CN104860276B - Method for reducing dilute nitric acid to nitrous acid - Google Patents
Method for reducing dilute nitric acid to nitrous acid Download PDFInfo
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- CN104860276B CN104860276B CN201410062618.0A CN201410062618A CN104860276B CN 104860276 B CN104860276 B CN 104860276B CN 201410062618 A CN201410062618 A CN 201410062618A CN 104860276 B CN104860276 B CN 104860276B
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- nitrous acid
- nitric acid
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- dust technology
- dilute nitric
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Abstract
The invention relates to a method for reducing dilute nitric acid to nitrous acid; in a coal-to-ethylene glycol process, a large amount of dilute nitric acid waste liquid can be produced, is discharged after NaOH neutralization, and can pollute water resources. According to the method for reducing dilute nitric acid to nitrous acid, a reaction is continuously carried out in a fixed bed reactor under normal pressure; under the catalytic action, in an N2 atmosphere and at a temperature of 30-100 DEG C, dilute nitric acid is reduced to nitrous acid; and nitrous acid can be further participated in the coal-to-ethylene glycol process. The process not only can improve economic benefits, but also lowers pollution to the water resources.
Description
Technical field
The invention belongs to coal chemical technology, the dilute nitre that specifically will produce during Coal Chemical Industry
Acid waste liquid reverts to nitrous acid, and nitrous acid further participates in reaction, reduces discharging of waste liquid.
Background technology
Ethylene glycol is a kind of important industrial chemicals, is mainly used as solvent, antifreezing agent and synthesis
The raw material of polyester resin etc..At present, ethylene glycol mainly uses oxirane direct hydration method to prepare.
Owing to the preparation of oxirane is with ethylene as raw material, a large amount of production depends on petroleum resources.
And the total energy of China is characterized as rich coal, has gas, few oil, it is therefore second two by coal Efficient Conversion
The industrial chemicals such as alcohol, reduce the industrial chemicals dependence to petroleum resources, be conducive to optimizing the energy,
Resource structures, has great importance.
During coal-ethylene glycol, substantial amounts of dust technology waste liquid can be produced.Current process side
Method is, the NaOH adding metering neutralizes, and then directly will arrange containing the waste liquid of a large amount of sodium nitrates
Put, cause the pollution of water resource.Because while human body is safe from harm by nitrate itself, but nitre
After hydrochlorate absorption human body, the effect lower part at reductive bacterium is reduced into nitrite.Nitrous
Hydrochlorate easily reacts formation metahemoglobin with the hemoglobin in blood, thus affects blood
Transmittability to oxygen.Therefore, how by dust technology waste liquid Appropriate application, it is coal-ethylene glycol
During, concern the important engineering of people's livelihood safe drinking water.
Dust technology is reduced to nitrous acid, and nitrous acid can further participate in coal-ethylene glycol
During go, can not only turn waste into wealth, increase economic efficiency, and can effectively reduce containing nitre
The discharge of acid waste liquor of sodium, reduces the pollution to water resource.
Summary of the invention
A kind of dust technology method to nitrous acid of reducing, under normal pressure in fixed bed reactors continuously
React, under catalytic action, at N2Under atmosphere, dust technology is reverted to by 30-100 DEG C
Nitrous acid.The nitrous acid generated goes during can further participating in coal ethanol.Therefore
Dust technology reverts to nitrous acid can not only increase economic efficiency, and discharging of waste liquid pair can be reduced
The pollution of water resource.
The concentration of described dust technology is 1-5wt%.
Described catalyst is the metal-oxide CeO with redox property2、ZrO2、
Co3O4、MoO3、MnO2、V2O5In one or two or more kinds.
Reactor uses fixed bed reactors, described in there is the metal-oxide of redox property,
Before using through tabletting, pulverize, processs of sieving, selection particle diameter is the granule of 20-30 mesh, makes
With front, 300-600 DEG C of H2Reductase 12-10h.The oxide reduction dust technology being in reduction-state arrives
Nitrous acid, and self is oxidized.It is thus desirable to after intervals, by gas circuit by N2Cut
It is changed to H2, by catalyst again reducing/regenerating.
