CN106565498B - The production method of methyl nitrite - Google Patents
The production method of methyl nitrite Download PDFInfo
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- CN106565498B CN106565498B CN201510655388.3A CN201510655388A CN106565498B CN 106565498 B CN106565498 B CN 106565498B CN 201510655388 A CN201510655388 A CN 201510655388A CN 106565498 B CN106565498 B CN 106565498B
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Abstract
The present invention relates to a kind of production methods of methyl nitrite.Mainly solve the problems, such as that nitrogen oxides present in existing synthesis gas preparing ethylene glycol technology feeds of high cost and equipment seriously corroded.The technical solution that the present invention reacts the step of obtaining methyl nitrite by using the liquid phase feed made containing nitric oxide production phase feed and containing nitric acid and methanol in trickle bed reactor preferably solves the problems, such as this, can be used for the industrial production of methyl nitrite in synthesis gas preparing ethylene glycol technique.
Description
Technical field
The present invention relates to a kind of production methods of methyl nitrite.
Background technology
Ethylene glycol (EG) is a kind of important basic petrochemical Organic Ingredients, mainly for the production of polyester, anti-icing fluid, profit
Lubrication prescription, plasticizer, nonionic surfactant and explosive etc., purposes is very extensive.In recent years, with downstream polyester product city
The increase of field demand, world's ethylene glycol yield and demand all constantly expand, and China is the first big ethylene glycol consumption in the world
State, according to statistics annual consumption reach 10,000,000 tons or more, importation dependence is up to 70% or more.
The production line of ethylene glycol mainly has petroleum path and Non oil-based route two major classes, the production of conventional petroleum route at present
Ethylene glycol needs to consume substantial oil, and the economic benefit of this production technology, due to being restricted by oil price, fluctuation is larger.And
Energy characteristics of the Non oil-based route of ethylene glycol because meeting the few oil of China's richness coal are produced with synthesis gas made from natural gas or coal, and
This production technology has many advantages, such as that reaction condition is mild, high selectivity, becomes numerous domestic researcher and research institution's research and development
Hot spot.Especially growth momentum is powerful at home for coal-ethylene glycol in recent years, and domestic industry production technology is increasingly ripe at present,
Several coal-ethylene glycol commercialized devices have gone into operation or just in the Large scale construction stages, such as 200,000 t/a coal second of Tongliao
Glycol industrial demonstration unit gets through flow in December, 2009, and by 3 years trial operations, ethylene glycol will be realized in the end of the year 2012
Product 220nm UV transmittance stably reaching standards, product indices have reached the high-class product standard of national regulation.By Tongliao gold
Coal and the joint work of aurification forever of Henan coal industry have been planned in Henan is located at 5 of Xinxiang, Puyang, Anyang, Luoyang and Yongcheng
200000 tons/year of coal-ethylene glycol projects.Wherein Xinxiang project gets through flow in March, 2012, and Puyang project is thrown in August, 2012
Expect successfully, Anyang project is in December, 2012 output qualification high-class product.And Luoyang and Yongcheng project will go into operation in 2014.Separately
Outside, using the synthesis gas preparing ethylene glycol technology of sinopec Shanghai Petroleum Chemical Engineering Institute independent research, by Shanghai engineering company and
Sinopec Engineering Construction Company completes 200,000 t/a synthesis gas preparing ethylene glycol industrial demonstration units of engineering design in 2012 jointly
On August is put into operation for 30 in Hubei Chemical Fertilizer Co, and is completed and is gone into operation in 2013, successfully gets through whole process, output qualification is excellent
Product.High chemistry and Japanese remaining part and East China University of Science and Technology cooperate in Xingjiang Tianye Co. using calcium carbide stove exhaust as raw material, and 50,000 tons of construction/
Year ethylene glycol and 30,000 tons/year of Isosorbide-5-Nitrae butanediol projects, ethylene glycol project will enter trial production in the end of the year 2012, and in January, 2013
It successfully produces high-class product ethylene glycol, and mid-May, the ground breaking ceremony of 250,000 tons of ethylene glycol project thes second stage of the project of Xingjiang Tianye Co. is just
Formula starts.
