CN102247748A - Treatment method and treatment system of tail gas from glyoxylic acid production by nitric acid oxidation of glyoxal - Google Patents
Treatment method and treatment system of tail gas from glyoxylic acid production by nitric acid oxidation of glyoxal Download PDFInfo
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- CN102247748A CN102247748A CN201110185138XA CN201110185138A CN102247748A CN 102247748 A CN102247748 A CN 102247748A CN 201110185138X A CN201110185138X A CN 201110185138XA CN 201110185138 A CN201110185138 A CN 201110185138A CN 102247748 A CN102247748 A CN 102247748A
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- nitric acid
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- 238000000034 method Methods 0.000 title claims abstract description 50
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 34
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910017604 nitric acid Inorganic materials 0.000 title claims abstract description 26
- 230000003647 oxidation Effects 0.000 title claims abstract description 25
- 229940015043 glyoxal Drugs 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 238000010521 absorption reaction Methods 0.000 claims abstract description 92
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000000243 solution Substances 0.000 claims abstract description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000012670 alkaline solution Substances 0.000 claims abstract description 14
- 239000011780 sodium chloride Substances 0.000 claims abstract description 13
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 9
- 238000005119 centrifugation Methods 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 6
- 230000009102 absorption Effects 0.000 claims description 90
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 33
- 239000003513 alkali Substances 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 24
- 230000001590 oxidative effect Effects 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 4
- -1 polypropylene Polymers 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 210000000003 hoof Anatomy 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229910052573 porcelain Inorganic materials 0.000 claims description 2
- 239000008213 purified water Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 abstract 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 abstract 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract 2
- 238000002425 crystallisation Methods 0.000 abstract 2
- 230000008025 crystallization Effects 0.000 abstract 2
- 235000010344 sodium nitrate Nutrition 0.000 abstract 2
- 235000010288 sodium nitrite Nutrition 0.000 abstract 2
- 238000000926 separation method Methods 0.000 abstract 1
- 235000017550 sodium carbonate Nutrition 0.000 abstract 1
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 55
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 22
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 22
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 240000005265 Lupinus mutabilis Species 0.000 description 2
- 235000008755 Lupinus mutabilis Nutrition 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 235000019095 Sechium edule Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
A treatment method and a treatment system of tail gas from glyoxylic acid production by nitric acid oxidation of glyoxal belong to the fields of environmental protection, energy saving and consumption reduction. The method comprises the following steps: introducing air to oxidize NO in tail gas generated by nitric acid oxidation of glyoxal into NO2; performing six-grade water absorption continuously to absorb gas of NOx and HCl in the tail gas; absorbing the tail gas after six-grade water absorption by a NaOH or Na2CO3 solution to remove residual NO2 and HCl gas and to generate an alkaline solution containing NaNO3, NaNO2, and trace NaCl; discharging the treated tail gas by an induced draft fan; performing neutralization, concentration, crystallization, centrifugation and separation of the generated alkaline solution to obtain a mixed sodium salt containing NaNO3, NaNO2, and trace NaCl, returning the mixed sodium salt to an oxidation vessel to be used as a catalyst for recycle. The treatment system comprises: an oxidation reaction vessel, water absorbing towers from grade one to grade six, a seventh grade alkaline solution absorbing tower, a concentration and crystallization vessel, a centrifuge, and a induced draft fan.
Description
Technical field
The present invention relates to the glyoxal nitric acid oxidation and produce the exhaust gas treating method of the nitrogen-containing oxide of glyoxalic acid and hydrogen chloride and implement the needed treatment system of this technology, belong to environmental protection, energy-saving and cost-reducing field.
