CN1086146C - Tail gas contg. ammonia and methylamine - Google Patents
Tail gas contg. ammonia and methylamine Download PDFInfo
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- CN1086146C CN1086146C CN99113815A CN99113815A CN1086146C CN 1086146 C CN1086146 C CN 1086146C CN 99113815 A CN99113815 A CN 99113815A CN 99113815 A CN99113815 A CN 99113815A CN 1086146 C CN1086146 C CN 1086146C
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- tail gas
- absorption tower
- methylamine
- absorption
- ammonia
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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
The present invention relates to a method for absorbing tail gas containing ammonia and methylamine, which mainly solves the problem that in order to ensure that ammonia and amine in tail gas are fully absorbed, low methanol consumption and low energy consumption of repeated distillation can not be simultaneously obtained in the prior art. In the present invention, by adopting a two-segment single-tower absorption technology, tail gas at the lower segment of an absorption tower is firstly absorbed by methanol; then tail gas at the upper segment of the absorption tower is absorbed by water. By adopting the method of the present invention, the problem is completely solved. The method can be used in industrial production.
Description
The present invention relates to contain ammonia and methylamine tail gas absorption method.
Methylamine is the raw material of medicine, agricultural chemicals, solvent, dyestuff, resin, rubber and explosive, also can be used as color additive, catalyst, polymerization inhibitor and antioxidant, and purposes is very extensive.
Industrial normally in the presence of the silica-alumina catalyst of aluminium oxide, silica-aluminium oxide and so on, methyl alcohol and ammonia successive reaction are made methylamine.Reaction generally is in high pressure and 300～500 ℃ of temperature ranges, carries out in gas phase.Product monomethyl amine, dimethylamine and trimethylamine distribute and form near thermodynamical equilibrium, and trimethylamine content is the highest, and monomethyl amine and dimethylamine are lower, and this class catalyst is commonly referred to as equilibrium catalyst.Because dimethylamine is at the industrial chemical intermediate that is widely used as, therefore, the main purpose product of methyl alcohol or dimethyl ether aminating reaction is a dimethylamine.For improving dimethylamine output, reducing trimethylamine output, industrial common employing circulates unnecessary trimethylamine, adjust the catalyst of raw material nitrogen/carbon ratio and application enhancements.
The eighties mid-term, the industrial appearance uses zeolite catalyst to produce the method for methylamine, methyl alcohol and ammonia are made methylamine by the zeolite catalyst of modenite and so on, product monomethyl amine, dimethylamine, trimethylamine distribute away from thermodynamic equilibrium value, can generate dimethylamine by highly selective, greatly reduce the generation of trimethylamine, this type of catalyst is called the unbalanced type catalyst.But the greatest drawback that this type of unbalanced type catalyst exists is a trimethylamine can not be transformed into dimethylamine by the thermodynamical equilibrium circulation, can only go to be separated to subsequent processing, uses as the purpose product.In a sense, this method has limited the total output of dimethylamine greatly, and relevant technology in this respect has more document to mention.In the following passage, summarize relevant with the field of the invention representational unbalanced type catalyst aspect document.
In the United States Patent (USP) 4082805, Kaeding discloses ZSM-5, ZSM-11 or ZSM-21 zeolite catalyst has been used for ammonia and C
1～C
5Alcohol reacts the method for making amine.
In United States Patent (USP) 4254061, Weiget discloses a kind of modenite with Li, Na, K, Ca, Sr, Ba, Ce, Cr modification, ferrierite, erionite ore, clinoptilolite ore catalyst, methyl alcohol and ammonia react are to improve the methylamine manufacture method of monomethyl amine productive rate.
Introduce in the flat 2-2876 of Japan special permission communique, Alkali-Metal Na, K and be catalyst through the natural H type modenite or the synthetic H type modenite of steam treatment modification are carried out methyl alcohol and ammonia aminating reaction and can preferentially be generated dimethylamine and monomethyl amine.