On the whole, in recent years, the country is with synthesis gas gas phase reaction synthesis of oxalate, oxalate repeated hydrogenation to ethylene glycol
Two-step method synthesis gas preparing ethylene glycol industrial production technology is increasingly ripe, but in industrialized course, and also many need are perfect
The problem of optimization.CO gas phase couplings and oxidation are especially broadly divided into the reaction of synthesis gas gas phase reaction synthesis of oxalic acid ester moiety
Two steps are esterified, and oxidative esterification reaction is more complicated.From the article, paper or patent published at present it is found that about NO
Oxidative esterification generates nitrous acid ester and mostly uses packed tower as main reactor.But it is limited by gas-liquid contact feature in packed tower
System, while oxidative esterification reaction generates nitrous acid ester, it is difficult to avoid the generation of by-product nitric acid.The generation of the part nitric acid
Coupling system nitrogen oxides supply cost is not only increased, material consumption is increased, while increasing the corrosion of equipment, in equipment investment
And larger burden is brought on operating cost；Meanwhile material consumption on nitric acid aftertreatment systems and energy consumption are also very important
's.For this purpose, how to reduce nitrogen oxides supplement to greatest extent, the efficient technique of rainwater utilization of by-product nitric acid is developed, is turned waste into wealth, simplified
Material consumption and energy consumption is greatly reduced in flow, and the competitiveness for further promoting synthesis gas preparing ethylene glycol technology has extremely great
Meaning.
Invention content
The technical problem to be solved by the present invention is to nitrogen oxides present in existing synthesis gas preparing ethylene glycol technology to feed
The problem of of high cost and equipment seriously corroded, provide a kind of production method of new methyl nitrite.This method turns with nitric acid
The high feature of rate.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of production method of methyl nitrite,
It is sub- including making the liquid phase feed containing nitric oxide production phase feed and containing nitric acid and methanol react acquisition in trickle bed reactor
The step of methyl nitrate；
The trickle bed reactor includes distributor；The distributor is equipped with gas passage pipe (8) on distribution grid (6)
With fluid passage pipe (7), gas passage pipe is uniformly distributed between fluid passage pipe；Gas passage pipe (8) by circular cone head cover (9) and
Upright short tube (10) composition, there are the gap of supplied gas disengaging, gas passage pipe (8) positions between circular cone head cover (9) and short tube (10)
Top in gas-liquid distribution grid (6)；Fluid passage pipe (7) is vertical short tube (11), and distribution grid (6) is stretched out in the upper end of short tube (11)
The lower end of 10~100 millimeters of top, short tube (11) stretches out below distribution grid (6) 200~1000 millimeters, is located under distribution grid (6)
The short tube (11) of side is partly equably provided with aperture (12), the diameter d of aperture (12) on the cross section of axially displaced section
Ratio with the internal diameter D of fluid passage pipe (7) is 0.01~0.2: 1.0, area S1 and the fluid passage pipe of all apertures (12)
(7) ratio of the area S2 of interior cross section is 0.75~1.10: 1.0；Percent opening of the gas passage pipe (8) on distribution grid (6)
It is 5~30%, percent opening of the fluid passage pipe (7) on distribution grid (6) is 5~50%.
In above-mentioned technical proposal, it is preferable that gas passage pipe (8) or fluid passage pipe (7) on distribution grid (6) are positive three
Triangular arrangement.
In above-mentioned technical proposal, it is preferable that it is 10~60 millimeters that the upper end of short tube (11), which is stretched out above distribution grid (6), under
It is 300~800 millimeters that end, which is stretched out below distribution grid (6),.
