram
2O
3On the bead, 140 ℃ of dryings 4 hours.The inferior palladium acid of chlorine is dissolved in the ethanolic soln, is immersed in once more on the carrier, 140 ℃ of dryings 4 hours; Then roasting 4 hours in 450 ℃ of air atmospheres, reduction is 4 hours in 450 ℃ of hydrogen atmospheres, then in nitrogen atmosphere, is cooled to room temperature; Obtain catalyzer D, form and see table 1.
The catalyzer D that takes by weighing above-mentioned preparation packs in the reactor drum of accompanying drawing 1 shown device, and first, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure; Realize the difference of temperature; Thereby the control of realization response device catalyst bed temperature 350 ℃ of reduction 4 hours, uses the Co mixed gas of hydrogen content 1% to be raw material with hydrogen then; 130 ℃ of temperature of reaction, volume space velocity 800 hours
-1, oxygen/hydrogen mol ratio is 8: 1, and reaction pressure is under the condition of 5.0MPa, and reaction result is: the rate of loss of carbon monoxide is 0.15%, and the content of hydrogen is 0 in the reaction effluent.
[embodiment 5]
Iron nitrate, nitrate of baryta are dissolved in the water respectively, and the vacuum rotary dipping is 200 meters in the specific surface agent
2The Al of/gram
2O
3On the bead, 140 ℃ of dryings 4 hours.Ammonium palladic chloride is dissolved in the ethanolic soln, is immersed in once more on the carrier, 140 ℃ of dryings 4 hours, then 450 ℃ of roastings 4 hours, reduction is 4 hours in 350 ℃ of hydrogen atmospheres, then in nitrogen atmosphere, is cooled to room temperature, obtains catalyzer E, forms and sees table 1.
The catalyzer E that takes by weighing above-mentioned preparation packs in the reactor drum of accompanying drawing 1 shown device, and first, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure; Realize the difference of temperature; Thereby the control of realization response device catalyst bed temperature 350 ℃ of reduction 4 hours, uses the Co mixed gas of hydrogen content 0.5% to be raw material with hydrogen then; 100 ℃ of temperature of reaction, volume space velocity 500 hours
-1, oxygen/hydrogen mol ratio is 5: 1, and reaction pressure is under the condition of 4.0MPa, and reaction result is: the rate of loss of carbon monoxide is 0.12%, and the content of hydrogen is 0 in the reaction effluent.
[embodiment 6]
Getting 200 grams is 250 meters in the specific surface agent
2The Al of/gram
2O
3Bead; Be immersed in the 200 ml water solution that contain 8.0 gram Platinic chlorides, 14 gram magnesium nitrates, 15 milliliters of hydrochloric acid, take out the back, then roasting 2 hours in 450 ℃ of air atmospheres 140 ℃ of oven dry 4 hours; Reduction is 4 hours in 350 ℃ of hydrogen atmospheres; Then in nitrogen atmosphere, be cooled to room temperature, obtain catalyzer F, form and see table 1.
The catalyzer F that takes by weighing above-mentioned preparation packs in the reactor drum of accompanying drawing 1 shown device, and first, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure; Realize the difference of temperature; Thereby the control of realization response device catalyst bed temperature 350 ℃ of reduction 4 hours, uses the Co mixed gas of hydrogen content 0.5% to be raw material with hydrogen then; 250 ℃ of temperature of reaction, volume space velocity 8000 hours
-1, oxygen/hydrogen mol ratio is 0.7: 1, and reaction pressure is under the condition of 0.2MPa, and reaction result is: the rate of loss of carbon monoxide is 0.20%, and the content of hydrogen is 0 in the reaction effluent.
[embodiment 7]
Cerous nitrate, zirconium nitrate, iron nitrate are dissolved in the water respectively, and the vacuum rotary dipping is 120 meters in the specific surface agent
2The Al of/gram
2O
3On the bead, 140 ℃ of dryings 4 hours.Ammonium palladic chloride is dissolved in the ethanolic soln, is immersed in once more on the carrier, 140 ℃ of dryings 4 hours; Then roasting 2 hours in 450 ℃ of air atmospheres, reduction is 4 hours in 300 ℃ of hydrogen atmospheres, then in nitrogen atmosphere, is cooled to room temperature; Obtain catalyzer G, form and see table 1.
The catalyzer G that takes by weighing above-mentioned preparation packs in the reactor drum of accompanying drawing 1 shown device, and first, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure; Realize the difference of temperature; Thereby the control of realization response device catalyst bed temperature 350 ℃ of reduction 4 hours, uses the Co mixed gas of hydrogen content 5% to be raw material with hydrogen then; 190 ℃ of temperature of reaction, volume space velocity 5000 hours
-1, oxygen/hydrogen mol ratio is 2: 1, and reaction pressure is under the condition of 2.0MPa, and reaction result is: the rate of loss of carbon monoxide is 0.38%, and the content of hydrogen is 0 in the reaction effluent.
