CN104152200A - Water-saving type compressed natural gas production system and production method thereof - Google Patents
Water-saving type compressed natural gas production system and production method thereof Download PDFInfo
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Abstract
The invention discloses a water-saving type compressed natural gas production system, which comprises a carbonaceous substance gasification unit 1, wherein the outlet of the carbonaceous substance gasification unit 1 is communicated to a purifying unit 2, the outlet pipeline of the purifying unit 2 is divided into two branch pipes, the first branch pipe is communicated to a combustion chamber of a coke oven unit 3, the second branch pipe and the coke oven gas outlet pipe of the coke oven unit 3 are combined and then communicated to a compression unit 4, and a fine desulfurization unit 5, a methanation unit 6 and a demercuration-drying unit 7 are arranged at downstream of the compression unit 4 in order. The invention also discloses a water-saving type compressed natural gas production method by using the above system. The system and method of the present invention can effectively use the carbonaceous substance generated in a coking process, superfluous hydrogen in coke oven gas can be fully used, coke oven gas consumption for producing per unit of liquefied natural gas can be greatly reduced through gas distribution, yield of liquefied natural gas can be increased by more than 30% under same consumption of coke oven gas, and the usage amount of water can be greatly reduced by the system.
Description
Technical field
The invention belongs to Sweet natural gas production technical field.
Technical background
Natural gas liquids is important energy source product, and main component is methane, and being recognized is the energy the cleanest on the earth.Colourless, tasteless, nontoxic and non-corrosiveness, its volume is about with 1/625 of amount gaseous natural gas volume, and the weight of natural gas liquids is only 45% left and right of consubstantiality ponding.Its manufacturing processed is the natural gas purification processing of first gas field being produced, and after a succession of very low temperature liquefaction, utilizes liquefied natural gas carrier to transport.Very little to atmospheric pollution after natural gas liquids burning, and liberated heat is large, so natural gas liquids is a kind of more advanced energy.
On the other hand, China Middle Eastern is also faced with the air pollution problems inherent such as comparatively serious oxynitride, oxysulfide, haze, is necessary to promote for the use of natural gas liquids.But due to the energy background of China's " many coals, few oil, deficency " cause China Middle Eastern natural gas liquids be becoming tight supply day.
Coke is by coke oven, coal being carried out to the solid phase prod obtaining after destructive distillation, goes back by-product coke producer gas in retort process, in coke-oven gas, and H
2account for more than 56%% CH
4more than accounting for 25%-30%, all the other are CO and CO
2and other gas.It is reported, China's coke ultimate production in 2012 reaches 4.43 hundred million tons, accounts for global ultimate production more than 60%, and coke-oven gas output reaches 1,905 hundred million sides.The medium-and-large-sized coal chemical enterprise of part, in order effectively to utilize the maximization of coke-oven gas realized value, has been invested deep processing project, is mainly urea and methyl alcohol.But for most coke-oven plants, approximately more than 50% coke-oven gas loops back coking chamber as just fuel gas and burns.The coke-oven gas of part coke-oven plant by-product supplies outward as city pipeline gas.Disadvantage using coke-oven gas as fuel is to have utilized its calorific value, and carbon hydrogen element value does not have fully to realize (for example the, more than methane of 25%-30% and 56% H
2).In addition, owing to containing a large amount of H in coke-oven gas
2, it is difficult to be liquefied, and this makes coke-oven gas be not so good as natural gas liquids like that can canned use or depart from pipeline and seagoing transport, and the mode that is only suitable for carrying with pipeline is used nearby.
In order more effectively to utilize coke-oven gas, the present invention, according to the production feature of coking enterprise, proposes the method that the coke oven device in a kind of carbonaceous material gasification unit and existing coke-oven plant is coupled to produce compressed natural gas.
Summary of the invention
First aspect, the invention provides a kind of water-saving compressed natural gas production system, it comprises: carbonaceous material gasification unit 1, its outlet is communicated with clean unit 2, the export pipeline of clean unit 2 is divided into two arms, the first arm leads to the combustion chamber of coke oven unit 3, after the coke-oven gas outlet pipe of the second arm and coke oven unit 3 converges, leads to compressed element 4, and compressed element 4 downstreams are smart desulfurization unit 5, methanation unit 6 and demercuration-drying unit 7 successively; Wherein said carbonaceous material gasification unit 1 is taking purity oxygen as vaporized chemical.