In above-mentioned technical proposal, it is preferable that the diameter d of aperture (12) and the ratio of the internal diameter D of fluid passage pipe (7) are
(0.01~0.1):1.0, the area S1 and the ratio of the area S2 of fluid passage pipe (7) interior cross section of all apertures (12) are
(0.85~1.05):1.0.
In above-mentioned technical proposal, it is preferable that percent opening of the gas passage pipe (8) on distribution grid (6) is 5~20%, liquid
Percent opening of the body tube channel (7) on distribution grid (6) is 5~30%.、
In above-mentioned technical proposal, it is preferable that the phase feed and liquid phase feed are anti-from nitric oxide, oxygen and methanol
The step of methyl nitrite should be generated.
In above-mentioned technical proposal, it is preferable that with volume percentage, in the phase feed, the content of CO is 0~
The content of 30%, NO are 5~15%, CO2Content be 0~15%, the content of nitrous acid ester is 0~5%, N2Content be 35
~70%.
In above-mentioned technical proposal, it is preferable that by weight percentage, in the liquid phase feed, the content of nitric acid is 1~
15%, the content of water is 0~30%, and the content of methanol is 55~99%.
In above-mentioned technical proposal, it is preferable that the reaction condition is：Reaction temperature is 70~120 DEG C, and reaction pressure is with table
Pressure 0~1.5MPa of meter, liquid hourly space velocity (LHSV) 0.5~8 hour-1, the molar ratio 2.5~10 of NO and nitric acid.It is highly preferred that the reaction item
Part is：Reaction temperature is 75~100 DEG C, reaction pressure 0~1.0MPa in terms of gauge pressure, liquid hourly space velocity (LHSV) 0.5~6 hour-1, NO and nitre
The molar ratio 3~8 of acid.
In above-mentioned technical proposal, it is preferable that the reaction carries out in the presence of a catalyst.
In above-mentioned technical proposal, it is preferable that the catalyst is nickeliferous catalyst or palladium-containing catalyst.
In above-mentioned technical proposal, it is preferable that by weight percentage, the catalyst includes 5~25% nickel, 0~
10% be selected from least one of iron or titanium auxiliary agent, 75~95% carrier.
In above-mentioned technical proposal, it is preferable that by weight percentage, the catalyst includes 0.2~2% palladium, 0~
10% be selected from least one of iron or titanium auxiliary agent, 88~98% carrier.
In catalyst carrier select be known in the art, such as silica or activated carbon can be selected from.
It is well known that CO coupling synthesizing dimethyl oxalates are the important components of synthesis gas preparing ethylene glycol technology.CO gas
Phase catalytic coupling prepares dimethyl oxalate reaction and is broadly divided into two step of coupling and oxidative esterification, and the reaction equation of oxidative esterification is such as
Under：2NO+2CH3OH+1/2O2→2CH3ONO+H2O。
But oxidative esterification reaction is more complicated, is related to a series of following key reactions：
2NO+O2→2NO2
CH3OH+N2O3→CH3ONO+HONO
CH3OH+HONO→CH3ONO+H2O
CH3OH+N2O4→CH3ONO+HNO3
Currently, from the article, paper or patent published it is found that in terms of NO oxidative esterifications generate nitrous acid ester
Research emphasis is concentrated mainly on the optimization of process conditions, the state of charging and mixed mode etc., the type about reactor
Formula mostly uses packed tower as main reactor.But limited by gas-liquid contact feature in packed tower, it is given birth in oxidative esterification reaction
While at nitrous acid ester, it is difficult to the generation of by-product nitric acid is avoided, and the presence of these nitric acid not only will increase coupling system
Nitrogen oxides of uniting feeds cost, increases material consumption, and increase the corrosion of equipment and the energy consumption of later separation.
