CN105272859A - Production method for alkyl nitrite - Google Patents
Production method for alkyl nitrite Download PDFInfo
- Publication number
- CN105272859A CN105272859A CN201410314279.0A CN201410314279A CN105272859A CN 105272859 A CN105272859 A CN 105272859A CN 201410314279 A CN201410314279 A CN 201410314279A CN 105272859 A CN105272859 A CN 105272859A
- Authority
- CN
- China
- Prior art keywords
- reactor
- alkyl
- nitrogen
- alkyl nitrite
- nitrite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a production method for alkyl nitrite. The method mainly solves the technical problems of low yield of alkyl nitrite or high energy consumption of equipment in the prior art. A technical scheme of the invention adopts a reactor which is divided into three sections, i.e., an upper section, a middle section and a lower section, wherein the middle section is a reaction section, and reaction temperature is controlled through outside-cycled cooling; the upper section is an absorption section which absorbs nitric acid and water in gaseous reaction products; and the lower section is a rectification section which recovers alkyl nitrite in liquid reaction products; thus, the problem is well solved, and the production method for alkyl nitrite can be applied in industrial production of alkyl nitrite.
Description
Technical field
The present invention relates to a kind of production method of alkyl nitrite.
Background technology
Barkite is a kind of important Organic Chemicals, can be used for producing various dyestuff, solvent, extraction agent and various intermediate, is widely used in fine chemistry industry.In addition, barkite can be used for preparing ethylene glycol by hydrogenation reaction, is a kind of new heavy industrialization ethylene glycol synthesis route.Ethylene glycol mainly relies on petroleum path to prepare for a long time, and cost is high.
Traditional barkite synthesis technique adopts the long-time heating esterification in toluene solvant of oxalic acid and alcohols to obtain, and the method production cost is high, energy consumption is large, wastewater discharge is large, seriously polluted.In the sixties in last century, the D.F.Fenton research of American Association oil company finds, carbon monoxide, alcohol and oxygen can by being oxidized the direct synthesis of oxalic acid dialkyl of hydroxylating.Through the effort of several generations researcher, the route of the most applicable industrialized carbon monoxide coupling producing oxalic ester is at present, carbon monoxide and alkyl nitrite linked reaction oxalic dialkyl, and generate nitrogen protoxide, nitrogen protoxide regenerates alkyl nitrite with methyl alcohol, oxygen reaction again, and reaction equation is as follows:
Linked reaction: 2CO+2RONO → 2NO+ (COOR) 2 (1)
Esterification: 2ROH+0.5O
2+ 2NO → 2RONO+H
2o (2)
Wherein, R represents alkyl.Nitrogen protoxide in this route and alkyl nitrite cyclic regeneration in systems in which.In the esterification reaction, main reactant is alkyl alcohol, NO and O
2.Owing to there is NO and O in reaction system
2, cause nitrogen oxide in this reaction system various informative, and be in unstable change procedure always, comprise NO, NO
2, N
2o
3, N
3o
4, the effective oxide wherein participating in reaction generation alkyl nitrite is N
2o
3, remaining oxide compound is at generation N
2o
3while also can there is the side reaction generating the materials such as nitric acid.The oxynitride, the alkyl nitrite that contain in material are put in the side reaction and speeding generating nitric acid all can cause oxynitride loss in the cycle gas system of whole synthesis of oxalate, must pass through other oxynitride generating unit and supplements.Such as, Ube Industries, Ltd (CN1218032A) discloses a kind of preparation method of alkyl nitrite, be provided with the charging of fresh alkyl alcohol at the epimere of reaction tower, oxynitride and alkyl alcohol counter current contact in reaction tower generates alkyl nitrite.But part alkyl nitrite is dissolved in alkyl alcohol solution and is pulled away with tower reactor liquid phase, reduce the yield of alkyl nitrite.
The mode that Shanghai Jiaohua Co., Ltd and Shanghai Communications University (CN101190884A) disclose a kind of reactive distillation carries out synthesis methyl nitrite, and tower reactor, tower top are provided with reboiler and condenser respectively.Tower reactor is boiled again can efficient recovery methyl nitrite, but a large amount of methyl alcohol that simultaneously gasifies also considerably increases the energy consumption of device.