[embodiment 8]
Cupric nitrate, Lanthanum trinitrate, nickelous nitrate are dissolved in the water respectively, and the vacuum rotary dipping is 180 meters in the specific surface agent
2The Al of/gram
2O
3On the bead, 140 ℃ of dryings 4 hours.Ammonium palladic chloride is dissolved in the ethanolic soln, is immersed in once more on the carrier, 140 ℃ of dryings 4 hours; Then roasting 4 hours in 450 ℃ of air atmospheres, reduction is 4 hours in 300 ℃ of hydrogen atmospheres, then in nitrogen atmosphere, is cooled to room temperature; Obtain catalyzer H, form and see table 1.
The catalyzer H that takes by weighing above-mentioned preparation packs in the reactor drum of accompanying drawing 1 shown device, and first, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure; Realize the difference of temperature; Thereby the control of realization response device catalyst bed temperature 350 ℃ of reduction 4 hours, uses the Co mixed gas of hydrogen content 1% to be raw material with hydrogen then; 90 ℃ of temperature of reaction, volume space velocity 200 hours
-1, oxygen/hydrogen mol ratio is 1: 1, and reaction pressure is under the condition of 1.0MPa, and reaction result is: the rate of loss of carbon monoxide is 0.58%, and the content of hydrogen is 0 in the reaction effluent.
[comparative example 1]
Adopt identical catalyzer, raw material and the condition of embodiment 1, just adopt the fixed-bed reactor of one section heat exchange, reaction result is: the rate of loss of carbon monoxide is 1.2%, and the content of hydrogen is 12ppm in the reaction effluent.
[comparative example 2]
Adopt identical catalyzer, raw material and the condition of embodiment 2,, just adopt the fixed-bed reactor of one section heat exchange, reaction result is: the rate of loss of carbon monoxide is 1.1%, the content of hydrogen is 18ppm in the reaction effluent.
Obviously the inventive method is used for the selective oxidation of CO mixed gas except that H-H reaction, has higher hydrogen decreasing ratio and lower CO rate of loss.
The composition of table 1 catalyzer
| The catalyzer numbering | Catalyst weight is formed (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 (7)
1. the method for a CO gas oxydehydrogenation is a raw material with the gas mixture that contains carbon monoxide and hydrogen, and catalyzer is an active ingredient with platinum or palladium, is 80～260 ℃ in temperature of reaction, and volume space velocity is 100～10000 hours
-1, oxygen/hydrogen mol ratio is 0.5～10: 1, and reaction pressure is under the condition of-0.08～5.0MPa, and raw material contacts with catalyst reactor, generates the elute that contains water, it is characterized in that said reactor drum is the shell-and-tube reactor of subregion heat exchange.
2. according to the method for the said CO gas oxydehydrogenation of claim 1, it is characterized in that 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.
3. according to the method for the said CO gas oxydehydrogenation of claim 1, it is characterized in that platinum or palladium simple substance consumption are 0.003～1 part in the catalyst weight umber; Support of the catalyst is selected from aluminum oxide, and consumption is 99～99.997 parts.
4. according to the method for the said CO gas oxydehydrogenation of claim 1; It is characterized in that reactor drum mainly exports (12) 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 and forms, 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) in proper order according to the mobile direction of reaction gas; The first heat exchange block (22) links to each other with first district's heat transferring medium inlet (21) with first district's heat transferring medium outlet (23); The second heat exchange block (19) links to each other with second district's heat transferring medium outlet (20) with second district's heat transferring medium inlet (8), links to each other with the 3rd district's heat transferring medium outlet (17) with the 3rd district's heat transferring medium inlet (15) with the 3rd heat exchange block (16).
5. according to the method for the said CO gas oxydehydrogenation of claim 4; It is characterized in that reactor drum 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 to be heat transferring medium.
6. according to the method for the said CO gas oxydehydrogenation of claim 4; It is characterized in that separating through the first subregion dividing plate (6) between the reactor drum first heat exchange block (22) and the second heat exchange block (19), separate through the second subregion dividing plate (9) between the second heat exchange block (19) and the 3rd heat exchange block (16).
7. according to the method for the said CO gas oxydehydrogenation of claim 6, it is characterized in that the reactor drum first subregion dividing plate (6) is 1/8～1/3 of reactor length apart from reactor drum upper tubesheet (4) is following; The second subregion dividing plate (9) distance, the first subregion dividing plate (6) is 1/8～1/3 of reactor length down.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109433192A (en) * | 2018-12-07 | 2019-03-08 | 东北大学 | A kind of noble metal single atomic dispersion type cleaning 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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| 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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