Second aspect, the invention provides a kind of water-saving compressed natural gas production system, it comprises: the first carbonaceous material gasification unit 1-1 and the second carbonaceous material gasification unit 1-2, wherein the first carbonaceous material gasification unit 1-1 taking oxygen-containing gas as vaporized chemical and its outlet be communicated with the first clean unit 2-1, the combustion chamber of coke oven unit 3 is led in the outlet of the first clean unit 2-1; Wherein the second carbonaceous material gasification unit 1-2 taking purity oxygen as vaporized chemical and its outlet be communicated with the second clean unit 2-2, after the coke-oven gas outlet pipe of the outlet pipe of the second clean unit 2-2 and coke oven unit 3 converges, lead to compressed element 4, compressed element 4 downstreams are smart desulfurization unit 5, methanation unit 6 and demercuration-drying unit 7 successively.
In first aspect and second aspect preferred version separately, also comprise liquefaction unit 8 in described demercuration-drying unit 7 downstreams.
In first aspect and second aspect preferred version separately, wherein said carbonaceous material gasification unit 1 is selected from one or more the combination in airflow bed gasification furnace, fluidized-bed gasification furnace or fixed-bed gasification furnace.
In the present invention in full, described carbonaceous material is selected from coke powder, Jiao Li, coal, biomass or refinery coke, and the volume percent of the oxygen in described oxygen-containing gas is 10%-100%.
The third aspect, the invention provides a kind of water-saving compressed natural gas production method, and it comprises the following steps:
A. carbonaceous material and purity oxygen are passed in vapourizing furnace 1 and gasified, obtain crude synthesis gas, wherein said carbonaceous material is selected from coke powder, Jiao Li, coal, biomass or refinery coke;
B. described crude synthesis gas is passed into clean unit 2, to remove solid particulate and sulphur, the synthetic gas after being purified;
C. the synthetic gas after described purification is divided into two strands, first strand passes into the fuel that is used as this coke oven unit 3 in coke oven unit 3, second strand mix with the coke-oven gas of discharging from described coke oven unit 3, form gas mixture, this gas mixture enters compressed element 4 and compresses, and obtains the gas mixture after compression;
D. the gas mixture after described compression is passed in smart desulfurization unit 5 and carries out desulfurization;
E. the gas after smart desulfurization enters in methanation unit 6 and carries out methanation, then, after demercuration-drying unit 7 is processed, obtains compressed natural gas.
Fourth aspect, the present invention relates to a kind of water-saving compressed natural gas production method, and it comprises the following steps:
A. carbonaceous material and oxygen-containing gas are passed in the first vapourizing furnace 1-1 and gasified, obtain the first crude synthesis gas, wherein said carbonaceous material is selected from coke powder, Jiao Li, coal, biomass or refinery coke, and the volume percent of the oxygen in described oxygen-containing gas is 10%-100%; And described the first crude synthesis gas is passed in the first clean unit 2-1 to remove solid particulate and sulphur to the first synthetic gas after being purified; The first synthetic gas after described purification is passed into the fuel that is used as this coke oven unit 3 in coke oven unit 3;
B. separately carbonaceous material and purity oxygen are passed in the second vapourizing furnace 1-2 and gasified, obtain the second crude synthesis gas; And described the second crude synthesis gas is passed in the second clean unit 2-2 to remove solid particulate and sulphur, the second synthetic gas after being purified, then mixing with the coke-oven gas of discharging from described coke oven unit 3, form gas mixture, this gas mixture enters compressed element 4 and compresses, and obtains the gas mixture after compression;
D. the gas mixture after described compression is passed in smart desulfurization unit 5 and carries out desulfurization;
E. the gas after smart desulfurization enters in methanation unit 6 and carries out methanation, then, after demercuration-drying unit 7 is processed, obtains compressed natural gas.
In the third aspect and fourth aspect preferred version separately, also comprise step f: described compressed natural gas is passed into liquefaction unit 8 and liquefy, obtain natural gas liquids.