Background technology
Glyoxalic acid is a kind of important Organic Chemicals, is widely used in the synthetic field of light industrial goods such as spices, medicine, agricultural chemicals, papermaking, coating, paint, leather and food additives.Process for production of glyoxalic acid can be divided into chemical synthesis and electrochemistry synthetic method two big classes, industrial the most frequently used two kinds of glyoxal nitric acid oxidation method and maleic acid (acid anhydride) the ozone oxidation methods that have.Wherein, the glyoxal nitric acid oxidation method is that this method reaction condition gentleness, technology are simply ripe with nitric acid as oxidant selective oxidation glyoxal, and equipment investment is few, is the main production method that at present domestic and international most of producer adopts.The glyoxal nitric acid oxidation is produced glyoxalic acid, main reaction formula CHO-CHO+HNO
3→ CHO-COOH+NO ↑+H
2O, the tail gas of generation contains a large amount of nitrogen oxide.
As everyone knows, nitrogen oxide is very harmful, mainly shows: 1. form photochemical fog; 2. combine with hemochrome in the animal blood; 3. destroy atmospheric ozone layer; 4. can generate bigger nitric acid of toxicity or nitrate aerosol, form acid rain.In addition, the also perishable environment of hydrogen chloride has the strong stimulation effect to biology.In view of the extremely strong harmfulness of nitrogen oxide, countries in the world all are devoted to adopt the whole bag of tricks that nitrogen oxide is handled at present, mainly contain ammine selectivity catalytic reduction method, liquid absorption method, solid absorption method and Chemical Inhibition Method.But problem such as these methods exist to some extent all that processing step is loaded down with trivial details, equipment investment is big, operating cost is high and recovery utilization rate is low.
Summary of the invention
The tail gas treatment process that the present invention is intended to solve nitrogen-containing oxide and hydrogen chloride in the prior art does not interrelate with the reaction of formation of tail gas, the utility that reclaims in the tail gas treatment process is not returned the reaction of formation of tail gas, tail gas treatment process complex steps, energy consumption height, and the low technical problem of utility recovery utilization rate in the tail gas.
The invention provides a kind of glyoxal nitric acid oxidation and produce the exhaust gas treating method of glyoxalic acid, may further comprise the steps:
(1) oxidation reaction process, the NO that introduces in the tail gas that air produces after with the glyoxal nitric acid oxidation is oxidized to NO
2
Chemical equation is as follows:
CHO-CHO+HNO
3→CHO-COOH+NO↑+H
2O
2NO+O
2＝2NO
2
(2) water absorption process is carried out six grades of water absorption techniques continuously, absorbs the NO in the tail gas
xWith HCl gas;
The main chemical reactions formula is:
2NO+O
2＝2NO
2
3NO
2+H
2O＝2HNO
3+NO
4NO
2+O
2+2H
2O＝4HNO
3
(3) the mixed acid solution concentration that contains nitric acid and small amount of hydrochloric acid that after first order water absorbs, generates in the regulating step (2), being adjusted to mass percent concentration with red fuming nitric acid (RFNA) is 30～45% o'clock, returns step (1) circulation and carries out oxidation reaction;
(4) alkali lye absorption process will be through the tail gas after six grades of water absorb with NaOH or Na
2CO
3Solution absorbs, to remove NO
2With micro-HCl gas, generate and contain NaNO
3And NaNO
2And the alkaline solution of micro-NaCl, the tail gas after the processing is discharged by air-introduced machine;
Related chemical equation is as follows:
Na
2CO
3+2H
2O＝2NaOH+H
2O+CO
2↑
2NO
2+2NaOH＝NaNO
3+NaNO
2+H
2O
HCl+NaOH＝NaCl+H
2O
(5) its pH value of alkaline solution of alkali lye absorption process generation is 9.0～11.5 o'clock, with the acid solution neutralization, after condensing crystallizing, centrifugation, obtains containing NaNO again
3, NaNO
2And the mixing sodium salt of micro-NaCl returns step (1) and applies mechanically as the catalyst circulation of oxidation reaction, centrifuge mother liquor returns condensing crystallizing still recycled, when the pH value of the alkaline solution that generates greater than 11.5 the time, return step (4) and be used for the circulation of alkali lye absorption process and absorb.
NaOH or Na in the described step (4)
2CO
3The solution quality percent concentration is 15～30%.
The temperature of six grades of water absorptions is 20～35 ℃ in the described step (2).
Be used in the described step (5) and the acid solution of alkaline solution, adopt dilute acid soln from the absorption tower extraction of first order water.