The present invention according to nitric acid, methanol and NO react generate methyl nitrite reaction mechanism (2NO+3CH3OH+HNO3 →
2CH3ONO+H2O), using trickle bed reactor.Wherein, the gas phase of distributor can from gas passage pipe vertically into reactor,
Also reactor can be entered laterally from the top aperture on fluid passage pipe, and liquid is flowed out from the aperture of fluid passage pipe, is formed
The annular spread of different-diameter.Therefore, gas-liquid distributor changes gas-liquid circulating direction, promotes gas-liquid contact, energy from multi-angle
Enough gas-liquid distribution situations significantly improved inside trickle bed reactor can preferably ensure and improve the reaction effect of trickle bed
Rate.Specifically, the mixing liquid containing nitric acid, first alcohol and water that oxidative esterification tower tower reactor is discharged in synthesis gas preparing ethylene glycol technology
Enter in trickle bed reactor with the recyclegas containing NO in CO coupling systems, ensure that gas containing NO and containing nitric acid,
The liquid of methanol enters being uniformly distributed on entire bed section after reactor, has given full play to the effect of catalyst, ensures
The conversion ratio of nitric acid, has achieved the purpose that turn waste into wealth and lower consumption to subtract corruption.Using the present invention, in reactor Raney nickel or
It it is 70~120 DEG C in reaction temperature under the action of palladium catalyst, reaction pressure is 0~1.5MPa, and liquid hourly space velocity (LHSV) is 0.5~8 small
When-1, NO reacts under conditions of being 2.5~10 with the molar ratio of nitric acid generates methyl nitrite, and nitric acid conversion ratio >=95% obtains
Preferable technique effect.
Description of the drawings
Figure 1A, 1B, 1C, 1D are the trickle bed reactor used in the present invention and gas-liquid distributor schematic diagram therein.
In Figure 1A, 1B, 1C, 1D, 1 is gas-liquid import distributor, and 2 be trickle bed reactor, and 3 is logical for gas-liquid distributor gas
Road, 4 be porcelain ball, and 5 be catalyst bed, and 6 be gas-liquid distributor distribution grid, and 7 be gas-liquid distributor fluid passage pipe, and 8 be gas-liquid
Distributor gas passage pipe, 9 be the conical head cover of gas passage pipe, and 10 be the upright short tube of gas passage pipe, and 11 be liquid
The vertical short tube of tube channel, 12 be the aperture on the vertical short tube of fluid passage pipe.
In Fig. 1, gas-liquid mixture fluid enters trickle bed reactor from gas-liquid import distributor 1, is distributed by gas-liquid import
After the initial distribution of device 1, into gas-liquid distributor 3.Liquid enters 3 fluid passage pipe 7, through the side on fluid passage pipe 7
Aperture 12 flows out, and forms transverse annular distribution and enters catalyst bed；Meanwhile being flowed out through the aperture 12 of 7 bottom of fluid passage pipe,
Form axial liquid distribution.In addition, fluid passage pipe 7 is not full liquid, the 12 supplied gas stream of aperture at 7 top of fluid passage pipe
Go out, forms lateral annular gas distribution.Gas is from the gas passage pipe 8 of gas-liquid distributor 3 by circular cone head cover 9 and upright short tube
10 annular gaps formed flow into, and form axial gas distribution.
The present invention will be further described below by way of examples.
Specific implementation mode
【Embodiment 1】
Using trickle bed reactor shown in FIG. 1.Wherein, 6 top of distribution grid is stretched out in the upper end of gas-liquid distributor short tube 11
50 millimeters, 6 500 millimeters of lower section of distribution grid is stretched out in lower end, and the diameter d of aperture 12 and the ratio of the internal diameter D of fluid passage pipe 7 are
0.015: 1.0, the ratio of the area S1 and the area S2 of cross section in fluid passage pipe 7 of all apertures 12 are 1.01: 1.0；Gas
Percent opening of the body tube channel 8 on distribution grid 6 is 15%, percent opening 20% of the fluid passage pipe 7 on distribution grid 6.
