CN102649568B - Selective catalytic oxidative dehydrogenation method for CO mixed gas - Google Patents
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Abstract
The invention relates to a selective catalytic oxidative dehydrogenation method for CO mixed 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: treating a catalyst taking platinum metals as active components for 0.01-40 hours under a pretreatment gas atmosphere containing 1-100% oxygen and under the conditions of temperature at 100-400 DEG C, hourly space velocity at 100-10000 per hour and pressure at 0-2.0MPa, and then taking the CO mixed gas containing more than 0-10% of hydrogen as the raw material, and contacting the raw material with the catalyst through a reactor filled with the catalyst taking platinum metals as active components, under the conditions of mole ratio of oxygen to hydrogen in the raw material being (0.5-5):1, reaction temperature at 100-300 DEG C, hourly space velocity at 100-10000 per hour and reaction pressure at -0.08-5.0MPa, thereby hydrogenating the hydrogen in the reacted effluent 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 CO mixed gas.
Description
Technical field
The present invention relates to a kind of CO mixed gas gating catalytic oxidation except the method for hydrogen, particularly the method except hydrogen about the oxidation of CO coupling producing oxalic ester unstripped gas.
Background technology
Barkite is important Organic Chemicals, in a large number for fine chemistry industry, produces various dyestuffs, medicine, important solvent, 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., 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 pharmaceutically as the chest acyl alkali of 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 compare Gao， China needs a large amount of import ethylene glycol every year, and within 2007 years, import volume is nearly 4,800,000 tons.
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.And adopt carbon monoxide coupling technology to produce the focus that barkite has become domestic and international research.
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 separated carbon monoxide comprises: the tail gas of synthetic gas, water-gas, semi-water gas and Steel Plant, calcium carbide factory and Yellow Phosphorous Plant that Sweet natural gas and oil transform etc.The main method of existing CO separating-purifying is pressure swing adsorption process, China You Duo company has developed the separated carbon monoxide new technology of pressure-variable adsorption, especially the high-efficiency adsorbent of developing, 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, generally the content of its hydrogen can reach more than 1%.And research shows that the existence of hydrogen can cause follow-up CO coupling reaction catalyst activity decreased, until reaction cannot be carried out, therefore, exploitation carbon monoxide selects dehydrogenation technical meaning great.
Existing oxydehydrogenation technology, majority is hydrocarbon oxidation dehydrogenation under the condition of high temperature, and the bibliographical information of CO (carbon monoxide converter) gas oxydehydrogenation is less.As patent CN96118939.8 discloses a kind of method of making ethylene from ethane oxidative dehydrogenation, the catalyzer that this invention adopts is Na
2wO
4-Mn
2o
3(S is SiO
2, TiO
2(rutile), MgO etc.), can when under temperature of reaction, obtain ethane conversion and ethylene selectivity higher than 70% at higher air speed, suitable alcoxyl, the yield of ethene generally can reach more than 50%, the CO raw material that is 3% by hydrogen volume content with this catalyzer, is 180 ℃ in temperature, volume space velocity 2000h-1, reaction pressure is 0.2MPa, under the condition that oxygen/hydrogen mol ratio is 0.8, in reaction product hydrogen volume content still up to 0.2%, CO rate of loss also up to 2%.
In obvious above-mentioned technology, exist hydrogen decreasing ratio low, the shortcoming that CO rate of loss is high.
Summary of the invention
Technical problem to be solved by this invention is that prior art gating catalytic oxidation under carbon monoxide exists exists CO rate of loss high except in hydrogen process, the technical problem that hydrogen decreasing ratio is low, provides the method for a kind of new CO mixed gas gating catalytic oxidation except hydrogen.It is low that the method has CO rate of loss, the advantage that hydrogen decreasing ratio is high.
