CN111269127A - Nitric acid purification process and device for methyl nitrite regeneration section - Google Patents
Nitric acid purification process and device for methyl nitrite regeneration section Download PDFInfo
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- C07C201/04—Preparation of esters of nitrous acid
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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Abstract
The invention relates to a novel nitric acid replenishment purification process and a device matched with a Methyl Nitrite (MN) regeneration section in a coal-to-ethylene glycol process, which utilize a jet type collision flow reaction purification device, spray and atomize esterification residual liquid containing nitric acid in a purification tower in multiple stages, perform an enhanced reaction with circulating gas from the shunting of a dimethyl oxalate (DMO) synthesis ring, gradually degrade the nitric acid in the purification tower to below 0.2 percent (mass fraction), and increase the concentration of MN in outlet gas to 8-13 percent and return the concentration to the DMO synthesis ring. Compared with the currently adopted single-stage kettle type nitric acid replenishing process, nitric acid concentration process and catalytic nitric acid reduction process, the method has the advantages of short process, small occupied area, low investment and low consumption, and has very obvious effects of resource recovery and emission reduction.
Description
Technical Field
The invention belongs to the technical field of energy-saving technology and novel high-efficiency equipment of a new process in coal chemical industry, relates to a novel nitric acid layer-by-layer degradation purification technology, and particularly relates to a nitric acid supply purification process and a nitric acid supply purification device matched with a Methyl Nitrite (MN) regeneration section in a process of preparing ethylene glycol from coal.
Background
The major utilization of alcohols (such as methanol) and NO in the current large-scale industrial coal-to-ethylene glycol process route2Methyl Nitrite (MN) is generated through reaction, the MN is oxidized and coupled on a palladium (Pd) catalyst to obtain dimethyl oxalate (DMO), and Ethylene Glycol (EG) is obtained through catalytic hydrogenation. Among them, the Methyl Nitrite (MN) regeneration section plays a very critical role in the whole process, and its core reaction equipment is often called an esterification column, "diester column" or "triester column". N generated in the reaction process is discharged intermittently in MN regeneration equipment2O by-product gas, in order to compensate for the nitrogen oxide loss, part of nitric acid is added into the system in the prior art to generate enough NO and NO2The addition of nitric acid is mainly completed by a multistage reaction kettle or a tower and other equipment.
The concentration and the amount of the liquid of the kettle liquid from the MN esterification tower can be different according to the used process, and the concentration of the nitric acid contained in the kettle liquid also has difference. If the amount of methanol added into the system is larger, the amount of the kettle liquid is larger, and the concentration of nitric acid is lower and is approximately 1.5-4%; the amount of methanol is small, the amount of the kettle liquid is small, and the concentration of nitric acid is higher and reaches 4-7%. The kettle liquid and the added nitric acid react with the circulating gas shunted by the DMO synthesis ring in the kettle, and the main reaction formula is as follows: main reaction HNO3+2NO+3CH3OH→3CH3ONO(MN)+2H2O; side reaction HNO3+CO+CH3OH→CH3ONO(MN)+CO2+H2O, through these two reactions, nitric acid purification and MN regeneration are achieved. However, in the acid-containing wastewater after the residual liquid after the reaction is evaporated to remove methanol, if the content of nitric acid is more than 0.4%, neutralization treatment with alkaline solution is required, which wastes nitric acid and alkaline solution resources and causes an increase in treatment cost. Taking a device for producing 20 ten thousand tons of ethylene glycol per year in the A process as an example, the kettle liquid entering a nitric acid reduction system is about 6-10 m3A concentration of 0.5 to e,/h (mass concentration of nitric acid about 5 to 7%, 50% methanol, 20 to 30% water), and a concentration of nitric acid in the effluent0.8 percent, and the content of nitric acid in the wastewater after the methanol is steamed reaches 1 to 1.5 percent; taking a device for producing 20 ten thousand tons of ethylene glycol per year in the process B as an example, the kettle liquid entering a nitric acid reduction system is about 30-50 m3The concentration of nitric acid in the initial discharge liquid is generally 0.2-0.3% per hour (the mass concentration of nitric acid is about 1.5-3%, methanol is 60-80%, and water is 10-15%). Although the latter seems to be low in concentration, the total amount of nitric acid is not low due to the large treatment amount of the raw material liquid, and the acid concentration in the wastewater rapidly rises far above the emission limit after the methanol is recovered by distillation, and more methanol needs to be recovered by evaporation due to the large liquid amount, so that the power consumption and the steam consumption are higher.
