CN103923706B - A kind of coke oven gas purification method and system - Google Patents
A kind of coke oven gas purification method and system Download PDFInfo
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- CN103923706B CN103923706B CN201410160726.1A CN201410160726A CN103923706B CN 103923706 B CN103923706 B CN 103923706B CN 201410160726 A CN201410160726 A CN 201410160726A CN 103923706 B CN103923706 B CN 103923706B
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Abstract
The embodiment of the invention discloses a kind of coke oven gas purification method and system, described method comprises: carry out cooling process to the coke-oven gas that coal coking produces, make its temperature be less than default temperature threshold; Deamination process is carried out to the coke-oven gas after cooling process, makes its ammonia content be less than default ammonia content threshold value; Depriving hydrogen sulphide and de-prussic acid process are carried out to the coke-oven gas after deamination process, makes its hydrogen sulfide and hydrogen cyanide content be less than default hydrogen sulfide content threshold value and hydrogen cyanide content threshold value respectively; De-aromatic hydrocarbon process is carried out to the coke-oven gas after depriving hydrogen sulphide and de-prussic acid process, makes its aromatic hydrocarbon content be less than default aromatic hydrocarbon content threshold value; Namely the coke-oven gas be purified.Before deamination unit is arranged on desulfurization unit, can first by mordant ammonia removal, the relevant device of such desulfurization unit need not adopt corrosion resistant special equipment, greatly reduces production cost.
Description
Technical field
The present invention relates to coal chemical technology, particularly a kind of coke oven gas purification method and system.
Background technology
In the process of coal coking, can produce much useful material, in these materials, about 75% is coke, and the material of other about 25% is coke-oven gas and other Chemicals.
The coke-oven gas produced after coal coking, its main component has clean coke-oven gas, water vapour, coal tar oil gas, ammonia, benzene hydrocarbon, hydrogen sulfide, other sulfide etc.This coke-oven gas containing impurity through purification, after extracting the Chemicals such as coal tar, ammonia, naphthalene, hydrogen sulfide, prussic acid and crude benzol, just will can obtain clean coke-oven gas.
In existing coke oven gas purification technology, when coke-oven gas from coke oven out after, first enter cold drum unit, be mainly used in reducing the temperature of coke-oven gas, make its temperature reduce to less than 40 DEG C, and remove water wherein, and partial impurities.Coke-oven gas from cold drum unit out after, enter desulfurization unit, remove the sulphur in coke-oven gas, its sulfur method is: absorb the sour gas such as the hydrogen sulfide in coke-oven gas with ammonia as alkali source.Coke-oven gas from desulfurization unit out after, enter deamination unit, remove the ammonia in coke-oven gas, finally enter de-benzene unit, remove the arene material in coke-oven gas, obtain clean coke-oven gas.
In above-mentioned coke oven gas purification technology, owing to being using ammonia as alkali source to absorb the sour gas such as hydrogen sulfide in coke-oven gas, so before desulfurization unit must be positioned at deamination unit.Because the ammonia in coke-oven gas has corrosive nature to equipment, so before coke-oven gas deamination, the cold drum unit of its process and the relevant device pipeline etc. of desulfurization unit must adopt corrosion resistant special equipment, greatly will increase production cost like this.
Summary of the invention
For solving the problem, the embodiment of the invention discloses a kind of coke oven gas purification method and system; Technical scheme is as follows:
A kind of coke oven gas purification method, comprising:
Cooling process is carried out to the coke-oven gas that coal coking produces, makes its temperature be less than default temperature threshold;
Deamination process is carried out to the coke-oven gas after cooling process, makes its ammonia content be less than default ammonia content threshold value;
Depriving hydrogen sulphide and de-prussic acid process are carried out to the coke-oven gas after deamination process, makes its hydrogen sulfide and hydrogen cyanide content be less than default hydrogen sulfide content threshold value and hydrogen cyanide content threshold value respectively;
De-aromatic hydrocarbon process is carried out to the coke-oven gas after depriving hydrogen sulphide and de-prussic acid process, makes its aromatic hydrocarbon content be less than default aromatic hydrocarbon content threshold value; Namely the coke-oven gas be purified.
In the preferred embodiment of the present invention, after described deamination process, before described depriving hydrogen sulphide and de-prussic acid process, also comprise: depickling process is carried out to the coke-oven gas after deamination process;
Described depriving hydrogen sulphide and de-prussic acid process are carried out to the coke-oven gas after deamination process, be specially: after deamination process, and the coke-oven gas after depickling process carries out depriving hydrogen sulphide and de-prussic acid process.