Described dust technology reverts to the optimization reaction temperature of nitrous acid and is 50-80 DEG C.
The present invention uses continuous reaction, uses fixed-bed reactor, reduces catalyst and product
The separating step of thing.Whole course of reaction is at normal pressure N2Or H2Under carry out, greatly reduce
Requirement to equipment, has the biggest prospects for commercial application.
Accompanying drawing explanation
Fig. 1 fixed bed reactors device.
Wherein, 1. hydrogen cylinder；2. nitrogen cylinder；3. three-way valve；4. dust technology feed pump；5.
Reduction reaction tower；6. nitrous acid fluid reservoir；7. waste gas absorption tank.
Detailed description of the invention
As it is shown in figure 1, it is the process chart of the present invention；
Described dust technology reverts to nitrite reaction to be carried out, by grain on fixed-bed reactor
Footpath is that 20-30 mesh has the metal oxide catalyst of oxidizing property and joins glass pipe type reaction
In device, silicon oxide bead (preheating material), under-filled rustless steel are filled in the top of catalyst
Silk (support catalyst layer).Under hydrogen atmosphere, by 300-600 DEG C of reductase 12-10h of catalyst；
Under nitrogen atmosphere, reaction unit is heated to uniform temperature, adds dilute nitric acid solution with dosing pump.
Wherein said reaction temperature is 30-100 DEG C, optimizes reaction temperature and is 50-80 DEG C, and pressure is
Normal pressure.Ionic liquid chromatography analyzes nitric acid and the content of nitrous acid in effluent, and calculates nitric acid
Conversion ratio and the selectivity of nitrous acid.
Below by way of example, the present invention is further described (in example, agents useful for same is
Analytical pure), it should be noted that the following examples are used only as illustrating, in the present invention
Appearance is not limited thereto.
Embodiment 1
By the 5g CeO that particle diameter is 20-30 mesh2Catalyst loads the glass of a diameter of 15mm
In pipe reactor, under hydrogen atmosphere, 400 DEG C of reduction 5h.Then switch to nitrogen atmosphere, use
Dosing pump adds 1wt% dilute nitric acid reaction liquid, and reaction temperature is 40 DEG C, and WHSV is 1.2h-1,
Reduction reaction is carried out under normal pressure blanket of nitrogen.The conversion ratio of nitric acid is 90%, the selection of nitrous acid
Property is 95%.
Embodiment 2
By the 5g ZrO that particle diameter is 20-30 mesh2Catalyst loads the glass of a diameter of 15mm
In pipe reactor, under hydrogen atmosphere, 450 DEG C of reduction 8h.Then switch to nitrogen atmosphere, use
Dosing pump adds 2wt% dilute nitric acid reaction liquid, and reaction temperature is 60 DEG C, and WHSV is 1.5h-1,
Reduction reaction is carried out under normal pressure blanket of nitrogen.The conversion ratio of nitric acid is 88%, the selection of nitrous acid
Property is 97%.
Embodiment 3
By the 5g MoO that particle diameter is 20-30 mesh3Catalyst loads the glass of a diameter of 15mm
In pipe reactor, under hydrogen atmosphere, 390 DEG C of reduction 4h.Then switch to nitrogen atmosphere, use
Dosing pump adds 2wt% dilute nitric acid reaction liquid, and reaction temperature is 100 DEG C, and WHSV is 2.0h-1,
Reduction reaction is carried out under normal pressure blanket of nitrogen.The conversion ratio of nitric acid is 96%, the selection of nitrous acid
Property is 90%.