The nitric acid supplemented in the regeneration process of MN adopts a reaction kettle stirring and dripping nitric acid process in the early stage, and in order to meet sufficient reaction retention time, more than 3 nitric acids with the capacity of 30-100 m are needed by only 5 ten thousand tons of devices3The reaction kettles are completed together, so that the floor area is large, the space utilization rate is low, the equipment investment is high, the control is unstable, and the gap between the stirring shaft and the reaction kettle is easy to leak and even explode; meanwhile, the large-capacity reaction kettle has remarkable amplification effect and uneven mixing reaction, which all result in low efficiency and high discharge of the nitric acid supply purification device. Later, a technical route of concentrating nitric acid and steaming methanol under a vacuum system is adopted, the concentration of the nitric acid in the wastewater can reach below 0.1%, but a large amount of steam and electricity consumption are consumed, about 20-25 tons of steam are consumed in each hour on the scale of only 20 ten thousand tons, and the cost is high. At present, the widely adopted method is a nitric acid catalytic reduction method, and a solid-phase catalyst is used for degrading and purifying nitric acid in a fixed bed tower type device. However, in the actual production process, the nitric acid catalytic reduction method is easy to generate trace amino impurities due to over reduction of nitric acid by the catalyst, so that the quality of the final EG product is influenced, the activated carbon carrier in the catalyst is slowly broken along with the use time, secondary carbon black wastewater is generated and is difficult to treat, and in addition, the performance of the catalyst is gradually reduced in the process, the service life is short, and the cost is high.
The invention provides a novel nitric acid purification process scheme and a novel nitric acid purification device matched with a Methyl Nitrite (MN) regeneration section in a coal-to-ethylene glycol process, which are based on the principle that injection type collision flow reaction purification equipment is utilized, esterification residual liquid containing nitric acid is injected and atomized in a purification tower in multiple stages and is subjected to enhanced reaction with circulating gas from DMO synthesis ring shunting, the nitric acid in the esterification residual liquid is gradually degraded to be below 0.2 percent (mass fraction), and meanwhile, the concentration of MN in outlet gas is increased to 6-13 percent and returns to the DMO synthesis ring. Compared with the currently adopted single-stage kettle type nitric acid replenishing process, nitric acid evaporation concentration process and nitric acid catalytic reduction process, the method has the advantages of short process, small occupied area, low investment and energy consumption, and has very obvious effects of resource recovery, energy conservation and emission reduction.
Disclosure of Invention
The invention relates to a novel nitric acid purification process and a novel nitric acid purification device, and aims to solve the problems that nitric acid purification tail liquid at a regeneration section of Methyl Nitrite (MN) exceeds the standard, equipment investment is large, occupied area is large, treatment energy consumption is high, operation is unstable, product quality is easily influenced and the like in the existing process of preparing ethylene glycol from coal.
In order to achieve the purpose, the invention adopts the following technical scheme:
a novel nitric acid purification process and a device matched with a Methyl Nitrite (MN) regeneration section in a process of preparing ethylene glycol from coal comprise: gas-liquid reaction equipment, gas-liquid inlet and outlet, retention plate and liquid-phase jet atomizer. It is characterized in that 1 or more stay plates are distributed on the main body part of the gas-liquid reaction equipment, and a liquid phase jet atomizer is arranged above the stay plates or between the stay plates; the middle and upper parts of the gas-liquid reaction equipment are provided with a liquid phase inlet and a gas phase outlet; the lower part of the gas-liquid reaction equipment is provided with a gas phase inlet, and the lower part or the bottom of the gas-liquid reaction equipment is provided with a liquid phase outlet; the upper part of the gas-liquid reaction device is provided with a certain space which is a gas-liquid separation area.
Further, the gas-liquid reaction equipment can be a tower reactor, or a reaction kettle or a reaction tank can be adopted, and the tower reactor is preferentially used.
Further, the number of the gas-liquid reaction equipment is 1, and 2 or more gas-liquid reaction equipment can be adopted to carry out series or parallel operation.
