CN102078752A - Method for preparing sodium nitrite from nitric oxide waste gas through multistage oxidation absorption - Google Patents
Method for preparing sodium nitrite from nitric oxide waste gas through multistage oxidation absorption Download PDFInfo
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- CN102078752A CN102078752A CN201010606805.2A CN201010606805A CN102078752A CN 102078752 A CN102078752 A CN 102078752A CN 201010606805 A CN201010606805 A CN 201010606805A CN 102078752 A CN102078752 A CN 102078752A
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 65
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 title claims abstract description 20
- 230000003647 oxidation Effects 0.000 title claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 13
- 235000010288 sodium nitrite Nutrition 0.000 title claims abstract description 10
- 239000002912 waste gas Substances 0.000 title abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 49
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 85
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 74
- 235000019391 nitrogen oxide Nutrition 0.000 claims description 31
- 239000003513 alkali Substances 0.000 claims description 28
- 229960003753 nitric oxide Drugs 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 11
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- 238000009434 installation Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims 1
- 238000007906 compression Methods 0.000 claims 1
- 238000003672 processing method Methods 0.000 claims 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 abstract description 15
- 239000004317 sodium nitrate Substances 0.000 abstract description 8
- 235000010344 sodium nitrate Nutrition 0.000 abstract description 8
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000010531 catalytic reduction reaction Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 238000005304 joining Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- -1 salt sodium nitrate Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention relates to a method for preparing sodium nitrite from nitric oxide waste gas with low oxidation degree in the industrial process, which comprises the following steps of: after water is removed from the nitric oxide waste gas, mixing the nitric oxide waste gas with oxygen supplying air according to a certain ratio, and introducing the mixture into multistage serial alkaline liquor absorption towers from the bottom of the first stage of absorption tower, wherein the temperature of the absorption liquor is below 50 DEG C, and the pressure inside the tower is 0.03-0.08 MPa; discharging the purified gas up to the standard from the top of the tail tower; and extracting a sodium nitrite solution from the bottom of the first stage of absorption tower. During the serial absorption process, after water is removed from the nitric oxide gas discharged by the last stage of tower, the concentrations of NO2 and NO are measured according to an online nitric oxide analyzer, and the oxygen supplying air is input through PRC control. During the absorption process, the circular absorption liquor of each absorption tower is first conveyed to a cooling device to cool, and thus, the temperature in the absorption tower is controlled. In the invention, common tower equipment with low cost is adopted to obtain sodium nitrate/sodium nitrite (0.02 sodium nitrite solution), the emission of nitric oxide is reduced, and the purposes of energy saving, emission reducing and recycling are achieved.
Description
Technical field
The present invention relates to the improvement and the recycling of nitrous oxides exhaust gas, specifically, is the method that multi-stage oxidizing absorbing NOx waste gas prepares natrium nitrosum.
Background technology
Nitrogen oxide (mainly refers to NO and NO
2, common name NOx) and waste gas not only can cause acid rain, acid mist, can also damage the ozone layer, and brings serious harm for natural environment and human being's production, life.Nitrogen oxide in the atmosphere is mainly from the fuel combustion waste gas of the process gas of nitric acid industry, oil burning boiler and motor-vehicle tail-gas etc.Therefore, to reducing discharged nitrous oxides, strengthening the improvement of nitrogen oxides pollution, become in the environmental protection work one very urgent task.