In the preferred embodiment of the present invention, after described depriving hydrogen sulphide and de-prussic acid process, before described de-aromatic hydrocarbon process, also comprise: de-solid particulate matter process is carried out to the coke-oven gas after depriving hydrogen sulphide and de-prussic acid process;
Described de-aromatic hydrocarbon process is carried out to the coke-oven gas after depriving hydrogen sulphide and de-prussic acid process, be specially: after depriving hydrogen sulphide and de-prussic acid process, and the coke-oven gas after de-solid particulate matter process carries out de-aromatic hydrocarbon process.
A kind of coke oven gas purification system, comprising:
Cold drum unit, the coke-oven gas for producing coal coking carries out cooling process, makes its temperature be less than default temperature threshold;
Deamination unit, for carrying out deamination process to the coke-oven gas after cooling process, makes its ammonia content be less than default ammonia content threshold value;
Desulfurization unit, for carrying out depriving hydrogen sulphide and de-prussic acid process to the coke-oven gas after deamination process, makes its hydrogen sulfide and hydrogen cyanide content be less than default hydrogen sulfide content threshold value and hydrogen cyanide content threshold value respectively;
De-benzene unit, for carrying out de-aromatic hydrocarbon process to the coke-oven gas after depriving hydrogen sulphide and de-prussic acid process, makes its aromatic hydrocarbon content be less than default aromatic hydrocarbon content threshold value.
In the preferred embodiment of the present invention, also comprise: first catches mist unit, for after described deamination unit carries out deamination process, described desulfurization unit carries out depickling process to the coke-oven gas after deamination process before carrying out depriving hydrogen sulphide and de-prussic acid process;
Described desulfurization unit specifically for: after deamination process, and the coke-oven gas after depickling process carries out depriving hydrogen sulphide and de-prussic acid process.
In the preferred embodiment of the present invention, also comprise: second catches mist unit, for carry out depriving hydrogen sulphide and de-prussic acid process at described desulfurization unit after, before described de-benzene unit carries out de-aromatic hydrocarbon process, de-solid particulate matter process is carried out to the coke-oven gas after depriving hydrogen sulphide and de-prussic acid process;
Described de-benzene unit specifically for: after depriving hydrogen sulphide and de-prussic acid process, and the coke-oven gas after de-solid particulate matter process carries out de-aromatic hydrocarbon process.
The present invention removes sulphur in coke-oven gas, so before deamination unit can being arranged on desulfurization unit owing to adopting the suspension liquid of brown iron oxide; So just can first by mordant ammonia removal, owing to eliminating mordant ammonia, the relevant device of desulfurization unit need not adopt corrosion resistant special equipment, greatly reduces production cost.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the schema of a kind of coke oven gas purification method of the embodiment of the present invention;
Fig. 2 is the schema of the first preferred implementation of a kind of coke oven gas purification method of the embodiment of the present invention;
Fig. 3 is the schema of the second preferred implementation of a kind of coke oven gas purification method of the embodiment of the present invention;
Fig. 4 is the structural representation of a kind of coke oven gas purification system of the embodiment of the present invention;
Fig. 5 is the structural representation of the first preferred implementation of a kind of coke oven gas purification system of the embodiment of the present invention;
Fig. 6 is the structural representation of the second preferred implementation of a kind of coke oven gas purification system of the embodiment of the present invention.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Below in conjunction with Fig. 1, a kind of coke oven gas purification method of the embodiment of the present invention is described.
S101 carries out cooling process to the coke-oven gas that coal coking produces.
Coke-oven gas mentioned here is by being produced after coal coking.General, in the process of coal coking, can produce much useful material, in these materials, about 75% is coke, and the material of other about 25% is coke-oven gas and other Chemicals.Coal coking is prior art, is not here described in detail.
The coke-oven gas that coal coking produces, because temperature is very high, first to carry out cooling process to coke-oven gas, its temperature is made to be less than default temperature threshold, here the temperature threshold said can be determined according to the requirement of fine purification technique for coke oven gas by those skilled in the art, and temperature threshold itself can not become limitation of the present invention.In embodiments of the present invention, temperature threshold is 40 DEG C.Meanwhile, carrying out coke-oven gas lowering the temperature in the process of process, also can by impurity higher for some boiling points, such as (water, tar, part ammonia) condensation is got off.