The described absorption liquid of finishing after the 6th grade of water absorbs changes level V water absorption tower over to as its absorption liquid, the rest may be inferred, every back one-level water absorbs the absorption liquid that the absorption liquid after finishing all absorbs as previous stage water, until first order water absorption tower, described the 6th grade of water absorption tower adds fresh purified water or running water, and first order tower is unique extraction point that whole system absorbs the gained acid solution.
Described air-introduced machine gas flow is 9000～10000m
3/ h, the pressure of generation be-0.005～-0.003MPa.
A kind of glyoxal nitric acid oxidation is produced the exhaust treatment system of glyoxalic acid, it is characterized in that, comprising:
Oxidizing reactor is used for the glyoxal nitric acid oxidation and introduces air the NO of tail gas is oxidized to NO
2
Six grades of water absorption towers, first order water absorption tower to the, series connection successively, connecting with oxidizing reactor in first order water absorption tower, is used for the NO of continuous six grades of water absorption by the oxidizing reactor last person of institute gas
xWith HCl gas;
Connecting with the 6th grade of water absorption tower in the 7th grade of alkali lye absorption tower, is used for alkali lye and absorbs by the 6th grade of residual micro-NO of the water absorption tower last person of institute gas
xWith HCl gas;
Condensing crystallizing still and centrifuge place bottom, the 7th grade of alkali absorption tower one side, be used for neutralization that the 7th grade of alkali lye absorption tower discharged completely solution carry out condensing crystallizing, centrifugation, to obtain to contain NaNO
3, NaNO
2And the mixing sodium salt of micro-NaCl;
Air-introduced machine is connected in the 7th grade of alkali lye absorption tower outlet pipe end, is used to make in seven grades of absorption towers of the oxidizing reactor and the first order to the produce negative pressure, keeping along first to the 7th grade of tower forward flow of air-flow, and tail gas is discharged.
Described oxidizing reactor is provided with air intake.Six grades of water absorption towers of the described first order to the and the 7th grade of alkali lye absorption tower material are polypropylene, and inner-tower filling material is PP material baton round or shape of a hoof porcelain ring filler, and filler is multistage distribution.
Six grades of water absorption towers of the described first order to the and the 7th grade of alkali lye absorption tower all are connected with centrifugal pump of single stage type.
Use glyoxal nitric acid oxidation provided by the invention to produce the exhaust gas treating method and the treatment system of glyoxalic acid, behind the purified treatment tail gas, wherein the above harmful substance of 96% (percentage by volume) is recovered utilization, NO in the tail gas
xBe lower than the index of 190ppm, wherein NO with the HCl total content
xContent is lower than 180ppm, and HCl content is lower than 10ppm, and discharge tail gas meets national environmental standard, directly enters atmosphere and does not pollute the environment.
Glyoxal nitric acid oxidation provided by the invention is produced the exhaust gas treating method and the treatment system of glyoxalic acid, the mixing sodium salt that tail gas alkali lye absorbs and aftertreatment technology obtains can be used as the catalyst of main oxidation reaction, can be with the reactant of the oxidation reaction of deciding by the diluted acid of first order water absorption tower extraction, first to six grade of water absorbs the neutralization reaction that the dilute acid soln that generates can be used for the 7th grade of alkali lye, absorption liquid after first absorption liquid that absorbs to Pyatyi water is all finished from the upper level absorption process, thereby, the intermediate material that in whole vent gas treatment process, produces, all obtained effective recycling, a large amount of raw material have been saved, greatly reduce production cost, realized the double benefit of energy-saving and cost-reducing and environmental protection.Processes and apparatus of the present invention is simple, and operation and maintenance cost is low, raw material rate of recovery height, remarkable in economical benefits.
Description of drawings
Fig. 1 is the process flow diagram that glyoxal nitric acid oxidation of the present invention is produced the exhaust gas treating method of glyoxalic acid.
Fig. 2 is the equipment flowsheet schematic diagram that glyoxal nitric acid oxidation of the present invention is produced the exhaust treatment system of glyoxalic acid.