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 CO mixed gas gating catalytic oxidation is except the method for hydrogen, the catalyzer that is active ingredient by platinum metals, in the pretreatment gas atmosphere that is 1～100% at oxygen content, in temperature, be 100～400 ℃, volume space velocity is 100～10000 hours
-1, under the condition that pressure is 0～2.0MPa, process 0.01～40 hour; Then, the hydrogen content of take is raw material as being greater than 0～10% CO mixed gas, and in oxygen and raw material, the mol ratio of hydrogen is 0.5～5: 1, and temperature of reaction is 100～300 ℃, and volume space velocity is 100～10000 hours
-1, under the condition that reaction pressure is-0.08～5.0MPa, raw material is that active constituent catalyst reactor contacts with catalyzer by platinum metals is housed, in reaction effluent, hydrogen is hydrogenated as water.
In technique scheme, catalyzer take in silicon oxide, aluminum oxide or molecular sieve at least one be carrier, preferably take aluminum oxide as carrier, take vehicle weight as benchmark, the weight percentage preferable range of the platinum metals active ingredient of catalyzer is 0.05～1.0%, more preferably scope is 0.08～1.0%, and platinum metals active ingredient is preferably from platinum or palladium, more preferably from palladium.
In technique scheme, the pretreatment condition of the catalyzer that platinum metals is active ingredient is preferably: pretreatment gas oxygen content is 10～100%, and temperature is 150～300 ℃, and volume space velocity is 500～8000 hours
-1, pressure is 0～1.0MPa; Pretreatment condition is more preferably: pretreatment gas oxygen content is 20～100%, and temperature is 150～250 ℃, and volume space velocity is 1000～6000 hours
-1, pressure is 0～0.5MPa.Oxidative dehydrogenation reactor reaction conditions is preferably: 150～280 ℃ of temperature of reaction, volume space velocity is 800～8000 hours
-1, reaction pressure is 0～2.0MPa; Oxidative dehydrogenation reactor reaction conditions is more preferably: 180～260 ℃ of temperature of reaction, volume space velocity is 1000～6000 hours
-1, reaction pressure is 0～1.0MPa.In the CO gas raw material of hydrogen, the preferable range of the volumn concentration of hydrogen is 0.01～5%.
As everyone knows, carbon monoxide and hydrogen are the gas that reductibility is stronger, and under the condition coexisting at the two and oxygen, normal conditions are when gating catalytic oxidation is removed hydrogen, and CO equally also can react and lose larger.Even occur that only CO reacts and the nonreactive situation of hydrogen.Therefore, how developing the method that CO gas exists lower high selection to remove hydrogen is challenging problem.And we are surprised to find in large quantity research, adopt the inventive method under carrying out carbon monoxide existence, to select in dehydrogenation reaction process, CO rate of loss is lower, and hydrogen can take off to 1ppm.And further dynamics research is found, adopt the inventive method in carrying out the high selection of CO gas 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 transforms hydrogen for realizing maximizing, and avoids to greatest extent the oxidational losses of CO simultaneously, from reaction kinetics angle, provides most important theories basis and theoretical support.Further reaction mechanism further investigation is found, carbon monoxide and hydrogen gas mixture oxidation are removed in the process of hydrogen, the existence of " lattice oxygen " in catalyzer, for the deep removal of hydrogen and the loss of reduction carbon monoxide, all there is vital role, and by pre-treatment, introduce enough " lattice oxygen " at the catalyst reaction initial stage, for starting carbon monoxide, remove reacting of hydrogen with hydrogen gas mixture oxidation, and the continuous relay of follow-up " lattice oxygen " all has important effect.
