CN1393405A - Process for purifying and recovering ammonia gas - Google Patents
Process for purifying and recovering ammonia gas Download PDFInfo
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- CN1393405A CN1393405A CN 01114164 CN01114164A CN1393405A CN 1393405 A CN1393405 A CN 1393405A CN 01114164 CN01114164 CN 01114164 CN 01114164 A CN01114164 A CN 01114164A CN 1393405 A CN1393405 A CN 1393405A
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- ammonia
- hydrogen sulfide
- ammonia gas
- crystallizer
- purifying
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Abstract
A process for purifying and recovering ammonia gas as a chemical feed gas includes such steps as adding the raw ammonia gas containing hydrogen sulfide in a crystallizer, carrying on reaction between ammonia gas and hydrogen sulfide at 0-25 deg.C and under 0.3 MPa while crystallizing through desublimation, removing the crystal, loading the residual gas in an adsorption tower, adsorbing the hydrogen sulfide at 20-40 deg.c by an adsorbent which removes hydrogen sulfide, and liquefying the ammonia gas by a compressor. Its advantages are no secondary pollution and simple operation.
Description
The present invention relates to the method for purifying and recovering of ammonia, mainly relate to contain the ammonia decontamination recovery method of hydrogen sulfide.
In the rich gas washing process of devices such as refinery secondary processing process such as catalytic cracking, coking, desulfurization, reformation, hydrogenation, can produce acid waste water (waste water of sulfur-bearing and ammonia), the most frequently used treatment process of these waste water is a steam stripped, and stripping has two kinds in double tower and single tower.These two kinds of gas stripping process all can remove sour gas and (mainly contain H
2S) and ammonia (include the H of different concns
2S) or ammoniacal liquor.
Be commonly used to purify H in the ammonia at present
2The method of impurity such as S is the strong aqua washing, H in the ammonia
2Impurity and strong aqua reaction generation sulphur hydrogenation ammonia, sulfuration ammonia etc. such as S, thereby with H
2Impurity such as S are removed, and to reach the purpose that purifies ammonia, the subject matter that this method exists has: 1, H in the ammonia
2The S remaining quantity is higher, about 100 μ g/g; 2, secondary pollution is arranged, it is pending to produce alkaline residue; 3, the liquefied ammonia consumption is big; 4, flow process is complicated, and equipment is many.
English Patent GB2252308 discloses a kind of method that removes sour gas from gaseous mixture, this method mainly comprises with the solvent absorbing acid gas with the vaporizing extract process spent solvent of regenerating, used solvent is made up of the aqueous mixture of dimethylethanolamine, and the concentration of dimethyl ethanol is between the 30%-70% (weight).Though this method can remove sour gas preferably, but still exist the running cost height, there are shortcomings such as environmental pollution in complicated operation.
For overcoming above deficiency, the invention provides a kind of method that removes hydrogen sulfide in the ammonia, flow process is simple, processing ease, the ammonia purity height after the purification.
We find in experiment, NH
3And H
2S under the condition that reaches below 25.5 ℃, wherein a part of NH
3And H
2S begins to be become by gaseous state solid-state, and temperature reduces, and crystallisate increases, and is called the process of sublimating, the resultant mica shape that is white in color.After deliberation, think that its cardinal principle is because following reaction has taken place:
1、
2、
According to above-mentioned discovery, the method that we have invented a kind of crying " crystallization-absorption " is made with extra care the ammonia behind the stripping, comprise: the described ammonia raw material that contains hydrogen sulfide impurities at first enters crystallizer, at pressure is normal pressure～0.30Mpa, be preferably normal pressure～0.13Mpa, temperature is 0～25 ℃, be preferably under 3～10 ℃ the condition, hydrogen sulfide is sublimated into crystallization with the reactant of ammonia, attached on the crystallization plates of crystallizer and be removed, unreacted minute quantity hydrogen sulfide and ammonia enter the adsorption tower that sorbent material is housed, and temperature is generally 20～40 ℃ in the tower, be preferably 25～35 ℃, pressure is generally normal pressure～0.20Mpa, is preferably normal pressure～0.10Mpa, and hydrogen sulfide is adsorbed agent absorption and removes, ammonia after the purification can be used as product and directly uses, and for example is compressed into liquefied ammonia and directly makes industrial chemicals.
The concentration of hydrogen sulfide can be 0.01%～1.00% (in the scope v) in the ammonia that contains hydrogen sulfide of the present invention, generally be 0.10%～0.50% (v), the acid waste water that produced of refinery secondary processing device for example is through the resulting ammonia that contains hydrogen sulfide of deamination treating processes.
Low temperature environment in the described crystallizer can adopt the method for injecting liquefied ammonia to realize, and inject the amount of liquefied ammonia and mainly adjust according to the service temperature of crystallizer, generally be 5%～10% of handled ammonia gross weight.
Sorbent material in the described adsorption tower generally is porous masses such as gac or aluminum oxide.