Among the flat 2-16743 of Japan's special permission communique, a kind of natural mordenite zeolite of Alkali-Metal Na, K, Li modification or method that synthesizing flokite is selected synthesizing dimethylamine of adding disclosed.
In United States Patent (USP) 4398041, disclose a kind of with C
1～C
4Alcohol and ammonia be converted into that non-equilibrium thermodynamics distributes primary, the method for the second month in a season and alkyl amine.This method is used two reactors, and first reactor charge is selected shape crystal aluminosilicate unbalanced type catalyst, can selectivity generate an alkyl replacement and two fatty amines that alkyl replaces; Second reactor is equipped with equilibrium catalyst, a first reactor effluent part is sent to centrifugal station, a part is sent to centrifugal station then by second reactor, in first reactor part distillate that centrifugal station merges and second reactor effluent primary, secondary, tertiary amine be distributed as non-equilibrium composition.
Ri Dong chemical company dimethylamine selects synthesis technique also to be to use two reactors, first reactor charge " is selected shape " acid-treated natural mordenite catalyst, and what reaction generation ratio was higher is dimethylamine, but still has unnecessary monomethyl amine and trimethylamine.Unnecessary monomethyl amine and trimethylamine are by filling equilibrium catalyst (SiO for example
2-Al
2O
3) second reactor and be partially converted to dimethylamine.
The processing method that does not all relate to ammonia and methylamine tail gas in the production of methylamine in the above-mentioned document.And in methylamine is produced, can produce some tail gas, its source mainly is that each tower is to keep the gas that routine operating pressure discharges.Because methylamine has the strong impulse smell, is the chemical substance of strict control in the environmental protection.Therefore, must adopt a kind of absorption technique, the tail gas that this part is discharged absorbs reuse, to reduce the pollution to atmosphere, also can reduce material consumption simultaneously.
The absorption technique of present industrial employing has two kinds.A kind of is to be that absorbent absorbs ammonia and the methylamine in the tail gas with methyl alcohol, and its flow process is the double-column process (see figure 1).Reclaiming methyl alcohol 7 descends to the absorption tower top spray after the chilled brine cooling of absorption liquid cooler 3 with the fresh methanol of adding 8.Tail gas enters 1 bottom, first absorption tower behind surge tank 4, with methyl alcohol absorption liquid counter current contacting, be absorbed most of ammonia, methylamine after, come out to enter 2 bottoms, second absorption tower from cat head, after absorbing with methyl alcohol absorption liquid counter current contacting again, emptying.The characteristics of this flow process are to utilize methyl alcohol to ammonia, characteristics that methylamine solubility is big, and the direct dereaction of the methanol solution workshop section after absorbing simultaneously can not influence the performance of catalyst as the charging of reactor, and energy consumption is lower.Its shortcoming is the flow process more complicated, carries a part of methyl alcohol in the tail gas of emptying secretly, can increase the consumption of methyl alcohol like this.
The another kind of absorption technique of industrial utilization is to be absorbent with water, single tower flow process (see figure 2).This tail gas absorption technology flow process is simple, does not increase the consumption of methyl alcohol.Its shortcoming is to fluctuate when big when tail gas, and water absorbs insufficient, and the unabsorbed ammonia of part, methylamine emptying are arranged, and influences environmental protection, has increased consumption.The absorption liquid concentration of its water is not high simultaneously, goes deammoniation tower to repeat distillation, will increase public work consumption.
To the objective of the invention is in order overcoming in the prior art lowly and consume the low defective that can not get both simultaneously of energy input, a kind of new ammonia and methylamine tail gas absorption method of containing to be provided because of repeating to distill for guaranteeing in the tail gas that methylamine fully absorbs the consumption that has methyl alcohol.This method has methylamine in the tail gas, ammonia can fully absorb, and the consumption of methyl alcohol is low, simultaneously the also low characteristics of the energy consumption of Xiao Haoing.