Furthermore, the gas-phase material is preferably introduced into the liquid phase at the bottom by a pipeline for bubbling feeding, or directly enters into the reaction equipment by a pipeline, or is conveyed by a gas distributor.
Furthermore, different types of tower plates can be used as the stay plates, and the spacing between the stay plates is 0.3-1.5 m, preferably 0.5-0.8 m.
Further, the liquid phase spray atomizer is a shaped conduit, a liquid flow channel, or a combination thereof.
Further, the liquid phase spray atomizer can be continuously installed in each layer of the gas-liquid reaction zone step by step, and can also be intermittently installed in a part of the gas-liquid reaction zone step by step.
Further, when the liquid phase spray atomizer is installed in a stepwise intermittent manner, the liquid phase spray atomizer may be arranged at equal intervals or may be arranged at unequal intervals.
Furthermore, a demister can be arranged in the upper separation area of the gas-liquid reaction equipment or not.
The invention enhances the gas-liquid contact reaction by forming jet type collision flow, sprays and atomizes esterification residual liquid containing nitric acid in a purification tower in multiple stages, and enhances the reaction with circulating gas from DMO synthesis ring shunt, so as to degrade the nitric acid in the esterification residual liquid to below 0.2 percent (mass fraction) step by step. Compared with the currently adopted single-stage kettle type nitric acid replenishing process, nitric acid evaporation concentration process and nitric acid catalytic reduction process, the method has the advantages of short process, small occupied area, low investment and energy consumption, and has very obvious effects of resource recovery, energy conservation and emission reduction.
The invention also provides a process for purifying nitric acid by adopting the device, which comprises the following steps:
liquid phase materials enter from a liquid phase feed inlet on the reaction equipment and flow downwards, gas phase materials enter the equipment from the lower part of the reaction equipment in a bubbling or gas distributor mode and flow upwards, and gas and liquid phases are contacted and mixed on a retention plate and react; after the liquid flows to the bottom of the bottom reaction equipment, most of the liquid is sent into the liquid phase jet atomizer between the stay plates after heat exchange through the heat exchanger by the circulating pump, is jetted at high speed between the stay plates and is further contacted and reacted with the rising gas phase, and the gas phase material further rises to the separation zone and is separated from the entrained liquid and then is extracted through the gas phase outlet.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
(1) the purification process of the nitric acid matched with the MN regeneration section provided by the invention has the advantages of short flow, small occupied area of equipment, less investment, low energy consumption, easily controlled process and convenient operation, effectively realizes resource recovery, energy conservation and emission reduction, and has better industrial popularization and application values.
(2) The nitric acid purification process and the equipment provided by the invention have the advantages that the gas-liquid reaction process is enhanced through the spray atomization and the collision flow reaction, and meanwhile, the graded degradation design is adopted, so that the conversion rate of the nitric acid in the raw materials is greatly improved. The catalyst is not needed to be used in the process, the processes such as catalyst replacement and the like are omitted, the equipment structure and operation are simpler and more stable, and the automatic control is easy to realize. Meanwhile, as no amino byproducts exist, the quality of the final product EG can be effectively ensured.
(3) The nitric acid purification process and the nitric acid purification equipment provided by the invention have the advantages of wide treatment load range, small occupied area and high space utilization rate, and the reaction stage number can be adjusted according to the actual raw material quantity. The nitric acid content in the effluent directly meets the discharge standard, so that a rear-end neutralization treatment or evaporation concentration working section is omitted, the environmental protection of the whole process is improved, and the energy consumption and the treatment cost are greatly reduced. Therefore, the invention has important significance for improving the MN regeneration section in the domestic process of preparing the ethylene glycol from the coal and even the technical performance and the environmental protection performance of the whole industry of preparing the ethylene glycol from the coal.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings required to be used in the technical description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention application, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic view of a gas-liquid reaction apparatus according to the present invention.
Wherein, T1 is a gas-liquid reaction tower, A1 is a gas-liquid separation zone, A2 is a gas-liquid reaction zone, A3 is a gas-phase distribution zone or a bubbling zone, I1 is a liquid-phase inlet, I2 is a gas-phase inlet, O1 is a gas-phase outlet, O2 is a liquid-phase outlet, P1 is a circulating pump, E1 is a heat exchanger, B1 is a retention plate, and B2 is a liquid-phase jet atomizer.
