CN102583374A - Purification process of industrial CO gas for preparing oxalate or carbonic ester - Google Patents
Purification process of industrial CO gas for preparing oxalate or carbonic ester Download PDFInfo
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- CN102583374A CN102583374A CN2012100291722A CN201210029172A CN102583374A CN 102583374 A CN102583374 A CN 102583374A CN 2012100291722 A CN2012100291722 A CN 2012100291722A CN 201210029172 A CN201210029172 A CN 201210029172A CN 102583374 A CN102583374 A CN 102583374A
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Abstract
The invention discloses a purification process of industrial CO gas for preparing oxalate or carbonic ester. The method comprises the two steps of: removing a little amount of H2 in the industrial CO by adopting noble metal catalyst Pd/Al2O3 or Pd-M/Al2O3 (M is additive metal) and using a process of oxygenation and dehydrogenation; and after drying, enabling the dried reactive gas to enter an oxidative-esterification reaction tower, and then enabling residual O2 generated by oxygenation and dehydrogenation reaction to participate in oxidative-esterification reaction so as to remove the O2. After two-step purification, H2 in the industrial CO gas can be below 100ppm by remove, the O2 can be below 500ppm , and the requirement for CO feed gas for preparing the oxalate or carbonic ester is met, so that the problem for CO gas purification in the oxo synthesis industry can be effectively realized.
Description
Technical field
The present invention relates to a kind of industrial CO gas small amount of H that is used for removing
2The two-step approach purification process, particularly provide a kind of preparation barkite or carbonic ether with industrial CO gas cleaning technology.
Background technology
In conjunction with China's oil starvation, weak breath, the relative rich in natural resources present situation of coal resources, development is that the chemical industry technical meaning of raw material is very great with the coal.CO with after the synthetic gas separation is that raw material can prepare multiple large chemicals, like barkite, carbonic ether etc.Barkite is important Organic Chemicals; Be used for fine chemistry industry in a large number and prepare various dyestuffs, medicine, important solvent, extraction agent and various midbody; The barkite hydrogenation can get terepthaloyl moietie (China's demand is big, needs a large amount of imports every year), and hydrolysis can get oxalic acid.Carbonic ether is a kind of important industrial chemicals with extensive use; It is the green chemical that the whole world is assert; Particularly oxygen level is high in the methylcarbonate, is used for substituting MTBE (MTBE) and makes gasoline dope, can increase the octane value of oil product; The carbonic ether polymerization can get polycarbonate, and market demand is very big.
Separate the industrial CO gas that obtains by water-gas transformation fractionation by adsorption or cryogenics and unavoidably have certain amount of H
2Remaining (content about 0.1～5.0%), this part a spot of H
2Can the follow-up oxonation of influence, be the efficient stable operation that guarantees oxonation, must be earlier a spot of H in the industrial CO gas
2Remove.The method that is adopted in the coal-ethylene glycol technology of Fujian Inst. of Matter Structure, Chinese Academy of Sciences's exploitation is to adopt noble metal catalyst, through adding O
2, remove a spot of H in the industrial CO gas with selective oxidation at a certain temperature
2In the recent period; The patent that Huashuo Science Co., Ltd applied for " dehydrogenation catalyst for feed gas containing carbon monoxide and methods for making and using same thereof " (application number: CN200910061853; Publication number: CN101543776); " method of CO mixed gas selective oxidation dehydrogenation " that Sinopec Group applied for (application number: also be to adopt similar method CN102219214), but all not mentionedly how eliminate after the oxygenation dehydrogenation excessive O in the tail gas
2Method.In the oxygenation dehydrogenating technology, in order to remove a spot of H in the industrial CO gas efficiently
2, need to add excessive O
2Could make reacted H
2Reach very low concentration (being usually less than 100ppm), this just inevitably causes reacting the O in the tail gas of back
2Too high levels, and too high oxygen content can influence follow-up oxonation.
Oxonation takes place for nitrous acid ester and CO can generate barkite and carbonic ether; Also can generate NO, generate nitrous acid ester behind the NO oxidative esterification again, so nitrous acid ester takes place can recycle in oxonation generation barkite and the carbonic ether process at CO; Not loss in theory, concrete reaction formula is following:
The synthesis of oxalate reaction:
2RONO+2CO＝(ROOC)
2+2NO
The synthesizing carbonate ester reaction:
2RONO+CO＝(RO)
2OC+2NO
Oxidative esterification reaction:
4NO+O
2+4ROH＝4RONO+2H
2O
Oxidative esterification reaction is with NO, O
2Reaction generates the reaction of nitrous acid ester, the excessive O that industrial CO produces after dehydrogenation purifies with alcohols
2Can participate in the oxidative esterification reaction of NO and alcohols and play the purpose that removes, and CO does not participate in oxidative esterification reaction.
