CN105218374A - The method of synthesis alkyl nitrite - Google Patents
The method of synthesis alkyl nitrite Download PDFInfo
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- CN105218374A CN105218374A CN201410314417.5A CN201410314417A CN105218374A CN 105218374 A CN105218374 A CN 105218374A CN 201410314417 A CN201410314417 A CN 201410314417A CN 105218374 A CN105218374 A CN 105218374A
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Abstract
The present invention relates to a kind of method of synthesizing alkyl nitrite, mainly solve prior art and there is the problem that reactor diameter is large, investment cost is high, process cost is high.The present invention is comprised the following steps by employing: the gas of nitrogen-containing oxide, oxygen and first strand of alkyl alcohol enter esterifier, flow through described reactor from top to down, gas and liquid flowing contact reacts obtains gaseous stream at the bottom of the tower reactor liquid phase stream containing alkyl alcohol and the tower containing alkyl nitrite; By the described tower reactor liquid phase stream containing alkyl alcohol of circulation approach circulation; The described tower spirit phases containing alkyl nitrite flows to the bottom into washing tower, with the second burst of alkyl alcohol counter current contact entered from washing tower top, the washings that wash tower bottoms obtains enters esterifier top, the technical scheme that washing tower top obtains alkyl nitrite product stream solves this problem preferably, can be used in the industrial production of alkyl nitrite.
Description
Technical field
The present invention relates to a kind of method of synthesizing 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 prepare 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 higher.
Traditional barkite synthesis technique adopts oxalic acid and alcohols in toluene solvant, heat esterification 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.And nitric acid has severe corrosive, must remove as far as possible completely from regeneration gas product in time.In addition, the water that main reaction generates can not enter linked reaction system, otherwise hydrolysis reaction oxalic easily occurs the dialkyl oxalate chance water capacity that linked reaction generates, and oxalic acid and water are all coupling catalyst poisonous substances.Therefore, the gas-phase product band nitric acid effectively solving esterification has just become one of gordian technique of barkite synthesis technique long-period stable operation with water problem.
Ube Industries, Ltd (CN1218032A) discloses a kind of preparation method of alkyl nitrite, and oxynitride and alkyl alcohol counter current contact in reaction tower generates alkyl nitrite.But in order to ensure the normal running of reaction tower, avoid the generation of Concerning Flooding Phenomenon, the tower diameter of design is usually very large, and the investment cost of equipment is higher.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, and energy consumption and facility investment are all higher.Shanghai Jiaohua Co., Ltd (CN202022868U) also discloses a kind of device adopting cocurrent cooling operation to produce methyl nitrite, and the gas-phase product of reaction is by going linked reaction to produce dimethyl oxalate again after washing and drying.But water-washing method brings waste water handling problem, the drying process after washing must cause siccative to need frequent regeneration, thus adds the process cost of device.
Summary of the invention
Technical problem to be solved by this invention is the problem that prior art exists that reactor diameter is large, investment cost is high, process cost is high, provides a kind of method of synthesis alkyl nitrite newly.The method has the advantages that equipment size is little, investment cost is low, energy consumption is low, process cost is low.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of synthesizing alkyl nitrite, comprises the following steps:
1) gas of nitrogen-containing oxide, oxygen and first strand of alkyl alcohol enter esterifier, flow through described reactor from top to down, and gas and liquid flowing contact reacts obtains gaseous stream at the bottom of the tower reactor liquid phase stream containing alkyl alcohol and the tower containing alkyl nitrite;
2) by the described tower reactor liquid phase stream containing alkyl alcohol of circulation approach circulation: discharge the described tower reactor liquid phase stream containing alkyl alcohol from the bottom of esterifier, the tower reactor liquid phase stream that cooling is discharged, then the tower reactor liquid phase stream of cooling is back to esterifier top, makes the liquid phase stream returned be downward through esterifier thus;
3) the described tower spirit phases containing alkyl nitrite flows to the bottom into washing tower, with the second burst of alkyl alcohol counter current contact entered from washing tower top, the washings that wash tower bottoms obtains enters esterifier top, and washing tower top obtains alkyl nitrite product stream.