In a word, it is low to there is the alkyl nitrite yield that alkyl alcohol solution that alkyl nitrite is dissolved in outer row causes in prior art, the problem that reactive distillation causes plant energy consumption high.
Summary of the invention
The invention provides a kind of production method of new alkyl nitrite, the method has the advantage that alkyl nitrite yield is high, energy consumption is low.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of production method of alkyl nitrite, comprises the following steps:
A) provide the reactor of synthesis alkyl nitrite, described reactor at least comprises upper, middle and lower segment;
B) fresh alkyl alcohol enters reactor from the top of reactor epimere, flows downward, and with gas phase counter current contact upwards, be absorbed liquid logistics bottom reactor epimere;
C) by the liquid stream of circulation approach circulation containing alkyl alcohol, the liquid stream containing alkyl alcohol is discharged thus from the bottom in reactor stage casing, the liquid stream that cooling is discharged, then the liquid stream of cooling is back to the top in reactor stage casing, makes the liquid stream returned be downward through reactor stage casing;
D) unstripped gas of first strand of nitrogen-containing oxide and oxygen stream enter reactor from the bottom in reactor stage casing, and upwards flow, with the liquid stream counter current contact containing alkyl alcohol of the absorption liquid logistics and circulation that are downward through stage casing, thus the gas-liquid reaction carrying out oxynitride, oxygen and alkyl alcohol in unstripped gas in stage casing is to generate alkyl nitrite, and bottom stage casing, obtain the liquid stream containing alkyl alcohol;
E) obtain bottom described stage casing containing alkyl alcohol liquid stream in major part by step c) circulation, small portion enters the top of reactor hypomere, the gaseous stream counter current contact produced with unstripped gas and the vaporizer of the second strand of nitrogen-containing oxide entered bottom reactor hypomere, to reclaim the alkyl nitrite wherein contained;
F) obtain substantially not containing the liquid stream of alkyl nitrite from reactor bottom; A part for described logistics is arranged outward, and another part enters vaporizer, with generating step e) described in vaporizer produce gaseous stream;
G) gas stream containing alkyl nitrite generated is discharged from reactor head.
In technique scheme, preferably, the ratio of reactor upper, middle and lower segment is (1 ~ 5): (2 ~ 10): 1.More preferably, ratio is (2 ~ 4): (3 ~ 8): 1.
In technique scheme, preferably, the unstripped gas of described first strand of nitrogen-containing oxide contains the nitrogen protoxide of 1 ~ 50 % by mole, and the unstripped gas of second strand of nitrogen-containing oxide contains the nitrogen protoxide of 1 ~ 50 % by mole.
In technique scheme, preferably, contained in the unstripped gas of first strand of nitrogen-containing oxide and the unstripped gas of second strand of nitrogen-containing oxide nitrogen protoxide total amount and total mol ratio of oxygen are (2 ~ 12): 1.
In technique scheme, preferably, the unstripped gas scale of construction of second strand of nitrogen-containing oxide is 0 ~ 40% of the unstripped gas of first strand of nitrogen-containing oxide and the unstripped gas total amount of second strand of nitrogen-containing oxide.
In technique scheme, preferably, the service temperature of described reactor is 0 ~ 150 DEG C, and pressure counts 0 ~ 1.0MPa with gauge pressure.
In technique scheme, preferably, the water-content in fresh alkyl alcohol is lower than 0.5 % by weight, and the ratio of the inlet amount of fresh alkyl alcohol and the liquids flow containing alkyl alcohol of circulation is 1:(2 ~ 100).
In technique scheme, preferably, the rear temperature of the cooling of the liquid stream containing alkyl alcohol of described circulation is 0 ~ 60 DEG C.
In technique scheme, preferably, the liquids flow substantially not containing alkyl nitrite of described outer row accounts for 0.5 ~ 20 % by weight of the liquids flow containing alkyl alcohol of described circulation.
In technique scheme, preferably, described alkyl nitrite is methyl nitrite, and described alkyl alcohol is methyl alcohol.
In technique scheme, preferably, in the unstripped gas of fresh alkyl alcohol and nitrogen-containing oxide, nitric oxide production mol ratio is (0.5 ~ 10): 1.