The CO rate of loss of indication of the present invention obtains by following account form:
Quality * 100% of CO rate of loss=(quality of quality-product C O of raw material CO)/raw material CO
Adopting technical scheme of the present invention, in the pretreatment gas atmosphere that the catalyzer that is 0.05～1.5% is 1～100% at oxygen content, is 100～400 ℃ in temperature by platinum metals active component content, and volume space velocity is 100～10000 hours
-1, under the condition that pressure is 0～2.0MPa, process 0.01～40 hour; Then, the CO mixed gas of hydrogen of take is raw material, and in oxygen and raw material, the mol ratio of hydrogen is 0.5～5: 1, and temperature of reaction is 100～300 ℃, and volume space velocity is 100～10000 hours
-1, under the condition that reaction pressure is-0.08～5.0MPa, raw material is that active constituent catalyst reactor contacts with catalyzer by platinum metals is housed, in reaction effluent, hydrogen is oxidized to water; Its reaction result is that the rate of loss of CO can be lower than 1%, and hydrogen can be removed to below 1ppm, has obtained good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Catalyzer preparation:
Take specific surface and be 100 grams of the alumina supporters of 50 meters squared per gram, according to 0.5%Pd/Al
2o
3content configuration catalyzer, its step is as follows: choose Palladous nitrate, according to palladium charge capacity, be made into steeping fluid, alumina supporter is flooded in this solution after 10 hours, at room temperature vacuum-drying 12 hours solids.Again solid is obtained to required 0.5%Pd/Al for dry 4 hours at 120 ℃
2o
3catalyzer.
By the above-mentioned catalyzer making, at oxygen content, being in the pretreatment gas atmosphere of 5% (nitrogen of surplus), is 200 ℃ in temperature, and volume space velocity is 800 hours
-1, under the condition that pressure is 0.5MPa, process 35 hours; Then, the CO gas that the hydrogen content of take is 1.2% is raw material, and in oxygen and raw material, the mol ratio of hydrogen is 0.85: 1,180 ℃ of reactor reaction temperature, and volume space velocity is 600 hours
-1, under the condition that reaction pressure is 3.2MPa, its reaction result is: the rate of loss of CO is 0.33%, in reaction effluent, the content of hydrogen is 1ppm.
[embodiment 2]
Method for preparing catalyst according to [embodiment 1] makes 0.7%Pd/Al
2o
3catalyzer.
By the catalyzer making, at oxygen content, being in the pretreatment gas atmosphere of 30% (nitrogen of surplus), is 300 ℃ in temperature, and volume space velocity is 1500 hours
-1, under the condition that pressure is 0.8MPa, process 30 hours; Then, the CO gas that the hydrogen content of take is 2.5% is raw material, and in oxygen and raw material, the mol ratio of hydrogen is 2: 1,180 ℃ of reactor reaction temperature, and volume space velocity is 1800 hours
-1, under the condition that reaction pressure is 2.2MPa, its reaction result is: the rate of loss of CO is 0.6%, in reaction effluent, the content of hydrogen is 2ppm.
[embodiment 3]
Method for preparing catalyst according to [embodiment 1] makes 1.1%Pd/Al
2o
3catalyzer.
By the catalyzer making, at oxygen content, being in the pretreatment gas atmosphere of 50% (nitrogen of surplus), is 380 ℃ in temperature, and volume space velocity is 8500 hours
-1, under the condition that pressure is 1.8MPa, process 2 hours; Then, the CO gas that the hydrogen content of take is 0.4% is raw material, and in oxygen and raw material, the mol ratio of hydrogen is 4.5: 1,210 ℃ of reactor reaction temperature, and volume space velocity is 5000 hours
-1, under the condition that reaction pressure is 0.05MPa, its reaction result is: the rate of loss of CO is 0.66%, in reaction effluent, the content of hydrogen is 0.
[embodiment 4]
According to the method for preparing catalyst of [embodiment 1], make the catalyzer of 1.0%Pd+0.3%Fe/ silicon oxide.
By the catalyzer making, at oxygen content, being in the pretreatment gas atmosphere of 50% (nitrogen of surplus), is 380 ℃ in temperature, and volume space velocity is 5000 hours
-1, under the condition that pressure is 1.5MPa, process 1 hour; The CO gas that the hydrogen content of take is 0.8% is raw material, and in oxygen and raw material, the mol ratio of hydrogen is 1: 1,240 ℃ of reactor reaction temperature, and volume space velocity is 6000 hours
-1, reaction pressure is-condition of 0.05MPa under, its reaction result is: the rate of loss of CO is 0.38%, in reaction effluent, the content of hydrogen is 3ppm.