Using activated carbon as carrier, catalyst group becomes catalyst in reactor：Metallic nickel 12%, metal promoter iron 3%,
Metal promoter titanium 3%, surplus are carrier.Mixing liquid (the nitric acid that oxidative esterification tower tower reactor is discharged：1%wt, methanol：99%
Wt mixed gas (the CO) and containing NO：25%v/v, NO：10%v/v, CO2：15%v/v, MN：5%v/v, N2：45%v/v)
Trickle bed reactor is each led into, is 70 DEG C in reaction temperature, reaction pressure is normal pressure, liquid hourly space velocity (LHSV) 0.5h-1, NO and nitric acid
Molar ratio be 8 under conditions of react and generate methyl nitrite, the conversion ratio of nitric acid is 95.1%.
【Embodiment 2】
Using trickle bed reactor shown in FIG. 1.Wherein, 6 top of distribution grid is stretched out in the upper end of gas-liquid distributor short tube 11
25 millimeters, 6 800 millimeters of lower section of distribution grid is stretched out in lower end, and the diameter d of aperture 12 and the ratio of the internal diameter D of fluid passage pipe 7 are
0.011: 1.0, the ratio of the area S1 and the area S2 of cross section in fluid passage pipe 7 of all apertures 12 are 0.95: 1.0；Gas
Percent opening of the body tube channel 8 on distribution grid 6 is 10%, percent opening 15% of the fluid passage pipe 7 on distribution grid 6.
Using silica as carrier, catalyst group becomes catalyst in trickle bed reactor：Metallic nickel 5%, metal promoter
Titanium 10%, surplus are carrier.Mixing liquid (the nitric acid that oxidative esterification tower tower reactor is discharged：15%wt, water：30%wt, methanol：
Mixed gas (CO 55%wt) and containing NO：30%v/v, NO：15%v/v, CO2：15%v/v, MN：5%v/v, N2：35%
V/v trickle bed reactor) is each led into, is 75 DEG C, reaction pressure 0.35MPa, liquid hourly space velocity (LHSV) 6h in reaction temperature-1, NO
Molar ratio with nitric acid reacts under conditions of being 2.5 generates methyl nitrite, and the conversion ratio of nitric acid is 95.8%.
【Embodiment 3】
Using trickle bed reactor shown in FIG. 1.Wherein, 6 top of distribution grid is stretched out in the upper end of gas-liquid distributor short tube 11
80 millimeters, 6 650 millimeters of lower section of distribution grid is stretched out in lower end, and the diameter d of aperture 12 and the ratio of the internal diameter D of fluid passage pipe 7 are
0.15: 1.0, the ratio of the area S1 and the area S2 of cross section in fluid passage pipe 7 of all apertures 12 are 1.1: 1.0；Gas
Percent opening of the tube channel 8 on distribution grid 6 is 20%, percent opening 30% of the fluid passage pipe 7 on distribution grid 6.
Using activated carbon as carrier, catalyst group becomes catalyst in trickle bed reactor：Metallic nickel 25%, metal promoter
Iron 1%, metal promoter titanium 0.5%, surplus are carrier.Mixing liquid (the nitric acid that oxidative esterification tower tower reactor is discharged：5%wt,
Water：8%wt, methanol：Mixed gas (CO 87%wt) and containing NO：20%v/v, NO：15%v/v, CO2：10%v/v, MN：
3%v/v, N2：Trickle bed reactor 52%v/v) is each led into, is 80 DEG C, reaction pressure 0.6MPa in reaction temperature, when liquid
Air speed is 8h-1, the molar ratio of NO and nitric acid reacts under conditions of being 3 and generates methyl nitrite, and the conversion ratio of nitric acid is
96.7%.
