CN102649558B - Catalytic oxidative dehydrogenation method for raw material containing CO gas - Google Patents
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Abstract
The invention relates to a catalytic oxidative dehydrogenation method for a raw material containing CO gas. According to the method, the technical problems of the prior art of low hydrogen desorption rate and high CO loss rate are solved. The method comprises the following steps of: taking CO-containing gas as the raw material, and contacting the raw material with a noble metal fluid catalyst under the conditions of reaction temperature at 80-260 DEG C, hourly space velocity at 100-10000 per hour, mole ratio of oxygen to hydrogen being (0.5-10):1 and reaction pressure at -0.08-5.0MPa, thereby oxidizing the hydrogen in the raw material into water. According to the technical scheme, the problems are more efficiently solved. The method is suitable for the industrial production of oxidative dehydrogenation of the raw material containing CO gas.
Description
Technical field
The present invention relates to a kind of method containing CO gas raw material catalytic oxidative dehydrogenation, particularly remove the method for hydrogen about synthetic gas preparing ethylene glycol CO unstripped gas.
Background technology
Barkite is important Organic Chemicals, produces various dyestuff, medicine, important solvent in a large number for fine chemistry industry, extraction agent and various intermediate.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., such as, carries out various condensation reaction with fatty acid ester, hexamethylene phenyl methyl ketone, amido alcohol and many heterogeneous ring compounds.It can also synthesize at the chest acyl alkali being pharmaceutically used as hormone.In addition, barkite low-voltage hydrogenation can prepare 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, and seriously polluted, prepared using is unreasonable.And adopt carbon monoxide coupling technology production barkite to become the focus of research both at home and abroad.
As everyone knows, carbon monoxide can from the various gas mixture containing carbon monoxide separation and Extraction, the industrial unstripped gas that can be used for being separated carbon monoxide comprises: the tail gas etc. of the synthetic gas of Sweet natural gas and oil conversion, water-gas, semi-water gas and Steel Plant, calcium carbide factory and Yellow Phosphorous Plant.The main method of existing CO separating-purifying is pressure swing adsorption process, You Duo company of China develops pressure-variable adsorption and is separated carbon monoxide new technology, especially the high-efficiency adsorbent developed, high loading capacity and selectivity is had to carbon monoxide, the difficult problem isolating high-purity carbon monooxide from nitrogen or the high unstripped gas of methane content can be solved, can design and build up large-scale carbon monoxide separation plant.However, by this technology isolated carbon monoxide from synthetic gas, under the prerequisite taking into account carbon monoxide yield, the content of its hydrogen can reach more than 1% under normal circumstances.And research shows that the existence of hydrogen can cause follow-up CO coupling reaction catalyst activity to reduce, until reaction cannot be carried out, therefore, exploitation carbon monoxide selects dehydrogenation technical meaning great.
At present, the dehydrogenation catalyst of report mainly contains Pd/Al both at home and abroad
2o
3, CoMo/Al
2o
3deng, also have the dehydrogenating agent based on manganese series metal oxide, but these catalyzer or dehydrogenating agent are generally used for the dehydrogenation purification of the non-reducing gas such as High Purity Nitrogen, high purity oxygen and carbonic acid gas, and existing dehydrogenating technology mainly adopts fixed bed reaction technique.And for CO reducing gas exist under, existing catalyzer and the decreasing ratio of technique to hydrogen low, the rate of loss of CO is high.As adopted method and the catalyzer of catalytic oxidative dehydrogenation disclosed in document CN97191805.8, be raw material at the CO mixed gas for hydrogen content 10%, temperature of reaction 220 DEG C, 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 in reaction effluent, the content of hydrogen is up to 1000ppm.