In technique scheme, preferably, in the reactor bottom liquid stream of discharging the content of methyl nitrite lower than 0.5 % by weight.
Accompanying drawing explanation
Fig. 1 is the inventive method schematic diagram.
In Fig. 1,1 is reactor, 1a is reactor epimere, 1b is reactor stage casing, 1c is reactor hypomere, 2 is vaporizer, 3 is recycle pump, and 4 is water cooler, and 5a is the unstripped gas (unstripped gas of first strand of nitrogen-containing oxide) entering reactor stage casing, 5b is the unstripped gas (unstripped gas of second strand of nitrogen-containing oxide) entering reactor hypomere, 6 is oxygen, and 7 is fresh alkyl alcohol, and 8 is outer row's logistics, 9 is the gas stream containing alkyl nitrite, and 10 is the liquid stream containing alkyl alcohol circulated.
As shown in Figure 1, the unstripped gas 5a of first strand of nitrogen-containing oxide and oxygen 6 enter the bottom of reactor stage casing 1b, and upwards flow; Fresh alkyl alcohol 7 enters the top of esterifier epimere 1a, flows downward, and with gas phase counter current contact washing reaction gas-phase product upwards, remove contained minor amount of water, nitric acid wherein; Mix with the liquid stream 10 containing alkyl alcohol of cooled circulation after absorption liquid flows out from the bottom of reactor epimere 1a, enter the top of reactor stage casing 1b; Alkyl alcohol with containing NO, O
2gas in the reactor in section 1b counter current contact reaction generate alkyl nitrite, the alkyl nitrite mainly dereaction device epimere 1a together with gas of generation, is dissolved in the liquid phase containing alkyl alcohol on a small quantity, flows out bottom the 1b of reactor stage casing; The major part of the liquid stream containing alkyl alcohol flowed out bottom the 1b of reactor stage casing by recycle pump 3, then goes back to the top of reactor stage casing 1b through supercooler 4 Posterior circle, a small amount of liquid stream containing alkyl alcohol enters reactor hypomere 1c; Reactor hypomere, the profit reduction and reserving section of suitable rectifying tower, enter the liquid stream containing alkyl alcohol of reactor hypomere 1c, the gaseous stream counter current contact produced with unstripped gas 5b and the vaporizer 2 of the second strand of nitrogen-containing oxide entered bottom reactor hypomere, to reclaim the alkyl nitrite wherein contained, and enter the bottom of esterifier stage casing 1b; Substantially do not discharge containing the liquid 8 of alkyl nitrite.
In the inventive method, reactor is divided into upper, middle and lower segment, and the ratio of three sections of height is (1 ~ 5): (2 ~ 20): 1.Be preferably (2 ~ 4): (3 ~ 8): 1.Because alkyl nitrite differs comparatively large with the boiling point of alkyl alcohol, less number of theoretical plate just can realize being separated, therefore hypomere height is relatively minimum.And the absorber portion on top and the conversion zone at middle part, owing to needing to provide enough gas liquid interfacial area, relative height is higher.
In the inventive method, reactor stage casing is oxidative esterification reaction section, reaction produces a large amount of reaction heat, needs to remove these reaction heat expeditiously, so that stable reaction is avoided unnecessary side reaction at conditions suitable.For this reason, reaction heat removes by arranging outer circulation by the inventive method in time.Epimere is absorber portion, and fresh methanol rinses reaction gas-phase product, absorbs the nitric acid in gaseous reaction product and water; Hypomere is stripping section, with the alkyl nitrite in recovering liquid reaction product.
In the inventive method, the ratio of the inlet amount of fresh alkyl alcohol and the liquids flow containing alkyl alcohol of circulation is 1:(2 ~ 100), preferred 1:(5 ~ 50).When internal circulating load is too little, the removing of reaction heat can not all evenly fully be carried out; Or the filler being seated in reactor can not be kept uniform wet state by the alkyl alcohol existed with liquid state; Therefore NO, O in reactor
2evenly can not carry out under stable condition with the gas-to-liquid contact esterification of alkyl alcohol.When internal circulating load is too large, cooling and working cycle need large energy, are disadvantageous economically.In circulation step, the temperature of the liquid stream containing alkyl alcohol of described circulation controls at 0 ~ 60 DEG C.