【Embodiment 4】
Using【Embodiment 1】Trickle bed reactor.Catalyst in trickle bed reactor is using activated carbon as carrier, catalysis
Agent group becomes：Metal Palladium 0.2%, metal promoter titanium 8%, surplus are carrier.The mixing liquid that oxidative esterification tower tower reactor is discharged
(nitric acid：6%wt, water：15%wt, methanol：Mixed gas (CO 79%wt) and containing NO：22%v/v, NO：14%v/v,
CO2：8%v/v, MN：2%v/v, N2：Trickle bed reactor 54%v/v) is each led into, is 120 DEG C in reaction temperature, reaction pressure
Power is 1.5MPa, liquid hourly space velocity (LHSV) 3h-1, the molar ratio of NO and nitric acid reacts under conditions of being 10 and generates methyl nitrite,
The conversion ratio of nitric acid is 98%.
【Embodiment 5】
Using【Embodiment 2】Trickle bed reactor.Catalyst in trickle bed reactor is using activated carbon as carrier, catalysis
Agent group becomes：Metal Palladium 2%, surplus are carrier.Mixing liquid (the nitric acid that oxidative esterification tower tower reactor is discharged：3%wt, water：
10%wt, methanol：Mixed gas (CO 87%wt) and containing NO：18%v/v, NO：10%v/v, CO2：5%v/v, MN：
1.5%v/v, N2：Trickle bed reactor 65.5%v/v) is each led into, is 100 DEG C in reaction temperature, reaction pressure is
1.0MPa, liquid hourly space velocity (LHSV) 2h-1, the molar ratio of NO and nitric acid reacts under conditions of being 4.5 and generates methyl nitrite, nitric acid
Conversion ratio be 99%.
【Embodiment 6】
Using【Embodiment 3】Trickle bed reactor.Catalyst in trickle bed reactor is using activated carbon as carrier, catalysis
Agent group becomes：Metal Palladium 1.2%, metal promoter titanium 2%, surplus are carrier.The mixing liquid that oxidative esterification tower tower reactor is discharged
(nitric acid：1%, water：10%, ethyl alcohol：89%) mixed gas (CO and containing NO：18%, NO：12%, CO2：5%, MN：
2%, N2：63%) above-mentioned trickle bed reactor is each led into, reaction temperature is 95 DEG C, reaction pressure 0.8MPa, liquid hourly space velocity (LHSV)
For 2h-1, the molar ratio of NO and nitric acid reacts under conditions of being 6 and generates methyl nitrite, and the conversion ratio of nitric acid is 99.2%.
【Comparative example 1】
Using packed-bed reactor, using with【Embodiment 1】In identical raw material, reaction condition, implementation steps carry out it is sub-
Methyl nitrate produces, and nitric acid conversion ratio is 82.3%.
Claims (9)
1. a kind of production method of methyl nitrite, including make the liquid phase containing nitric oxide production phase feed and containing nitric acid and methanol
Raw material reacts the step of obtaining methyl nitrite in trickle bed reactor；
The trickle bed reactor includes distributor；The distributor is equipped with gas passage pipe (8) and liquid on distribution grid (6)
Body tube channel (7), gas passage pipe (8) are uniformly distributed between fluid passage pipe (7)；Gas passage pipe (8) is by circular cone head cover (9)
It is formed with upright short tube (10), there are the gap of supplied gas disengaging, gas passage pipes between circular cone head cover (9) and upright short tube (10)
(8) it is located at the top of gas-liquid distribution grid (6)；Fluid passage pipe (7) is vertical short tube (11), and the upper end of vertical short tube (11) is stretched out
10~100 millimeters above distribution grid (6), the lower end of vertical short tube (11) stretches out below distribution grid (6) 200~1000 millimeters, position
Vertical short tube (11) below distribution grid (6) is partly equably provided with aperture on the cross section of axially displaced section
(12), the ratio of the diameter d of aperture (12) and the internal diameter D of fluid passage pipe (7) is 0.01~0.2:1.0 all apertures (12)
The ratio of area S2 of area S1 and fluid passage pipe (7) interior cross section be 0.75~1.10:1.0；Gas passage pipe (8) exists
Percent opening on distribution grid (6) is 5~30%, and percent opening of the fluid passage pipe (7) on distribution grid (6) is 5~50%；It is described
Reaction condition is：Reaction temperature is 70~120 DEG C, reaction pressure 0~1.5MPa in terms of gauge pressure, liquid hourly space velocity (LHSV) 0.5~8 hour-1,
The molar ratio 2.5~10 of NO and nitric acid.
