CN102583374B - One prepares barkite or the industrial CO gas cleaning technique of carbonic ether - Google Patents
One prepares barkite or the industrial CO gas cleaning technique of carbonic ether Download PDFInfo
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- CN102583374B CN102583374B CN201210029172.2A CN201210029172A CN102583374B CN 102583374 B CN102583374 B CN 102583374B CN 201210029172 A CN201210029172 A CN 201210029172A CN 102583374 B CN102583374 B CN 102583374B
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Abstract
The open one of the present invention prepares barkite or the industrial CO gas cleaning technique of carbonic ether.The method comprises two steps: adopt noble metal catalyst Pd/Al
2o
3or Pd-M/Al
2o
3(M is promoter metal), removes a small amount of H in industrial CO by the technique of oxygenation dehydrogenation
2; Above-mentioned reactant gases enters oxidative esterification reaction tower after drying, O residual after making oxygenation dehydrogenation reaction
2participate in oxidative esterification reaction to be removed.After two step purifications, can the H in industrial CO gas
2be removed to below 100ppm, O
2be removed to below 500ppm, meet the CO unstripped gas requirement preparing barkite or carbonic ether, can effectively solve in oxo process industry CO gas cleaning problem.
Description
Technical field
The present invention relates to a kind of for removing a small amount of H in industrial CO gas
2two-step approach purification process, in particular, provide one and prepare barkite or the industrial CO gas cleaning technique of carbonic ether.
Background technology
In conjunction with the current resources situation of China's oil starvation, weak breath, coal resources relative abundance, developing with coal is that the Chemical Engineering Technology meaning of raw material is very great.With the CO after synthetic gas separation for raw material can prepare multiple large chemicals, as barkite, carbonic ether etc.Barkite is important Organic Chemicals, various dyestuff, medicine, important solvent, extraction agent and various intermediate is prepared in a large number for fine chemistry industry, barkite hydrogenation can obtain ethylene glycol (China's demand is large, needs a large amount of import every year), and hydrolysis can obtain 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 in methylcarbonate, oxygen level is high, gasoline dope is made for alternative methyl tertiary butyl ether (MTBE), the octane value of oil product can be increased, carbonic ether polymerization can obtain polycarbonate, and market demand is very large.
To be separated by water-gas pressure-variable adsorption or cryogenics is separated the industrial CO gas that obtains unavoidably with a certain amount of H
2remaining (content about 0.1 ~ 5.0%), this part a small amount of H
2can affect follow-up oxonation, be ensure that the efficient stable of oxonation runs, must first H a small amount of in industrial CO gas
2remove.The method adopted in the coal-ethylene glycol technology of Fujian Inst. of Matter Structure, Chinese Academy of Sciences's exploitation adopts noble metal catalyst, by adding O
2, at a certain temperature with H a small amount of in selective oxidation removing industrial CO gas
2.In the recent period, patent " dehydrogenation catalyst for feed gas containing carbon monoxide and methods for making and using same thereof the " (application number: CN200910061853 that Huashuo Science Co., Ltd applies for, publication number: CN101543776), " method of CO mixed gas selective oxidation dehydrogenation " (application number: CN102219214) that Sinopec Group applies for also is adopt similar method, but all not mentionedly how to eliminate after oxygenation dehydrogenation excessive O in tail gas
2method.In oxygenation dehydrogenating technology, in order to remove H a small amount of in industrial CO gas efficiently
2, need to add excessive O
2just can make reacted H
2reach very low concentration (being usually less than 100ppm), this just inevitably causes reacting the O in rear tail gas
2too high levels, and too high oxygen content can affect follow-up oxonation.
Oxonation occurs for nitrous acid ester and CO can oxalic ester and carbonic ether, also can generate NO, generate nitrous acid ester again after NO oxidative esterification, therefore nitrous acid ester occurs can recycle in oxonation oxalic ester and carbonic ether process at CO, not loss in theory, concrete reaction formula is as follows:
Synthesis of oxalate reacts:
2RONO+2CO＝(ROOC)
2+2NO
Synthesizing carbonate ester reacts:
2RONO+CO＝(RO)
2OC+2NO
Oxidative esterification reaction:
4NO+O
2+4ROH＝4RONO+2H
2O
Oxidative esterification reaction is with NO, O
2the reaction of nitrous acid ester is generated, the excessive O that industrial CO produces after dehydrogenation purification with alcohols reaction
2can participate in the oxidative esterification reaction of NO and alcohols and play the object removed, and CO does not participate in oxidative esterification reaction.