It should be noted that, to coke-oven gas carry out lower the temperature process relevant device and processing parameter be state of the art, those skilled in the art do not need creative work to realize, and no further details to be given herein in the present invention.
S102, carries out deamination process to the coke-oven gas after cooling process.
After coke-oven gas being carried out to cooling process, deamination process is carried out to the coke-oven gas after cooling process, makes its ammonia content be less than default ammonia content threshold value.Here the ammonia content threshold value said can be determined according to the requirement of fine purification technique for coke oven gas by those skilled in the art, and ammonia content threshold value itself can not become limitation of the present invention.In embodiments of the present invention, ammonia content threshold value is 50mg/m
3.
It should be noted that, carry out the relevant device of deamination process to coke-oven gas and processing parameter is state of the art, those skilled in the art do not need creative work to realize, and no further details to be given herein in the present invention.
S103, carries out depriving hydrogen sulphide and de-prussic acid process to the coke-oven gas after deamination process.
After deamination process is carried out to coke-oven gas, depriving hydrogen sulphide and de-prussic acid process are carried out to the coke-oven gas after deamination process, make its hydrogen sulfide and hydrogen cyanide content be less than default hydrogen sulfide content threshold value and hydrogen cyanide content threshold value respectively.Here the hydrogen sulfide content threshold value said and hydrogen cyanide content threshold value can be determined according to the requirement of fine purification technique for coke oven gas by those skilled in the art, and hydrogen sulfide content threshold value and hydrogen cyanide content threshold value itself can not become limitation of the present invention.In embodiments of the present invention, hydrogen sulfide content threshold value and hydrogen cyanide content threshold value are 20mg/m
3.
It should be noted that, carry out the relevant device of depriving hydrogen sulphide and prussic acid process to coke-oven gas and processing parameter is the state of the art, those skilled in the art do not need creative work to realize, and no further details to be given herein in the present invention.
S104, carries out de-aromatic hydrocarbon process to the coke-oven gas after depriving hydrogen sulphide and de-prussic acid process.
After depriving hydrogen sulphide and prussic acid process are carried out to coke-oven gas, de-aromatic hydrocarbon process is carried out to the coke-oven gas after depriving hydrogen sulphide and prussic acid process, make its aromatic hydrocarbon content be less than default aromatic hydrocarbon content threshold value; Here the aromatic hydrocarbon content threshold value said can be determined according to the requirement of fine purification technique for coke oven gas by those skilled in the art, and aromatic hydrocarbon content threshold value itself can not become limitation of the present invention.In embodiments of the present invention, aromatic hydrocarbon content threshold value is 4g/m
3.
It should be noted that, carry out the relevant device of de-aromatic hydrocarbon process to coke-oven gas and processing parameter is the state of the art, those skilled in the art do not need creative work to realize, and no further details to be given herein in the present invention.
After de-aromatic hydrocarbon process is carried out to coke-oven gas, the coke-oven gas be namely purified.
Such as, because the deamidization used when carrying out deamination process to coke-oven gas is acid, the vitriol oil, so after deamination process, coke-oven gas can carry a small amount of acid secretly.The suspension liquid that a small amount of acid of coke-oven gas entrained with will affect sweetening agent brown iron oxide when carrying out depriving hydrogen sulphide and prussic acid process to coke-oven gas like this removes the effect of hydrogen sulfide and prussic acid.
So as shown in Figure 2, in a kind of preferred implementation of the embodiment of the present invention, a step S102A can also be increased, depickling process is carried out to coke-oven gas.
Carrying out after S102 carries out deamination process to coke-oven gas, first carrying out S102A, carrying out depickling process to the coke-oven gas after deamination process, and then carry out S103.
It should be noted that, carry out de-acid-treated relevant device to coke-oven gas and processing parameter is the state of the art, those skilled in the art do not need creative work to realize, and no further details to be given herein in the present invention.
Because the suspension liquid employing brown iron oxide carries out depriving hydrogen sulphide and prussic acid process to coke-oven gas, after depriving hydrogen sulphide and prussic acid process, coke-oven gas can carry a small amount of brown iron oxide secretly, adds the solid particulate matter foreign matter content in coke-oven gas.
Therefore, as shown in Figure 3, in a kind of preferred implementation of the embodiment of the present invention, a step S103A can also be increased, de-solid particulate matter process is carried out to coke-oven gas.