2. the production method of methyl nitrite according to claim 1, which is characterized in that the gas passage on distribution grid (6)
It is equilateral triangle arrangement to manage (8) or fluid passage pipe (7)；The upper end of vertical short tube (11) stretches out above distribution grid (6) for 10~
60 millimeters, it is 300~800 millimeters that lower end, which is stretched out below distribution grid (6),.
3. the production method of methyl nitrite according to claim 1, which is characterized in that the diameter d and liquid of aperture (12)
The ratio of the internal diameter D of tube channel (7) is 0.01~0.1:1.0, the area S1 of all apertures (12) and cross in fluid passage pipe (7)
The ratio of the area S2 in section is 0.85~1.05:1.0；
Percent opening of the gas passage pipe (8) on distribution grid (6) is 5~20%, and fluid passage pipe (7) is on distribution grid (6)
Percent opening is 5~30%.
4. the production method of methyl nitrite according to claim 1, which is characterized in that the phase feed and liquid phase feed
The step of generating methyl nitrite is reacted from nitric oxide, oxygen and methanol.
5. the production method of methyl nitrite according to claim 1, which is characterized in that it is characterized in that, with volume basis
Than counting, in the phase feed, the content that the content of CO is 0~30%, NO is 5~15%, CO2Content be 0~15%, it is sub-
The content of nitrate is 0~5%, N2Content be 35~70%；By weight percentage, in the liquid phase feed, nitric acid
Content is 1~15%, and the content of water is 0~30%, and the content of methanol is 55~99%.
6. the production method of methyl nitrite according to claim 1, which is characterized in that the reaction is in the presence of a catalyst
It carries out.
7. the production method of methyl nitrite according to claim 6, which is characterized in that the catalyst is nickeliferous catalysis
Agent or catalyst containing palladium.
8. the production method of methyl nitrite according to claim 7, which is characterized in that by weight percentage, described to urge
Agent includes 5~25% nickel, and 0~10% is selected from least one of iron or titanium auxiliary agent, 75~95% carrier.
9. the production method of methyl nitrite according to claim 7, which is characterized in that by weight percentage, described to urge
Agent includes 0.2~2% palladium, and 0~10% is selected from least one of iron or titanium auxiliary agent, 88~98% carrier.
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| CN111196758B (en) * | 2018-11-20 | 2022-04-05 | 上海浦景化工技术股份有限公司 | Nitric acid reduction and conversion process |
| 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 |
| CN111530407B (en) * | 2020-04-30 | 2022-01-28 | 中国神华煤制油化工有限公司 | Esterification reactor and esterification reaction method |
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| CN101279228A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Gas-liquid distributor of trickle bed reactor |
| CN101314569A (en) * | 2008-07-04 | 2008-12-03 | 天津大学 | Reaction system and preparation method for nitrous alkyl ester |
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| CN104411677A (en) * | 2012-04-02 | 2015-03-11 | 宇部兴产株式会社 | Method for producing nitrous acid ester, and method for producing dialkyl oxalate and dialkyl carbonate |
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|---|---|---|---|---|
| CN1267401C (en) * | 2002-03-18 | 2006-08-02 | 宇部兴产株式会社 | Method for producing arrcostab nitrite |
| CN101279228A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Gas-liquid distributor of trickle bed reactor |
| CN101314569A (en) * | 2008-07-04 | 2008-12-03 | 天津大学 | Reaction system and preparation method for nitrous alkyl ester |
| CN104411677A (en) * | 2012-04-02 | 2015-03-11 | 宇部兴产株式会社 | Method for producing nitrous acid ester, and method for producing dialkyl oxalate and dialkyl carbonate |
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