The object of this invention is to provide a kind of two-step approach purification process preparing barkite or carbonic ether industrial CO gas, can efficient economy a small amount of O that must remove a small amount of H2 in industrial CO gas and produce due to oxygenation dehydrogenation
2purification process, making full use of the oxidative esterification process unit in technique unit, not needing additional process equipment for removing excessive O
2, can effectively solve in oxo process industry CO gas cleaning problem.
Summary of the invention
The step preparing the two-step approach purification process of barkite or carbonic ether industrial CO gas of the present invention is as follows:
The first step, makes the O of industrial CO gas and metering
2by being filled with the reactor bed reaction of noble metal catalyst, reactor can be fixed-bed reactor or fluidized-bed reactor, the H in industrial CO
2content is about 0.1 ~ 5.0%, the O added
2amount is about H
20.5 ~ 5.0 times of content, the noble metal catalyst adopted is Pd/Al
2o
3or Pd-M/Al
2o
3(M is promoter metal, can be one or both in alkaline-earth metal or lanthanide series metal.), aluminum oxide used is γ-Al
2o
3, θ-Al
2o
3with α-Al
2o
3in a kind of crystalline form, temperature of reaction controls at 100 ~ 250 DEG C, and air speed controls at 200 ~ 12000h
-1, reaction pressure controls at 0 ~ 3.5MPa, controls reacted H
2content is lower than 100ppm, O
2content at hundreds of to ppm up to ten thousand, after reaction, gas is again by water that molecular sieve removing oxygenation dehydrogenation reaction generates.
Second step, above-mentioned gas is passing into oxidative esterification tower, makes O a small amount of in system
2participate in oxidative esterification reaction and play the object removed, the temperature of reaction of oxidative esterification tower controls at 0 ~ 90 DEG C, and oxidative esterification tower can adopt packing tower or spray column, the alcohols added, NO and O
2amount controls as alcohol: NO: O
2=4 ~ 100: 4 ~ 20: 1, reaction pressure controls at 0 ~ 1.5MPa, and the gas phase composition of oxidative esterification tower also can (main component be CO, NO, N with the reacted tail gas of carbonylation
2, CH
3oNO) supplementary NO and O is added
2as reaction raw materials, the total air speed of gas controls at 200 ~ 15000h
-1, the alcohols added can use the alkyl alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, determines according to carbonylation target product, the O after reaction in system
2content can be removed to below 500ppm, can meet the purity requirement preparing barkite or carbonic ether CO unstripped gas.
Accompanying drawing explanation
Accompanying drawing is for preparing barkite or the industrial CO gas cleaning process flow diagram of carbonic ether.
Embodiment
The present invention is further illustrated by following embodiment.
Embodiment 1
The first step, adopts flow process shown in the drawings, and reactor 2 is single hose stainless steel fixed-bed reactor, the inertia magnet ring of 5 ~ 15cm height is filled in reactor upper end, as preheating gas use, middle 5 ~ 30cm is the isothermal reaction region of loading catalyst, and lower end 5 ~ 20cm filler is inertia magnet ring.The actual loadings of catalyzer is 10ml, and catalyzer is the Pd/Al containing palladium 2.0%wt
2o
3, contain the H of by volume 1.5%
2, 98.5% CO mixed gas with the speed of 167ml/min, oxygen enters oxygenation dehydrogenation reactor with the speed of 6ml/min, and reactor preheating temperature controls at 125 DEG C, and reaction zone point for measuring temperature temperature of reaction is 137 DEG C, H in tail gas after reaction
2content is 58ppm, O
2content is 3580ppm, and all the other are CO and a small amount of CO
2, CH
4, H
2o, reacted gas passes through the moisture eliminator 3 that 5A molecular sieve is housed, the H generated after reaction
2o removes.
Second step, the gas after dehydration, through passing into oxidative esterification reaction tower 4, mixes with the gaseous component of oxidative esterification tower, contains the O of by volume 15%
2, 85% NO mixed gas enter oxidative esterification reaction device with the speed of 380ml/min, methyl alcohol spray flux is 2.8ml/min, and temperature of reaction controls at 50 DEG C, the O after reaction in gas phase composition
2content is 380ppm, and all the other compositions are CO, NO, CH
3oNO and a small amount of CH
4, CO
2, CH
3oH and H
2o, gas phase composition enters moisture eliminator 5 from reactor upper end outlet, the CH in gas
3oH and H
2synthesis reactor reaction directly can be entered, as the unstripped gas of carbonylation barkite or carbonic ether after O removes.
Embodiment 2
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 tail gas after reaction
2content is 42ppm, O
2content is 4350ppm.Second step in embodiment 1, O
2be 10: 90 with the volume ratio of NO, other condition is identical, the O after reaction in gas phase composition
2content is 320ppm.I.e. cost example.
Embodiment 3
The methyl alcohol of spray in embodiment 1 is changed into ethanol, i.e. cost example.
