CN104945262A - Method for preparing prepare methyl nitrite by catalyzing methanol to reduce dilute nitric acid - Google Patents
Method for preparing prepare methyl nitrite by catalyzing methanol to reduce dilute nitric acid Download PDFInfo
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- CN104945262A CN104945262A CN201410123581.8A CN201410123581A CN104945262A CN 104945262 A CN104945262 A CN 104945262A CN 201410123581 A CN201410123581 A CN 201410123581A CN 104945262 A CN104945262 A CN 104945262A
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Abstract
The invention discloses a method for preparing methyl nitrite by catalyzing methanol to reduce dilute nitric acid. The method comprises the following steps: by taking methanol as a reducing agent, under the action of catalysis of a carbon-based catalyst, reducing dilute nitric acid into nitrous acid at 30-100 DEG C, and esterifying nitrous acid and methanol, thereby preparing methyl nitrite. A fixed bed is adopted as a reactor, and nitrogen is taken as a carrier gas. The method is high in dilute nitric acid conversion efficiency, the prepared methyl nitrite is a gas, and raw material separation can be easily achieved.
Description
Technical field
The invention belongs to coal chemical technology, specifically using methyl alcohol as reductive agent, by the dust technology waste liquid catalytic reduction that produces in Coal Chemical Industry process to nitrous acid, nitrous acid and methyl alcohol carry out esterification, obtain methyl nitrite.Methyl nitrite is intermediate important in coal-ethylene glycol technique.This process can improve effective utilization of nitrogenous source, reduces discharging of waste liquid, can improve the economic benefit of enterprise further.
Background technology
Ethylene glycol is large petrochemicals, is mainly used in deicing fluid and preparation PET polyester.Ethylene glycol mainly adopts petrochemical technology route to produce at present: be raw material with ethene, and prepare oxyethane by epoxidation, then ethylene glycol is prepared in hydration; This technology needs to consume bulk petroleum resource, and dehydration separating energy consumption is very large.The development of coal chemical technology and application, produce ethylene glycol for Non oil-based route and provide a new technology path.
Methyl nitrite is intermediate important in coal-ethylene glycol technological process.Methyl nitrite and CO are obtained by reacting dimethyl oxalate through being oxidized carbonization; The further Hydrogenation of dimethyl oxalate obtains ethylene glycol.Methyl nitrite reacts through methyl alcohol and nitric acid-Sodium Nitrite to prepare by coal.In the process, a large amount of dust technology waste liquids can be produced.Current treatment process is, adds the NaOH neutralization of metering, is then directly discharged by the waste liquid containing a large amount of SODIUMNITRATE, cause the pollution of water resources.Can be reduced into nitrite in the effect lower part at reductive bacterium after human body because nitrate is ingested, and the oxyphorase of nitrite easily and in blood reacts and forms methemoglobin, thus affect the transmittability of blood to oxygen.Therefore, by dust technology waste liquid Appropriate application, turn waste into wealth, effectively can not only reduce the discharge containing SODIUMNITRATE waste liquid, reduce the pollution to water resources, and can enterprise cost be reduced, improve Business Economic Benefit and social benefit further.
Summary of the invention
A kind of method of catalysis methanol reduction dust technology methyl nitrite:
In fixed-bed reactor, carry out successive reaction under normal pressure, methyl alcohol as reductive agent, N
2under atmosphere, under carbon-supported catalysts katalysis, 30-100 ° of C, is reduced to nitrous acid by dust technology, and nitrous acid and methanol esterification, prepare methyl nitrite.
Described carbon-supported catalysts is: one or more in activated carbon, mesoporous carbon, carbon fiber, carbon nanotube, Graphene, graphite, C60.
The concentration of described dust technology is 0.1-5wt%.
The weight hourly space velocity (WHSV) of fixed-bed reactor charging is 0.1-20h
-1.
Described carbon-supported catalysts, use before through compressing tablet, pulverize, process of sieving, selection particle diameter be 5-20 object particle.
Described Reduction of methanol dust technology is 50-80 ° of C to the temperature of reaction of nitrous acid, nitrous acid and methanol esterification.
The present invention adopts continuous reaction, uses fixed-bed reactor.Products therefrom methyl nitrite is gas, directly can be separated with reaction system.Whole reaction process is carried out under normal pressure N2, greatly reduces the requirement to equipment, has very large prospects for commercial application.
Accompanying drawing explanation
Fig. 1 fixed bed reaction apparatus.
Wherein, 1. nitrogengas cylinder; 2. two-way valve; 3. dust technology fresh feed pump; 4. gas-liquid separator 5. reaction tower; 6. reaction solution stores and fills with; 7. methyl nitrite scavenging tower; 8. methyl nitrite hold-up vessel.