In the third aspect and fourth aspect preferred version separately, described carbonaceous material is selected from coke powder, Jiao Li, coal, biomass or refinery coke; The volume percent of the oxygen in described oxygen-containing gas is 10%-100%.More preferably, described carbonaceous material, from the carbonaceous material such as coke powder and Jiao Li of by-product in coking, has been realized the recycle of these refuse material.
In the third aspect and fourth aspect preferred version separately, when the synthetic gas after described second burst of purification and coke-oven gas carry out distribution, the synthetic gas after second burst of purification and the volume ratio of coke-oven gas are 0.1-1
In the third aspect and fourth aspect preferred version separately, the volume ratio of the synthetic gas after synthetic gas and second burst of purification after described first burst of purification is 50:50 to 95:5.
In the present invention, first carbonaceous material is gasified in gasification unit in oxygen-containing gas, produce crude synthesis gas (also having other gas and solid particulate etc. except hydrogen and carbon monoxide).Wherein the main reaction of carbonaceous material and oxygen-containing gas is as follows:
2C+O
2＝2CO
In gasification unit of the present invention, can not use water vapor as vaporized chemical, but use more cheap air, oxygen-rich air or pure oxygen as vaporized chemical.When taking purity oxygen as vaporized chemical, the nonnitrogenous gas of the crude synthesis gas of generation; When the mixture taking for example oxygen of oxygen-containing gas and nitrogen is during as vaporized chemical, the crude synthesis gas producing also contains nitrogen.
In addition, for some carbonaceous material for example coal, refinery coke and biomass, wherein also how much contain protium, these protiums can with oxygen-containing gas water generation reaction, and then water can in gasification unit, react with carbon generate some hydrogen, as shown in reaction formula below:
C+H
2O＝CO+H
2
Therefore, no matter the crude synthesis gas generating in carbonaceous material gasification unit of the present invention, be with purity oxygen or taking oxygen-containing gas as vaporized chemical, all also contains a small amount of H
2.Due to H
2content is very low, and this crude synthesis gas is difficult to directly be converted into methane, therefore in general coal gasification apparatus, generally also need to make this crude synthesis gas by carbon monodixe conversion workshop section, by passing into water vapor, a part of CO is transformed to H there
2, as shown in reaction below:
CO+H
2O＝CO
2+H
2
Therefore, the device of traditional gasification methane processed need to consume a large amount of water vapors because of the existence of this carbon monodixe conversion workshop section, this not only causes energy consumption to increase, and can cause a large amount of uses to local water resources, especially in the time that the device of gasification methane processed is positioned at lack of water area, northwest, this the consumption of water resources is further aggravated to local lack of water situation, and in the time of local lack of water, can affect the steady running of gasification methane device processed.In addition,, from above formula, this carbon monoxide transformation process also can be introduced a large amount of CO in synthetic gas
2, before synthetic gas enters methanation unit, these CO
2must be removed, this has additionally increased facility investment and energy consumption.
Aforementioned crude synthetic gas removes solid particulate desulfurization through clean unit, and this clean unit and purification techniques are technology known in the art, repeat no more.Taking purity oxygen as the production system of a first aspect of the present invention of carbonaceous material vaporized chemical with in the production method of the third aspect, synthetic gas after purifying is divided into two strands, wherein the volume of first strand accounts for the 75-85% of the synthetic gas volume after this purification, and the volume of second strand accounts for the 15-25% of the synthetic gas volume after this purification.Originally be returned to the part coke-oven gas of coke oven unit as fuel using this first strand for replacing, as the fuel of coke oven unit.This first strand also can be according to being selected with the principle being originally returned as calorific values such as the part coke-oven gas of fuel with the allocation proportion of second strand.Thus, the combustion chamber that the part of coke-oven gas of no longer coke oven unit being discharged is returned to coke oven is as fuel, but can be by whole coke-oven gas for follow-up conversion.All coke-oven gas mixes with the synthetic gas after second burst of purification, obtains mixed gas.Generally, the synthetic gas after second burst of purification and the volume ratio of coke-oven gas are 0.1-1, and certainly, concrete blending ratio can be adjusted according to the processing requirement of follow-up methanation unit 6.