The technology main flow of removal of nitrogen oxide process is broadly divided into four classes: i.e. catalytic reduction method, solvent absorption, solid absorption method and biologic treating technique.Catalytic reduction method comprises selective catalytic reduction (SCR) and SNCR method (SNCR).Using more reducing agent in the catalytic reduction method is urea and ammonium sulfite, and these reducing agents can be under the effect of uniform temperature and catalyst be reduced to NOx harmless nitrogen and other unazotized components.The solvent absorption techniques is different according to acid gas and solvent combination, is divided into direct absorption process, oxidation absorption process, redox absorption process, liquid phase and absorbs reducing process and complexed absorption method etc.Wherein directly absorption process can be divided into several groups such as water absorption, nitric acid absorption, alkaline solution (akaline liquids such as NaOH, sodium carbonate, ammoniacal liquor) absorption and concentrated sulfuric acid absorption by the difference of the primary solvent that uses.It is simple that traditional solvent absorbs the denitration technology technical process, invest less, so extensive use in enterprise.The solid absorption method adopts anti-its of the method for adsorbents adsorb nitrogen oxide to pollute, and adsorbent commonly used at present has molecular sieve, active carbon, silica gel etc.It is just progressively to grow up in nearly 10 years that biochemical process is handled the nitrous oxides exhaust gas technology, the essence that bioanalysis is handled is to utilize the vital movement of microorganism that NOx is converted into harmless inorganic matter and cells of microorganisms matter (Jiang Ran, Huang Shaobin, Fan Lirong, under aerobic conditions, remove NOx. ACTA Scientiae Circumstantiae, 2007 (09): 1469-1475.) with biological filter system.In addition, also developed the plasma method gas denitrifying technology abroad, as electron beam irradiation method, pulse current corona method etc., these methods are comparatively advanced, but there are technical sophistication, problem (Wei Enzong, Lin He, Gao Xiang that cost is high, the coal burning boiler flue gas nitrogen oxide pollutes plasma and administers technology. Techniques and Equipment for Environmental Pollution Control, 2003. 4 (1): 58-62.).Water or rare nitric acid absorbing NOx are domestic nitrogen oxide improvement methods commonly used, and this method can obtain industrial chemicals such as nitric acid simultaneously, and this method generally requires nitrous oxides exhaust gas to have higher concentration and oxidizability.Patent (ZL100396360C) proposes a kind of industrial process nitrous oxides exhaust gas and administers and method of resource, has both guaranteed the environment protection emission of NOx, can effectively reclaim emophysematous NOx again, and the nitric acid of generation can use for industrial cycle.Absorbing treatment technology with alkali lye also is environment-protective process commonly used during nitrogen oxide is handled, it is fast that this method has infiltration rate, the advantage that the waste gas purification rate is high, it not only can realize the qualified discharge of NOx waste gas, the NOx of the overwhelming majority in the waste gas can also be converted into nitrate and nitrite and supply enterprise recycling.
The alkali lye absorbing NOx is identical with the mechanism of water absorbing NOx, the abnormal reaction complexity, in absorption process, comprise the nitrogen oxide intermediate product that there are dispute in a plurality of reversible and irreversible chemical reactions and academia, the association because each reaction influences each other, be difficult to understand each step link wherein, therefore usually it was reduced to for two steps at research process: the first step is a gas phase oxidation: replenish air in the waste gas that contains nitrogen oxide, make NO be oxidized into the NO that can be absorbed by water
2: 2NO+O
2=2NO
2(1); Second step was liquid phase absorption reaction, NO
2In liquid phase, can generate sodium nitrate and natrium nitrosum: 3NO with NO with alkali reaction
2+ 2NaOH=2NaNO
3+ NO+H
2O (2); NO
2+ NO+2NaOH=2NaNO
2+ H
2O(3), the NO of generation again with O
2Again reaction generates NO
2Thereby circular response absorbs preparation nitrate and nitrite.The reaction of sodium carbonate and oxides of nitrogen gas similarly just has carbon dioxide to emit in course of reaction.Usually, NO
2--Can irreversible reaction (2) fast take place with water or alkali lye, therefore simple alkali lye absorbing NOx finally obtains the mixture of nitrate and nitrite.(Jiang Yan brief talks and improves alkali lye absorption of N Ox gained neutralizer NaNO the method for tradition raising nitrite ratio in order to adopt lower NOx oxidizability and bigger spray flux
2With NaNO
3The approach of ratio, nitrogenous fertilizer information, 1994. 2:11-13).Independent NO not with water or alkaline reaction, and work as NO
2/ NO is 1 o'clock, and reaction (3) can very fast generation.Because the price of natrium nitrosum is far above sodium nitrate at present, therefore, the alkali lye absorbing NOx preferably can obtain higher NaNO in absorption liquid
2/ NaNO
3, concentrate then, utilize NaNO
2The little characteristics of solubility, crystallization removes by filter sodium nitrate.Domestic have report to adopt nitric acid tail gas to produce inferior sodium technology, adopted higher absorption temperature, and the absorption efficiency of NOx is not high.Because the condensing crystallizing operation is wanted more equipment investment, so enterprise generally tends to obtain the lower sodium nitrite solution of sodium nitrate content.Since in the NOx absorption process, NO-
2In liquid phase, emit NO and send a large amount of heat, have part water to enter gas phase in the absorption process, the easy and NO of this part water electrode with alkali reaction
2Reaction forms nitric acid, has increased nitrate content in absorption process, therefore is must guarantee two aspects by the content of control nitrate:
NO in the gas phase
2The ratio of/NO;
Moisture in the strict control gas phase.