Fig. 2 is a side view of the spray of a liquid spray atomizer.
FIG. 3 is a diagram showing the distribution effect of liquid sprayed onto the surface of a residence plate by a liquid-phase spray atomizer.
Fig. 4 to 7 are diagrams illustrating the distribution effect of the piping and nozzles of several different types of liquid phase spray atomizers, respectively.
Detailed Description
The embodiment of the application provides a novel nitric acid purification process and device matched with a Methyl Nitrite (MN) regeneration section in a coal-to-ethylene glycol process.
In order to make the technical solutions in the present application better understood by those skilled in the art, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are only a part of embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, shall fall within the scope of the present invention.
Example 1
A novel nitric acid purification process and a device matched with a Methyl Nitrite (MN) regeneration section in a process of preparing ethylene glycol from coal comprise: gas-liquid reaction equipment, gas-liquid inlet and outlet, retention plate and liquid-phase jet atomizer.
The gas-liquid reaction equipment is 1 tower reactor.
The gas phase material enters the liquid phase through a gas phase distribution pipe at the lower part of the reaction tower and forms bubbles.
The stay plate adopts sieve mesh tower plates, and the plate interval is 0.5 m.
The liquid phase spray atomizer adopts a parallel pipe (figure 4) distribution mode, and a series of liquid spray holes are uniformly formed on the pipe.
The liquid phase jet atomizer is arranged in the gas-liquid reaction area in a separation layer mode.
A demister is arranged in the gas-liquid separation zone at the upper part of the gas-liquid reaction equipment.
The bottom of the gas-liquid reaction equipment is provided with a circulating pump, liquid in the tower is pumped out and then sent into a heat exchanger for heat exchange and temperature reduction, and then the liquid is sent into a liquid phase jet atomizer.
The heat exchanger is a tube type heat exchanger.
The reactor is operated at normal pressure, and the treatment capacity of liquid-phase materials is 20m3The mass concentration of the main components is about: 4.3% of nitric acid, 56% of methanol and 15% of water, wherein the total number of the nitric acid, the methanol and the water is 20 tower plates and 10 liquid-phase jet atomizers, liquid-phase materials enter a reaction tower from the uppermost liquid-phase jet atomizer, gas from a DMO synthesis loop enters the tower bottom and bubbles in tower bottom liquid, the reaction temperature in the tower is room temperature, about 80% of tower bottom liquid is pumped out by a circulating pump, the temperature of the tower bottom liquid is controlled within the range of 65-70 ℃ through heat exchange of a heat exchanger, then the tower bottom liquid is sent into each stage of liquid-phase jet atomizer, about 20% of the tower bottom liquid is extracted and discharged, the concentration of the nitric acid is reduced to 0.14%, and the content of MN in a top outlet gas phase is about.
Example 2
A novel nitric acid purification process and a device matched with a Methyl Nitrite (MN) regeneration section in a process of preparing ethylene glycol from coal comprise: gas-liquid reaction equipment, gas-liquid inlet and outlet, retention plate and liquid-phase jet atomizer.
The gas-liquid reaction equipment is 1 tower reactor.
The gas phase material enters the tower through a gas distributor through the gas phase at the lower part of the reaction tower.
The stay plate adopts a floating valve tower plate, and the distance between the plates is 0.65 m.
The liquid phase spray atomizer adopts a cross annular (figure 6) distribution form, and a series of liquid spray holes are uniformly formed on the tube.
The liquid phase jet atomizer is continuously arranged in each layer of the gas-liquid reaction area.
A demister is arranged in the gas-liquid separation zone at the upper part of the gas-liquid reaction equipment.
The bottom of the gas-liquid reaction equipment is provided with a circulating pump, liquid in the tower is pumped out and then sent into a heat exchanger for heat exchange and temperature reduction, and then the liquid is sent into a liquid phase jet atomizer.
The heat exchanger is a tube type heat exchanger.