In the production system of a second aspect of the present invention and the production method of fourth aspect, the first gasification unit 1-1 is taking oxygen-containing gas as vaporized chemical, the first crude synthesis gas of its generation contains nitrogen, therefore be not suitable for directly mixing with coke-oven gas, but be suitable for the combustion chamber towards coke oven unit 3, displace and pass into the coke-oven gas of this combustion chamber as fuel originally.The second gasification unit 1-2 is taking purity oxygen as vaporized chemical, the nonnitrogenous gas of the second crude synthesis gas of its generation, substantially taking CO as main, through the second clean unit 2-2 to remove solid particulate and sulphur, the second synthetic gas after being purified, then, mixing with the coke-oven gas of discharging from described coke oven unit 3, form gas mixture.
No matter above which kind of situation, then all this mixed gas being passed into conventional gas compression unit compresses, and gas mixture after compression is sent in smart desulfurization unit 5 and is carried out further desulfurization, because sulphur can be toxic to the catalyzer in follow-up methanation unit, this essence desulfurization unit will remove sulphur as far as possible completely.Desulfurization unit and desulfurization technology are also that technician is known, repeat no more.
Then the gas after smart desulfurization is entered and in methanation unit 6, carry out methanation.Methanation is by the CO in gas mixture and H under the effect of catalyzer
2be converted into CH
4process, reaction formula is as follows:
CO+3H
2＝CH
4+H
2O
After this methanation reaction, the CH in mixed gas
4content increases greatly.And then make mixed gas after methanation reaction after demercuration-drying unit 7 is processed, and remove mercury and moisture content, obtain substantially with CH
4for the compressed natural gas of main ingredient, wherein CH
4volume content can account for more than 95%.
Can according to circumstances further make this compressed natural gas liquefy through liquefaction unit, to obtain natural gas liquids.Liquefaction unit and liquefaction technology are well known in the art, repeat no more.
Method of the present invention has the following advantages:
1) with the H that is rich in that replaces high value taking CO as main synthetic gas of low value
2and CH
4coke-oven gas as coke oven fuel, make coke-oven gas can obtain more valuable utilization.For example, in general coke-oven plant, have more than 50 volume % coke-oven gas and be returned in coke oven and burn as fuel, do not obtain more valuable utilization.And after use the present invention, the coke-oven gas that is used as fuel is originally freed, can be for the preparation of compressed natural gas, or, can be used in methyl alcohol product installation etc., or, a part is for the preparation of compressed natural gas, and another part is used for being supplied to methyl alcohol product installation.First this solved the problem of being unable to supply more multifocal producer gas in the existing coke-oven plant that is equipped with methyl alcohol product installation.
2) adopt coke-oven gas and synthetic gas distribution, the composition of gas is more suitable for follow-up methanation reaction, the output of utilizing coke-oven gas to produce natural gas liquids is increased more than 30%, reduce the coke-oven gas consumption of production unit compressed natural gas, there is raw material self-sufficiency, less investment, energy consumption low, and the advantage high to compressed natural gas productive rate.
3) saved traditionally by the carbon monodixe conversion workshop section in coal preparing natural gas process, and then greatly alleviated the CO that will remove from gas mixture
2amount, work simplification, facility investment are reduced, and there is raw material self-sufficiency, system production intensity is high, turndown ratio is large, process is continuous and is suitable for the advantages such as maximization operation.
4) owing to having saved CO conversion stages, and in carbonaceous material gasification, also can not use water vapor or only use minimum water vapor that (for example airflow bed gasification furnace, fluidized-bed gasification furnace or fixed-bed gasification furnace all can directly be used solid coal and oxygen-containing gas direct reaction, only need the water of minute quantity as subsystem water), and do not need to make water in dry distillation of coal coke process processed yet, therefore the water loss of whole production system of the present invention is extremely low, even can accomplish zero water consumption.This is that any gasification methane series processed technique of unifying can not be accomplished in the past.Therefore, system and method for the present invention is particularly suitable for the use of western water-deficient area.
Brief description of the drawings
Fig. 1 is the process flow sheet of a first aspect of the present invention compressed natural gas production system.
Fig. 2 is the process flow sheet of the compressed natural gas production system of a second aspect of the present invention.
In figure: 1. gasification unit, 2. clean unit, 3. coke oven unit, 4. compressed element, 5. smart desulfurization unit, 6. methanation unit, 7. demercuration, drying unit, 8. liquefaction unit, 1-1. the first gasification unit, 1-2. the second gasification unit, 2-1. the first clean unit, 2-2. the second clean unit.