The objective of the invention is to realize: a kind of ammonia and methylamine tail gas absorption method of containing by following technical scheme, use and divide upper and lower two sections absorption tower, the tail gas that contains ammonia and methylamine enters from the bottom, absorption tower, earlier through absorption tower hypomere top spray and the absorption of methyl alcohol down, gas after the absorption tower hypomere absorbs is again through absorption tower epimere top spray and water down absorbs, and the gas after the absorption of absorption tower epimere is discharged by top, absorption tower.
Absorption tower epimere or hypomere adopt filler or column plate in the technique scheme.Filler is selected from dumped packing or structured packing, and material adopts pottery, carbon steel or stainless steel.The theoretical cam curve of absorption tower epimere is 4～15, the theoretical cam curve of hypomere is 5～20, absorption tower hypomere top spray and under the temperature of methyl alcohol be 4～40 ℃, preferable range is 15～25 ℃, absorption tower epimere top spray and under the temperature of water be 0～20 ℃, preferable range is 0～5 ℃.The absorbent spray flux does not limit, and can determine according to the tower of specific design.
Under the condition of 20 ℃ of normal pressures, one, two, the solubility of trimethylamine in methanol solvate is respectively: 1.049 gram/grams, 2.310 gram/grams, 1.751 gram/grams.Solubility in water is respectively: 0.00155 gram/gram, 0.00376 gram/gram, 0.00158 gram/gram.From above data as can be seen, one, two, the solubility of trimethylamine in methyl alcohol is much larger than the solubility in water.
In this technology, the absorption tower is single tower two-period form structure.The absorption tower hypomere utilizes the big characteristics of methyl alcohol solubility that the very big part ammonia of tail gas, methylamine are absorbed, the methyl alcohol absorption liquid can be directly as the charging of reactor.The absorption tower epimere uses water as absorbent, and circulation absorbs, the gap discharging.Its effect mainly is that water further absorbs when the big and methyl alcohol of tail gas fluctuation can not absorb fully, guaranteeing that ammonia, methylamine content reach the discharge value of permission in the tower top discharge tail gas, and farthest reclaims materials such as ammonia, methylamine, the reduction material consumption.
Owing to absorb with methyl alcohol earlier, water absorbs then among the present invention, when making the tail gas fluctuation big, need not to absorb with a large amount of methyl alcohol, has reduced the consumption of methyl alcohol.The amount of ammonia and methylamine seldom in the tail gas after methyl alcohol absorbs, water further absorbs, can guarantee the abundant absorption of ammonia in the tail gas, methylamine amount on the one hand, on the other hand, because the water yield that consumes is also lower, reduced the energy consumption that repeats to distill, the third aspect is because the saturated vapor of methyl alcohol is water-soluble, guaranteed not contain methyl alcohol, ammonia, methylamine in the tail gas of emptying, reduced influence, obtained effect preferably environment.
Fig. 1 absorbs double-column process figure for methyl alcohol.
Fig. 2 absorbs tail gas list tower flow chart for water.
Fig. 3 absorbs flow chart for tail gas of the present invention.
In Fig. 1,1 is the 1st absorption tower, and 2 is the 2nd absorption tower, and 3 is the absorption liquid cooler, and 4 is surge tank, and 5 is the methyl alcohol storage tank, and 6 is tail gas, and 7 for reclaiming methyl alcohol, and 8 for replenishing fresh methanol, and 9 is dereaction workshop section.
In Fig. 2,10 is the absorption tower, and 11 is cooler, and 12 is surge tank, and 13 is tail gas, and 14 for removing the deammoniation tower absorption liquid, and 15 is supplementing water.
In Fig. 3,16 is the absorption tower, and 17-1 is the absorption tower epimere, and 17-2 is the absorption tower hypomere, and 18 is cooler, and 19 is tail gas, and 20 is methyl alcohol, and 21 is the charging of dereaction device, and 22 is supplementing water, and 23 for removing the deammoniation tower material.
