CN102649570A - Method for oxidative dehydrogenation of CO gas through catalytic reaction - Google Patents
Method for oxidative dehydrogenation of CO gas through catalytic reaction Download PDFInfo
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Abstract
The invention relates to a method for oxidative dehydrogenation of CO gas through catalytic reaction, and mainly solves the technical problems of low hydrogen desorbing rate and high loss rate of CO in the reaction process of oxidative dehydrogenation of CO gas raw material. In the invention, by adopting the mixture gas containing carbon monoxide and hydrogen as the raw material, and under the conditions that catalyst takes platinum or palladium as an active constituent, the reaction temperature ranges from 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 is 0.08 below zero to 5.0 MPa, the invention adopts the technical scheme that the raw material is sequentially in contact with catalysts inside a reactor, the reactor is a combined reactor with a combined bed structure and a heat exchange pipe is arranged in a heat exchange catalyst bed. Therefore, the problems are well solved, and the method can be used in industrial production of dehydrogenation of CO gas through catalytic oxidation.
Description
Technical field
The present invention relates to the method for a kind of CO gas catalyzed reaction oxydehydrogenation; Particularly about adopting the combined reactor of multiple-hearth structure; Carry out the method for CO gas feed oxygen fluidized dehydrogenation, be useful in the CO gas feed oxygen fluidized dehydrogenation reaction process.
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.
Existing oxydehydrogenation technology, majority is hydrocarbon oxidation dehydrogenation under the condition of high temperature, and the bibliographical information of CO gas oxydehydrogenation is less.Disclose a kind of method of making ethylene from ethane oxidative dehydrogenation like patent CN96118939.8, the catalyzer that this invention is adopted is Na
2WO
4-Mn
2O
3(S is SiO
2, TiO
2(rutile); MgO etc.), can when under the temperature of reaction, obtain to be higher than 70% ethane conversion and ethylene selectivity at higher air speed, suitable alcoxyl; The yield of ethene generally can reach more than 50%; Using this catalyzer is 3% CO raw material with hydrogen volume content, is 180 ℃ in temperature, volume space velocity 2000h
-1, reaction pressure is 0.2MPa, and oxygen/hydrogen mol ratio is that hydrogen volume content is still up to 0.2% in the reaction product under 0.8 the condition, and the CO rate of loss is also up to 2%.
In the obvious above-mentioned technology, exist the hydrogen decreasing ratio low, the shortcoming that the CO rate of loss is high.
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 catalytic oxidative dehydrogenation reaction 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 catalyzed reaction oxydehydrogenation.This method is used for through 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: the method for a kind of CO gas catalyzed reaction 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, reaction pressure is that raw material contacts with catalyst reactor successively under the condition of-0.08～5.0MPa, comprises the steps:
A) raw material is at first introduced by feed(raw material)inlet (1), and the further mixed distribution of gas entering distributing chamber (4) after porous gas grid distributor (3) distributes gets into then and goes up adiabatic catalyst beds (5) and catalyzer contact reacts, gets reaction effluent I;
B) reaction effluent I gets into heat exchange catalyst bed (6), with the catalyzer contact reacts, gets reaction effluent II;
C) reaction effluent II gets into down adiabatic catalyst beds (7) and catalyzer again and further reacts, and reacted elute gets into collection chamber (8), gets into follow-up system through porous gas collection plate (9) through pneumatic outlet (10).
Wherein, said reactor drum is the combined reactor of multiple-hearth structure, and the heat exchange catalyst bed is provided with heat transfer tube in (6).
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.Catalyzer is in catalyst weight per-cent, and platinum or palladium simple substance consumption are 0.003～0.8%.
The reactor drum of inventive method mainly is made up of feed(raw material)inlet (1), porous gas grid distributor (3), gas distribution chamber (4), last adiabatic catalyst beds (5), heat exchange catalyst bed (6), following adiabatic catalyst beds (7), heat transfer tube (13), collection chamber (8) and porous gas collection plate (9) in the technique scheme; Be primarily characterized in that heat exchange catalyst bed (6) is positioned at the bottom of adiabatic catalyst beds (5); The top of following adiabatic catalyst beds (7), and heat transfer tube (13) is set in the heat exchange catalyst bed (6).
Porous gas collection plate (9) is positioned at collection chamber (8) in the technique scheme, 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).Last 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 following adiabatic catalyst beds (7) is 1/30～1/6 of a height for reactor apart from the vertical height on porous gas collection plate (9) top.The height of last adiabatic catalyst beds (5) is 1/6～3/2 of heat exchange catalyst bed (a 6) height, and following adiabatic catalyst beds (7) is 1/6～1/1 of heat exchange catalyst bed (a 6) height.