Embodiment
Below in conjunction with drawings and Examples, the specific embodiments of compressed natural gas production system of the present invention and method is described further.
Embodiment 1
Coal, air enter gasification in the first fixed-bed gasification furnace and produce the first crude synthesis gas, the first crude synthesis gas generating enters clean unit and removes solid particulate and the sulphur in synthetic gas, then be all sent to coke oven unit and use as fuel, for replacing coke-oven gas.Separately coal and purity oxygen are entered to gasification in the second fixed-bed gasification furnace and produce the second crude synthesis gas, this second crude synthesis gas, after the second clean unit purifies, enters compressed element after mixing further compress with the coke-oven gas displacing.Gas mixture after compression enters smart desulfurization unit and carries out desulfurization.Gas after essence desulfurization enters methanation unit and carries out methanation generation methane, and the methane of generation further purifies and obtains product compressed natural gas through demercuration, drying unit.
Embodiment 2
Coke powder, oxygen enter fluidized-bed gasification furnace gasification and produce crude synthesis gas, the crude synthesis gas generating enters clean unit and removes solid particulate and the sulphur in synthetic gas, 85 volume % of the synthetic gas after purification lead to coke oven unit and use as fuel, be used for replacing coke-oven gas, after all the other 15 volume % mix with the coke-oven gas displacing, enter compressed element and further compress.Gas mixture after compression enters smart desulfurization unit and carries out desulfurization.Gas after essence desulfurization enters methanation unit and carries out methanation generation methane, and the methane of generation further purifies and obtains product compressed natural gas through demercuration, drying unit, and compressed natural gas is produced natural gas liquids through further liquefaction.
Embodiment 3
Refinery coke and oxygen level are that the gas (all the other are nitrogen) of 80 volume % enters the first airflow bed gasification furnace gasification and produces the first crude synthesis gas, the first crude synthesis gas generating enters the first clean unit and removes solid particulate and the sulphur in synthetic gas, then all use as fuel towards coke oven unit, for replacing coke-oven gas.Separately refinery coke and purity oxygen are entered to gasification in the second fixed-bed gasification furnace and produce the second crude synthesis gas, this second crude synthesis gas, after the second clean unit purifies, enters compressed element after mixing further compress with the coke-oven gas displacing.Gas mixture after compression enters smart desulfurization unit and carries out desulfurization.The gas of essence after desulfurization enters methanation unit to carry out methanation and generates methane, and the methane of generation further purifies through demercuration, drying unit, then liquefies and obtain product natural gas liquids.
Embodiment 4
Biomass and oxygen level are that 10% gas (all the other are nitrogen) enters the gasification of first class bed gasification furnace and produces the first crude synthesis gas, the first crude synthesis gas generating enters the first clean unit and removes solid particulate and sulphur wherein, then all use as fuel towards coke oven unit, for replacing coke-oven gas.Separately biomass and purity oxygen are entered to gasification in the second fixed-bed gasification furnace and produce the second crude synthesis gas, this second crude synthesis gas, after the second clean unit purifies, enters compressed element after mixing further compress with the coke-oven gas displacing.Gas mixture after compression enters smart desulfurization unit and carries out desulfurization.Gas after essence desulfurization enters methanation unit and carries out methanation generation methane, and the methane of generation further purifies through demercuration, drying unit, liquefies and obtains product natural gas liquids.
Claims (9)
1. a water-saving compressed natural gas production system, it comprises: carbonaceous material gasification unit (1), its outlet is communicated with clean unit (2), the export pipeline of clean unit (2) is divided into two arms, the first arm leads to the combustion chamber of coke oven unit (3), after the coke-oven gas outlet pipe of the second arm and coke oven unit (3) converges, lead to compressed element (4), compressed element (4) downstream is smart desulfurization unit (5), methanation unit (6) and demercuration-drying unit (7) successively; Wherein said carbonaceous material gasification unit (1) is taking purity oxygen as vaporized chemical.