The invention will be further elaborated below by embodiment.[embodiment 1]
The tail gas that contains ammonia and methylamine consists of: hydrogen per hour is 4.5 kilograms, and CO per hour is 35.3 kilograms, NH
3Per hour be 16.2 kilograms, monomethyl amine per hour is 16.5 kilograms, and dimethylamine per hour is 8.7 kilograms, and trimethylamine per hour is 18.6 kilograms, and nitrogen is 83.0 kilograms.Exhaust temperature is 25 ℃, and pressure is 0.15MPa.This tail gas enters the bottom of absorption tower hypomere among Fig. 3.The two sections on absorption tower are respectively adorned the metal intalox saddle of 25 millimeters of 8 meters high φ.The absorption tower diameter is 0.6 meter, and the temperature of absorption tower hypomere recycle methanol is 20 ℃, and the temperature of absorption tower epimere recirculated water is 4 ℃.Per hour replenish and reclaim 103.20 kilograms of methyl alcohol (the methyl alcohol concentration expressed in percentage by weight is 90%, and all the other are water).Upper and lower two sections circulation fluid scale of constructions are 3.0 times of charging tolerance.Tail gas enters the amine and the methyl alcohol that have only trace in the gas of epimere after hypomere methyl alcohol absorbs, all the other are H
2, CO, N
2, after water absorbs, have only H in the discharging tail gas again
2, CO, N
2And saturated vapor.[embodiment 2]
Press each Step By Condition of embodiment 1, just change the tail gas inlet amount, make tail gas inlet amount 1.5 times for embodiment 1.Tail gas is after hypomere methyl alcohol absorbs, and entering in the gas of epimere still has 3 kilograms ammonia and 7.9 kilograms total amine amount and saturated methyl alcohol, and all the other are H
2, CO, N
2After epimere water absorbs, has only H in the discharging tail gas again
2, CO, N
2And saturated vapor.[comparative example 1]
The tail gas of pressing among the embodiment 1 is formed and inlet amount, and the methyl alcohol that enters among Fig. 1 absorbs double-column process.The metal intalox saddle of 25 millimeters of 8 meters high φ is respectively loaded on two methyl alcohol absorption towers, the tower diameter of two towers is 0.6 meter, the methanol loop absorption liquid temperature of two towers is 20 ℃, per hour additional methyl alcohol is 103.20 kilograms, and (concentration expressed in percentage by weight is 98.0%, all the other are water), the circulation fluid scale of construction is 3.0 times of charging tolerance.After two towers absorb, do not contain ammonia and amine substantially in the discharging tail gas, the overwhelming majority is H in the discharging tail gas
2, CO, N
2With the methyl alcohol of carrying secretly.The methyl alcohol amount of carrying secretly is 4.0 kilograms.[comparative example 2]
The tail gas of pressing among the embodiment 1 is formed and inlet amount, and the water that enters among Fig. 2 absorbs tail gas list tower flow process.The metal intalox saddle that the φ that this absorption tower filling is 16 meters is 25 millimeters, the absorption tower diameter is 0.6 meter, and the temperature of water circulating absorption solution is 4 ℃, and per hour supplementing water is 415 kilograms, and the circulation fluid scale of construction is 3.0 times of air inflow.After water absorbs, do not contain ammonia and amine in the discharge tail gas substantially, the overwhelming majority is H
2, CO, N
2With the water of carrying secretly.In the water absorption liquid, moisture 85.0% (weight), all the other are ammonia and methylamine.This absorption liquid returns distillation system and repeats distillation increase energy consumption more than 150 kilowatts.[comparative example 3]
Press each condition and the step of comparative example 2, just charging tail gas amount is 1.5 times of comparative example 2.After water absorbs, also contain 2.0 kilograms of ammonia and 5.8 kilograms of amine in the discharging tail gas, all the other are H
2, CO, N
2With the water of carrying secretly.Moisture 78.0% (weight) in the water absorption liquid, all the other are ammonia and amine.This absorption liquid returns distillation system and repeats rectifying increase energy consumption more than 120 kilowatts.