Embodiment
As shown in Figure 1, it is process flow sheet of the present invention;
Described catalysis methanol reduction dust technology methyl nitrite reaction is carried out on fixed-bed reactor, be that 5-20 order carbon-supported catalysts joins in glass pipe type reactor by particle diameter, silicon oxide bead (preheating material) is filled, under-filled Stainless Steel Wire (support catalyst layer) in the top of catalyzer.Under nitrogen atmosphere, reaction unit is heated to certain temperature, adds dust technology methanol aqueous solution with volume pump.Wherein said temperature of reaction is 30-100 ° of C, and optimizing temperature of reaction is 50-80 ° of C, and pressure is normal pressure.With nitric acid content in ionic liquid chromatography analysis stream fluid, and calculate the transformation efficiency of nitric acid; With the content of methyl nitrite in gas chromatographic analysis gas, and calculate the yield of methyl nitrite.
Be further described (in example, agents useful for same is analytical pure) the present invention below by way of example, it should be noted that the following examples only as illustrating, content of the present invention is not limited thereto.
The reaction of embodiment 1 different carbon-supported catalysts catalysis methanol reduction dust technology methyl nitrite
By particle diameter be 10 object 5g carbon-supported catalysts load diameters be in the Glass tubing reactor of 15mm, under nitrogen atmosphere, add 1wt% dust technology 18wt% water methanol solution reaction liquid with volume pump, temperature of reaction is 70 ° of C, WHSV is 1.0h
-1, carry out at ambient pressure reducing, esterification.Acquired results is in table 1.
Table 1 different carbon-supported catalysts catalysis methanol reduction dust technology methyl nitrite
From table 1 result, different carbon-supported catalysts catalysis methanol reduction methyl nitrite reaction processed, all obtain good effect, the transformation efficiency of dust technology is more than 85%, and the yield of methyl nitrite is more than 90%.
Embodiment 2 catalyst particle size affects
By particle diameter be 5-20 object 5g activated carbon load diameter be in the Glass tubing reactor of 15mm, under nitrogen atmosphere, add 1wt% dust technology 18wt% water methanol solution reaction liquid with volume pump, temperature of reaction is 70 ° of C, WHSV is 1.0h
-1, carry out at ambient pressure reducing, esterification.Acquired results is in table 2.
Table 2 different-grain diameter activated carbon catalysis methanol reduction dust technology methyl nitrite
From table 2 result, there is remarkably influenced in catalyst activity carbon granules footpath on dust technology transformation efficiency, and increase with particle diameter, dust technology transformation efficiency reduces gradually.Reason may be that particle diameter is larger, and specific surface is less, piles up Kong Yue great, causes dust technology and catalyst activity position contact area to diminish, therefore transformation efficiency reduces.The yield impact of catalyst particle size on methyl nitrite is less, all more than 95%.
Embodiment 3 dust technology concentration affects
By particle diameter be 5 object 5g activated carbon load diameters be in the Glass tubing reactor of 15mm, under nitrogen atmosphere, add 0.1-5wt% dust technology 18wt% water methanol solution reaction liquid with volume pump, temperature of reaction is 70 ° of C, WHSV is 1.0h
-1, carry out at ambient pressure reducing, esterification.Acquired results is in table 3.
Table 3 activated carbon catalysis methanol reduction different concns dust technology methyl nitrite
From table 3 result, dust technology concentration has remarkably influenced to dust technology transformation efficiency, increases with dust technology concentration, and dust technology transformation efficiency raises rear maintaining an equal level gradually.The yield impact of dust technology concentration on methyl nitrite is less.Consider in coal-ethylene glycol process, gained dust technology waste liquid is at about 2wt%, and the following examples all select the concentration of dust technology to be 2wt%.
Embodiment 4 reaction temperatures affect
By particle diameter be 5 object 5g activated carbon load diameters be in the Glass tubing reactor of 15mm, under nitrogen atmosphere, add 2wt% dust technology 18wt% water methanol solution reaction liquid with volume pump, temperature of reaction is 30-100 ° of C, WHSV is 1.0h
-1, carry out at ambient pressure reducing, esterification.Acquired results is in table 4.
Activated carbon catalysis methanol reduction dust technology methyl nitrite at table 4 differential responses temperature
From table 4 result, temperature of reaction has remarkably influenced to dust technology transformation efficiency, raises with temperature of reaction, and dust technology transformation efficiency raises rear maintaining an equal level gradually, and optimal reaction temperature is 70 ° of C.The yield impact of temperature of reaction on methyl nitrite is less.