For the catalytic exothermic reaction 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, shows as anterior mid-way partially and occurs significant hot spot region easily; And the rear portion with reaction near balance, speed of response slows down, it is also few to emit reaction heat; If adopt conventional shell-and-tube reactor, the same before and after the temperature of its refrigerant, if reduce coolant temperature like this; Strengthen heat transfer temperature difference and move heat; Reach the heat request that moves of high speed of response of middle front part and strong reaction heat, then reactor lower part or rear portion reaction heat reduce, and move heat and cause temperature of reaction to descend greater than reaction heat; 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.The present invention is directed to this fundamental contradiction, and, heat transfer zone is set at the reactor drum middle part according to the characteristic exotherm that reacts; And the reactor drum two ends are provided with adiabatic region, make the hot spot region flattening, and temperature distribution more becomes evenly rationally; 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.
The CO gas raw material oxidative dehydrogenation reactor that contains of the inventive method is used to contain CO gas raw material oxidative dehydrogenation; Use device shown in Figure 1; Adopt focus distributed areas heat exchange; Using precious metal palladium or platinum load aluminum oxide to be catalyzer, is 80～260 ℃ in the reaction temperature in, 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 CO gas catalyzed reaction oxidative dehydrogenation reactor synoptic diagram among the present invention.
1 is the feed(raw material)inlet among Fig. 1, the 2nd, and manhole, the 3rd, porous gas grid distributor, the 4th, gas distribution chamber; The 5th, last adiabatic catalyst beds, the 6th, heat exchange catalyst bed, the 7th, following 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, the heat transferring medium outlet; The 13rd, heat transfer tube, the 14th, heat transferring medium inlet, the 15th, reactor drum tank body.
Raw material is introduced by feed(raw material)inlet 1 among Fig. 1; Gas gets into distributing chamber's 4 further mixed distribution after porous gas grid distributor 3 distributes; Get into then and go up adiabatic catalyst beds 5 and catalyzer contact reacts, have the reaction effluent of certain temperature rise to get into heat exchange catalyst bed 6 again, the heat that discharges in the reaction process carries out shifting out of heat through heat transfer tube 13; Keep the temperature in the heat exchange catalyst bed 6 even; After adiabatic catalyst beds 7 further reacted completely under the last entering of elute behind most of raw material reaction, elute got into collection chamber 8, gets into follow-up system through porous gas collection plate 9 through pneumatic outlet 10.Because the hot(test)-spot temperature distributed areas adopt heat transfer tube to carry out shifting out and controlling of heat, thereby reach the effect that the whole reactor catalyst bed temperature is uniformly distributed with.
Through embodiment the present invention is done further elaboration below.
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; Wherein, The height of following adiabatic catalyst layer is 1/20 of a heat exchange catalyst bed height, and the height of last adiabatic catalyst layer is 1/15 of a heat exchange catalyst bed height, uses the Co mixed gas of hydrogen content 10% to be raw material; Concrete steps are (as follows): (a) raw material is at first introduced by feed(raw material)inlet 1; Gas gets into distributing chamber's 4 further mixed distribution after 3 distributions of porous gas grid distributor, get into then and go up adiabatic catalyst beds 5 and catalyzer contact reacts, gets reaction effluent I; (b) reaction effluent I gets into heat exchange catalyst bed 6, with the catalyzer contact reacts, gets reaction effluent II; (c) reaction effluent II gets into down adiabatic catalyst beds 7 again and further reacts with catalyzer, and reacted elute gets into collection chamber 8, gets into follow-up systems through porous gas collection plate 9 through pneumatic outlet 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 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; Wherein, The height of following adiabatic catalyst layer is 1/10 of a heat exchange catalyst bed height, and the height of last adiabatic catalyst layer is 1/10 of a heat exchange catalyst bed height, uses 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; Wherein, The height of following adiabatic catalyst layer is 1/4 of a heat exchange catalyst bed height, and the height of last adiabatic catalyst layer is 1/5 of a heat exchange catalyst bed height, uses 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; Wherein, the height of following adiabatic catalyst layer is 1/8 of a heat exchange catalyst bed height, and the height of last adiabatic catalyst layer is 1/6 of a heat exchange catalyst bed height; Reduced 4 hours at 350 ℃ with hydrogen; Use the Co mixed gas of hydrogen content 1% to be raw material 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; Wherein, the height of following adiabatic catalyst layer is 1/10 of a heat exchange catalyst bed height, and the height of last adiabatic catalyst layer is 1/15 of a heat exchange catalyst bed height; Reduced 4 hours at 350 ℃ with hydrogen; Use the Co mixed gas of hydrogen content 0.5% to be raw material 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; Wherein, the height of following adiabatic catalyst layer is 1/12 of a heat exchange catalyst bed height, and the height of last adiabatic catalyst layer is 1/8 of a heat exchange catalyst bed height; Reduced 4 hours at 350 ℃ with hydrogen; Use the Co mixed gas of hydrogen content 0.5% to be raw material 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; Wherein, the height of following adiabatic catalyst layer is 1/16 of a heat exchange catalyst bed height, and the height of last adiabatic catalyst layer is 1/10 of a heat exchange catalyst bed height; Reduced 4 hours at 350 ℃ with hydrogen; Use the Co mixed gas of hydrogen content 5% to be raw material 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; Wherein, the height of following adiabatic catalyst layer is 1/8 of a heat exchange catalyst bed height, and the height of last adiabatic catalyst layer is 1/10 of a heat exchange catalyst bed height; Reduced 4 hours at 350 ℃ with hydrogen; Use the Co mixed gas of hydrogen content 1% to be raw material 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]
Shown in [embodiment 2] that the U.S. Pat of the preparation reference of this oxy-dehydrogenation catalyst is 4812597 li.Contain Pt 0.20% according to the mass fraction meter, Sn 0.23%, and Li 0.20%.