Embodiment 4
The first step, according to the condition in embodiment 1, changes the gas phase composition volume ratio in embodiment 1 as N into
2: NO: O
2=25: 65: 10, feed rate changes 400ml/min into, and temperature of reaction controls at 35 DEG C, and methyl alcohol spray flux is 2.3ml/min, the O after reaction in gas phase composition
2content is 220ppm.I.e. cost example.
Embodiment 5
The first step, according to the condition in embodiment 1, changes the gas phase composition volume ratio in embodiment 1 as CH into
3oNO: N
2: NO: O
2=12: 25: 53: 10, temperature of reaction controls at 60 DEG C, and feed rate changes 400ml/min into, and methyl alcohol spray flux is 1.8ml/min, the O after reaction in gas phase composition
2content is 240ppm.I.e. cost example.
Claims (7)
1. prepare barkite or the industrial CO gas cleaning technique of carbonic ether, comprise the steps:
(1) employing noble metal catalyst oxygenation dehydrogenating technology removes a small amount of H in industrial CO
2;
(2) gas after oxygenation dehydrogenation reaction enters oxidative esterification reaction tower after drying and participates in oxidative esterification reaction, O residual in removing system
2, the O after reaction in system
2content is removed to below 500ppm.
2. prepare barkite or the industrial CO gas cleaning technique of carbonic ether as claimed in claim 1, it is characterized in that: described noble metal catalyst is Pd/Al
2o
3or Pd-M/Al
2o
3, wherein M is promoter metal, and be selected from one or both in alkaline-earth metal or lanthanide series metal, wherein aluminum oxide is selected from γ-Al
2o
3, θ-Al
2o
3with α-Al
2o
3in a kind of crystalline form.
3. prepare barkite or the industrial CO gas cleaning technique of carbonic ether as claimed in claim 1, it is characterized in that: described oxygenation dehydrogenation reaction technique, the hydrogen content in industrial CO gas is between 0.1 ~ 5.0%, and all the other are CO gas.
4. prepare barkite or the industrial CO gas cleaning technique of carbonic ether as claimed in claim 1, it is characterized in that: described oxygenation dehydrogenation reaction technique, the O added
2amount is H
20.5 ~ 5.0 times of content, temperature of reaction controls at 100 ~ 250 DEG C, and air speed controls at 200 ~ 12000h
-1, reaction pressure controls at 0 ~ 3.5MPa, adopts fixed-bed reactor or fluidized-bed reactor.
5. prepare barkite or the industrial CO gas cleaning technique of carbonic ether as claimed in claim 1, it is characterized in that: described oxidative esterification reaction technique, the esterification reaction tower adopted is packing tower or spray column.
6. prepare barkite or the industrial CO gas cleaning technique of carbonic ether as claimed in claim 1, it is characterized in that: described oxidative esterification reaction technique, the main raw material adopted is NO, O
2, alcohols, containing a certain amount of nitrous acid ester and N in raw material
2, the alcohols methyl alcohol, ethanol, propyl alcohol, the butanols that adopt.
7. prepare barkite or the industrial CO gas cleaning technique of carbonic ether as claimed in claim 1, it is characterized in that: described oxidative esterification reaction technique, the temperature of reaction of oxidative esterification tower controls at 0 ~ 90 DEG C, the alcohols added, NO and O
2amount controls as alcohol: NO: O
2=4 ~ 100: 4 ~ 20: 1, reaction pressure controls at 0 ~ 1.5MPa, and the reacted tail gas of gas phase composition carbonylation of oxidative esterification tower adds supplementary NO and O
2as reaction raw materials, the total air speed of gas controls at 200 ~ 15000h
-1.
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|---|---|---|---|
| CN201210029172.2A CN102583374B (en) | 2012-02-09 | 2012-02-09 | One prepares barkite or the industrial CO gas cleaning technique of carbonic ether |
Applications Claiming Priority (1)
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|---|---|---|---|
| CN201210029172.2A CN102583374B (en) | 2012-02-09 | 2012-02-09 | One prepares barkite or the industrial CO gas cleaning technique of carbonic ether |
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| CN102583374A CN102583374A (en) | 2012-07-18 |
| CN102583374B true CN102583374B (en) | 2016-01-13 |
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Families Citing this family (8)
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| CN109433192B (en) * | 2018-12-07 | 2021-06-01 | 东北大学 | Noble metal monoatomic dispersion type purification catalyst and preparation method thereof |
| 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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| CN101993072B (en) * | 2009-08-31 | 2012-11-14 | 中国石油化工股份有限公司 | 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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| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
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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| PE01 | Entry into force of the registration of the contract for pledge of patent right |
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 |
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