In technique scheme, preferably, the gas of described nitrogen-containing oxide contains the nitrogen protoxide of 1 ~ 50 % by mole.
In technique scheme, preferably, the gas of described nitrogen-containing oxide is provided by the method preparing oxalic acid alkyl ester.
In technique scheme, preferably, the ratio control containing alkyl alcohol amount in the tower reactor liquid phase stream of alkyl alcohol of second burst of alkyl alcohol inlet amount and described circulation is in 1:(2 ~ 100).
In technique scheme, preferably, entering nitric oxide production mol ratio in the alkyl alcohol of esterifier and the gas of nitrogen-containing oxide is (1 ~ 100): 1.
In technique scheme, preferably, in the gas of oxygen and nitrogen-containing oxide, nitric oxide production mol ratio is 1:(4 ~ 12).
In technique scheme, preferably, in circulation step, the cooled temperature of tower reactor liquid phase stream containing alkyl alcohol of described circulation controls at 0 ~ 60 DEG C.
In technique scheme, preferably, what a part was discharged bottom esterifier releases from circulation approach containing the tower reactor liquid phase stream of alkyl alcohol, and the tower reactor liquid phase stream containing alkyl alcohol of the discharge of the rest part Posterior circle that is cooled is back to esterifier top; The tower bottoms phase logistics capacity containing alkyl alcohol of described releasing accounts for 0.5 ~ 20 % by mole of the tower bottoms phase logistics capacity containing alkyl alcohol of described circulation.
In technique scheme, preferably, in esterifier, temperature is 0 ~ 90 DEG C, and pressure counts 0 ~ 0.6MPa with gauge pressure.
In technique scheme, preferably, esterifier is built with 1 ~ 8 section of filler; Oxygen adopts sectional feeding, hop count 1 ~ 8 section.
In technique scheme, preferably, alkyl nitrite is methyl nitrite, and alkyl alcohol is methyl alcohol.
Accompanying drawing explanation
Fig. 1 is the inventive method schematic flow sheet.
Fig. 2 is the schematic flow sheet of [comparative example 1] described method.
In Fig. 1,1 is esterifier, 2 is reactor cycles pump, 3 is water cooler, 4 is washing liquid pump, 5 is washing tower, and 6 is the gas of nitrogen-containing oxide, and 7 is oxygen, 8 is first strand of alkyl alcohol, 9 is esterification liquid product (liquid phase stream containing alkyl alcohol), and 10 is the cyclic part of esterification liquid product, and 11 is esterification gas-phase product (gaseous stream containing alkyl nitrite), 12 is second strand of alkyl alcohol, 13 is alkyl nitrite product stream, and 14 is washings, and 15 is the releasing part of esterification liquid product.
Equipment, logistics representated by numbering of each in Fig. 2 is completely the same with Fig. 1, just changes esterifier 1 into counter-current operation by cocurrent cooling operation.
As shown in Figure 1, the gas 6 of nitrogen-containing oxide and first strand of alkyl alcohol 8 enter the top of esterifier 1, and oxygen 7 segmentation enters esterifier 1; Second strand of alkyl alcohol 12 enters the top of washing tower 5, and for washing reaction gas-phase product, washings 14 is discharged, through liquid transporting apparatus, such as, after washing liquid pump 4 supercharging, mix with the cyclic part 10 of cooled esterification liquid product, enter the top of esterifier 1; The liquid product 9 of esterifier 1 is discharged from bottom, and through liquid transporting apparatus, such as, after reactor cycles pump 2 supercharging, major part goes water cooler 3 to cool, a small amount of 15 outer venting alkyl alcohol recovery units; The gas-phase product 11 of esterifier 1 enters the bottom of washing tower 5, and after second burst of alkyl alcohol 12 counter current contact, the target product alkyl nitrite gas products 13 being stripped of nitric acid and water is discharged from tower top.
In the inventive method, gas-liquid contact reaction carries out in esterifier, reaction produces a large amount of reaction heat, needs to remove these reaction heat expeditiously, so that stable reaction is avoided irregular side reaction at conditions suitable.For this reason, reaction heat removes by arranging outer circulation by the inventive method in time.
