CN1827561B - Process for nitrification of organics - Google Patents
Process for nitrification of organics Download PDFInfo
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- CN1827561B CN1827561B CN200610012586A CN200610012586A CN1827561B CN 1827561 B CN1827561 B CN 1827561B CN 200610012586 A CN200610012586 A CN 200610012586A CN 200610012586 A CN200610012586 A CN 200610012586A CN 1827561 B CN1827561 B CN 1827561B
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Abstract
A new technology technology for nitration of organic material is disclosed that belongs to the field of nitrifying organic material, turning liquid ammonia as raw material into nitrogen oxide after the technique of catalytic oxidation, getting them into the waste gas absorption tower of the technique of nitrifying organic material, turning into diluted hydrogene nitrate or mixed acid after being absorbed as nitrosation agent of the said technology of nitrifying organic material, no using adscititious hydrogene nitrate in this process, so changing the route of traditional technologic raw material, and this productive technology can save raw material and productive cost and bring considerable economical benefit.
Description
Technical field
The invention discloses a kind of organic process for nitrification, belong to organic nitration processes field.
Technical background
Nitrated is in organic molecule, to introduce nitro (NO
2) reaction process, different according to by the character of itrated compound and used nitrating agent, nitrifying method be mainly rare nitric acid nitrating, concentrated nitric acid nitrated, in the vitriol oil with nitric acid nitrating and heterogeneous mixed acid nitrification etc.Wherein mixed acid nitrification is mainly used in the nitrated of benzene, toluene and chlorobenzene etc.With the oil of mirbane production technique is example; Present traditional nitrofication process is benzene and nitric acid, sulfuric acid (being nitration mixture) to be added in the kettle type nitration device (also claiming nitrated pot) carry out, and reaction can intermittence or carried out continuously, and used nitration mixture consists of: sulfuric acid 56%-65%; Nitric acid 20%-26%; Water 15%-18% (quality), nitrated temperature is controlled at 50-55 ℃, and the reaction later stage can rise to 70-75 ℃.
Kettle type nitration technology is domestic and international traditional nitration processes, reacts more steady, is easy to control, constant product quality, and equipment manufacturing cost is lower, and technology maturation is still adopted by most of full scale plants so far.But what consume during mixed acid nitrification is nitric acid, nitro (NO of every introducing
2) consume the nitric acid of a molecule, produce the water of a molecule simultaneously, so along with the carrying out of technological process, the spent acid that is produced is the sulfuric acid of lower concentration, must go to utilize through concentrating in the ability retrieval system again.For a long time, the spissated method first of spent acid is used the coal direct heating with big iron pan boiling.Because service temperature is high, equipment corrosion is serious, and maintenance workload is big, and the waste water and gas amount of generation is big, severe operational environment; It two is electron tubes type thickeners, service temperature 150-160 ℃, adopt the MP steam heating because temperature is higher, well heater is selected the tantalum material for use, tantalum is a precious metal, the per kilogram price up to 8000 yuan about.
Technology contents
The objective of the invention is to disclose a kind of organic process for nitrification, this technology still is still formula continuous nitrification technology basically, just on spent acid is handled, does not adopt the heating concentrating means, in spent acid, introduces NO and adopt
2Method, with spent acid absorption of N O
2, produce the nitration mixture of desired concn ratio simultaneously.Because molecule nitric acid of the every consumption of nitration reaction process just can produce the moisture of a molecule, and the NO of a molecule of the every absorption of spent acid
2The moisture that then needs a molecule, the result except product carry secretly small amount of moisture and acid need adjustment a little additional, the whole process of production material is in equilibrium state.Need not add nitric acid in the production, thereby change the traditional technology raw material route.
The present invention realizes through following technical scheme:
A kind of organic process for nitrification; Used nitrating agent is nitric acid or the nitration mixture be made up of sulfuric acid and nitric acid; Raw material is a liquefied ammonia, after catalyzed oxidation technology, becomes oxynitride by liquefied ammonia; Get into the spent acid absorption tower in the organic nitration processes again, become rare nitric acid or nitration mixture after being absorbed by spent acid.
