CN104945262B - A kind of method of catalysis methanol reduction dust technology methyl nitrite - Google Patents
A kind of method of catalysis methanol reduction dust technology methyl nitrite Download PDFInfo
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- CN104945262B CN104945262B CN201410123581.8A CN201410123581A CN104945262B CN 104945262 B CN104945262 B CN 104945262B CN 201410123581 A CN201410123581 A CN 201410123581A CN 104945262 B CN104945262 B CN 104945262B
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- dust technology
- methanol
- methyl nitrite
- carbon
- nitrous acid
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Abstract
A kind of method of catalysis methanol reduction dust technology methyl nitrite, a kind of methanol is as reducing agent, under carbon-supported catalysts catalytic action, 30 100 ° of C, dust technology is reduced to nitrous acid, nitrous acid and methanol esterification, the method preparing methyl nitrite.Reactor used for fixed bed, carrier gas is nitrogen.The method dust technology transformation efficiency is high, and gained methyl nitrite is gas, it is easy to reaction raw materials separates.
Description
Technical field
The invention belongs to coal chemical technology, specifically using methanol as reducing agent, during Coal Chemical Industry
The dust technology waste liquid catalysis produced reverts to nitrous acid, and nitrous acid and methanol carry out esterification, obtains nitrous
Acid methyl ester.Methyl nitrite is intermediate important in coal-ethylene glycol technique.This process can improve nitrogen source
Effective utilization, reduce discharging of waste liquid, the economic benefit of enterprise can be improved further.
Background technology
Ethylene glycol is large petrochemicals, is mainly used in anti-icing fluid and preparation PET polyester.Ethylene glycol mesh
Front mainly employing petrochemical technology route produces: with ethylene as raw material, prepare epoxy second by epoxidation
Alkane, then ethylene glycol is prepared in hydration；This technology needs to consume bulk petroleum resource, and dehydration separating energy consumption is the biggest.
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 technical process.Methyl nitrite and CO warp
Oxidation carburizing reagent obtains dimethyl oxalate.；The further Hydrogenation of dimethyl oxalate. obtains ethylene glycol.Nitrous acid first
Ester is to react with nitric acid-sodium nitrite through methanol to prepare by coal.In the process, can produce in a large number
Dust technology waste liquid.Current processing method is, the NaOH adding metering neutralizes, then will be containing a large amount of
The waste liquid of sodium nitrate directly discharges, and causes the pollution of water resource.Because nitrate is ingested after human body can
The effect lower part of reductive bacterium is reduced into nitrite, and nitrite easily blood red with blood
Albumino reaction forms metahemoglobin, thus affects the blood transmittability to oxygen.Therefore, by dust technology
Waste liquid Appropriate application, turns waste into wealth, and can not only effectively reduce the discharge containing sodium nitrate waste liquid, reduces water
The pollution of resource, and entreprise cost can 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:
Carrying out successive reaction under normal pressure in fixed bed reactors, methanol is as reducing agent, N2Under atmosphere,
Under carbon-supported catalysts catalytic action, 30-100 ° of C, dust technology is reduced to nitrous acid, nitrous acid and methanol ester
Change, prepare methyl nitrite.
Described carbon-supported catalysts is: activated carbon, mesoporous carbon, carbon fiber, CNT, Graphene, graphite,
One or more in C60.
The concentration of described dust technology is 0.1-5wt%.
The weight (hourly) space velocity (WHSV) (WHSV) of fixed bed reactors charging is 0.1-20h-1。
Described carbon-supported catalysts, use before through tabletting, pulverize, processs of sieving, selection particle diameter be 5-20 mesh
Granule.
Described Reduction of methanol dust technology is 50-80 ° of C to the reaction temperature of nitrous acid, nitrous acid and methanol esterification.
The present invention uses continuous reaction, uses fixed-bed reactor.Products therefrom methyl nitrite is gas
Body, can be directly separated with reaction system.Whole course of reaction is carried out under normal pressure N2, and it is right to greatly reduce
The requirement of equipment, has the biggest prospects for commercial application.