The purpose of this invention is to provide a kind of two-step approach purification process for preparing barkite or carbonic ether with industrial CO gas, can must remove small amount of H 2 and because a small amount of O that the oxygenation dehydrogenation is produced in the industrial CO gas by highly economical
2Purification process, make full use of the oxidative esterification technique unit in the technique unit, do not need extra increase processing unit to be used to remove excessive O
2, can effectively solve in the oxo process industry CO gas cleaning problem.
Summary of the invention
Preparation barkite of the present invention or carbonic ether are following with the step of the two-step approach purification process of industrial CO gas:
The first step makes the O of industrial CO gas and metering
2Through being filled with the reactor bed reaction of noble metal catalyst, reactor drum can be fixed-bed reactor or fluidized-bed reactor, the H among the industrial CO
2Content is about 0.1～5.0%, the O that is added
2Amount is about H
20.5～5.0 times of content, the noble metal catalyst that is adopted is Pd/Al
2O
3Or Pd-M/Al
2O
3(M is a promoter metal, can be in earth alkali metal or the lanthanide series metal one or both.), used aluminum oxide is γ-Al
2O
3, θ-Al
2O
3And α-Al
2O
3In a kind of crystalline form, temperature of reaction is controlled at 100～250 ℃, air speed is controlled at 200～12000h
-1, reaction pressure is controlled at 0～3.5MPa, controls reacted H
2Content is lower than 100ppm, O
2Content at hundreds of to ppm up to ten thousand, reaction back gas is removed the water that the oxygenation dehydrogenation reaction is generated through molecular sieve again.
In second step, above-mentioned gas makes a spot of O in the system feeding the oxidative esterification tower
2Participate in oxidative esterification reaction and play the purpose that removes, the temperature of reaction of oxidative esterification tower is controlled at 0～90 ℃, and the oxidative esterification tower can adopt packing tower or spray column, the alcohols that is added, NO and O
2Amount is controlled to be alcohol: NO: O
2=4～100: 4～20: 1, reaction pressure is controlled at 0～1.5MPa, and the gas phase composition of oxidative esterification tower also can be used tail gas after the carbonylation building-up reactions, and (staple is CO, NO, N
2, CH
3ONO) add additional NO and O
2As reaction raw materials, the total air speed of gas is controlled at 200～15000h
-1, the alcohols that is added can be used alkyl alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, decides the O in the system of reaction back according to the carbonylation title product
2Content can be removed to below the 500ppm, can meet the purity requirement with the CO virgin gas of preparation barkite or carbonic ether.
Description of drawings
Accompanying drawing is for preparing barkite or carbonic ether with industrial CO gas cleaning process flow diagram.
Embodiment
The present invention is further specified by following embodiment.
Embodiment 1
The first step adopts flow process shown in the drawings, and reactor drum 2 is single hose stainless steel fixed-bed reactor; The inertia magnet ring of 5～15cm height is filled in the reactor drum upper end; As preheating gas usefulness, the isothermal reaction zone that middle 5～30cm is a loading catalyst, lower end 5～20cm filler is the inertia magnet ring.The actual loadings of catalyzer is 10ml, and catalyzer is the Pd/Al that contains palladium 2.0%wt
2O
3, contain 1.5% H by volume
2, 98.5% CO mixed gas is with the speed of 167ml/min, oxygen gets into the oxygenation dehydrogenation reactor with the speed of 6ml/min, the reactor drum preheating temperature is controlled at 125 ℃, reaction zone point for measuring temperature temperature of reaction is 137 ℃, H in the tail gas of reaction back
2Content is 58ppm, O
2Content is 3580ppm, and all the other are CO and a spot of CO
2, CH
4, H
2O, reacted gas is through being equipped with the moisture eliminator 3 of 5A molecular sieve, the H of reaction back generation
2O removes.
In second step, the gas after the dehydration mixes with the gaseous component of oxidative esterification tower through feeding oxidative esterification reaction tower 4, contains 15% O by volume
2, 85% NO mixed gas gets into the oxidative esterification reaction device with the speed of 380ml/min, the methyl alcohol spray flux is 2.8ml/min, temperature of reaction is controlled at 50 ℃, the O in the gas phase composition of reaction back
2Content is 380ppm, and all the other compositions are CO, NO, CH
3ONO and a spot of CH
4, CO
2, CH
3OH and H
2O, gas phase composition gets into moisture eliminator 5 from the outlet of reactor drum upper end, the CH in the gas
3OH and H
2After removing, O can directly get into the synthesis reactor reaction, as the unstripped gas of carbonylation synthesis of oxalate or carbonic ether.