In the inventive method, first strand of alkyl alcohol and second strand of alkyl alcohol can be optionally fresh alkyl alcohol.
In the inventive method, the ratio control containing alkyl alcohol amount in the tower reactor liquid phase stream 10 of alkyl alcohol of second burst of alkyl alcohol inlet amount and described circulation is in 1:(2 ~ 100), preferred 1:(5 ~ 50), more preferably 1:(10 ~ 20).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 tower reactor liquid phase stream containing alkyl alcohol of described circulation controls at 0 ~ 60 DEG C.
In the inventive method, the liquid product that small portion is discharged from the bottom of esterifier is optionally discharged out-of-bounds after flowing through pump 2 and before arrival water cooler 3.The flow of the tower reactor liquid phase stream 15 containing alkyl alcohol of described releasing accounts for 0.5 ~ 20 % by mole of tower reactor liquid phase stream 10 flow containing alkyl alcohol of described circulation.
In the inventive method, entering nitric oxide production mol ratio (alcohol/NO) in the alkyl alcohol of esterifier and the gas of nitrogen-containing oxide is (1 ~ 100): 1, be preferably (2 ~ 50): 1, be more preferably (2 ~ 10): 1.Wherein, the alkyl alcohol entering esterifier described in is the total amount of all alkyl alcohols from the steam of the outside input reactor of reactor and liquid state.Such as, with reference to figure 1, the alkyl alcohol entering esterifier comprises first strand of alkyl alcohol, 8, the second strand of alkyl alcohol 12 entered with liquid state, and is present in the alkyl alcohol in the gas 7 of nitrogen-containing oxide with steam condition, but does not comprise alkyl alcohol contained in liquid product cyclic part 10.When alcohol/NO is than time too little, esterification can not efficiently be carried 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, is disadvantageous economically.
In the inventive method, in the gas of oxygen and nitrogen-containing oxide, nitric oxide production mol ratio is 1:(4 ~ 12), be preferably 1:(5 ~ 10), be more preferably 1:(6 ~ 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 and ethanol.
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, is more preferably 10 ~ 25 % by mole.
In the inventive method, the 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 gas-liquid contact reaction temperature of oxynitride and alkyl alcohol is 0 ~ 90 DEG C, and pressure counts 0 ~ 0.6MPa with gauge pressure.
In the inventive method, described esterifier adopts gas/liquid two-phase and the tower reactor of stream contact, and reactor is built with multistage filler, and gas/liquid two-phase is all flow from top to bottom, filler hop count 1 ~ 8 section.Based on this, oxygen preferably adopts sectional feeding, hop count 1 ~ 8 section.
The gas of the inventive method nitrogen-containing oxide and alkyl alcohol pass through esterifier in the mode also flowed, by the circulation fluid phase control temperature of reaction bottom cooling reactor, reaction gas-phase product is uncoupled in washing tower and after the fresh alkyl alcohol counter current contact of supplementing and is joined Reactive Synthesis barkite.The inventive method, compared with the esterifier of counter-current operation, can reduce reactor diameter greatly, economy system investment cost, and the operating method of stream is also conducive to improving vapour-liquid mass intensity, improves the selectivity of reaction.Reaction product is after the washing of alkyl alcohol, ensure that the objectionable impurities such as water and nitric acid in the recycle gas of linked reaction is substantially eliminated, the stable long-term operation of implement device, it also avoid the frequent regeneration of siccative in washing, drying process, reduces the process cost of device.Adopt technical scheme of the present invention, the water in the alkyl nitrite gas-phase product obtained and nitric acid content are all lower than 0.01 % by weight.
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, mole composition NO=15%, CO=8%, methyl nitrite=5%, methyl alcohol=6%, N
2=66%.
Oxygen flow 12.9Nm
3/ h, purity is 99.8 % by weight, and all the other are N
2.
Esterifier diameter is 0.25m, and height 8.2m, adopt packing tower form, have four sections of fillers, packed height is respectively 1/1/1/2m, and reactor head pressure-controlling is 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 the temperature of esterifier tower reactor controls at 45 DEG C.