2. a water-saving compressed natural gas production system, it comprises: the first carbonaceous material gasification unit (1-1) and the second carbonaceous material gasification unit (1-2), wherein the first carbonaceous material gasification unit (1-1) taking oxygen-containing gas as vaporized chemical and its outlet be communicated with the first clean unit (2-1), the combustion chamber of coke oven unit (3) is led in the outlet of the first clean unit (2-1); Wherein the second carbonaceous material gasification unit (1-2) taking purity oxygen as vaporized chemical and its outlet be communicated with the second clean unit (2-2), after the coke-oven gas outlet pipe of the outlet pipe of the second clean unit (2-2) and coke oven unit (3) converges, lead to compressed element (4), compressed element (4) downstream is smart desulfurization unit (5), methanation unit (6) and demercuration-drying unit (7) successively.
3. according to the water-saving compressed natural gas production system of claim 1 or 2, wherein also comprise liquefaction unit (8) in described demercuration-drying unit (7) downstream.
4. according to the water-saving compressed natural gas production system of claim 1 or 2, wherein said carbonaceous material gasification unit (1) or the first carbonaceous material gasification unit (1-1) or the second carbonaceous material gasification unit (1-2) are selected from one or more the combination in airflow bed gasification furnace, fluidized-bed gasification furnace or fixed-bed gasification furnace independently of one another.
5. a water-saving compressed natural gas production method, it comprises the following steps:
A. carbonaceous material and purity oxygen are passed in vapourizing furnace (1) and gasified, obtain crude synthesis gas, wherein said carbonaceous material is selected from coke powder, Jiao Li, coal, biomass or refinery coke;
B. described crude synthesis gas is passed into clean unit (2), to remove solid particulate and sulphur, the synthetic gas after being purified;
C. the synthetic gas after described purification is divided into two strands, first strand passes into the fuel that is used as this coke oven unit (3) in coke oven unit (3), second strand with from the coke-oven gas of described coke oven unit (3) discharge mixes, form gas mixture, this gas mixture enters compressed element (4) and compresses, and obtains the gas mixture after compression;
D. the gas mixture after described compression is passed in smart desulfurization unit (5) and carries out desulfurization;
E. the gas after smart desulfurization enters in methanation unit (6) and carries out methanation, then, after demercuration-drying unit (7) is processed, obtains compressed natural gas.
6. a water-saving compressed natural gas production method, it comprises the following steps:
A. carbonaceous material and oxygen-containing gas are passed in the first vapourizing furnace (1-1) and gasified, obtain the first crude synthesis gas, wherein said carbonaceous material is selected from coke powder, Jiao Li, coal, biomass or refinery coke, and the volume percent of the oxygen in described oxygen-containing gas is 10%-100%; And described the first crude synthesis gas is passed in the first clean unit (2-1) to remove solid particulate and sulphur to the first synthetic gas after being purified; The first synthetic gas after described purification is passed into the fuel that is used as this coke oven unit (3) in coke oven unit (3);
B. separately carbonaceous material and purity oxygen are passed in the second vapourizing furnace (1-2) and gasified, obtain the second crude synthesis gas; And described the second crude synthesis gas is passed in the second clean unit (2-2) to remove solid particulate and sulphur, the second synthetic gas after being purified, then mixing with the coke-oven gas of discharging from described coke oven unit (3), form gas mixture, this gas mixture enters compressed element (4) and compresses, and obtains the gas mixture after compression;
D. the gas mixture after described compression is passed in smart desulfurization unit (5) and carries out desulfurization;
E. the gas after smart desulfurization enters in methanation unit (6) and carries out methanation, then, after demercuration-drying unit (7) is processed, obtains compressed natural gas.
7. according to the water-saving compressed natural gas production method of claim 5 or 6, it also comprises step f: described compressed natural gas is passed into liquefaction unit (8) and liquefy, obtain natural gas liquids.
8. according to the water-saving compressed natural gas production method of claim 5 or 6, when the synthetic gas after wherein said purification and coke-oven gas carry out distribution, the synthetic gas after purification and the volume ratio of coke-oven gas are 0.1-1.
9. according to the water-saving compressed natural gas production method of claim 5, the volume ratio of the synthetic gas after synthetic gas and second burst of purification after wherein said first burst of purification is 50:50 to 95:5.
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| CN106433826A (en) * | 2016-08-18 | 2017-02-22 | 北京三聚环保新材料股份有限公司 | Method and device for preparing liquefied natural gas through replacement of coke-oven gas by gas |
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Application publication date: 20141119 |