Summary of the invention
Technical scheme of the present invention is as follows:
A kind of industrial process suboxides degree nitrogen oxide (NOx) waste gas prepares the method for natrium nitrosum, flow process as shown in Figure 1, it is that the oxidation of a kind of plural serial stage alkali lye absorption tower combination absorbs the method for preparing natrium nitrosum, it comprises the steps:
Step 1. with suboxides degree nitrous oxides exhaust gas through after de-watering apparatus dewaters, with the content that keeps water in the nitrous oxides exhaust gas and nitric acid below 1%, the NO that measures according to online nitrogen-oxide analyzer, then
2With NO concentration, by PRC control, the oxidizability of oxygen air with the control nitrogen oxide joined in input, to guarantee NO
2The ratio of/NO between 0.4~1, preferred NO
2The ratio of/NO is less than 0.8;
The suboxides degree nitrous oxides exhaust gas that step 2. will be joined behind the oxygen feeds first order absorption tower from the bottom on first order absorption tower, absorb alkali lye from the top spray on first order absorption tower, and absorbing alkali lye can be NaOH or Na
2CO
3Solution, the absorption liquid temperature remains on below 50 ℃ in the absorption tower, amount with moisture in the control gas phase, the absorption liquid temperature can be cooled off or installation cooling heat transferring device in tower in the tower outer circulation by absorption liquid, take absorption reaction liberated heat in the tower out of, with the temperature in the control absorption tower, pressure is between 0.03~0.8MPa in the tower, and optimal absorption pressure is 0.2~0.8MPa;
After the suboxides degree nitrous oxides exhaust gas that step 3. is discharged from top, first order absorption tower through first order absorption dewaters through de-watering apparatus once more, according to the NO of online nitrogen-oxide analyzer, mensuration
2With NO concentration, by PRC control, the input oxygen content greater than 40% join the oxidizability of oxygen air with the control nitrogen oxide, to guarantee NO
2The ratio of/NO is between 0.2~1;
Step 4. is joined the bottom feeding second level absorption tower of oxygen Air mixing gas from absorption tower, the second level with step 3 input, and from the top spray absorption alkali lye on absorption tower, the second level, absorbing alkali lye can be NaOH or Na
2CO
3The aqueous solution, the absorption liquid temperature remains on below 50 ℃ in the absorption tower, amount with moisture in the control gas phase, the absorption liquid temperature can be cooled off or installation cooling heat transferring device in tower in the tower outer circulation by absorption liquid, take absorption reaction liberated heat in the tower out of, with the temperature in the control absorption tower, pressure is between 0.03~0.8MPa in the tower, and optimal absorption pressure is 0.2~0.8MPa;
Repeating step 3 like this and step 4, down first grade absorption tower is proceeded to absorb, and the concentration of the nitrogen oxide until the suboxides degree nitrous oxides exhaust gas of discharging from top, n level absorption tower is to qualified discharge.
Above-mentioned method, the described nitrous oxides exhaust gas of step 2 absorption tower can be packed tower or bubble column, preferably packed tower.
Above-mentioned method, the described absorption alkali lye of step 2 can be that mass percentage concentration is NaOH or the Na of 5-30%
2CO
3Solution.
Above-mentioned method, the sprinkle density that the described absorption tower of step 2 top spray absorbs alkali lye is 2-20.
Above-mentioned method, described next stage absorb the absorption alkali lye that the absorption alkali lye of discharging at the bottom of the Tata can be used as the upper level absorption tower, and so, output is the sodium nitrite solution that contains quality 10-50% at the bottom of the first order absorption Tata.
Above-mentioned method, the theoretical cam curve on described absorption tower are 5-30, and first order tower theoretical cam curve is below 15, along with the increase of progression, and all corresponding increase of the oxidizability of nitrogen oxide and the number of plates.