In the inventive method, in the unstripped gas of fresh alkyl alcohol and nitrogen-containing oxide, nitric oxide production mol ratio (alcohol/NO) is (0.5 ~ 10): 1, is preferably (1 ~ 5): 1.Wherein, when alcohol/NO is than time too little, oxidative esterification reaction can not efficiently carry out uniformly, or local reacts, and thus can not control temperature of reaction in high stability ground.When alcohol/NO is than time too large, the quantitative change of the unreacted alkyl alcohol that need reclaim and circulate obtains too large, and energy consumption increases, and is disadvantageous economically.
In the inventive method, in the unstripped gas of oxygen and nitrogen-containing oxide, nitric oxide production mol ratio is 1:(4 ~ 12), be preferably 1:(5 ~ 8).Control O
2with the mol ratio of NO, make reaction to generation effective oxide N
2o
3direction carry out.
In the inventive method, described alkyl alcohol is determined according to the type of required alkylidene group nitric ether.Such as there is 1-8 carbon atom, a preferred 1-6 carbon atom, the more preferably lower alkyl alcohol of 1-2 carbon atom, such as methyl alcohol.
In the inventive method, the gas of described nitrogen-containing oxide, containing the nitrogen protoxide of 1 ~ 50 % by mole, is preferably 5 ~ 30 % by mole.
In the inventive method, the unstripped gas of described nitrogen-containing oxide can be provided by the method preparing oxalic acid alkyl ester.In the preparation method of oxalic acid alkyl ester, CO and alkyl nitrite react the gas fraction generated containing dialkyl oxalate in the presence of a catalyst; The gas fraction input absorption tower generated, wherein gas fraction contact with the absorbing fluid containing alkyl alcohol obtain containing be absorbed in containing the dialkyl oxalate in the absorbing fluid of alkyl alcohol condensed fluid cut and contain the uncondensed gas cut of alkyl alcohol. vapor and gaseous state NO; Uncondensed gas cut is carried by absorption tower, as unstripped gas input esterifier to prepare alkyl nitrite.
In the inventive method, the service temperature of described reactor is 0 ~ 150 DEG C, and pressure counts 0 ~ 0.6MPa with gauge pressure.
The inventive method, the alkyl alcohol liquid containing alkyl nitrite that the rectifying section of hypomere alkyl nitrite is externally arranged distills, and achieves the recovery of alkyl nitrite, improves the yield of alkyl nitrite.In addition, compared with the mode of reactive distillation, because the alkyl alcohol liquid containing alkyl nitrite only externally arranged distills, so while raising alkyl nitrite yield, also reduce plant energy consumption, save process cost.
In oxidative esterification reaction, usually have the side reaction generating nitric acid and occur, and nitric acid has severe corrosive, must remove as far as possible completely from oxidative esterification gaseous product in time.The water that main reaction generates can not enter linked reaction system, otherwise the dialkyl oxalate that linked reaction generates is met the water capacity and hydrolysis reaction oxalic is easily occurred, and oxalic acid and water are all coupling catalyst poisonous substances, the gas-phase product band nitric acid effectively solving esterification has just become one of gordian technique of whole barkite synthesis technique long-period stable operation with water problem.Adopt the inventive method, reactor epimere adds fresh methanol rinses section, because the water-content in fresh methanol is lower, guarantee that in the gas of linked reaction, the objectionable impurities such as water and nitric acid is substantially eliminated, be conducive to the stable long-term operation of whole synthesis of oxalic acid ester apparatus.
Adopt technical scheme of the present invention, the yield of alkyl nitrite can improve 5%, and the water in the alkyl nitrite gas-phase product obtained and nitric acid content, all lower than 0.01%, achieve good technique effect.
Below by embodiment, the invention will be further elaborated, but these embodiments are in no case construed as limiting scope of the present invention.
Embodiment
[embodiment 1]
The methyl nitrite production technique of the present embodiment is the scale for producing 1000 tons of dimethyl oxalates per year.
Containing NO circulation gas flow 500Nm
3/ h, volume consists of: NO15%, CO8%, methyl nitrite 5%, methyl alcohol 6%, N
2be 66%.The circulation gas wherein entering reactor hypomere accounts for 8% of total amount.