The specific embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail.
As shown in Figure 1 and Figure 2, oxidizing reactor is discharged contains NO
xWith the tail gas of HCl, terminal air-introduced machine (gas flow 9000～10000m on the 7th grade of alkali absorption tower
3/ h) produce negative pressure (0.005～-0.003MPa) effect (contains 21% O with the air that enters oxidizing reactor down
2) after the mixing, the six grades of water absorption towers of the first order to that enter series connection are successively carried out water and absorbed, with water generation Physical Absorption and chemical reaction process, with most NO, NO in the tail gas
2Be converted into the mixed acid solution that contains nitric acid and small amount of hydrochloric acid with HCl gas.Wherein, regulate after mixed acid solution concentration after first order water absorption tower absorbs reaches 30～45% (mass percents), return the oxidizing reactor circular response with red fuming nitric acid (RFNA).The absorption temperature on six grades of water absorption towers of the first order to the is controlled at 20～35 ℃.Tail gas behind six grades of water absorption towers enters the 7th grade of alkali lye absorption tower again, with concentration be the NaOH solution or the Na of 15～30% (mass percents)
2CO
3Solution reaction generates and contains NaNO
3And NaNO
2And the alkaline solution of micro-NaCl, its pH value is 9.0～11.5.With the mixed acid solution from the absorption tower extraction of first order water neutralize this alkaline solution to PH be 7.0, again through condensing crystallizing and centrifugation, gained contain NaNO
3, NaNO
2And the mixing sodium salt of micro-NaCl returns oxidizing reactor as catalyst circulation reaction, and centrifuge mother liquor returns condensing crystallizing still recycled.When the absorption liquid pH value greater than 11.5 the time, absorption liquid is refused extraction, continues to absorb.
After above-mentioned technical process finishes, finally by air-introduced machine outlet discharging tail gas, NO in this tail gas
xWith the total content of HCl be 180～190ppm, wherein NO
xContent 172～180ppm, HCl content 5～10ppm has realized qualified discharge.Tail gas before handling wherein has the harmful substance of 95～97% (percentage by volumes) to be recovered utilization through the processing of this system.
In addition, those skilled in the art also can do other variation in spirit of the present invention, and certainly, the variation that these are done according to spirit of the present invention all should be included within the present invention's scope required for protection.
Embodiment 1
Oxidizing reactor is discharged contains NO
xWith the tail gas of HCl, terminal air-introduced machine (the gas flow 9500m on the 7th grade of alkali absorption tower
3/ h) negative pressure of generation (0.003MPa) under the effect, (contains 21% O with the air that enters oxidizing reactor
2) after the mixing, the six grades of water absorption towers of the first order to that enter series connection are successively carried out water and absorbed, with most NO, NO in the tail gas
2Be converted into the mixed acid solution that contains nitric acid and small amount of hydrochloric acid with HCl gas.Then, regulate mixed acid solution from the absorption tower extraction of first order water with red fuming nitric acid (RFNA), make its concentration reach 45% (mass percent) after, return the oxidizing reactor circular response.The absorption temperature on six grades of water absorption towers of the first order to the is controlled at 35 ℃.Tail gas behind six grades of water absorption towers enters the 7th grade of alkali lye absorption tower again, with concentration be the NaOH solution reaction of 15% (mass percent), generate and to contain NaNO
3And NaNO
2And the alkaline solution of micro-NaCl, its PH is 9.0～10.0.Neutralize this alkaline solution to PH=7.0 with mixed acid solution from the absorption tower extraction of first order water, again through condensing crystallizing and centrifugation, gained contain NaNO
3, NaNO
2And the mixing sodium salt of micro-NaCl returns oxidizing reactor as catalyst circulation reaction, and centrifuge mother liquor returns condensing crystallizing still recycled.
After above-mentioned technical process is finished, finally by air-introduced machine outlet discharging tail gas, NO in this tail gas
xWith the total content of HCl be 190ppm, wherein NO
xContent 180ppm, HCl content 10ppm has realized qualified discharge.Tail gas before handling wherein has the harmful substance of 96% (percentage by volume) to be recovered utilization through the processing of this system.