Summary of the invention
Technical problem to be solved by this invention is that the hydrogen decreasing ratio existed in previous literature technology is low, the technical problem that CO rate of loss is high, provides a kind of method of the catalytic material oxydehydrogenation containing CO gas newly.It is high that the method has hydrogen decreasing ratio, the advantage that CO rate of loss is low.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of the catalytic material oxydehydrogenation containing CO gas, with the gas containing CO for raw material, be 80 ~ 260 DEG C in temperature of reaction, 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 precious metal fluid catalyst, hydrogen in raw material is oxidized to water, it is characterized in that precious metal fluid catalyst comprises carrier, active ingredient and auxiliary agent, by weight percentage, catalyzer comprises following component:
A) at least one be selected from platinum metals is active ingredient, be catalyst weight in simple substance consumption 0.003 ~ 1%;
B) at least one be selected from basic metal, alkaline-earth metal or transition metal element compound is auxiliary agent, be catalyst weight in simple substance consumption 0.005 ~ 15%;
C) carrier of 84 ~ 99.5%;
Wherein support selected from alumina, and alumina particle diameter average out to 20 ~ 300 microns.
In technique scheme, alumina catalyst support particle diameter preferable range average out to 30 ~ 200 microns; Active ingredient is preferably selected from platinum in platinum metals or palladium, and be catalyst weight in simple substance consumption preferable range 0.02 ~ 0.8%.Auxiliary agent is preferably selected from least one in K, Mg, Ba, V, Mn, Fe, Cu, Ce, La or Sn compound, and be catalyst weight in simple substance consumption preferable range 0.01 ~ 10%.Auxiliary agent is more preferably selected from least one in K, Fe or Sn compound, in simple substance consumption more preferably scope be catalyst weight 0.05 ~ 8%.Reaction conditions is preferably: temperature of reaction is 130 ~ 240 DEG C, and volume space velocity is 1000 ~ 8000 hours
-1, oxygen/hydrogen mol ratio is 0.6 ~ 8: 1, and reaction pressure is 0 ~ 3.0MPa.Containing in the gas raw material of CO, the volumn concentration preferable range of hydrogen is for being greater than 0 ~ 15%.The volumn concentration of hydrogen more preferably scope is 0.01 ~ 8%.
The preparation method of catalyzer of the present invention is as follows:
Catalyst activity component, as elements such as platinum metals, promotor basic metal, alkaline-earth metal, can be dispersed on carrier by any method being suitable for obtaining surface impregnation.When preparing catalyzer of the present invention, any decomposable platinum group compound can be used, as halogenide, nitrate, oxide compound etc.; Such as chlorine palladium acid sodium, tetrachloro-palladium acid sodium, potassium palladichloride, chlorine four ammonia palladium, palladous oxide, the acid of chlorine palladium, ammonium palladic chloride, the sub-palladium acid of chlorine.Platinum metals active ingredient and auxiliary agent can be combined with carrier with random order.Can first platinum-impregnated Group Component on carrier surface, then again at one or more auxiliary agents of surface impregnation or modifier, also first one or more auxiliary agents or modifier can be flooded on carrier surface, then again in surface impregnation platinum-group component, platinum-impregnated Group Component and auxiliary agent or modifier also can of course simultaneously.
Promotor there is no special restriction to its source, comparatively suitable with nitrate, oxalate, ammonium salt or muriate.Promotor can first load on carrier, also after palladium load, surface impregnation can be carried out again.Comparatively conventional method is first load cocatalyst, after drying and roasting, adopts Surface soaking method dipping containing palladium solution.Finally, by the catalyst precursor containing active ingredient first 80 ~ 140 DEG C of dryings 2 ~ 20 hours, then 180 ~ 700 DEG C of roastings 2 ~ 20 hours, namely obtain for the catalyzer of CO mixed gas selective oxidation except H-H reaction.