Oxygen flow 13.0Nm
3/ h, purity is 99.8v%, and all the other are N
2.
Esterifier is packing tower, and adopt Raschig ring filler, diameter is 0.4m, epimere 1a packed height 2m, and stage casing 1b filler divides two-layer filling, every layer of packed height 2m, hypomere 1c packed height 2m, esterifier height overall 10.6m.
Reactor head pressure-controlling at 0.25MPag, fresh methanol purity 99.9%, flow 0.13m
3/ h, temperature 20 DEG C.Recycle methanol 3.9m
3/ h, recycle methanol is cooled by interchanger, and in esterifier, the temperature of pars infrasegmentalis controls at 45 DEG C, and the temperature bottom reactor hypomere is 109 DEG C.
Esterifier tower reactor arranges 0.08m outward
3the liquid of/h, weight consists of: nitric acid=1.8%, methyl alcohol=56.1%, water=42.1%, and methyl nitrite is less than 0.01%.
Go out the gas-phase product flow 480Nm of washing tower
3/ h, mole consists of: methyl nitrite=15.5%, NO=5.1%, CO=7.2%, N
2=68.0%, methyl alcohol=4.2%.Wherein the content of water and nitric acid is all lower than 0.01 % by weight.
[embodiment 2]
The methyl nitrite production technique of the present embodiment is the scale for producing 10000 tons of dimethyl oxalates per year.
Containing NO circulation gas flow 4960Nm
3/ h, mole composition NO=15%, CO=8%, methyl nitrite=5%, methyl alcohol=6%, N
2=66%.The circulation gas wherein entering reactor hypomere accounts for 1% of total amount.
Oxygen flow 126Nm
3/ h, purity is 99.8%, and all the other are N
2.
Esterifier is packing tower, and adopt Raschig ring filler, diameter is 1.5m, epimere 1a packed height 2m, and stage casing 1b filler divides two-layer filling, every layer of packed height 3m, hypomere 1c packed height 2m, esterifier height overall 13.2m.
Reactor head pressure-controlling at 0.25MPag, fresh methanol purity 99.9%, flow 1.3m
3/ h, temperature 20 DEG C.Recycle methanol 38.7m
3/ h, recycle methanol is cooled by interchanger, and in esterifier, the temperature of pars infrasegmentalis controls at 45 DEG C, and the temperature bottom reactor hypomere is 108 DEG C.
Fresh methanol purity 99.9%, flow 1.3m
3/ h, temperature 20 DEG C.Recycle methanol 38.7m
3/ h, recycle methanol is cooled by interchanger, and the temperature of esterifier tower reactor controls at 45 DEG C.
Esterifier tower reactor arranges 0.65m outward
3the liquid of/h, weight consists of: nitric acid=1.8%, methyl alcohol=56.7%, water=41.5%, and methyl nitrite is less than 0.01%.
Go out the gas-phase product flow 4880Nm of washing tower
3/ h, mole consists of: methyl nitrite=15.6%, NO=5.0%, CO=8.1%, N2=67.1%, methyl alcohol=4.1%.Wherein the content of water and nitric acid is all lower than 0.01%.
[embodiment 3]
The methyl nitrite production technique of the present embodiment is the scale for producing 100000 tons of dimethyl oxalates per year.
Containing NO circulation gas flow 49550Nm
3/ h, mole composition NO=15%, CO=8%, methyl nitrite=5%, methyl alcohol=6%, N
2=66%.The circulation gas wherein entering reactor hypomere accounts for 20% of total amount.
Oxygen flow 1246Nm
3/ h, purity is 99.8%, and all the other are N
2.
Esterifier diameter is 3.8m, and epimere 1a adopts valve tray, stage number 10 pieces, distance between plates 0.5m; Stage casing 1b adopts Raschig ring filler, point three layers of filling, and every layer of packed height 4m, hypomere 1c adopt Raschig ring filler height 4m, esterifier height overall 25.2m.
Reactor head pressure-controlling at 0.1MPag, fresh methanol purity 99.9%, flow 12.9m
3/ h, temperature 20 DEG C.Recycle methanol 387.1m
3/ h, recycle methanol is cooled by interchanger, and in esterifier, the temperature of pars infrasegmentalis controls at 45 DEG C, and the temperature bottom reactor hypomere is 92 DEG C.