Washing tower diameter is 0.25m, and height 5.6m, adopts packing tower form, divides two sections, every section of 1.8m.
Esterifier tower reactor arranges 0.08m outward
3the liquid of/h, weight consists of: methyl nitrite=1.2%, nitric acid=1.7%, methyl alcohol=55.4%, water=41.7%.
Go out the gas-phase product flow 485Nm of washing tower
3/ h, mole consists of: methyl nitrite=15%, NO=5%, CO=7%, N
2=67%, methyl alcohol=6%.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%.
Oxygen flow 126Nm
3/ h, purity is 99.8%, and all the other are N
2, point four section feedings.
Esterifier diameter is 0.9m, and height 14.5m, adopt packing tower form, have four sections of fillers, packed height is respectively 2/2/2/3m, and reactor head pressure-controlling is 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 the temperature of esterifier tower reactor controls at 45 DEG C.
Washing tower diameter is 0.9m, and height 10.6m, adopts packing tower form, divides two sections, every section of 3m.
Esterifier tower reactor arranges 0.65m outward
3the liquid of/h, weight consists of: methyl nitrite=1.2%, nitric acid=1.6%, methyl alcohol=56.2%, water=41.0%.
Go out the gas-phase product flow 4880Nm of washing tower
3/ h, mole consists of: methyl nitrite=15.3%, NO=5.0%, CO=8.1%, N
2=67.0%, methyl alcohol=4.5%.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%.
Oxygen flow 1246Nm
3/ h, purity is 99.8%, and all the other are N
2, point four section feedings,
Esterifier diameter is 2.6m, and height 20.5m, adopt packing tower form, have four sections of fillers, packed height is respectively 3/3/3/4m, and reactor head pressure-controlling is at 0.25MPag.
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 the temperature of esterifier tower reactor controls at 45 DEG C.
Washing tower diameter is 2.6m, and height 13.6m, adopts packing tower form, divides two sections, every section of 4m.
Esterifier tower reactor arranges 6.4m outward
3the liquid of/h, weight consists of: methyl nitrite=1.2%, nitric acid=1.6%, methyl alcohol=56.5%, water=40.7%.
Go out the gas-phase product flow 48550Nm of washing tower
3/ h, mole consists of: methyl nitrite=15.1%, NO=5.2%, CO=8.2%, N
2=67.4%, 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 washing tower 5, fresh methanol directly enters esterifier 1, 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 3], esterifier is changed into countercurrent flow operation as shown in Figure 2, identical with Fig. 1 of the equipment in Fig. 2, logistics numbering.
Go out the gas-phase product flow 48800Nm of washing tower
3/ h, mole consists of: methyl nitrite=15.2%, NO=5.0%, CO=8.1%, N
2=66.8%, methyl alcohol=4.9%.Wherein the content of water and nitric acid is all lower than 0.01%.
The diameter of esterifier 1 needs 4.2m, considerably increases the investment cost of equipment.
Esterifier tower reactor arranges 6.4m outward
3the liquid of/h, weight consists of: methyl nitrite=1.2%, nitric acid=1.7%, methyl alcohol=56.9%, water=40.2%.
Claims (10)
1. synthesize a method for alkyl nitrite, comprise the following steps:
1) gas of nitrogen-containing oxide, oxygen and first strand of alkyl alcohol enter esterifier, flow through described reactor from top to down, and gas and liquid flowing contact reacts obtains gaseous stream at the bottom of the tower reactor liquid phase stream containing alkyl alcohol and the tower containing alkyl nitrite;
2) by the described tower reactor liquid phase stream containing alkyl alcohol of circulation approach circulation: discharge the described tower reactor liquid phase stream containing alkyl alcohol from the bottom of esterifier, the tower reactor liquid phase stream that cooling is discharged, then the tower reactor liquid phase stream of cooling is back to esterifier top, makes the liquid phase stream returned be downward through esterifier thus;
3) the described tower spirit phases containing alkyl nitrite flows to the bottom into washing tower, with the second burst of alkyl alcohol counter current contact entered from washing tower top, the washings that wash tower bottoms obtains enters esterifier top, and washing tower top obtains alkyl nitrite product stream.