Above-mentioned method is fit to handle described original nitrogen oxides of exhaust gas concentration at 200mg/m
3More than, NO
2The mol ratio of/NO is less than 0.4 nitrous oxides exhaust gas, if NO
2/ NO〉0.4, then adopt water to absorb earlier and remove part NO
2
The present invention adopts the alkali lye multi-stage oxidizing to absorb the absorption efficiency that suboxides degree oxides of nitrogen gas can greatly improve NOx, adopt the common equipment of tower cheaply, can obtain the sodium nitrite solution of sodium nitrate/natrium nitrosum<0.02, can realize the income of waste gas pollution control and treatment, reduce the NOx discharging, reach the purpose of energy-saving and emission-reduction.
The advantage of patent of the present invention is:
1. before nitrogen oxide alkali lye absorbs, at NO
2Very easily, adopt the dry mode that dewaters and remove liquid, the content of nitrate in the minimizing absorption liquid with the problem of water generation irreversible reaction;
2. adopt the method that heat exchanger is set in cooling and absorbing liquid or the tower, the absorption liquid temperature is controlled in 50 ℃, to reduce the volatilization of moisture.
3. before nitrous oxides exhaust gas enters every grade of absorption tower, adopt online nitrogen-oxide analyzer, to measure wherein NO
2With the concentration of NO, then according to NO
2The mol ratio of/NO, feed join the oxygen air with the oxidizability of regulating nitrogen oxide between 0.2~1.
4. the NOx in the tail gas is recovered and changes certain density inferior salt sodium nitrate into, can sell to obtain income or recycling.
5. do not produce secondary spent acid, waste water, environmental protection in the governance process.
6. discharging tail gas is detected by the nitrogen-oxide analyzer, device, can guarantee qualified discharge.
7. output of the present invention/output investment ratio height adopts common tower absorption technique, is particularly suitable for the suboxides degree, and the NOx waste gas that NO concentration is high meets the principle of the environmental protection and the utilization of resources.
Description of drawings
Fig. 1 is the flow chart of the embodiment of the invention 1, wherein: 1,2 and 3 dewater/liquid removing device for gas phase; 4,5,6 are the oxidation case; 7,8,9 is the absorption tower; 10 is NOx on-line analysis equipment; 11,12,13 fluid reservoirs that are respectively tower 7,8,9; 14,15,16 condensers that are respectively tower 7,8,9.
The specific embodiment
Adopt three tower cascade connected absorption, absorbent is a NaOH solution, and concentration is 20%, joins that oxygen content is 40% in the oxygen air, and air inlet is the NOx gaseous mixture, and tolerance is 600Nm
3/ h, pressure is 0.3MPa, NO
2/ NO is 0.2.Adopt three grades of towers to absorb operation to obtain sodium nitrite solution, three towers all adopt the structured packing of 350Y type.Nitrogen oxide Primordial Qi at first enters the molecular sieve fixed bed drying of drying, dry back moisture 0.8ppm, and in oxidation case 4, the input quantity of joining the oxygen air is 125Nm
3/ h, oxidation case exit gas pressure is 0.5MPa, and the packed height on absorption tower 7 is 4m, and operation pressure 0.6MPa absorbs 40 ℃ of temperature, and the sprinkle density of NaOH liquid is 8.6m
3/ m
2.h, condensation area is 20m
2Absorption tower 7 overhead gas enter the molecular sieve fixed bed drying of drying, dry back moisture 0.8ppm, NO
2/ NO is 0.03, and in the oxidation case 5, the input quantity of joining the oxygen air is 250Nm
3/ h, oxidation case exit gas pressure is 0.6MPa, and the packed height on absorption tower, the second level 8 is 6m, and operation pressure 0.7MPa absorbs 45 ℃ of temperature, and the sprinkle density of NaOH liquid is 7.2 m
3/ m
2.h, condensation area is 20m
2Absorption tower 8 overhead gas enter the molecular sieve fixed bed drying of drying, dry back moisture 0.8ppm, NO
2/ NO is 0.01, and in the oxidation case 6, the input quantity of joining the oxygen air is 125Nm
3/ h, oxidation case exit gas pressure is 0.6MPa, the packed height 7m on third level absorption tower 9, operation pressure 0.7MPa absorbs 45 ℃ of temperature, and the sprinkle density of NaOH liquid is 7.2 m
3/ m
2.h, condensation area 20m
2NO in the tail gas
XConcentration of emission 68ppm, speed 0.085kg/h.Flow out mass concentration from first order absorption tower bottom and be 35% nitrous acid solution, wherein sodium nitrate/natrium nitrosum is 0.015.