According to the identical raw material and the condition of [embodiment 1], just adopt one section adiabatic fixed-bed reactor, reaction result is: the rate of loss of carbon monoxide is 2.5%, the content of hydrogen is 150ppm in the reaction effluent.
[comparative example 2]
Shown in [embodiment 3] that the U.S. Pat of the preparation reference of this oxy-dehydrogenation catalyst is 6858769 li.Contain Pt 0.14% according to the mass fraction meter, Sn 0.16%, and Li 0.72%.
According to the identical raw material and the condition of [embodiment 2], just adopt one section adiabatic fixed-bed reactor, reaction result is: the rate of loss of carbon monoxide is 3.1%, the content of hydrogen is 180ppm 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.
Table 1
| 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 (8)
1. the method for CO gas catalyzed reaction 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, reaction pressure is that raw material contacts with catalyst reactor successively under the condition of-0.08～5.0MPa, comprises the steps:
A) raw material is at first introduced by feed(raw material)inlet (1), and the further mixed distribution of gas entering distributing chamber (4) after porous gas grid distributor (3) distributes gets into then and goes up adiabatic catalyst beds (5) and catalyzer contact reacts, gets reaction effluent I;
B) reaction effluent I gets into heat exchange catalyst bed (6), with the catalyzer contact reacts, gets reaction effluent II;
C) reaction effluent II gets into down adiabatic catalyst beds (7) and catalyzer again and further reacts, and reacted elute gets into collection chamber (8), gets into follow-up system through porous gas collection plate (9) through pneumatic outlet (10).
Wherein, said reactor drum is the combined reactor of multiple-hearth structure, and the heat exchange catalyst bed is provided with heat transfer tube in (6).
2. according to the method for the said CO gas catalyzed reaction of claim 1 oxydehydrogenation, it is characterized in that temperature of reaction is 130～240 ℃, 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 catalyzed reaction of claim 1 oxydehydrogenation, it is characterized in that platinum or palladium simple substance consumption are 0.003～0.8% in catalyst weight per-cent.
4. according to the method for the said CO gas catalyzed reaction of claim 1 oxydehydrogenation; It is characterized in that reactor drum mainly is made up of feed(raw material)inlet (1), porous gas grid distributor (3), gas distribution chamber (4), last adiabatic catalyst beds (5), heat exchange catalyst bed (6), following adiabatic catalyst beds (7), heat transfer tube (13), collection chamber (8) and porous gas collection plate (9); Be primarily characterized in that heat exchange catalyst bed (6) is positioned at the bottom of adiabatic catalyst beds (5); The top of following adiabatic catalyst beds (7), and heat transfer tube (13) is set in the heat exchange catalyst bed (6).
5. according to the method for the said CO gas catalyzed reaction of claim 4 oxydehydrogenation, it is characterized in that porous gas collection plate (9) is positioned at collection chamber (8), and be connected with pneumatic outlet (10).
6. according to the method for the said CO gas catalyzed reaction of claim 4 oxydehydrogenation, it is characterized in that porous gas grid distributor (3) is positioned at gas distribution chamber (4), and be connected with feed(raw material)inlet (1).
7. according to the method for the said CO gas catalyzed reaction of claim 4 oxydehydrogenation, it is characterized in that 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 following adiabatic catalyst beds (7) is 1/30～1/6 of a height for reactor apart from the vertical height on porous gas collection plate (9) top.
8. according to the method for the said CO gas catalyzed reaction of claim 4 oxydehydrogenation; The height that it is characterized in that adiabatic catalyst beds (5) is 1/6～3/2 of heat exchange catalyst bed (a 6) height, and following adiabatic catalyst beds (7) is 1/6～1/1 of heat exchange catalyst bed (a 6) height.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105253856A (en) * | 2015-10-29 | 2016-01-20 | 中国人民解放军防化学院 | Carbon-based fuel reforming hydrogen production device |
| CN105800614A (en) * | 2016-05-03 | 2016-07-27 | 中国科学院福建物质结构研究所 | Method for removing hydrogen gas impurity in CO feed gas in segmented manner |
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| CN105253856B (en) * | 2015-10-29 | 2017-04-05 | 中国人民解放军防化学院 | A kind of carbon-based fuel reforming hydrogen production device |
| CN105800614A (en) * | 2016-05-03 | 2016-07-27 | 中国科学院福建物质结构研究所 | Method for removing hydrogen gas impurity in CO feed gas in segmented manner |
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