The first step in embodiment 1 changes catalyzer into the Pd-Mg/Al of 1.0%wt
2O
3, the component proportions of CO gas mixture is 99.0%CO, 1.0%H
2, mixed gas flow is 167ml/min, and oxygen flow is with 5.5ml/min, and other condition is identical, H in the tail gas of reaction back
2Content is 42ppm, O
2Content is 4350ppm.Second step in embodiment 1, O
2With the volume ratio of NO be 10: 90, other condition is identical, the O in the gas phase composition of reaction back
2Content is 320ppm.It is the cost example.
Change the methyl alcohol of spray among the embodiment 1 into ethanol, i.e. the cost example.
Embodiment 4
The first step changes the gas phase composition volume ratio among the embodiment 1 into N according to the condition among the embodiment 1
2: NO: O
2=25: 65: 10, air inlet speed changed 400ml/min into, and temperature of reaction is controlled at 35 ℃, and the methyl alcohol spray flux is 2.3ml/min, the O in the gas phase composition of reaction back
2Content is 220ppm.It is the cost example.
Embodiment 5
The first step changes the gas phase composition volume ratio among the embodiment 1 into CH according to the condition among the embodiment 1
3ONO: N
2: NO: O
2=12: 25: 53: 10, temperature of reaction was controlled at 60 ℃, and air inlet speed changes 400ml/min into, and the methyl alcohol spray flux is 1.8ml/min, the O in the gas phase composition of reaction back
2Content is 240ppm.It is the cost example.
Claims (7)
1. one kind prepares barkite or carbonic ether with industrial CO gas cleaning technology, comprises the steps:
(1) adopt noble metal catalyst to remove the small amount of H among the industrial CO with the oxygenation dehydrogenating technology
2
(2) gas after the oxygenation dehydrogenation reaction gets into the oxidative esterification reaction tower and participates in oxidative esterification reaction after drying, removes O residual in the system
2
2. preparation barkite as claimed in claim 1 or carbonic ether is characterized in that with industrial CO gas cleaning technology: described noble metal catalyst is Pd/Al
2O
3Or Pd-M/Al
2O
3, wherein M is a promoter metal, is selected from earth alkali metal or the lanthanide series metal one or both, wherein aluminum oxide is selected from γ-Al
2O
3, θ-Al
2O
3And α-Al
2O
3In a kind of crystalline form.
3. preparation barkite as claimed in claim 1 or carbonic ether is characterized in that with industrial CO gas cleaning technology: described oxygenation dehydrogenation reaction technology, the hydrogen content in the industrial CO gas are between 0.1～5.0%, and all the other are CO gas.
4. preparation barkite as claimed in claim 1 or carbonic ether is characterized in that with industrial CO gas cleaning technology: described oxygenation dehydrogenation reaction technology, the O that is added
2Amount is about H
20.5～5.0 times of content, temperature of reaction is controlled at 100～250 ℃, and air speed is controlled at 200～12000h
-1, reaction pressure is controlled at 0～3.5MPa, can adopt fixed-bed reactor or fluidized-bed reactor.
5. preparation barkite as claimed in claim 1 or carbonic ether is characterized in that with industrial CO gas cleaning technology: described oxidative esterification reaction technology, the esterification reaction tower that is adopted can be packing tower or spray column.
6. preparation barkite as claimed in claim 1 or carbonic ether is characterized in that with industrial CO gas cleaning technology: described oxidative esterification reaction technology, the main raw material that is adopted is NO, O
2, alcohols, also can contain a certain amount of nitrous acid ester and N in the raw material
2, the alcohols that is adopted can be used alkyl alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols.