The reactor is operated at normal pressure, and the treatment capacity of liquid-phase materials is 15m3The mass concentration of the main components is about: 6% of nitric acid, 50% of methanol and 20% of water, wherein the total number of the nitric acid, the methanol and the water is 10 tower plates and 10 liquid phase jet atomizers, liquid phase materials enter a reaction tower from the uppermost liquid phase jet atomizer, gas from a DMO synthesis ring enters the reaction tower from a bottom gas distributor, the reaction temperature in the tower is controlled to be below 80 ℃, about 85% of liquid in a tower kettle is pumped out by a circulating pump, the temperature of the liquid in the tower kettle is controlled to be within the range of 75-80 ℃ through heat exchange of a heat exchanger, then the liquid phase materials are sent into each stage of liquid phase jet atomizer, about 15% of the tower kettle liquid is extracted and discharged, the concentration of the nitric acid is reduced to 0.1%, and the content of MN in a top outlet gas phase.
While the present application has been described with reference to embodiments, those skilled in the art will appreciate that there are numerous variations and permutations of the present application without departing from the spirit of the application, and it is intended that the appended claims encompass such variations and modifications without departing from the spirit of the application.
Claims (10)
1. A novel nitric acid purification process and a device matched with a Methyl Nitrite (MN) regeneration section in a process of preparing ethylene glycol from coal comprise: gas-liquid reaction equipment, gas-liquid inlet and outlet, retention plate and liquid-phase jet atomizer. It is characterized in that 1 or more stay plates are distributed on the main body part of the gas-liquid reaction equipment, and a liquid phase jet atomizer is arranged above the stay plates or between the stay plates; the middle and upper parts of the gas-liquid reaction equipment are provided with a liquid phase inlet and a gas phase outlet; the lower part of the gas-liquid reaction equipment is provided with a gas phase inlet, and the lower part or the bottom of the gas-liquid reaction equipment is provided with a liquid phase outlet; the upper part of the gas-liquid reaction device is provided with a certain space which is a gas-liquid separation area.
2. The process and apparatus for purifying nitric acid according to claim 1, wherein the gas-liquid reaction equipment is a tower reactor, or a reaction kettle or tank, preferably a tower reactor.
3. The novel nitric acid purification process and apparatus of claim 1, wherein the number of gas-liquid reaction units is 1, and 2 or more units may be used in series or in parallel.
4. A novel nitric acid purification process and apparatus as claimed in claim 1, wherein the gaseous material is preferably bubbled into the liquid phase at the bottom through a pipeline, or directly enters the reaction equipment through a pipeline, or is transported by a gas distributor.
5. A novel nitric acid purification process and apparatus according to claim 1, wherein said stay plates are adapted to use different types of trays with a spacing of 0.3 to 1.5m, preferably 0.5 to 0.8 m.
6. The novel nitric acid purification process and apparatus of claim 1, wherein said liquid phase spray atomizer is a shaped pipe, a liquid flow trough or a combination thereof.
7. The novel nitric acid purification process and apparatus of claim 1, wherein the liquid phase spray atomizer is installed in each layer of the gas-liquid reaction zone continuously in stages or in part of the gas-liquid reaction zone intermittently in stages.
8. A liquid phase spray atomizer according to claim 7, wherein said liquid phase spray atomizers are arranged in a stepwise intermittent manner, and are arranged at equal or unequal intervals.
9. The process and apparatus for purifying nitric acid as claimed in claim 1, wherein a demister may or may not be provided in the upper separation zone of the gas-liquid reaction apparatus.