After carrying out S103 and depriving hydrogen sulphide and prussic acid process are carried out to coke-oven gas, first carry out S103A, de-solid particulate matter process is carried out to coke-oven gas after depriving hydrogen sulphide and prussic acid process, and then carries out S104.
It should be noted that, carry out the relevant device of de-solid particulate matter process to coke-oven gas and processing parameter is state of the art, those skilled in the art do not need creative work to realize, and no further details to be given herein in the present invention.
Be understandable that, above each embodiment both can be implemented separately, also can combine enforcement, adopted which kind of embodiment, and can be determined according to the condition of production of reality by those skilled in the art, the present invention does not do concrete restriction at this.
Corresponding to embodiment of the method above, present invention also offers a kind of coke oven gas purification system, as shown in Figure 4, comprising:
Cold drum unit 101, the coke-oven gas for producing coal coking carries out cooling process, makes its temperature be less than default temperature threshold;
Deamination unit 102, for carrying out deamination process to the coke-oven gas after cooling process, makes its ammonia content be less than default ammonia content threshold value;
Desulfurization unit 103, for carrying out depriving hydrogen sulphide and de-prussic acid process to the coke-oven gas after deamination process, makes its hydrogen sulfide and hydrogen cyanide content be less than default hydrogen sulfide content threshold value and hydrogen cyanide content threshold value respectively;
De-benzene unit 104, for carrying out de-aromatic hydrocarbon process to the coke-oven gas after depriving hydrogen sulphide and de-prussic acid process, makes its aromatic hydrocarbon content be less than default aromatic hydrocarbon content threshold value.
In a kind of preferred implementation of the embodiment of the present invention, as shown in Figure 5, also comprise: first catches mist unit 102A, for after deamination unit 102 carries out deamination process to the coke-oven gas after cooling process, and before coke-oven gas carries out depriving hydrogen sulphide and de-prussic acid process after desulfurization unit 103 pairs of deamination process, depickling process is carried out to the coke-oven gas after deamination process.
Catch after mist unit 102A carries out depickling process to the coke-oven gas after deamination process first, desulfurization unit 103 carries out depriving hydrogen sulphide and de-prussic acid process to the coke-oven gas after depickling process again.
In the another kind of preferred implementation of the embodiment of the present invention, as shown in Figure 6, also comprise: second catches mist unit 103A, for at desulfurization unit 103 after the coke-oven gas after deamination process being carried out to depriving hydrogen sulphide and de-prussic acid process, and before the coke-oven gas of de-benzene unit 104 pairs of depriving hydrogen sulphides and de-prussic acid process carries out de-aromatic hydrocarbon process, de-solid particulate matter process is carried out to the coke-oven gas after depriving hydrogen sulphide and de-prussic acid process.
Catch after mist unit 103A carries out de-solid particulate matter process to the coke-oven gas after depriving hydrogen sulphide and de-prussic acid process second, de-benzene unit 104 carries out de-aromatic hydrocarbon process to the coke-oven gas after de-solid particulate matter process again.
Each embodiment in this specification sheets all adopts the mode of going forward one by one to describe, between each embodiment identical similar part mutually see, what each embodiment stressed is the difference with other embodiments.Especially, for device or system embodiment, because it is substantially similar to embodiment of the method, so describe fairly simple, relevant part illustrates see the part of embodiment of the method.
It should be noted that, in this article, the such as relational terms of first and second grades and so on is only used for an entity or operation to separate with another entity or operational zone, and not necessarily requires or imply the relation that there is any this reality between these entities or operation or sequentially.And, term " comprises ", " comprising " or its any other variant are intended to contain comprising of nonexcludability, thus make to comprise the process of a series of key element, method, article or equipment and not only comprise those key elements, but also comprise other key elements clearly do not listed, or also comprise by the intrinsic key element of this process, method, article or equipment.When not more restrictions, the key element limited by statement " comprising ... ", and be not precluded within process, method, article or the equipment comprising described key element and also there is other identical element.
The foregoing is only preferred embodiment of the present invention, be not intended to limit protection scope of the present invention.All any amendments done within the spirit and principles in the present invention, equivalent replacement, improvement etc., be all included in protection scope of the present invention.