Embodiment 2
Technological process is identical with example 1, and technic index is done following adjustment:
Air-introduced machine gas flow 9000m
3/ h, oxidizing reactor still internal pressure-0.004MPa, the nitration mixture concentration that first order water absorption tower absorbs terminal point is 30% (mass percent), regulates its concentration with red fuming nitric acid (RFNA) and reaches 40% (mass percent) back cover and use the oxidation main reaction.The absorption temperature on six grades of water absorption towers of the first order to the is 25 ℃, and the Na of 30% (mass percent) is adopted on the 7th grade of alkali lye absorption tower
2CO
3Solution absorbs, and the pH value that alkali lye absorbs terminal point is 10.0-11.0, in and the pH value of terminal point be 7.0.
After above-mentioned technical process is finished, finally by air-introduced machine outlet discharging tail gas, NO in this tail gas
xWith the total content of HCl be 180ppm, wherein NO
xContent 172ppm, HCl content 8ppm has realized qualified discharge.Tail gas before handling wherein has the harmful substance of 97% (percentage by volume) to be recovered utilization through the processing of this system.
Embodiment 3
Technological process is identical with example 1, and technic index is done following adjustment:
Air-introduced machine gas flow 10000m
3/ h, oxidizing reactor still internal pressure-0.005MPa, the nitration mixture concentration that first order water absorption tower absorbs terminal point is 25% (mass percent), regulates its concentration with red fuming nitric acid (RFNA) and reaches 35% (mass percent) back cover and use the oxidation main reaction.Six grades of water absorption towers of the first order to the absorb temperature and are 20 ℃, and the 7th grade of alkali lye absorption tower adopts the NaOH solution of 25% (mass percent) to absorb, and the pH value that alkali lye absorbs terminal point is 10.5-11.5, in and the pH value of terminal point be 7.0.
After above-mentioned technical process is finished, finally by air-introduced machine outlet discharging tail gas, NO in this tail gas
xWith the total content of HCl be 185ppm, wherein NO
xContent 180ppm, HCl content 5ppm has realized qualified discharge.Tail gas before handling wherein has the harmful substance of 95% (percentage by volume) to be recovered utilization through the processing of this system.
Claims (10)
1. a glyoxal nitric acid oxidation is produced the exhaust gas treating method of glyoxalic acid, it is characterized in that may further comprise the steps:
(1) oxidation reaction process is introduced air the NO that the glyoxal nitric acid oxidation produces in the tail gas is oxidized to NO
2
(2) water absorption process is carried out six grades of water continuously and is absorbed, and absorbs the NO in the tail gas
xWith HCl gas;
(3) absorb the mixed acid solution concentration that contains nitric acid and small amount of hydrochloric acid that the back generates through first order water in the regulating step (2), after regulating its mass percent concentration and reach 30～45% with red fuming nitric acid (RFNA), return step (1) and circulate and carry out oxidation reaction;
(4) alkali lye absorption process will be through the tail gas after six grades of water absorb with NaOH or Na
2CO
3Solution absorbs, to remove micro-NO
xWith HCl gas, generate and contain NaNO
3And NaNO
2And the alkaline absorption solution of micro-NaCl, the tail gas after the processing is discharged by air-introduced machine;
When (5) the alkaline solution pH value that generates when the alkali lye absorption process is 9.0～11.5,, after condensing crystallizing, centrifugation, obtain containing NaNO again with the acid solution neutralization
3, NaNO
2And the mixing sodium salt of micro-NaCl returns step (1) and applies mechanically as the catalyst circulation of oxidation reaction, centrifuge mother liquor returns condensing crystallizing still recycled, when the alkaline solution pH value that generates greater than 11.5 the time, return step (4) and be used for the circulation of alkali lye absorption process and absorb.
2. exhaust gas treating method as claimed in claim 1 is characterized in that: NaOH or Na in the described step (4)
2CO
3The solution quality percent concentration is 15～30%.
3. exhaust gas treating method as claimed in claim 1 or 2 is characterized in that: the temperature of six grades of water absorptions is 20～35 ℃ in the described step (2).