Esterifier tower reactor arranges 6.4m outward
3the liquid of/h, weight consists of: nitric acid=1.9%, methyl alcohol=56.7%, water=40.4%, and methyl nitrite is less than 0.01%.
Go out the gas-phase product flow 48550Nm of washing tower
3/ h, mole consists of: methyl nitrite=15.5%, NO=5.1%, CO=8.1%, N2=67.2%, methyl alcohol=4.1%.Wherein the content of water and nitric acid is all lower than 0.01%.
[comparative example 1]
With the same procedure synthesis methyl nitrite in [embodiment 1], but cancel the epimere 1a of reactor, fresh methanol mixes the top of laggard esterifier 1b with recycle methanol, then moisturely in gas-phase product be respectively 0.85%, 0.12% with the massfraction of nitric acid, if directly enter coupler reactor, long period, the steady running of coupling catalyst will be affected.
[comparative example 2]
With the same procedure synthesis methyl nitrite in [embodiment 1], but cancel the hypomere 1c of reactor, the methyl nitrite contained containing 1.2% in methyl alcohol liquid phase that then reactor is arranged outward, reduce the yield of methyl nitrite, the loss of the oxynitride of whole synthesizing dimethyl oxalate device also significantly improves.
Claims (10)
1. a production method for alkyl nitrite, comprises the following steps:
A) provide the reactor of synthesis alkyl nitrite, described reactor at least comprises upper, middle and lower segment;
B) fresh alkyl alcohol enters reactor from the top of reactor epimere, flows downward, and with gas phase counter current contact upwards, be absorbed liquid logistics bottom reactor epimere;
C) by the liquid stream of circulation approach circulation containing alkyl alcohol, the liquid stream containing alkyl alcohol is discharged thus from the bottom in reactor stage casing, the liquid stream that cooling is discharged, then the liquid stream of cooling is back to the top in reactor stage casing, makes the liquid stream returned be downward through reactor stage casing;
D) unstripped gas of first strand of nitrogen-containing oxide and oxygen stream enter reactor from the bottom in reactor stage casing, and upwards flow, with the liquid stream counter current contact containing alkyl alcohol of the absorption liquid logistics and circulation that are downward through stage casing, thus the gas-liquid reaction carrying out oxynitride, oxygen and alkyl alcohol in unstripped gas in stage casing is to generate alkyl nitrite, and bottom stage casing, obtain the liquid stream containing alkyl alcohol;
E) obtain bottom described stage casing containing alkyl alcohol liquid stream in major part by step c) circulation, small portion enters the top of reactor hypomere, the gaseous stream counter current contact produced with unstripped gas and the vaporizer of the second strand of nitrogen-containing oxide entered bottom reactor hypomere, to reclaim the alkyl nitrite wherein contained;
F) obtain substantially not containing the liquid stream of alkyl nitrite from reactor bottom; A part for described logistics is arranged outward, and another part enters vaporizer, with generating step e) described in vaporizer produce gaseous stream;
G) gas stream containing alkyl nitrite generated is discharged from reactor head.
2. the production method of alkyl nitrite according to claim 1, is characterized in that the ratio of reactor upper, middle and lower segment is for (1 ~ 5): (2 ~ 10): 1.
3. the production method of alkyl nitrite according to claim 1, is characterized in that the unstripped gas of described first strand of nitrogen-containing oxide contains the nitrogen protoxide of 1 ~ 50 % by mole, and the unstripped gas of second strand of nitrogen-containing oxide contains the nitrogen protoxide of 1 ~ 50 % by mole;
Nitrogen protoxide total amount contained in the unstripped gas of the unstripped gas of first strand of nitrogen-containing oxide and second strand of nitrogen-containing oxide and total mol ratio of oxygen are (2 ~ 12): 1;
The unstripped gas scale of construction of second strand of nitrogen-containing oxide is 0 ~ 40% of the unstripped gas of first strand of nitrogen-containing oxide and the unstripped gas total amount of second strand of nitrogen-containing oxide.
4. the production method of alkyl nitrite according to claim 1, it is characterized in that the service temperature of described reactor is 0 ~ 150 DEG C, pressure counts 0 ~ 1.0MPa with gauge pressure.