Claims (4)
1. a coke oven gas purification method, is characterized in that, comprising:
Cooling process is carried out to the coke-oven gas that coal coking produces, makes its temperature be less than default temperature threshold;
Deamination process is carried out to the coke-oven gas after cooling process, makes its ammonia content be less than default ammonia content threshold value;
Depickling process is carried out to the coke-oven gas after deamination process;
After deamination process, and the coke-oven gas after depickling process carries out depriving hydrogen sulphide and de-prussic acid process, makes its hydrogen sulfide and hydrogen cyanide content be less than default hydrogen sulfide content threshold value and hydrogen cyanide content threshold value respectively;
De-aromatic hydrocarbon process is carried out to the coke-oven gas after depriving hydrogen sulphide and de-prussic acid process, makes its aromatic hydrocarbon content be less than default aromatic hydrocarbon content threshold value; Namely the coke-oven gas be purified.
2. the method for claim 1, is characterized in that, after described depriving hydrogen sulphide and de-prussic acid process, before described de-aromatic hydrocarbon process, also comprises: carry out de-solid particulate matter process to the coke-oven gas after depriving hydrogen sulphide and de-prussic acid process;
Described de-aromatic hydrocarbon process is carried out to the coke-oven gas after depriving hydrogen sulphide and de-prussic acid process, be specially: after depriving hydrogen sulphide and de-prussic acid process, and the coke-oven gas after de-solid particulate matter process carries out de-aromatic hydrocarbon process.
3. a coke oven gas purification system, is characterized in that, comprising:
Cold drum unit, the coke-oven gas for producing coal coking carries out cooling process, makes its temperature be less than default temperature threshold;
Deamination unit, for carrying out deamination process to the coke-oven gas after cooling process, makes its ammonia content be less than default ammonia content threshold value;
First catches mist unit, for carrying out depickling process to the coke-oven gas after deamination process;
Desulfurization unit, for after deamination process, and the coke-oven gas after depickling process carries out depriving hydrogen sulphide and de-prussic acid process, makes its hydrogen sulfide and hydrogen cyanide content be less than default hydrogen sulfide content threshold value and hydrogen cyanide content threshold value respectively;
De-benzene unit, for carrying out de-aromatic hydrocarbon process to the coke-oven gas after depriving hydrogen sulphide and de-prussic acid process, makes its aromatic hydrocarbon content be less than default aromatic hydrocarbon content threshold value.
4. system as claimed in claim 3, it is characterized in that, also comprise: second catches mist unit, for carry out depriving hydrogen sulphide and de-prussic acid process at described desulfurization unit after, before described de-benzene unit carries out de-aromatic hydrocarbon process, de-solid particulate matter process is carried out to the coke-oven gas after depriving hydrogen sulphide and de-prussic acid process;
Described de-benzene unit specifically for: after depriving hydrogen sulphide and de-prussic acid process, and the coke-oven gas after de-solid particulate matter process carries out de-aromatic hydrocarbon process.
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| CN104263421B (en) * | 2014-09-16 | 2015-05-13 | 山东洪达化工有限公司 | Coke oven gas purification method |
| CN104388127B (en) * | 2014-11-17 | 2016-09-07 | 石家庄新华能源环保科技股份有限公司 | A kind of method and apparatus of coke oven gas purification |
| CN110127613B (en) * | 2019-05-20 | 2021-02-26 | 广东国能中林实业有限公司 | Efficient and advanced hydrogen production process by using coke oven gas |
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| CN101955806B (en) * | 2010-09-19 | 2013-07-24 | 马鞍山钢铁股份有限公司 | Full negative pressure coke oven gas purification integrated process |
| CN102031159A (en) * | 2011-01-06 | 2011-04-27 | 姜辉 | Process for purifying and liquefying coke oven gas |
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| US2880061A (en) * | 1955-06-20 | 1959-03-31 | Crucible Steel Co America | Process for recovering useful values from waste pickle liquor and raw coke oven gas |
| US3014785A (en) * | 1958-05-22 | 1961-12-26 | Crucible Steel Co America | Method of producing ammonium sulfate from coke oven gas and waste ferrous sulfate pickle liquor |
| CN2808914Y (en) * | 2005-07-20 | 2006-08-23 | 沈阳东方钛业有限公司 | Spray-type saturator |
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Address after: 100176 Fifth Floor 501, Building 15, No. 2, No. 31 Courtyard, Kechuang Thirteenth Street, Daxing Economic and Technological Development Zone, Beijing Patentee after: HUATAI YONGCHUANG (BEIJING) TECHNOLOGY Co.,Ltd. Address before: 101318 14-C, Hui Hui Garden, B zone, Shunyi District airport industry, Beijing Patentee before: BEIJING HUATAI COKING ENGINEERING CONSULTING Corp. |