Embodiment 5 reaction velocity affects
By particle diameter be 5 object 5g activated carbon load diameters be in the Glass tubing reactor of 15mm, under nitrogen atmosphere, add 2wt% dust technology 18wt% water methanol solution reaction liquid with volume pump, temperature of reaction is 70 ° of C, WHSV is 0.1-20h
-1, carry out at ambient pressure reducing, esterification.Acquired results is in table 5.
Activated carbon catalysis methanol reduction dust technology methyl nitrite under table 5 differential responses air speed
From table 5 result, reaction velocity is at 0.1-5h
-1time, dust technology transformation efficiency is not had a significant effect, but reaction velocity is more than 5h
-1time, raise with reaction velocity, dust technology transformation efficiency obviously declines, and optimum response air speed is 5h
-1.The yield impact of reaction velocity on methyl nitrite is less.
This invention exploits the method for a kind of catalysis methanol reduction dust technology methyl nitrite, adopt fixed-bed reactor, simple to operate, reaction conditions is controlled.Products therefrom methyl nitrite is gas, directly can be separated with reaction system, has important application prospect in coal-ethylene glycol commercial run liquid waste disposal link.
Claims (6)
1. a method for catalysis methanol reduction dust technology methyl nitrite, is characterized in that:
In fixed-bed reactor, carry out successive reaction under normal pressure, methyl alcohol as reductive agent, N
2under atmosphere, under carbon-supported catalysts katalysis, 30-100 ° of C, is reduced to nitrous acid by dust technology, and nitrous acid and methanol esterification, prepare methyl nitrite.
2. according to the method for catalysis methanol reduction dust technology methyl nitrite described in claim 1, it is characterized in that: described carbon-supported catalysts is: one or more in activated carbon, mesoporous carbon, carbon fiber, carbon nanotube, Graphene, graphite, C60.
3. according to the method for Reduction of methanol dust technology methyl nitrite described in claim 1, it is characterized in that: the concentration of described dust technology is 0.1-5wt%.
4., according to the method for catalysis methanol reduction dust technology methyl nitrite described in claim 1, it is characterized in that: the weight hourly space velocity (WHSV) of fixed-bed reactor charging is 0.1-20h
-1.
5., according to the method for catalysis methanol reduction dust technology methyl nitrite described in claim 1 or 2, it is characterized in that: described carbon-supported catalysts, before using through compressing tablet, pulverize, process of sieving, selection particle diameter is 5-20 object particle.
6., according to the method for catalysis methanol reduction dust technology methyl nitrite described in claim 1, it is characterized in that: described Reduction of methanol dust technology is 50-80 ° of C to the temperature of reaction of nitrous acid, nitrous acid and methanol esterification.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106984294A (en) * | 2016-12-05 | 2017-07-28 | 武汉聚川科技有限公司 | A kind of oxidative carbonylation synthesis technique, its liquid waste processing catalyst and preparation method thereof |
| CN107033004A (en) * | 2017-05-31 | 2017-08-11 | 西安汉术化学工程股份有限公司 | Nitrate reductase method in methyl nitrite preparation process |
| CN107663152A (en) * | 2016-07-29 | 2018-02-06 | 中国科学院大连化学物理研究所 | A kind of method for being catalyzed dust technology methyl nitrite |
| CN107673974A (en) * | 2017-09-20 | 2018-02-09 | 上海华谊能源化工有限公司 | The recycling method and device of a kind of nitrogen oxides |
| CN108003029A (en) * | 2017-11-23 | 2018-05-08 | 南京偌赛医药科技有限公司 | A kind of method for preparing nitro compound using graphene catalysis nitric oxide |
| CN109456197A (en) * | 2018-10-26 | 2019-03-12 | 新疆天智辰业化工有限公司 | A kind of method that low concentration nitric acid solution recycles in calcium carbide stove exhaust preparing ethylene glycol |
| CN110013873A (en) * | 2019-05-10 | 2019-07-16 | 国家能源投资集团有限责任公司 | Catalytic decomposition nitrate, the catalyst of nitrite or dust technology and its preparation and application |
| CN110856818A (en) * | 2018-08-22 | 2020-03-03 | 上海浦景化工技术股份有限公司 | Catalyst for reduction and conversion of dilute nitric acid and preparation method and application thereof |