Claims (5)
1, a kind of ammonia and methylamine tail gas absorption method of containing, use and divide upper and lower two sections absorption tower, the tail gas that contains ammonia and methylamine enters from the bottom, absorption tower, earlier through absorption tower hypomere top spray and the absorption of methyl alcohol down, gas after the absorption tower hypomere absorbs is again through absorption tower epimere top spray and water down absorbs, and the gas after the absorption of absorption tower epimere is discharged by top, absorption tower.
2,, it is characterized in that absorption tower epimere or hypomere adopt filler or column plate according to described ammonia and the methylamine tail gas absorption method of containing of claim 1.
3, according to described ammonia and the methylamine tail gas absorption method of containing of claim 2, it is characterized in that the filler that adopts in the absorption tower is dumped packing or structured packing, material adopts pottery, carbon steel or stainless steel.
4, according to described ammonia and the methylamine tail gas absorption method of containing of claim 1, the theoretical cam curve that it is characterized in that the absorption tower epimere is 4～15, the theoretical cam curve of hypomere is 5～20, absorption tower hypomere top spray and under the temperature of methyl alcohol be 4～40 ℃, absorption tower epimere top spray and under the temperature of water be 0～20 ℃.
5, according to described ammonia and the methylamine tail gas absorption method of containing of claim 1, it is characterized in that absorption tower hypomere top spray and under the temperature of methyl alcohol be 15～25 ℃, absorption tower epimere top spray and under the temperature of water be 0～5 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113815A CN1086146C (en) | 1999-06-24 | 1999-06-24 | Tail gas contg. ammonia and methylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113815A CN1086146C (en) | 1999-06-24 | 1999-06-24 | Tail gas contg. ammonia and methylamine |
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| Publication Number | Publication Date |
|---|---|
| CN1287873A CN1287873A (en) | 2001-03-21 |
| CN1086146C true CN1086146C (en) | 2002-06-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99113815A Expired - Lifetime CN1086146C (en) | 1999-06-24 | 1999-06-24 | Tail gas contg. ammonia and methylamine |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101708453B (en) * | 2009-11-24 | 2013-03-27 | 中冶长天国际工程有限责任公司 | Separation tower plate for segmental type reaction tower |
| CN102179135B (en) * | 2011-04-26 | 2013-04-10 | 苏州利盛化工设备有限公司 | Ammonia absorption device |
| CN102794084A (en) * | 2011-05-27 | 2012-11-28 | 中国石油化工集团公司 | Absorption tower and gas recovery method |
| CN102343205B (en) * | 2011-07-18 | 2014-06-25 | 南京华基塔业有限公司 | Centralized purification treatment process and device of waste gas in spandex production process |
| CN102942488B (en) * | 2012-11-02 | 2014-10-15 | 天津大学 | Regeneration technology of recovered methylamine solution and device thereof |
| CN102976950A (en) * | 2012-12-18 | 2013-03-20 | 天津天智精细化工有限公司 | Improved process for preparing tertiary amine |
| CN103768923B (en) * | 2014-02-12 | 2015-01-28 | 南京大学环境规划设计研究院有限公司 | Multi-stage gradient absorption device and device for low- and medium-concentration dimethylamine waste gas |
| CN111905527A (en) * | 2020-07-07 | 2020-11-10 | 山西钢科碳材料有限公司 | Exhaust gas treatment system and treatment method thereof |
| CN114082746A (en) * | 2020-08-25 | 2022-02-25 | 中国石油化工股份有限公司 | Waste gas absorption treatment method in catalyst production process and system and application thereof |
-
1999
- 1999-06-24 CN CN99113815A patent/CN1086146C/en not_active Expired - Lifetime
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Granted publication date: 20020612 |