10. The novel nitric acid purification process of any one of claims 1 to 9, comprising the steps of:
liquid phase materials enter from a liquid phase feed inlet on the reaction equipment and flow downwards, gas phase materials enter the equipment from the lower part of the reaction equipment in a bubbling or gas distributor mode and flow upwards, and gas and liquid phases are contacted and mixed on a retention plate and react; after the liquid flows to the bottom of the bottom reaction equipment, most of the liquid is sent into the liquid phase jet atomizer between the stay plates after heat exchange through the heat exchanger by the circulating pump, is jetted at high speed between the stay plates and is further contacted and reacted with the rising gas phase, and the gas phase material further rises to the separation zone and is separated from the entrained liquid and then is extracted through the gas phase outlet.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113648959A (en) * | 2021-08-30 | 2021-11-16 | 江苏永大化工机械有限公司 | Circulating esterification tower |
| CN114288835A (en) * | 2021-12-02 | 2022-04-08 | 赛鼎工程有限公司 | Structure and method for improving oxidation degree and efficiency in 65% -68% high-concentration dilute acid preparation process |
| CN114768700A (en) * | 2022-03-31 | 2022-07-22 | 中国神华煤制油化工有限公司 | Nitric acid reduction device and method for reducing nitric acid |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103007842A (en) * | 2012-12-26 | 2013-04-03 | 安阳盈德气体有限公司 | Methyl nitrite synthesis reactor |
| CN104324587A (en) * | 2014-09-26 | 2015-02-04 | 常州友达环保科技有限公司 | Thin-hole sieve-plate-typed bubble column |
| CN106563394A (en) * | 2015-10-12 | 2017-04-19 | 中国石油化工股份有限公司 | Gas-liquid distributor, trickle-bed reactor and gas-liquid reaction method |
| CN106565495A (en) * | 2015-10-12 | 2017-04-19 | 中国石油化工股份有限公司 | Method for producing methyl nitrite |
| CN106588667A (en) * | 2015-10-20 | 2017-04-26 | 上海华谊能源化工有限公司 | Regeneration process and regeneration device system of methyl nitrite in process for preparation of ethylene glycol from synthesis gas |
| CN106669583A (en) * | 2017-02-21 | 2017-05-17 | 南京大学 | Nitric acid purification device and process for treating MN regeneration tower bottom solution |
| CN206731083U (en) * | 2017-04-28 | 2017-12-12 | 宁波中科远东催化工程技术有限公司 | A kind of synthesis gas preparing ethylene glycol technique nitrate reductase purifying column |
| CN109456197A (en) * | 2018-10-26 | 2019-03-12 | 新疆天智辰业化工有限公司 | A kind of method that low concentration nitric acid solution recycles in calcium carbide stove exhaust preparing ethylene glycol |
| CN110773085A (en) * | 2019-11-07 | 2020-02-11 | 浙江工业大学 | Gas-liquid reactor |
-
2020
- 2020-04-23 CN CN202010141855.1A patent/CN111269127A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103007842A (en) * | 2012-12-26 | 2013-04-03 | 安阳盈德气体有限公司 | Methyl nitrite synthesis reactor |
| CN104324587A (en) * | 2014-09-26 | 2015-02-04 | 常州友达环保科技有限公司 | Thin-hole sieve-plate-typed bubble column |
| CN106563394A (en) * | 2015-10-12 | 2017-04-19 | 中国石油化工股份有限公司 | Gas-liquid distributor, trickle-bed reactor and gas-liquid reaction method |
| CN106565495A (en) * | 2015-10-12 | 2017-04-19 | 中国石油化工股份有限公司 | Method for producing methyl nitrite |
| CN106588667A (en) * | 2015-10-20 | 2017-04-26 | 上海华谊能源化工有限公司 | Regeneration process and regeneration device system of methyl nitrite in process for preparation of ethylene glycol from synthesis gas |
| CN106669583A (en) * | 2017-02-21 | 2017-05-17 | 南京大学 | Nitric acid purification device and process for treating MN regeneration tower bottom solution |
| CN206731083U (en) * | 2017-04-28 | 2017-12-12 | 宁波中科远东催化工程技术有限公司 | A kind of synthesis gas preparing ethylene glycol technique nitrate reductase purifying column |
| CN109456197A (en) * | 2018-10-26 | 2019-03-12 | 新疆天智辰业化工有限公司 | A kind of method that low concentration nitric acid solution recycles in calcium carbide stove exhaust preparing ethylene glycol |
| CN110773085A (en) * | 2019-11-07 | 2020-02-11 | 浙江工业大学 | Gas-liquid reactor |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113648959A (en) * | 2021-08-30 | 2021-11-16 | 江苏永大化工机械有限公司 | Circulating esterification tower |
| CN113648959B (en) * | 2021-08-30 | 2023-04-07 | 江苏永大化工机械股份有限公司 | Circulating esterification tower |
| CN114288835A (en) * | 2021-12-02 | 2022-04-08 | 赛鼎工程有限公司 | Structure and method for improving oxidation degree and efficiency in 65% -68% high-concentration dilute acid preparation process |
| CN114768700A (en) * | 2022-03-31 | 2022-07-22 | 中国神华煤制油化工有限公司 | Nitric acid reduction device and method for reducing nitric acid |
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