[embodiment 5]
According to the method for preparing catalyst of [embodiment 1], make the catalyzer of 0.8%Pd+0.3%Fe/ZSM-5 (silica alumina ratio is 300: 1).
By the catalyzer making, at oxygen content, being in the pretreatment gas atmosphere of 90% (nitrogen of surplus), is 300 ℃ in temperature, and volume space velocity is 3000 hours
-1, under the condition that pressure is 1.0MPa, process 0.5 hour; Then, the CO gas that the hydrogen content of take is 2% is raw material, and in oxygen and raw material, the mol ratio of hydrogen is 0.65: 1,270 ℃ of reactor reaction temperature, and volume space velocity is 7800 hours
-1, reaction pressure is-condition of 0.04MPa under, its reaction result is: the rate of loss of CO is 0.215%, in reaction effluent, the content of hydrogen is 5ppm.
[embodiment 6]
Method for preparing catalyst according to [embodiment 1] makes 0.58%Pd/Al
2o
3catalyzer.
By the catalyzer making, in the pretreatment gas atmosphere of air, in temperature, be 360 ℃, volume space velocity is 2000 hours
-1, under the condition that pressure is 0.2MPa, process 0.1 hour; Then, the CO gas that the hydrogen content of take is 5% is raw material, and in oxygen and raw material, the mol ratio of hydrogen is 1.4: 1,220 ℃ of reactor reaction temperature, and volume space velocity is 3000 hours
- 1, under the condition that reaction pressure is 0.3MPa, its reaction result is: the rate of loss of CO is 0.7%, in reaction effluent, the content of hydrogen is 4ppm.
[embodiment 7]
According to the method for preparing catalyst of [embodiment 1], make the catalyzer of 0.60%Pd+0.2%Mn/ZSM-5 (silica alumina ratio is 400: 1).
By the catalyzer making, in the pretreatment gas atmosphere of air, in temperature, be 250 ℃, volume space velocity is 1000 hours
-1, under the condition that pressure is 0.02MPa, process 10 hours; Then, the CO gas that the hydrogen content of take is 8% is raw material, and in oxygen and raw material, the mol ratio of hydrogen is 0.55: 1,200 ℃ of reactor reaction temperature, and volume space velocity is 2500 hours
- 1, under the condition that reaction pressure is 0.8MPa, its reaction result is: the rate of loss of CO is 0.43%, in reaction effluent, the content of hydrogen is 2ppm.
[embodiment 8]
Method for preparing catalyst according to [embodiment 1] makes 0.22%Pt/Al
2o
3catalyzer.
By the catalyzer making, in the pretreatment gas atmosphere of air, in temperature, be 200 ℃, volume space velocity is 800 hours
- 1, under the condition that pressure is 0.2MPa, process 5 hours; Then, the CO gas that the hydrogen content of take is 0.2% is raw material, and in oxygen and raw material, the mol ratio of hydrogen is 0.6: 1,200 ℃ of reactor reaction temperature, and volume space velocity is 4000 hours
- 1, under the condition that reaction pressure is 0.3MPa, its reaction result is: the rate of loss of CO is 0.2%, in reaction effluent, the content of hydrogen is 0.
[embodiment 9]
Method for preparing catalyst according to [embodiment 1] makes 0.18%Pt/Al
2o
3catalyzer.
By the catalyzer making, in the pretreatment gas atmosphere of purity oxygen, in temperature, be 180 ℃, volume space velocity is 8000 hours
-1, under the condition that pressure is 1.0MPa, process 0.1 hour; Then, the CO gas that the hydrogen content of take is 0.2% is raw material, and in oxygen and raw material, the mol ratio of hydrogen is 0.6: 1,210 ℃ of reactor reaction temperature, and volume space velocity is 3000 hours
-1, under the condition that reaction pressure is 0.3MPa, its reaction result is: the rate of loss of CO is 0.35%, in reaction effluent, the content of hydrogen is 1ppm.