Claims (9)
1. an industrial process suboxides degree nitrous oxides exhaust gas prepares the method for natrium nitrosum, it is characterized in that it is that the oxidation of a kind of plural serial stage alkali lye absorption tower combination absorbs the method for preparing natrium nitrosum, and it comprises the steps:
Step 1. dewaters suboxides degree nitrous oxides exhaust gas through de-watering apparatus after, processing method can be the combination of one or more drying means in low temperature process, drier drying, the gas compression, with the content that keeps water in the nitrous oxides exhaust gas and nitric acid below 1%, the NO that measures according to online nitrogen-oxide analyzer, then
2With NO concentration, by PRC control, the input oxygen content greater than 40% join the oxidizability of oxygen air with the control nitrogen oxide, to guarantee NO
2The ratio of/NO is between 0.2~1;
The suboxides degree nitrous oxides exhaust gas that step 2. will be joined behind the oxygen feeds first order absorption tower from the bottom on first order absorption tower, absorb alkali lye from the top spray on first order absorption tower, and absorbing alkali lye is NaOH or Na
2CO
3Solution, the absorption liquid temperature remains on below 50 ℃ in the absorption tower, amount with moisture in the control gas phase, the absorption liquid temperature is cooled off or installation cooling heat transferring device in tower in the tower outer circulation by absorption liquid, take absorption reaction liberated heat in the tower out of, with the temperature in the control absorption tower, pressure is between 0.03~0.8MPa in the tower;
After the suboxides degree nitrous oxides exhaust gas that step 3. is discharged from top, first order absorption tower through first order absorption dewaters through de-watering apparatus once more, according to the NO of online nitrogen-oxide analyzer, mensuration
2With NO concentration, by PRC control, the input oxygen content greater than 40% join the oxidizability of oxygen air with the control nitrogen oxide, to guarantee NO
2The ratio of/NO is between 0.2~1;
Step 4. is joined the bottom feeding second level absorption tower of oxygen Air mixing gas from absorption tower, the second level with step 3 input, and from the top spray absorption alkali lye on absorption tower, the second level, absorbing alkali lye is NaOH or Na
2CO
3The aqueous solution, the absorption liquid temperature remains on below 50 ℃ in the absorption tower, amount with moisture in the control gas phase, the absorption liquid temperature can be cooled off or installation cooling heat transferring device in tower in the tower outer circulation by absorption liquid, take absorption reaction liberated heat in the tower out of, with the temperature in the control absorption tower, pressure is between 0.03~0.8MPa in the tower;
Repeating step 3 like this and step 4, down first grade absorption tower is proceeded to absorb, and the concentration of the nitrogen oxide until the suboxides degree nitrous oxides exhaust gas of discharging from top, n level absorption tower is to qualified discharge.
2. method according to claim 1 is characterized in that: the described input oxygen content of step 1 greater than 40% join the oxidizability of oxygen air with the control nitrogen oxide, to guarantee NO
2The ratio of/NO is less than 0.4.
3. method according to claim 1 is characterized in that: pressure is 0.2~0.8Mpa in the described tower of step 2 and step 4.
4. method according to claim 1 is characterized in that: the described nitrous oxides exhaust gas of step 2 absorption tower is packed tower or bubble column.
5. method according to claim 1 is characterized in that: the described absorption alkali lye of step 2 is that mass percentage concentration is NaOH or the Na of 5-30%
2CO
3Solution.
6. method according to claim 1 is characterized in that: the sprinkle density that the described absorption tower of step 2 top spray absorbs alkali lye is 2-20.
7. method according to claim 1 is characterized in that: the absorption alkali lye of discharging at the bottom of the described next stage absorption Tata is as the absorption alkali lye on upper level absorption tower, and so, output is the sodium nitrite solution that contains quality 10-50% at the bottom of the first order absorption Tata.