| CN111548274A (en) * | 2019-01-24 | 2020-08-18 | 上海诺哈尔化工技术有限公司 | Method for preparing methyl nitrite by utilizing reaction composite reinforcement |
| CN111943850A (en) * | 2019-05-15 | 2020-11-17 | 中国科学院大连化学物理研究所 | Method for preparing methyl nitrite by reaction of dilute nitric acid and methanol |
| CN111943851A (en) * | 2019-05-15 | 2020-11-17 | 中国科学院大连化学物理研究所 | Method for preparing methyl nitrite from nitric acid |
| CN112142600A (en) * | 2019-06-27 | 2020-12-29 | 中国科学院大连化学物理研究所 | Preparation method and application of methyl nitrite |
| CN112892432A (en) * | 2021-01-13 | 2021-06-04 | 中国神华煤制油化工有限公司 | Nitric acid reduction device and method for reducing nitric acid |
| CN113979867A (en) * | 2020-07-27 | 2022-01-28 | 中国石油化工股份有限公司 | Nitric acid reduction equipment and method |
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Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107663152A (en) * | 2016-07-29 | 2018-02-06 | 中国科学院大连化学物理研究所 | A kind of method for being catalyzed dust technology methyl nitrite |
| CN106984294A (en) * | 2016-12-05 | 2017-07-28 | 武汉聚川科技有限公司 | A kind of oxidative carbonylation synthesis technique, its liquid waste processing catalyst and preparation method thereof |
| CN106984294B (en) * | 2016-12-05 | 2018-04-10 | 武汉聚川科技有限公司 | A kind of oxidative carbonylation synthesis technique, its liquid waste processing catalyst and preparation method thereof |
| CN107033004A (en) * | 2017-05-31 | 2017-08-11 | 西安汉术化学工程股份有限公司 | Nitrate reductase method in methyl nitrite preparation process |
| CN107673974A (en) * | 2017-09-20 | 2018-02-09 | 上海华谊能源化工有限公司 | The recycling method and device of a kind of nitrogen oxides |
| CN107673974B (en) * | 2017-09-20 | 2023-09-26 | 上海华谊能源化工有限公司 | Recycling method and device for nitrogen oxides |
| CN108003029B (en) * | 2017-11-23 | 2020-11-13 | 南京偌赛医药科技有限公司 | Method for preparing nitro compound by catalyzing nitric oxide with graphene |
| CN108003029A (en) * | 2017-11-23 | 2018-05-08 | 南京偌赛医药科技有限公司 | A kind of method for preparing nitro compound using graphene catalysis nitric oxide |
| CN110856818A (en) * | 2018-08-22 | 2020-03-03 | 上海浦景化工技术股份有限公司 | Catalyst for reduction and conversion of dilute nitric acid and preparation method and application thereof |
| CN109456197A (en) * | 2018-10-26 | 2019-03-12 | 新疆天智辰业化工有限公司 | A kind of method that low concentration nitric acid solution recycles in calcium carbide stove exhaust preparing ethylene glycol |
| CN109456197B (en) * | 2018-10-26 | 2021-09-03 | 新疆天智辰业化工有限公司 | Method for recycling low-concentration nitric acid solution in process of preparing ethylene glycol from calcium carbide furnace tail gas |
| CN111548274A (en) * | 2019-01-24 | 2020-08-18 | 上海诺哈尔化工技术有限公司 | Method for preparing methyl nitrite by utilizing reaction composite reinforcement |
| CN110013873A (en) * | 2019-05-10 | 2019-07-16 | 国家能源投资集团有限责任公司 | Catalytic decomposition nitrate, the catalyst of nitrite or dust technology and its preparation and application |
| CN110013873B (en) * | 2019-05-10 | 2022-05-20 | 国家能源投资集团有限责任公司 | Catalyst for catalytic decomposition of nitrate, nitrite or dilute nitric acid and preparation and application thereof |
| CN111943850B (en) * | 2019-05-15 | 2022-08-02 | 中国科学院大连化学物理研究所 | Method for preparing methyl nitrite by reaction of dilute nitric acid and methanol |
| CN111943850A (en) * | 2019-05-15 | 2020-11-17 | 中国科学院大连化学物理研究所 | Method for preparing methyl nitrite by reaction of dilute nitric acid and methanol |
| CN111943851A (en) * | 2019-05-15 | 2020-11-17 | 中国科学院大连化学物理研究所 | Method for preparing methyl nitrite from nitric acid |
| CN111943851B (en) * | 2019-05-15 | 2022-08-02 | 中国科学院大连化学物理研究所 | Method for preparing methyl nitrite from nitric acid |
| CN112142600A (en) * | 2019-06-27 | 2020-12-29 | 中国科学院大连化学物理研究所 | Preparation method and application of methyl nitrite |
| CN113979867A (en) * | 2020-07-27 | 2022-01-28 | 中国石油化工股份有限公司 | Nitric acid reduction equipment and method |
| CN113979867B (en) * | 2020-07-27 | 2024-03-26 | 中国石油化工股份有限公司 | Nitric acid reduction equipment and method |
| CN112892432A (en) * | 2021-01-13 | 2021-06-04 | 中国神华煤制油化工有限公司 | Nitric acid reduction device and method for reducing nitric acid |
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