4. exhaust gas treating method as claimed in claim 1 is characterized in that: be used in the described step (5) and the acid solution of alkaline solution, adopt the dilute acid soln from the absorption tower extraction of first order water.
5. exhaust gas treating method as claimed in claim 1, it is characterized in that: the described absorption liquid of finishing after the 6th grade of water absorbs changes level V water absorption tower over to as its absorption liquid, the rest may be inferred, every back one-level water absorbs the absorption liquid that the absorption liquid after finishing all absorbs as previous stage water, until first order water absorption tower, described the 6th grade of water absorption tower adds fresh purified water or running water, and first order tower is unique extraction point that whole system absorbs the gained acid solution.
6. exhaust gas treating method as claimed in claim 1 is characterized in that: described air-introduced machine gas flow is 9000～10000m
3/ h, the pressure of generation be-0.005～-0.003MPa.
7. the exhaust treatment system of a glyoxal nitric acid oxidation production glyoxalic acid is characterized in that, comprising:
Oxidizing reactor is used for the glyoxal nitric acid oxidation and introduces air the NO of tail gas is oxidized to NO
2
Six grades of water absorption towers, first order water absorption tower to the, series connection successively, connecting with oxidizing reactor in first order water absorption tower, is used for the NO of continuous six grades of water absorption by the oxidizing reactor last person of institute gas
xWith HCl gas;
Connecting with the 6th grade of water absorption tower in the 7th grade of alkali lye absorption tower, is used for alkali lye and absorbs by the 6th grade of residual micro-NO of the water absorption tower last person of institute gas
xWith HCl gas;
Condensing crystallizing still and centrifuge place bottom, the 7th grade of alkali absorption tower one side, be used for neutralization that the 7th grade of alkali lye absorption tower discharged completely solution carry out condensing crystallizing, centrifugation, to obtain to contain NaNO
3, NaNO
2And the mixing sodium salt of micro-NaCl;
Air-introduced machine is connected in the 7th grade of alkali lye absorption tower outlet pipe end, is used to make in seven grades of absorption towers of the oxidizing reactor and the first order to the produce negative pressure, keeping along first to the 7th grade of tower forward flow of air-flow, and tail gas is discharged.
8. exhaust treatment system as claimed in claim 7 is characterized in that: described oxidizing reactor is provided with air intake.
9. exhaust treatment system as claimed in claim 7 is characterized in that: described the first six grade water absorption tower and the 7th grade of alkali lye absorption tower material are polypropylene, and inner-tower filling material is PP material baton round or shape of a hoof porcelain ring filler, and filler is multistage distribution.
10. exhaust treatment system as claimed in claim 7 is characterized in that: described the first six grade water absorption tower and the 7th grade of alkali lye absorption tower are connected with centrifugal pump of single stage type respectively.
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| CN103752159A (en) * | 2014-01-27 | 2014-04-30 | 北京航天动力研究所 | Flue gas treatment acid absorption system and method |
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| CN104649884A (en) * | 2013-11-21 | 2015-05-27 | 曾舟华 | Method and production device of preparing glyoxylic acid through catalytic oxidization of glyoxal by air with nitrogen oxide under normal pressure |
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Address after: 438600 Fengshan City, Huanggang province Luotian County, north of the town of water Yi Road, No. 428 Patentee after: HUBEI HONGYUAN PHARMACEUTICAL TECHNOLOGY CO., LTD. Address before: 438600 Fengshan City, Huanggang province Luotian County, north of the town of water Yi Road, No. 428 Patentee before: Hubei Hongyuan Pharmaceutical Co., Ltd. |
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Denomination of invention: Tail gas treatment method and system for producing glyoxylic acid by oxidation of glyoxal with nitric acid Effective date of registration: 20220512 Granted publication date: 20130731 Pledgee: Industrial and Commercial Bank of China Limited Luotian sub branch Pledgor: HUBEI HONGYUAN PHARMACEUTICAL TECHNOLOGY Co.,Ltd. Registration number: Y2022420000116 |
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