Hydrogen decreasing ratio and the CO rate of loss of indication of the present invention are obtained by following account form:
Quality × 100% of hydrogen decreasing ratio=(quality of the quality-hydrogen product of raw hydrogen)/raw hydrogen
Quality × 100% of CO rate of loss=(quality of the quality-product C O of raw material CO)/raw material CO
As everyone knows, carbon monoxide and hydrogen are the stronger gas of reductibility, and under the condition that the two and oxygen coexist, normal conditions are that CO equally also can react and lose larger selective oxidation removing hydrogen while.Be strong exothermal reaction for CO and the reaction of oxygen and the reaction of hydrogen and oxygen, reaction temperature rising can far up to more than 100 DEG C under to a certain degree.Research also finds, carbon monoxide exists in lower selective oxidation dehydrogenation process, the decreasing ratio of hydrogen and the rate of loss of CO and temperature of reaction closely related, the decreasing ratio of the higher hydrogen of temperature is higher, but the rate of loss of CO is also higher, and temperature is lower, the rate of loss of CO can be lower, but the decreasing ratio of hydrogen comparatively may be difficult to ensure card.Therefore, exist in lower selective oxidation dehydrogenation process for carbon monoxide, the control of temperature is extremely important.The present invention, by adopting fluid catalyst, by the characteristic that fluidized-bed temperature is evenly distributed, can realize higher hydrogen decreasing ratio and lower CO rate of loss.We are surprised to find in large quantity research in addition, and adopt palladium-based catalyst of the present invention carrying out selecting in dehydrogenation reaction process under carbon monoxide existence, CO loses hardly, and hydrogen can take off to below 1ppm.And further dynamics research finds, adopt palladium-based catalyst of the present invention to carry out CO gas height and select in dehydrogenation reaction process, the rate of adsorption in hydrogen and active centre is far faster than the rate of adsorption of CO, and CO and oxygen generate CO
2the reaction activity of step generates the activation energy of water reactions steps far above hydrogen and oxygen reaction, this maximizes convert hydrogen for realizing, and avoids the oxidational losses of CO to greatest extent simultaneously, provides most important theories basis and theories integration from reaction kinetics angle.
Adopt technical scheme of the present invention, with the precious metal fluid catalyst of the aluminum oxide of palladium load for catalyzer, be 80 ~ 260 DEG C in temperature of reaction, 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 precious metal fluid catalyst, and the hydrogen in raw material is oxidized to water, in the gas raw material containing CO, the volumn concentration of hydrogen is under the condition being greater than 0 ~ 15%, the rate of loss that the decreasing ratio of hydrogen can reach 100%, CO can be less than 0.5%, achieves good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Be dissolved in by ironic oxalate in water, be heated to 70 DEG C, vacuum rotating is immersed in the Al that average particulate diameter is 50 microns
2o
3on bead, then in 120 DEG C of dryings 6 hours.By SnCl
2, magnesium nitrate and Palladous nitrate be dissolved in the water respectively, its pH value is made to be about 4 with HCl regulator solution, then this solution is heated to 80 DEG C, again be immersed on carrier, then in 140 DEG C of dryings 8 hours, then roasting 4 hours in 450 DEG C of air atmospheres, reductase 12 hour in 400 DEG C of hydrogen atmospheres, obtain catalyst A, its composition is as shown in table 1:
The catalyst A taking above-mentioned preparation is 300 grams, and loading in small-sized fluidized bed reactor, is raw material with the CO mixed gas of hydrogen content 10%, temperature of reaction 220 DEG C, and 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 CO is 0.31%, and in reaction effluent, the content of hydrogen is 2ppm.
[embodiment 2]
Be dissolved in by iron nitrate in water, be heated to 80 DEG C, vacuum rotating is immersed in the Al that average particulate diameter is 60 microns
2o
3on bead, then in 120 DEG C of dryings 4 hours.Repone K and ammonium palladic chloride are dissolved in the water respectively, its pH value is made to be about 4 with HCl regulator solution, then this solution is heated to 80 DEG C, again be immersed on carrier, then in 140 DEG C of dryings 4 hours, then roasting 4 hours in 450 DEG C of air atmospheres, reductase 12 hour in 400 DEG C of hydrogen atmospheres, obtains catalyst B.
The catalyst B taking above-mentioned preparation is 300 grams, and loading in small-sized fluidized bed reactor, is raw material with the CO mixed gas of hydrogen content 8%, temperature of reaction 180 DEG C, and 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 CO is 0.21%, and in reaction effluent, the content of hydrogen is 5ppm.