Accompanying drawing explanation
Fig. 1 fixed bed reactors device.
Wherein, 1. nitrogen cylinder；2. two-way valve；3. dust technology feed pump；4. gas-liquid separator 5. reaction tower；
6. reactant liquor stores and fills；7. methyl nitrite purifying column；8. methyl nitrite holding vessel.
Detailed description of the invention
As it is shown in figure 1, it is the process chart of the present invention；
Described catalysis methanol reduction dust technology methyl nitrite reaction is carried out on fixed-bed reactor,
Being that 5-20 mesh carbon-supported catalysts joins in glass pipe type reactor by particle diameter, oxidation is filled on the top of catalyst
Silicon bead (preheating material), under-filled stainless steel silk (support catalyst layer).Under nitrogen atmosphere, will be anti-
Answer device to be heated to uniform temperature, add dust technology methanol aqueous solution with dosing pump.Wherein said reaction temperature
Degree is 30-100 ° of C, and optimizing reaction temperature is 50-80 ° of C, and pressure is normal pressure.Analyze with ionic liquid chromatography
Nitric acid content in effluent, and calculate the conversion ratio of nitric acid；With methyl nitrite in gas chromatographic analysis gas
Content, and calculate the yield of methyl nitrite.
Below by way of example, the present invention is further described (in example, agents useful for same is analytical pure),
It should be noted that the following examples are used only as illustrating, present invention is not limited thereto.
Embodiment 1 different carbon-supported catalysts catalysis methanol reduction dust technology methyl nitrite reaction
The 5g carbon-supported catalysts that particle diameter is 10 mesh is loaded in the glass tubing reactor of a diameter of 15mm,
Under nitrogen atmosphere, add 1wt% dust technology 18wt% water methanol solution reaction liquid, reaction temperature with dosing pump
Be 70 ° of C, WHSV be 1.0h-1, carry out at ambient pressure reducing, esterification.Acquired results is shown 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 methanols reduction methyl nitrite processed reaction, all
To good effect, the conversion ratio of dust technology is more than 85%, and the yield of methyl nitrite is more than 90%.
Embodiment 2 catalyst particle size affects
The 5g activated carbon that particle diameter is 5-20 mesh is loaded in the glass tubing reactor of a diameter of 15mm, nitrogen
Under atmosphere, adding 1wt% dust technology 18wt% water methanol solution reaction liquid with dosing pump, reaction temperature is 70 ° of C,
WHSV is 1.0h-1, carry out at ambient pressure reducing, esterification.Acquired results is shown in Table 2.
Table 2 different-grain diameter activated carbon catalysis methanol reduction dust technology methyl nitrite
From table 2 result, dust technology conversion ratio is had a significant impact, with particle diameter by catalyst activity carbon granules footpath
Increasing, dust technology conversion ratio is gradually lowered.It is the biggest that reason is probably particle diameter, and specific surface is the least, piles up Kong Yue
Greatly, cause dust technology to diminish with catalyst activity position contact area, therefore conversion ratio reduces.Catalyst particle size pair
The yield impact of methyl nitrite is less, all more than 95%.
Embodiment 3 dust technology concentration affects
The 5g activated carbon that particle diameter is 5 mesh is loaded in the glass tubing reactor of a diameter of 15mm, nitrogen gas
Under atmosphere, adding 0.1-5wt% dust technology 18wt% water methanol solution reaction liquid with dosing pump, reaction temperature is
70 ° of C, WHSV are 1.0h-1, carry out at ambient pressure reducing, esterification.Acquired results is shown in Table 3.