7. preparation barkite as claimed in claim 1 or carbonic ether is characterized in that with industrial CO gas cleaning technology: described oxidative esterification reaction technology, the temperature of reaction of oxidative esterification tower are controlled at 0～90 ℃, the alcohols that is added, NO and O
2Amount is controlled to be alcohol: NO: O
2=4～100: 4～20: 1, reaction pressure is controlled at 0～1.5MPa, and the gas phase composition of oxidative esterification tower also can add additional NO and O with the tail gas after the carbonylation building-up reactions
2As reaction raw materials, the total air speed of gas is controlled at 200～15000h
-1
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|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104192844A (en) * | 2014-09-01 | 2014-12-10 | 中国科学院福建物质结构研究所 | Method for reducing catalyst with carbon monoxide raw gas and purifying CO |
| CN104709907A (en) * | 2015-03-24 | 2015-06-17 | 中国五环工程有限公司 | Process and system for selectively removing small amount of H2 from high-concentrations CO gas |
| CN105080538A (en) * | 2015-06-26 | 2015-11-25 | 中国科学院福建物质结构研究所 | Catalyst for purifying and dehydrogenating CO raw material gas and preparation method for catalyst |
| 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 |
| CN106111127A (en) * | 2016-06-20 | 2016-11-16 | 中国科学院福建物质结构研究所 | A kind of nanoscale Pd/C catalyst and its preparation method and application |
| CN106554015A (en) * | 2016-11-07 | 2017-04-05 | 中国科学院福建物质结构研究所 | Evade the method for facing oxygen risk of explosion in the de- hydrogen purification process of CO unstripped gas |
| 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 |
| CN112129852A (en) * | 2020-08-31 | 2020-12-25 | 中国科学院福建物质结构研究所 | Reaction gas cyclic utilization and controllable CO dehydrogenation of atmosphere purifies catalyst evaluation device |
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| CN101993072A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司上海石油化工研究院 | Method for removing hydrogen through selective oxidation of CO gas mixture |
| CN102247851A (en) * | 2010-05-12 | 2011-11-23 | 中国科学院福建物质结构研究所 | Methanation process for removing a small amount of H2 from industrial CO gas and preparation method of catalyst |
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2012
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Patent Citations (2)
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| CN101993072A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司上海石油化工研究院 | Method for removing hydrogen through selective oxidation of CO gas mixture |
| CN102247851A (en) * | 2010-05-12 | 2011-11-23 | 中国科学院福建物质结构研究所 | Methanation process for removing a small amount of H2 from industrial CO gas and preparation method of catalyst |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104192844B (en) * | 2014-09-01 | 2016-01-20 | 中国科学院福建物质结构研究所 | Adopt the starting method of feed gas containing carbon monoxide reducing catalyst and purifying treatment CO |
| CN104192844A (en) * | 2014-09-01 | 2014-12-10 | 中国科学院福建物质结构研究所 | Method for reducing catalyst with carbon monoxide raw gas and purifying CO |
| CN104709907A (en) * | 2015-03-24 | 2015-06-17 | 中国五环工程有限公司 | Process and system for selectively removing small amount of H2 from high-concentrations CO gas |
| CN105080538B (en) * | 2015-06-26 | 2018-07-20 | 中国科学院福建物质结构研究所 | A kind of CO raw material gas purifyings catalyst for dehydrogen and preparation method thereof |
| CN105080538A (en) * | 2015-06-26 | 2015-11-25 | 中国科学院福建物质结构研究所 | Catalyst for purifying and dehydrogenating CO raw material gas and preparation method for catalyst |
| 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 |
| CN106111127A (en) * | 2016-06-20 | 2016-11-16 | 中国科学院福建物质结构研究所 | A kind of nanoscale Pd/C catalyst and its preparation method and application |
| CN106111127B (en) * | 2016-06-20 | 2018-05-11 | 中国科学院福建物质结构研究所 | A kind of nanoscale Pd/C catalyst and its preparation method and application |
| CN106554015A (en) * | 2016-11-07 | 2017-04-05 | 中国科学院福建物质结构研究所 | Evade the method for facing oxygen risk of explosion in the de- hydrogen purification process of CO unstripped gas |
| CN106554015B (en) * | 2016-11-07 | 2018-09-28 | 中国科学院福建物质结构研究所 | CO unstripped gas, which takes off in hydrogen purification process, evades the method for facing oxygen risk of explosion |
| 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 |
| CN109433192B (en) * | 2018-12-07 | 2021-06-01 | 东北大学 | Noble metal monoatomic dispersion type purification catalyst and preparation method thereof |
| CN112129852A (en) * | 2020-08-31 | 2020-12-25 | 中国科学院福建物质结构研究所 | Reaction gas cyclic utilization and controllable CO dehydrogenation of atmosphere purifies catalyst evaluation device |
| CN112129852B (en) * | 2020-08-31 | 2021-08-10 | 中国科学院福建物质结构研究所 | Reaction gas cyclic utilization and controllable CO dehydrogenation of atmosphere purifies catalyst evaluation device |
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Effective date of registration: 20171229 Address after: 562300 Guizhou Province, Xingren Buyi and Miao Autonomous Prefecture Xingren County Economic Development Zone (Industrial Park) Patentee after: Guizhou Xin alcohol science and Technology Development Co., Ltd. Address before: Fuzhou City, Fujian province 350002 Yangqiao Road No. 155 Patentee before: Fujian Institute of Research on the Structure of Matter, Chinese Academy of Scie |
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Denomination of invention: Purification process of industrial CO gas for preparing oxalate or carbonic ester Effective date of registration: 20200525 Granted publication date: 20160113 Pledgee: Guizhou Xinchun Energy Co., Ltd Pledgor: Guizhou Xin alcohol science and Technology Development Co., Ltd. Registration number: Y2020110000003 |