5. the production method of alkyl nitrite according to claim 1, it is characterized in that water-content in fresh alkyl alcohol is lower than 0.5 % by weight, the ratio of the inlet amount of fresh alkyl alcohol and the liquids flow containing alkyl alcohol of circulation is 1:(2 ~ 100).
6. the production method of alkyl nitrite according to claim 1, is characterized in that the rear temperature of the cooling of the liquid stream containing alkyl alcohol of described circulation is 0 ~ 60 DEG C.
7. the production method of alkyl nitrite according to claim 1, is characterized in that described outer row's does not account for 0.5 ~ 20 % by weight of the liquids flow containing alkyl alcohol of described circulation containing the liquids flow of alkyl nitrite substantially.
8. the production method of alkyl nitrite according to claim 1, it is characterized in that described alkyl nitrite is methyl nitrite, described alkyl alcohol is methyl alcohol.
9. the production method of alkyl nitrite according to claim 1, is characterized in that in the unstripped gas of fresh alkyl alcohol and nitrogen-containing oxide, nitric oxide production mol ratio is (0.5 ~ 10): 1.
10. the production method of alkyl nitrite according to claim 1, is characterized in that the content of methyl nitrite in the liquid stream that reactor bottom is discharged is lower than 0.5 % by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410314279.0A CN105272859B (en) | 2014-07-03 | 2014-07-03 | The production method of alkyl nitrite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410314279.0A CN105272859B (en) | 2014-07-03 | 2014-07-03 | The production method of alkyl nitrite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105272859A true CN105272859A (en) | 2016-01-27 |
| CN105272859B CN105272859B (en) | 2018-01-09 |
Family
ID=55142761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410314279.0A Active CN105272859B (en) | 2014-07-03 | 2014-07-03 | The production method of alkyl nitrite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105272859B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883127A (en) * | 2017-04-14 | 2017-06-23 | 高化学（江苏）化工新材料有限责任公司 | A kind of device for continuously generating methyl nitrite |
| CN106955649A (en) * | 2017-03-23 | 2017-07-18 | 宁波中科远东催化工程技术有限公司 | A kind of nitrate reductase device |
| CN111196758A (en) * | 2018-11-20 | 2020-05-26 | 上海浦景化工技术股份有限公司 | Nitric acid reduction and conversion process |
| CN111377819A (en) * | 2018-12-28 | 2020-07-07 | 上海浦景化工技术股份有限公司 | Alkyl nitrite synthesis process and reactor |
| CN111530407A (en) * | 2020-04-30 | 2020-08-14 | 中国神华煤制油化工有限公司 | Esterification reactor and esterification reaction method |
| CN113912498A (en) * | 2020-07-10 | 2022-01-11 | 中国石油化工股份有限公司 | Method and device for safely preparing methyl nitrite in oxidation esterification reactor and application of methyl nitrite |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0310191A2 (en) * | 1987-09-29 | 1989-04-05 | Union Carbide Corporation | Process and reaction vessel for production of alkyl nitrite |
| CN1218032A (en) * | 1997-10-21 | 1999-06-02 | 宇部兴产株式会社 | Process for producing alkyl nitrite |
| CN1445208A (en) * | 2002-03-18 | 2003-10-01 | 宇部兴产株式会社 | Method for producing arrcostab nitrite |
| CN101096340A (en) * | 2006-06-27 | 2008-01-02 | 上海焦化有限公司 | Process for the preparation of C1-C4-alkyl nitrites |
| CN103373925A (en) * | 2012-04-27 | 2013-10-30 | 上海浦景化工技术有限公司 | Preparation method for methyl nitrite |
-
2014
- 2014-07-03 CN CN201410314279.0A patent/CN105272859B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0310191A2 (en) * | 1987-09-29 | 1989-04-05 | Union Carbide Corporation | Process and reaction vessel for production of alkyl nitrite |
| CN1218032A (en) * | 1997-10-21 | 1999-06-02 | 宇部兴产株式会社 | Process for producing alkyl nitrite |
| CN1445208A (en) * | 2002-03-18 | 2003-10-01 | 宇部兴产株式会社 | Method for producing arrcostab nitrite |