In the described crystallizer some crystallization plates can be set, enlarging the crystallization area, the increase capacity, what of the size of crystallizer and crystallization plates mainly are to determine that according to institute's ammonia amount to be processed and ammonia character the crystallization plates number generally is 2～10.Usually, the volume space velocity of ammonia in crystallizer should be: 10～40h
-1, the volume space velocity of indication is per hour to enter the ammonia of crystallizer at the ratio of 25 ℃ of following standard volumes with the cubic capacity of crystallizer herein.Generally can be welded with spacing on the crystallization plates is 100-200mm, φ 10-φ 20, and height is the round steel post of 100-200mm, and crystallization plates is the 2/3-1/2 circle, and the crystallization plates spacing is 300-500mm.
The size of described adsorption tower and the loading amount of sorbent material are according to handled gas volume and gas property decision, and the volume space velocity of handled gas in adsorption tower is generally at 20～60h
-1Scope in, the indication volume space velocity is meant the ratio of the standard volume of the per hour handled gas of adsorption tower under 25 ℃ and the volume of sorbent material herein.
Crystallizer of the present invention can be by stopping transport or switch new crystallizer when using productive rate low, and the method that the water filling flushing dissolves away crystallisate in the crystallizer that lost efficacy is handled, and the crystallizer after the processing can continue to use.
When the adsorbents adsorb efficient of adsorption tower reduced, also changeable new adsorption tower or stoppage in transit fed superheated vapour in the adsorption tower that lost efficacy, sorbent material is regenerated.
Compared with prior art, the present invention has following beneficial effect:
The reactant that the present invention has utilized ammonia and hydrogen sulfide is the crystalline principle under given conditions, remove the hydrogen sulfide in the ammonia, 90%～95% hydrogen sulfide stripping in the ammonia can be fallen by crystallisation by cooling like this, remaining remaining hydrogen sulfide just can fall by adsorbents adsorb, thereby obtain more purified ammonia, just can obtain industrial liquefied ammonia after compression.This method does not have secondary pollution, and is simple to operate, is fit to industrial application.
Following examples are described in further details the present invention.
Embodiment 1-4
Following embodiment 1-4 handles that each component consists of in the unstripped gas: NH
398.3v%H
2S 0.6v% phenol＜0.25mg/l CN
-0.21mg/l O
20.25v%H
20.72v%.
The basic procedure that embodiment 1-4 is adopted is: above-mentioned raw materials gas at first enters to be handled in the crystallizer, then after adsorption tower absorption, enter the pressurized liquefied product liquefied ammonia that promptly gets of ammonia compressor again, the low temperature environment in the crystallizer is to realize by the method for injecting product liquefied ammonia.
The crystallization plates number is 5 in the described crystallizer, and being welded with spacing on the crystallization plates is 150mm, and φ 15, and height is the round steel post of 150mm, and crystallization plates is 2/3 circle.
Other actual conditions and result are as shown in the table.
Annotate: remove H in the gas after the processing
2Outside the S, other impurity is not measured.
| Example | 1 | 2 | 3 | 4 |
| Crystallizer pressure, Mpa | 0.07 | 0.10 | 0.15 | 0.20 |
| The crystallizer temperature, ℃ | 10 | 7 | 5 | 0 |
| The volume space velocity h of gas in crystallizer -1 | 13 | 11 | 20 | 35 |
| Concentration of hydrogen sulfide μ g/g in the ammonia after crystallizer is handled | 3.8 | 4.0 | 2.5 | 0.5 |
| Adsorption column pressure, MPa | 0.02 | 0.07 | 0.12 | 0.16 |
| The adsorption tower temperature, ℃ | 30 | 33 | 35 | 32 |
| The volume space velocity h of gas in adsorption tower -1 | 20 | 19 | 28 | 44 |
| H in the liquefied ammonia 2S，μg/g | 4 | 3.5 | 2 | 0.5 |
Claims (9)
1, a kind of method of purifying and recovering ammonia gas, comprise: make the ammonia raw material that contains hydrogen sulfide impurities at first enter crystallizer, at pressure is normal pressure～0.30Mpa, temperature is under 0～25 ℃ the condition, hydrogen sulfide is sublimated into crystallization with the reactant of ammonia, attached on the crystallization plates of crystallizer and be removed, unreacted minute quantity hydrogen sulfide and ammonia enter the adsorption tower that sorbent material is housed, temperature is 20～40 ℃ in the tower, pressure is normal pressure～0.20Mpa, hydrogen sulfide is adsorbed agent absorption and removes the ammonia after being purified.
2,, it is characterized in that directly making industrial chemicals after ammonia after the described purification is compressed into liquefied ammonia according to the method for the described purifying and recovering ammonia gas of claim 1.
3, according to the method for the described purifying and recovering ammonia gas of claim 1, it is characterized in that the treatment condition in the described crystallizer are: pressure is normal pressure～0.13Mpa, and temperature is 3～10 ℃.