[comparative example 1]
According to each step and the condition of [embodiment 1], just catalyzer is without pre-treatment, and at air speed, oxygen hydrogen ratio, under the identical condition of temperature of reaction, reaction pressure, reaction result is: the rate of loss of CO is 1.2%, and in reaction effluent, the content of hydrogen is 15ppm.
[comparative example 2]
According to each step and the condition of [embodiment 2], just catalyzer is without pre-treatment, and at air speed, oxygen hydrogen ratio, under the identical condition of temperature of reaction, reaction pressure, reaction result is: the rate of loss of CO is 1.5%, and in reaction effluent, the content of hydrogen is 20ppm.
Claims (5)
1. CO mixed gas gating catalytic oxidation is except the method for hydrogen, usings platinum metals as the active ingredient of catalyzer, in the pretreatment gas atmosphere that is 10～100%, in temperature, is 150～300 ℃ at oxygen content, and volume space velocity is 500～8000 hours
-1, under the condition that pressure is 0～1.0MPa, process 0.01～40 hour; Then, take hydrogen content as 0～10% and hydrogen content not as 0 CO mixed gas is raw material, in oxygen and raw material, the mol ratio of hydrogen is 0.5～5:1, temperature of reaction is 150～280 ℃, volume space velocity is 800～8000 hours
-1, under the condition that reaction pressure is 0～2.0MPa, raw material contacts with catalyzer by the reactor of catalyzer is housed, and usings platinum metals as the active ingredient of catalyzer, and in reaction effluent, hydrogen is oxidized to water.
2. CO mixed gas gating catalytic oxidation is except the method for hydrogen according to claim 1, and at least one that it is characterized in that catalyzer take in silicon oxide, aluminum oxide or molecular sieve is carrier; The platinum metals active ingredient of catalyzer is selected from platinum or palladium, take vehicle weight as benchmark, and the weight percentage of the platinum metals active ingredient of catalyzer is 0.05～1.0%.
3. CO mixed gas gating catalytic oxidation, except the method for hydrogen, is characterized in that catalyzer take aluminum oxide as carrier according to claim 2; The platinum metals active ingredient of catalyzer is selected from palladium, take vehicle weight as benchmark, and the weight percentage of the platinum metals active ingredient of catalyzer is 0.08～1.0%.
According to claim 1 CO mixed gas gating catalytic oxidation except the method for hydrogen, it is characterized in that platinum metals is that the pretreatment condition of the catalyzer of active ingredient is: pretreatment gas oxygen content is 20～100%, temperature is 150～250 ℃, and volume space velocity is 1000～6000 hours
-1, pressure is 0～0.5MPa; 180～260 ℃ of reactor reaction temperature, volume space velocity is 1000～6000 hours
-1, reaction pressure is 0～1.0MPa.
5. the method except hydrogen according to CO mixed gas gating catalytic oxidation described in claim 1, is characterized in that, in the CO gas raw material of hydrogen, the volumn concentration of hydrogen is 0.01～5%.
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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 |
| CN104888772A (en) * | 2014-03-03 | 2015-09-09 | 中国石油化工股份有限公司 | Oxidation catalyst, preparation method and application thereof |
| US20230382741A1 (en) * | 2020-10-08 | 2023-11-30 | Resonac Corporation | Method for removing oxygen molecule and method for purifying carbon monoxide |
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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 |
| CN101549856A (en) * | 2009-05-02 | 2009-10-07 | 大连理工大学 | Separation method of comprehensively recycled hydrogen and carbon monooxide from synthesis purge gas |
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| CN101549856A (en) * | 2009-05-02 | 2009-10-07 | 大连理工大学 | Separation method of comprehensively recycled hydrogen and carbon monooxide from synthesis purge gas |
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