Embodiment 4
By the 5g V that particle diameter is 20-30 mesh2O5Catalyst loads the glass of a diameter of 15mm
In pipe reactor, under hydrogen atmosphere, 550 DEG C of reduction 10h.Then switch to nitrogen atmosphere,
Adding 5wt% dilute nitric acid reaction liquid with dosing pump, reaction temperature is 70 DEG C, and WHSV is 2.5
h-1, under normal pressure blanket of nitrogen, carry out reduction reaction.The conversion ratio of nitric acid is 85%, nitrous acid
Selectivity is 92%.
Embodiment 5
By the 5g MnO that particle diameter is 20-30 mesh2Catalyst loads the glass of a diameter of 15mm
In pipe reactor, under hydrogen atmosphere, 500 DEG C of reductase 12 h.Then switch to nitrogen atmosphere, use
Dosing pump adds 2wt% dilute nitric acid reaction liquid, and reaction temperature is 50 DEG C, and WHSV is 1.8h-1,
Reduction reaction is carried out under normal pressure blanket of nitrogen.The conversion ratio of nitric acid is 94%, the selection of nitrous acid
Property is 99%.
Embodiment 6
By the 5g Co that particle diameter is 20-30 mesh3O4Catalyst loads the glass of a diameter of 15mm
In pipe reactor, under hydrogen atmosphere, 300 DEG C of reduction 10h.Then switch to nitrogen atmosphere,
Adding 3wt% dilute nitric acid reaction liquid with dosing pump, reaction temperature is 55 DEG C, and WHSV is 1.0
h-1, under normal pressure blanket of nitrogen, carry out reduction reaction.The conversion ratio of nitric acid is 90%, nitrous acid
Selectivity is 95%.
The present invention develops a kind of dust technology method to nitrous acid of reducing, and uses fixed bed reaction
Device, catalyst can be easily separated with product, simple to operate, and reaction condition is controlled, in coal second two
Alcohol industrial process liquid waste processing link has important application prospect.
Claims (3)
1. one kind is reduced the dust technology method to nitrous acid, it is characterised in that:
In fixed bed reactors, reaction it is carried out continuously under normal pressure, under catalyst effect,
N2Atmosphere, dust technology is reverted to nitrous acid by 30-100 DEG C；
Described catalyst is the metal-oxide CeO with redox property2、ZrO2、Co3O4、
MoO3、MnO2、V2O5In one or two or more kinds；
There is the metal-oxide of redox property, before using through tabletting, pulverize, sieve
Process, the granule selecting particle diameter to be 20-30 mesh, before using, 300-600 DEG C of H2Reductase 12-10
h。
2., according to reducing the dust technology method to nitrous acid described in claim 1, its feature exists
In: the concentration of described dust technology is 1-5wt%.
3., according to reducing the dust technology method to nitrous acid described in claim 1, its feature exists
In: described dust technology reverts to the reaction temperature of nitrous acid and is 50-80 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410062618.0A CN104860276B (en) | 2014-02-21 | 2014-02-21 | Method for reducing dilute nitric acid to nitrous acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410062618.0A CN104860276B (en) | 2014-02-21 | 2014-02-21 | Method for reducing dilute nitric acid to nitrous acid |
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| CN104860276A CN104860276A (en) | 2015-08-26 |
| CN104860276B true CN104860276B (en) | 2017-01-11 |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112142600A (en) * | 2019-06-27 | 2020-12-29 | 中国科学院大连化学物理研究所 | Preparation method and application of methyl nitrite |
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2014
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Non-Patent Citations (4)
| Title |
|---|
| NO_3_与NO_2_离子氧化性的比较;刘雪静;《枣庄师专学报》;19951231(第2期);第74-75页 * |
| 亚硝酸的氧化性比稀硝酸强的研究分析;张益海等;《福州师专学报（自然科学版）》;19980930;第18卷(第1期);第39-42页 * |
| 低温选择性氮氧化物催化还原技术;王林;《赤峰学院学报（自然科学版）》;20131031;第29卷(第10期);第113-115页 * |
| 论硝酸的氧化性及还原产物;苏扬;《四川轻化工学院学报》;19960630;第12卷(第2期);第62-64页 * |
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