Above-mentioned a kind of organic process for nitrification, described liquefied ammonia catalyzed oxidation technology can be carried out under pressurization or non-pressure process.
The advantage of this process for nitrification:
1, spent acid need not concentrate, and economizes the heat-exchange equipment of doing except the expensive metal tantalum, has practiced thrift the energy simultaneously.In facility investment, the equipment of new oil (gas) filling device and saving is similar, but aspect energy conservation, is about 80 yuan by oil of mirbane finished product calculating per ton; NH
3The high temperature that catalyzed oxidation the produced value that is used to produce steam can offset NO
2The energy consumption of gas blower and water coolant is worth in the generating unit.
2, use NH
3Make raw material ratio and make raw material, produce cost-saved about 620 yuan of oil of mirbane per ton, calculate as follows with 98% concentrated nitric acid:
1., NH3 per ton is equivalent to 3.78 ton of 98% concentrated nitric acid
63/17÷0.98＝3.78
2., consume 98% concentrated nitric acid 550kg calculating by oil of mirbane finished product per ton, then
0.55 * [1600-(2000 ÷ 3.78)]=589 yuan/ton
The price of 98% concentrated nitric acid is 1600 yuan/ton, and the price of 100% liquefied ammonia is 2000 yuan/ton.Add the trucking costs of saving, oil of mirbane cost per ton reduces about 620 yuan approximately.
1,2 binomials add up to oil of mirbane cost per ton can practice thrift 700 yuan, calculate annual cost-saved 28,000,000 yuan by 40,000 tons of/year scales of producing oil of mirbane.
Description of drawings
Fig. 1 is that the nitration processes with benzene is the process flow sheet of example.
Among the figure 1, loop reactor 2,3,4, kettle type nitration pot 5, separator 6, washing pot 7, distillation tower 8, rectifying tower 9, ammonia strainer 10, ammonia, air mixer 11, air filter 12, gas blower 13, oxidized still 14, waste heat boiler 15, flash cooler 16, liquefied ammonia vaporizer 17, spent acid absorption tower.
Embodiment
Liquefied ammonia gets into liquefied ammonia vaporizer 16 after the under meter metering, the back of coming out becomes gas ammonia, behind the gas ammonia process ammonia strainer 9; Get into ammonia, air mixer 10, meanwhile, get into ammonia, air mixer 10 through gas meter metering back behind the bag filtration of air in air filter 11; Ammonia and air behind the thorough mixing, get into preheater through gas blower 12 pressurizations, with the high temperature nitrogen oxide gas heat exchange from waste heat boiler 14 in mixing tank; The temperature of mixed gas is preheating to 65-75 ℃ by 35 ℃, further purifies through the cardboard filter device again, gets into oxidized still 13; On three platinum guazes, carry out oxidation, temperature of reaction is about 800-820 ℃, and the high temperature nitrogen oxide gas directly gets into waste heat boiler 14 recovery waste heats; The gas temperature that goes out boiler is reduced to 150-170 ℃, gets in the flash cooler 15 again, is cooled 45-50 ℃ at this gas; Because gas directly contacts with liquid, the ammonia in the remaining ground gas is washed down, and prevents that ammonium salt from bringing the oil of mirbane system into.Oxides of nitrogen gas gets into liquefied ammonia vaporizer 16 to be continued to be cooled to below 20 ℃, and the moisture in the gas is further cooled and separates like this, and oxides of nitrogen gas low more helping more of temperature is absorbed simultaneously.Nitrogen protoxide gets into spent acid absorption tower 17, answers with the air generation oxidation that the bottom, absorption tower replenishes into, obtains the high oxide NO of nitrogen
2, N
2O
3, N
2O
4, its chemical equation is: 2NO+O
2=2NO
2Δ H=-112.6KJ
NO+NO
2＝N
2O
3?ΔH＝-40.6KJ
2NO
2＝N
2O
4?ΔH＝-56.9KJ
NO is a colourless gas, is slightly soluble in water, NO
2Be brown gas, generate nitric acid, gaseous state NO with the water effect