[embodiment 3]
Nitric acid niobium, rubidium nitrate are dissolved in the water respectively, vacuum impregnation is the Al of 100 microns at average particulate diameter
2o
3on bead, 140 DEG C of dryings 4 hours.Ammonium chloroplatinate is dissolved in ethanolic soln, is again immersed on carrier, 140 DEG C of dryings 4 hours, then roasting 4 hours in 450 DEG C of air atmospheres, reduces 4 hours, then in nitrogen atmosphere, is cooled to room temperature in 300 DEG C of hydrogen atmospheres, obtain catalyzer C, composition is in table 1.
The catalyzer C taking above-mentioned preparation is 300 grams, and loading in small-sized fluidized bed reactor, is raw material with the CO mixed gas of hydrogen content 0.5%, temperature of reaction 200 DEG C, and volume space velocity 3000 hours
-1, oxygen/hydrogen mol ratio is 1: 1, and reaction pressure is under the condition of-0.05MPa, and reaction result is: the rate of loss of CO is 0.33%, and in reaction effluent, the content of hydrogen is 0.
[embodiment 4]
Manganous nitrate, saltpetre are dissolved in the water respectively, vacuum rotating is immersed in the Al that average particulate diameter is 80 microns
2o
3on bead, 140 DEG C of dryings 4 hours.By sub-for chlorine palladium acid dissolve in ethanolic soln, be again immersed on carrier, 140 DEG C of dryings 4 hours, then roasting 4 hours in 450 DEG C of air atmospheres, reduces 4 hours, then in nitrogen atmosphere, is cooled to room temperature in 450 DEG C of hydrogen atmospheres, obtain catalyzer D, composition is in table 1.
The catalyzer D taking above-mentioned preparation is 300 grams, loads in small-sized fluidized bed reactor, with hydrogen 350 DEG C of reduction 4 hours, is then raw material with the CO mixed gas of hydrogen content 1%, temperature of reaction 130 DEG C, and 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 CO 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, vacuum rotating is immersed in the Al that average particulate diameter is 100 microns
2o
3on bead, 140 DEG C of dryings 4 hours.Be dissolved in by ammonium palladic chloride in ethanolic soln, be again immersed on carrier, 140 DEG C of dryings 4 hours, then 450 DEG C of roastings 4 hours, reduce 4 hours, then in nitrogen atmosphere, be cooled to room temperature, obtain catalyzer E in 350 DEG C of hydrogen atmospheres, composition is in table 1.
The catalyzer E taking above-mentioned preparation is 300 grams, loads in small-sized fluidized bed reactor, with hydrogen 350 DEG C of reduction 4 hours, is then raw material with the CO mixed gas of hydrogen content 0.5%, temperature of reaction 100 DEG C, and 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 CO is 0.12%, and in reaction effluent, the content of hydrogen is 0.
[embodiment 6]
Get the Al that 400 grams of average particulate diameters are 120 microns
2o
3on bead, be immersed in the 400 ml water solution containing 16.0 grams of Platinic chlorides, 28 grams of magnesium nitrates, 30 milliliters of hydrochloric acid, dry 4 hours at 140 DEG C after taking-up, then roasting 2 hours in 450 DEG C of air atmospheres, reduce 4 hours in 350 DEG C of hydrogen atmospheres, then in nitrogen atmosphere, be cooled to room temperature, obtain catalyzer F and form in table 1.
The catalyzer F taking above-mentioned preparation is 300 grams, loads in small-sized fluidized bed reactor, with hydrogen 350 DEG C of reduction 4 hours, is then raw material with the CO mixed gas of hydrogen content 0.5%, temperature of reaction 250 DEG C, and 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 CO 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, vacuum impregnation is the Al of 150 microns at average particulate diameter
2o
3on bead, 140 DEG C of dryings 4 hours.Ammonium palladic chloride is dissolved in ethanolic soln, is again immersed on carrier, 140 DEG C of dryings 4 hours, then roasting 2 hours in 450 DEG C of air atmospheres, reduces 4 hours, then in nitrogen atmosphere, is cooled to room temperature in 300 DEG C of hydrogen atmospheres, obtain catalyzer G, composition is in table 1.