8. method according to claim 1 is characterized in that: the theoretical cam curve on described absorption tower is 5-30, and first order tower theoretical cam curve is below 15, along with the increase of progression, and all corresponding increase of the oxidizability of nitrogen oxide and the number of plates.
9. method according to claim 1 is characterized in that: this method is fit to handle described original nitrogen oxides of exhaust gas concentration at 200mg/m
3More than, NO
2The mol ratio of/NO is less than 0.4 nitrous oxides exhaust gas, if NO
2The mol ratio of/NO〉0.4, then adopt water to absorb earlier and remove part NO
2
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3453071A (en) * | 1965-05-18 | 1969-07-01 | Hibernia Chemie Gmbh | Nitrogen oxide conversion |
JPH01232297A (en) * | 1988-03-11 | 1989-09-18 | Babcock Hitachi Kk | Retreated off-gas treatment equipment |
US6004523A (en) * | 1997-10-30 | 1999-12-21 | Alliedsignal Inc. | Process for abating NOx emissions from a manufacturing stream |
CN1864812A (en) * | 2006-04-24 | 2006-11-22 | 南京大学 | A nitric oxides (NOX) waste pollution control in industrial process and resource reclaiming method |
CN101244364A (en) * | 2008-03-04 | 2008-08-20 | 湖南金旺实业有限公司 | Negative pressure soda liquor absorption technique for oxides of nitrogen waste gas |
CN101352644A (en) * | 2008-08-29 | 2009-01-28 | 浙江大学 | Wet flue gas denitration technique for nitrite recovery |
-
2010
- 2010-12-27 CN CN201010606805.2A patent/CN102078752A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3453071A (en) * | 1965-05-18 | 1969-07-01 | Hibernia Chemie Gmbh | Nitrogen oxide conversion |
JPH01232297A (en) * | 1988-03-11 | 1989-09-18 | Babcock Hitachi Kk | Retreated off-gas treatment equipment |
US6004523A (en) * | 1997-10-30 | 1999-12-21 | Alliedsignal Inc. | Process for abating NOx emissions from a manufacturing stream |
CN1864812A (en) * | 2006-04-24 | 2006-11-22 | 南京大学 | A nitric oxides (NOX) waste pollution control in industrial process and resource reclaiming method |
CN101244364A (en) * | 2008-03-04 | 2008-08-20 | 湖南金旺实业有限公司 | Negative pressure soda liquor absorption technique for oxides of nitrogen waste gas |
CN101352644A (en) * | 2008-08-29 | 2009-01-28 | 浙江大学 | Wet flue gas denitration technique for nitrite recovery |
Non-Patent Citations (10)
Title |
---|
《化学反应工程与工艺》 19900930 荣桂安,林志祥 纯碱液喷射吸收高浓度NO和NO2混合气体的研究 74-81 第6卷, 第3期 * |
《化学工业与工程》 20031231 常明坤,胡金榜,宗润宽,王晋刚 利用空气氧化NO的技术探讨 518-522 第20卷, 第6期 * |
《化学工程》 20060930 任晓莉,张雪梅,张卫江,杨宝强,苗志超 碱液吸收法治理含NOx工艺尾气实验研究 63-66 第34卷, 第9期 * |
《化工设计通讯》 19900930 韦国昊 提高亚硝酸钠产率的一些措施 51-53 第16卷, 第3期 * |
《化肥工业》 19951031 朱为民 改进碱吸收法处理硝酸尾气技术及工业装置的运行 287-291 第22卷, 第5期 * |
《天津大学博士学位论文》 20060630 任晓莉 常压湿法治理化学工业中氮氧化物废气的研究 99-103 , * |
《小氮肥设计技术》 20040831 王金玉 硝盐生产碱吸收工艺分析 19-20 第25卷, 第4期 * |
《广州化工》 19830331 杨汝生,辜明铭 硝酸生产中氮氧化物的分段分流吸收 27-31 , 第1期 * |
《河北化工》 20080731 贾文清 碱吸收法治理硝酸尾气 59-60 第31卷, 第7期 * |
《环境工程》 20050430 乔军师,胡金榜,宗润宽,常明坤 NOx空气氧化与碱液吸收工艺实验研究 37-38 第23卷, 第2期 * |
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