Table 3 activated carbon catalysis methanol reduction variable concentrations dust technology methyl nitrite
From table 3 result, dust technology conversion ratio is had a significant impact by dust technology concentration, with dust technology concentration
Increasing, dust technology conversion ratio maintains an equal level after gradually rising.The yield of methyl nitrite is affected relatively by dust technology concentration
Little.During coal-ethylene glycol, gained dust technology waste liquid is in about 2wt%, the following examples
The concentration all selecting dust technology is 2wt%.
Embodiment 4 reaction temperatures affect
The 5g activated carbon that particle diameter is 5 mesh is loaded in the glass tubing reactor of a diameter of 15mm, nitrogen gas
Under atmosphere, adding 2wt% dust technology 18wt% water methanol solution reaction liquid with dosing pump, reaction temperature is 30-100
° C, WHSV are 1.0h-1, carry out at ambient pressure reducing, esterification.Acquired results is shown in Table 4.
Activated carbon catalysis methanol reduction dust technology methyl nitrite at a temperature of table 4 differential responses
From table 4 result, dust technology conversion ratio is had a significant impact by reaction temperature, raises with reaction temperature,
Dust technology conversion ratio maintains an equal level after gradually rising, and optimal reaction temperature is 70 ° of C.Reaction temperature is to methyl nitrite
Yield impact less.
Embodiment 5 reaction velocity affects
The 5g activated carbon that particle diameter is 5 mesh is loaded in the glass tubing reactor of a diameter of 15mm, nitrogen gas
Under atmosphere, adding 2wt% dust technology 18wt% water methanol solution reaction liquid with dosing pump, reaction temperature is 70 ° of C,
WHSV is 0.1-20h-1, carry out at ambient pressure reducing, esterification.Acquired results is shown 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 conversion ratio is had not significant impact,
But, reaction velocity is more than 5h-1Time, raising with reaction velocity, dust technology conversion ratio is decreased obviously, most preferably
Reaction velocity is 5h-1.The yield of methyl nitrite is affected less by reaction velocity.
The present invention develops the method for a kind of catalysis methanol reduction dust technology methyl nitrite, uses fixed bed
Reactor, simple to operate, reaction condition is controlled.Products therefrom methyl nitrite is gas, directly can with instead
Answer system to separate, have important application prospect in coal-ethylene glycol industrial process liquid waste processing link.
Claims (2)
1. the method for a catalysis methanol reduction dust technology methyl nitrite, it is characterised in that:
Carrying out successive reaction under normal pressure in fixed bed reactors, methanol is as reducing agent, N2Under atmosphere,
Under carbon-supported catalysts catalytic action, 30-100 DEG C, dust technology is reduced to nitrous acid, nitrous acid and methanol esterification,
Prepare methyl nitrite；
Described carbon-supported catalysts is: activated carbon, mesoporous carbon, carbon fiber, CNT, Graphene, graphite,
One or more in C60；
The concentration of described dust technology is 0.1-5wt%；
The weight (hourly) space velocity (WHSV) (WHSV) of fixed bed reactors charging is 0.1-20h-1；
Described carbon-supported catalysts, use before through tabletting, pulverize, processs of sieving, selection particle diameter be 5-20 mesh
Granule.
2. according to the method for catalysis methanol reduction dust technology methyl nitrite, its feature described in claim 1
It is: described Reduction of methanol dust technology to nitrous acid, nitrous acid are 50-80 DEG C with the reaction temperature of methanol esterification.
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
| 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 |
| CN110856818B (en) * | 2018-08-22 | 2022-10-25 | 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 |
| 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 |
| 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 |
| 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 |
| 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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| CN102442901A (en) * | 2010-10-15 | 2012-05-09 | 安徽淮化股份有限公司 | Method for producing dimethyloxalate |
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| CN103373925B (en) * | 2012-04-27 | 2015-05-20 | 上海浦景化工技术股份有限公司 | Preparation method for methyl nitrite |
| CN103435489B (en) * | 2013-09-13 | 2016-09-07 | 安徽淮化股份有限公司 | A kind of system synthesizing methyl nitrite and the method for synthesis methyl nitrite |
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