The catalyzer G taking above-mentioned preparation is 300 grams, loads in small-sized fluidized bed reactor, with hydrogen 350 DEG C of reduction 4 hours, is then raw material with the CO mixed gas of hydrogen content 5%, temperature of reaction 190 DEG C, and 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 CO 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, vacuum impregnation is the Al of 200 microns at average particulate diameter
2o
3on bead, 140 DEG C of dryings 4 hours.Ammonium palladic chloride is dissolved in ethanolic soln, is again immersed on carrier, 140 DEG C of dryings 4 hours, then roasting 4 hours in 450 DEG C of air atmospheres, reduces 4 hours, then in nitrogen atmosphere, is cooled to room temperature in 300 DEG C of hydrogen atmospheres, obtain catalyzer H, composition is in table 1.
The catalyzer H taking above-mentioned preparation is 300 grams, loads in small-sized fluidized bed reactor, with hydrogen 350 DEG C of reduction 4 hours, is then raw material with the CO mixed gas of hydrogen content 1%, temperature of reaction 90 DEG C, and 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 CO is 0.58%, and in reaction effluent, the content of hydrogen is 0.
[comparative example 1]
According to identical raw material, condition and the catalyzer of embodiment 1, just adopt fixed-bed reactor, reaction result is: the rate of loss of CO is 1.8%, and in reaction effluent, the content of hydrogen is 150ppm.
[comparative example 2]
According to identical raw material, condition and the catalyzer of embodiment 2, just adopt fixed-bed reactor, reaction result is: the rate of loss of CO is 1.3%, and in reaction effluent, the content of hydrogen is 180ppm.
Obvious the inventive method is used 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 is numbered | 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 (5)
1., containing a method for the catalytic material oxydehydrogenation of CO gas, with the gas containing CO for raw material, be 80 ~ 260 DEG C in temperature of reaction, 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 precious metal fluid catalyst, hydrogen in raw material is oxidized to water, it is characterized in that precious metal fluid catalyst comprises carrier, active ingredient and auxiliary agent, by weight percentage, catalyzer comprises following component:
A) platinum in platinum metals is selected from or palladium is active ingredient, be catalyst weight in simple substance consumption 0.02 ~ 0.8%;
B) at least one be selected from K, Mg, Ba, V, Mn, Fe, Cu, Ce, La or Sn compound is auxiliary agent, be catalyst weight in simple substance consumption 0.01 ~ 10%;
C) carrier of 84 ~ 99.5%;
Wherein support selected from alumina, and alumina particle diameter average out to 30 ~ 200 microns.
2., according to claim 1 containing the method for the catalytic material oxydehydrogenation of CO gas, it is characterized in that auxiliary agent is selected from least one in K, Fe or Sn compound, be catalyst weight in simple substance consumption 0.05 ~ 8%.
3., according to claim 1 containing the method for the catalytic material oxydehydrogenation of CO gas, it is characterized in that temperature of reaction 130 ~ 240 DEG C, volume space velocity is 1000 ~ 8000 hours
-1, oxygen/hydrogen mol ratio is 0.6 ~ 8: 1, and reaction pressure is 0 ~ 3.0MPa.
4., according to claim 1 containing the method for the catalytic material oxydehydrogenation of CO gas, it is characterized in that in the gas raw material containing CO, the volumn concentration of hydrogen is for being greater than 0 ~ 15%.
5., according to claim 4 containing the method for the catalytic material oxydehydrogenation of CO gas, it is characterized in that in the CO gas raw material of hydrogen, the volumn concentration of hydrogen is 0.01 ~ 8%.
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| JP2003144924A (en) * | 2001-11-09 | 2003-05-20 | Mitsubishi Chemicals Corp | Selective oxidation catalyst for hydrogen, selective oxidation method for hydrogen and dehydrogenation method for hydrocarbon |
| 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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| 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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