2Can partly be superimposed into N at low temperatures
2O
4, N
2O
3Be easy to resolve into NO and NO at normal temperatures
2Above-mentioned three reactions all are reversible exothermic reactions, and reaction back mole number reduces, so the carrying out that temperature reduces, pressure boost helps the NO oxidizing reaction.Oxynitride (mainly is NO
2) after the spent acid counter-current absorption under 17 bottoms, spent acid absorption tower and the cat head spray, become nitration mixture; Nitration mixture flows out the outer back of tower according to nitric acid and vitriolic part by weight, can mend into a certain amount of fresh vitriol oil, after nitric acid, sulfuric acid part by weight are qualified; Send into loop reactor 1 again; And in loop reactor 1, add excessive benzene, more successively through second, third, the 4th kettle type nitration pot 2,3,4 carries out continuous nitrification, advances separator 5 from the 4th kettle type nitration pot 4 effusive acid oil of mirbane; The acid oil of mirbane on upper strata advances the neutralization pot again and obtains thick oil of mirbane with washing pot 6, and thick oil of mirbane obtains finished product oil of mirbane through distillation tower 7, rectifying tower 8 again.The spent acid of separator lower floor (mainly being dilute sulphuric acid, about 0.5% nitric acid) is delivered to spent acid absorption tower 17 quantitatively by pump and is removed absorption of N O
2The waste gas that cat head comes out is handled according to the amount of nitrogen oxides situation, or emptying, or goes out-of-bounds to handle.
Claims (1)
1. the nitration processes of a benzene; Used nitrating agent is nitric acid or the nitration mixture be made up of sulfuric acid and nitric acid in the technology, and it is characterized in that: raw material is a liquefied ammonia, by liquefied ammonia after catalyzed oxidation technology; Become oxynitride; Get into the spent acid absorption tower in the nitration processes of benzene again, become rare nitric acid or nitration mixture after being absorbed by spent acid, as the nitrated used nitrating agent of benzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610012586A CN1827561B (en) | 2006-04-13 | 2006-04-13 | Process for nitrification of organics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610012586A CN1827561B (en) | 2006-04-13 | 2006-04-13 | Process for nitrification of organics |
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| Publication Number | Publication Date |
|---|---|
| CN1827561A CN1827561A (en) | 2006-09-06 |
| CN1827561B true CN1827561B (en) | 2012-08-29 |
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ID=36946145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200610012586A Expired - Fee Related CN1827561B (en) | 2006-04-13 | 2006-04-13 | Process for nitrification of organics |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114749005A (en) * | 2022-05-09 | 2022-07-15 | 盛隆资源再生（无锡）有限公司 | VOCs waste gas treatment method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035645A (en) * | 1988-03-10 | 1989-09-20 | 烟台合成革厂 | Aromatic hydrocarbon sulphuric acid after nitrifying cyclic utilization method |
| CN1038447A (en) * | 1988-06-06 | 1990-01-03 | 南京药物研究所 | Technology for nitration of ortho-dichlorobenzene with mixed acid processing |
-
2006
- 2006-04-13 CN CN200610012586A patent/CN1827561B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035645A (en) * | 1988-03-10 | 1989-09-20 | 烟台合成革厂 | Aromatic hydrocarbon sulphuric acid after nitrifying cyclic utilization method |
| CN1038447A (en) * | 1988-06-06 | 1990-01-03 | 南京药物研究所 | Technology for nitration of ortho-dichlorobenzene with mixed acid processing |
Non-Patent Citations (1)
| Title |
|---|
| 王明甫等."美国全高压法二手硝酸装置概况及开车总结".《泸天化科技》.1995,(第4期),241-247. |
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|---|---|
| CN1827561A (en) | 2006-09-06 |
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