4, according to the method for the described purifying and recovering ammonia gas of claim 1, it is characterized in that the operational condition of described adsorption tower is: temperature is 25～35 ℃, and pressure is normal pressure～0.10Mpa.
5, according to the method for the described purifying and recovering ammonia gas of claim 1, the concentration that it is characterized in that hydrogen sulfide in the described ammonia raw material is in the scope of 0.01v%～1.00v%.
6, according to the method for the described purifying and recovering ammonia gas of claim 1, the concentration that it is characterized in that hydrogen sulfide in the described ammonia raw material is in the scope of 0.10v%～0.50v%.
7,, it is characterized in that the low temperature environment in the described crystallizer is to adopt the method for injecting liquefied ammonia to realize according to the method for the described purifying and recovering ammonia gas of claim 1.
8,, it is characterized in that the sorbent material in the described adsorption tower is gac or aluminum oxide according to the method for the described purifying and recovering ammonia gas of claim 1.
9,, it is characterized in that described crystallizer intercrystalline plate number is 2～10 according to the method for the described purifying and recovering ammonia gas of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011141646A CN1159220C (en) | 2001-07-02 | 2001-07-02 | Process for purifying and recovering ammonia gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011141646A CN1159220C (en) | 2001-07-02 | 2001-07-02 | Process for purifying and recovering ammonia gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1393405A true CN1393405A (en) | 2003-01-29 |
| CN1159220C CN1159220C (en) | 2004-07-28 |
Family
ID=4660835
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011141646A Expired - Lifetime CN1159220C (en) | 2001-07-02 | 2001-07-02 | Process for purifying and recovering ammonia gas |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100411986C (en) * | 2007-01-03 | 2008-08-20 | 葫芦岛市锦隆石化高科技有限责任公司 | Desulfurization refining method for ammonia gas containing hydrogen sulfide and ammonia gas finisher |
| CN106345255A (en) * | 2015-07-15 | 2017-01-25 | 中国石油化工股份有限公司 | Hydrogen sulphide-containing gas treatment method and device |
| CN106345254A (en) * | 2015-07-15 | 2017-01-25 | 中国石油化工股份有限公司 | Method and device for treating hydrogen sulfide-containing gas |
| CN106345136A (en) * | 2015-07-15 | 2017-01-25 | 中国石油化工股份有限公司 | Crystallization tower for gas-gas reaction |
| CN106474896A (en) * | 2015-11-12 | 2017-03-08 | 中国石油化工股份有限公司 | The processing method of sulfide hydrogen hydrocarbon-contained waste gas |
| CN109336133A (en) * | 2018-11-15 | 2019-02-15 | 山东联盛环保科技有限公司 | A kind of device and technique of negative pressure low temperature recycling high concentration ammonium hydroxide |
| CN115849401A (en) * | 2022-07-26 | 2023-03-28 | 苏州源展材料科技有限公司 | Preparation method and device of ammonia gas for preparing active metal complex in laboratory |
-
2001
- 2001-07-02 CN CNB011141646A patent/CN1159220C/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100411986C (en) * | 2007-01-03 | 2008-08-20 | 葫芦岛市锦隆石化高科技有限责任公司 | Desulfurization refining method for ammonia gas containing hydrogen sulfide and ammonia gas finisher |
| CN106345255A (en) * | 2015-07-15 | 2017-01-25 | 中国石油化工股份有限公司 | Hydrogen sulphide-containing gas treatment method and device |
| CN106345254A (en) * | 2015-07-15 | 2017-01-25 | 中国石油化工股份有限公司 | Method and device for treating hydrogen sulfide-containing gas |
| CN106345136A (en) * | 2015-07-15 | 2017-01-25 | 中国石油化工股份有限公司 | Crystallization tower for gas-gas reaction |
| CN106345136B (en) * | 2015-07-15 | 2018-10-12 | 中国石油化工股份有限公司 | One kind being used for the crystallizing tower of gas-solid/liquid/gas reactions |
| CN106345254B (en) * | 2015-07-15 | 2019-01-25 | 中国石油化工股份有限公司 | Handle the method and device of H 2 S-containing gas |
| CN106345255B (en) * | 2015-07-15 | 2019-01-25 | 中国石油化工股份有限公司 | A kind of processing method and processing device of H 2 S-containing gas |
| CN106474896A (en) * | 2015-11-12 | 2017-03-08 | 中国石油化工股份有限公司 | The processing method of sulfide hydrogen hydrocarbon-contained waste gas |
| CN109336133A (en) * | 2018-11-15 | 2019-02-15 | 山东联盛环保科技有限公司 | A kind of device and technique of negative pressure low temperature recycling high concentration ammonium hydroxide |
| CN115849401A (en) * | 2022-07-26 | 2023-03-28 | 苏州源展材料科技有限公司 | Preparation method and device of ammonia gas for preparing active metal complex in laboratory |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1159220C (en) | 2004-07-28 |
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