2. synthesize the method for alkyl nitrite according to claim 1, it is characterized in that the gas of described nitrogen-containing oxide contains the nitrogen protoxide of 1 ~ 50 % by mole.
3. synthesize the method for alkyl nitrite according to claim 1, it is characterized in that the gas of described nitrogen-containing oxide is provided by the method preparing oxalic acid alkyl ester.
4. synthesize the method for alkyl nitrite according to claim 1, it is characterized in that the ratio control containing alkyl alcohol amount in the tower reactor liquid phase stream of alkyl alcohol of second burst of alkyl alcohol inlet amount and described circulation is in 1:(2 ~ 100);
Entering nitric oxide production mol ratio in the alkyl alcohol of esterifier and the gas of nitrogen-containing oxide is (1 ~ 100): 1.
5. synthesize the method for alkyl nitrite according to claim 1, it is characterized in that in the gas of oxygen and nitrogen-containing oxide, nitric oxide production mol ratio is 1:(4 ~ 12).
6. synthesize the method for alkyl nitrite according to claim 1, it is characterized in that in circulation step, the cooled temperature of tower reactor liquid phase stream containing alkyl alcohol of described circulation controls at 0 ~ 60 DEG C.
7. synthesize the method for alkyl nitrite according to claim 1, what it is characterized in that a part discharges bottom esterifier releases from circulation approach containing the tower reactor liquid phase stream of alkyl alcohol, and the tower reactor liquid phase stream containing alkyl alcohol of the discharge of the rest part Posterior circle that is cooled is back to esterifier top; The tower bottoms phase logistics capacity containing alkyl alcohol of described releasing accounts for 0.5 ~ 20 % by mole of the tower bottoms phase logistics capacity containing alkyl alcohol of described circulation.
8. synthesize the method for alkyl nitrite according to claim 1, it is characterized in that in esterifier, temperature is 0 ~ 90 DEG C, pressure counts 0 ~ 0.6MPa with gauge pressure.
9. synthesize the method for alkyl nitrite according to claim 1, it is characterized in that esterifier is built with 1 ~ 8 section of filler; Oxygen adopts sectional feeding, hop count 1 ~ 8 section.
10. synthesize the method for alkyl nitrite according to claim 1, it is characterized in that alkyl nitrite is methyl nitrite, alkyl alcohol is methyl alcohol.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112759518A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Treatment method and system for byproduct nitric acid in process of preparing ethylene glycol from synthesis gas |
| CN113648959A (en) * | 2021-08-30 | 2021-11-16 | 江苏永大化工机械有限公司 | Circulating esterification tower |
| CN114853611A (en) * | 2022-05-16 | 2022-08-05 | 华中科技大学 | Method for treating biomass pyrolysis gas |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898311A (en) * | 2012-10-12 | 2013-01-30 | 上海焦化有限公司 | Method and equipment for continuously producing methyl nitrite |
-
2014
- 2014-07-03 CN CN201410314417.5A patent/CN105218374A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898311A (en) * | 2012-10-12 | 2013-01-30 | 上海焦化有限公司 | Method and equipment for continuously producing methyl nitrite |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2020103556A1 (en) * | 2018-11-20 | 2020-05-28 | 上海浦景化工技术股份有限公司 | Nitric acid reduction conversion process |
| AU2019382545B2 (en) * | 2018-11-20 | 2022-03-10 | Pujing Chemical Industry Co., Ltd | Nitric acid reduction 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 |
| CN112759518A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Treatment method and system for byproduct nitric acid in process of preparing ethylene glycol from synthesis gas |
| CN112759518B (en) * | 2019-10-21 | 2023-04-07 | 中国石油化工股份有限公司 | Treatment method and system for byproduct nitric acid in process of preparing ethylene glycol from synthesis gas |
| CN113648959A (en) * | 2021-08-30 | 2021-11-16 | 江苏永大化工机械有限公司 | Circulating esterification tower |
| CN114853611A (en) * | 2022-05-16 | 2022-08-05 | 华中科技大学 | Method for treating biomass pyrolysis gas |
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Application publication date: 20160106 |