| CN101096340A (en) * | 2006-06-27 | 2008-01-02 | 上海焦化有限公司 | Process for the preparation of C1-C4-alkyl nitrites |
| CN103373925A (en) * | 2012-04-27 | 2013-10-30 | 上海浦景化工技术有限公司 | Preparation method for methyl nitrite |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106955649A (en) * | 2017-03-23 | 2017-07-18 | 宁波中科远东催化工程技术有限公司 | A kind of nitrate reductase device |
| CN106883127A (en) * | 2017-04-14 | 2017-06-23 | 高化学（江苏）化工新材料有限责任公司 | A kind of device for continuously generating methyl nitrite |
| CN106883127B (en) * | 2017-04-14 | 2019-03-05 | 高化学（江苏）化工新材料有限责任公司 | A kind of device continuously generating methyl nitrite |
| CN111196758A (en) * | 2018-11-20 | 2020-05-26 | 上海浦景化工技术股份有限公司 | Nitric acid reduction and conversion process |
| 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 |
| CN111377819A (en) * | 2018-12-28 | 2020-07-07 | 上海浦景化工技术股份有限公司 | Alkyl nitrite synthesis process and reactor |
| CN111377819B (en) * | 2018-12-28 | 2024-02-09 | 上海浦景化工技术股份有限公司 | Alkyl nitrite synthesis process and reactor |
| CN111530407A (en) * | 2020-04-30 | 2020-08-14 | 中国神华煤制油化工有限公司 | Esterification reactor and esterification reaction method |
| CN113912498A (en) * | 2020-07-10 | 2022-01-11 | 中国石油化工股份有限公司 | Method and device for safely preparing methyl nitrite in oxidation esterification reactor and application of methyl nitrite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105272859B (en) | 2018-01-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP4049748A1 (en) | Gas-liquid bubbling bed reactor, reaction system and method for synthesizing carbonate | |
| CN105272859A (en) | Production method for alkyl nitrite | |
| US20170267615A1 (en) | Method and device system for producing dimethyl oxalate through midhigh and high-pressure carbonylation of industrial synthesis gas and producing ethylene glycol through dimethyl oxalate hydrogenation | |
| CN103373925A (en) | Preparation method for methyl nitrite | |
| CN104761429A (en) | Dimethyl carbonate and ethylene glycol production process | |
| CN101830807B (en) | Synthesizing device and process for alkyl nitrite | |
| CN102775274B (en) | System and method for preparing ethylene glycol through oxalate hydrogenation | |
| CN205188178U (en) | Methyl nitrite's regenerating unit system in synthetic gas system ethylene glycol technology | |
| CN104250210A (en) | Method for production of acetic acid by methanol carbonylation | |
| Zomerdijk et al. | Technology for the manufacture of ethylene oxide | |
| CN105330542A (en) | Production method of dimethyl oxalate | |
| CN205188177U (en) | Methyl nitrite's regenerating unit system in synthetic gas system ethylene glycol technology | |
| CN105218374A (en) | The method of synthesis alkyl nitrite | |
| CN102911046A (en) | Dimethyl oxalate purification method during CO coupling dimethyl oxalate synthesis process | |
| CN102219680A (en) | Method for preparing oxalic ester by CO gas-phase process | |
| CN106478586A (en) | The synthesis technique of ethylene carbonate | |
| CN202022868U (en) | Device for producing methyl nitrite and device for producing oxalic acid dimethyl ester by continuous circulating esterification and carbonylation coupling | |
| CN104250209A (en) | Method for production of acetic acid by methanol carbonylation | |
| CN106518675B (en) | The method for producing dimethyl oxalate and by-product dimethyl carbonate | |
| CN101993350B (en) | Production method of glycol | |
| CN102218258A (en) | Technology and equipment for recycling nitric oxides and purifying tail gas | |
| CN105218309A (en) | Produce the method for ethylene glycol | |
| CN106608865A (en) | Energy-saving method for synthesizing ethylene carbonate | |
| CN102731300B (en) | Industrialization method for producing dimethyl oxalate by continuous cycle esterification and coupling carbonylation | |
| CN102964246A (en) | Method and device for manufacturing dialkyl oxalate or/and dialkyl carbonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |