CN102876411B - Method and device for producing synthetic natural gas - Google Patents
Method and device for producing synthetic natural gas Download PDFInfo
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- CN102876411B CN102876411B CN201210380047.6A CN201210380047A CN102876411B CN 102876411 B CN102876411 B CN 102876411B CN 201210380047 A CN201210380047 A CN 201210380047A CN 102876411 B CN102876411 B CN 102876411B
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Abstract
The invention provides a method and a device for producing synthetic natural gas. The method is a continuous process for producing methane-rich gas with methane molar percentage at least equal to 94% by taking coal or biomass gasification products as raw materials. By the method, operation temperature of a methane reactor can be controlled effectively, problems of temperature runaway and sintering of catalysts due to high fluctuation or accidents of the raw materials can be avoided. Besides, since a methane reaction heat utilization system is provided, comprehensive utilization rate of energy is increased.
Description
Technical field
The present invention relates to a kind of method and device of producing synthetic natural gas, relate to particularly and take method and the device that coal or gasifying biomass product be raw material production synthetic natural gas, belong to synthetic natural gas technical field.
Background technology
Since last century the seventies, be accompanied by oil crisis, preparing methane from coal (synthetic natural gas or substitute natural gas) is comparatively fast developed.The main method of preparing methane from coal comprises coal hydrogenation gasification direct production methane and indirectly produces methane through synthetic gas.
The raw methanogenic subject matter of coal hydrogenation gasification has: efficiency of carbon conversion is low, methane yield is low, gas composition is complicated, methane concentration is low and can not get high-quality synthetic natural gas etc.Comparatively speaking, coal is through the technique of the producing firedamp by syngas significant advantage that ripening degree is high, carbon utilisation rate is high and methane concentration is high that possesses skills.At the beginning of the eighties in last century, German LURGI has completed the exploitation of methanation process in conjunction with the methanation catalyst of BASF AG, and is successfully applied to the coal preparing natural gas factory of big plain in u.s.a factory 389 cubic meters per day; Company of Centrica has developed HICOM technique and corresponding catalyst for the synthetic gas feature of BGL vapourizing furnace, and has set up 2832m
3the pilot plant of/d; Rope company of Denmark Top has successfully developed the wide temperature range type catalyzer of 700 ℃ of high temperature of the highest ability, and has developed TREMP full methanation technique.
In China, take that to utilize coal production city coal gas be object, in last century, set up more ripe coal gas part methanation technology: as Dalian Chemiclophysics Inst., Chinese Academy of Sciences has researched and developed " Partial-methanation of Water-coal Gas At Atmospheric Pressure methanation production city coal gas " technology; Chemical fertilizer institute of the Ministry of Chemical Industry has developed that to take the RHM-266 type nickel that normal pressure semi-water gas is unstripped gas be methanation catalyst and technique; Coal Mining Research Institute has developed two stage furnace water gas methanation process.
Along with the needs of Sustainable development, energy-saving and cost-reducing, raising efficiency of energy utilization becomes direction and the trend of each technical development.For methanation, high temperature, high top pressure operation, wide temperature range type catalyzer are conducive to equipment and process intensification, and then reduce energy consumption, and improve the hot grade of methanation reaction by-product and recovery utilization rate.Given this, wide temperature range type methanation catalyst, high temperature, high pressure full methanation technology have become the development trend of current methanation technology.Only have in the world at present methanation commercialization factory of big plain in u.s.a, and in being, low temperature methanation technology, for high temperature, the high pressure full methanation technology of methanation development trend, still there is no the precedent of industrial applications.Domestic methanation technology only stays in part methanation at present, and catalyzer adaptive temperature narrow range, has greatly limited the comprehensive utilization ratio of energy; The part methanation technology carrying out under normal pressure is in addition unfavorable for reaction and equipment intensification, lacks the integrated optimization of reactor design and material-energy.
Summary of the invention
Therefore, the object of the present invention is to provide method and the device of a kind of generation synthetic natural gas (Synthetic Natural Gas, SNG).
The present invention realizes by the following technical solutions.
The invention provides a kind of method of producing synthetic natural gas.See figures.1.and.2, described method comprises the following steps:
A) unstripped gas (1) 1:(0.5 ~ 5 by volume after the first heat-exchange equipment (2) is warming up to 150 ~ 400 ℃): (0 ~ 0.5): (0 ~ 0.5) is divided into first strand of unstripped gas (4), second strand of unstripped gas (5), the 3rd strand of unstripped gas (6) and the 4th strand of unstripped gas (7);
B) the first strand of unstripped gas (4) in step a) and the first steam (39) and first strand of circulation gas (27) being mixed to get to temperature is first gas mixture (8) of 250 ~ 400 ℃, the first gas mixture (8) is passed in first paragraph methanator (9) and reacted, obtain temperature and be the first paragraph gas product (10) of 450 ~ 750 ℃, this first paragraph gas product (10) is through the second heat-exchange equipment (11,11 ') and the 3rd heat-exchange equipment (13,13 ') be cooled to 250 ~ 400 ℃ of first paragraph gas products (14) after being lowered the temperature;
C) it is second gas mixture (15) of 250 ~ 400 ℃ that the first paragraph gas product (14) after cooling step b) being obtained and described second strand of unstripped gas (5), the second steam (40), second strand of circulation gas (28) are mixed to get temperature, the second gas mixture (15) is passed in second segment methanator (16) and reacted, obtain temperature and be the second segment gas product (17) of 450 ~ 700 ℃, this second segment gas product (17) is cooled to 200 ~ 400 ℃ of second segment gas products (19) after the cooling obtaining through the 4th heat-exchange equipment (18,18 ');
D) the second segment gas product (19) after cooling step c) being obtained is (0.3 ~ 5) by volume: 1 is divided into circulation gas (20) and second strand of second segment gas product (21), described circulation gas (20) is cooled to and after 100 ~ 350 ℃, sends into recycle compressor (24) supercharging and obtain the circulation gas (25) after supercharging through the 5th heat-exchange equipment (22), circulation gas after supercharging (25) is warmed up to 200 ~ 350 ℃ through the 5th heat-exchange equipment (22), then by its (0.5 ~ 1) by volume: (0 ~ 0.5) is divided into described first strand of circulation gas (27) and second strand of circulation gas (28),
E) it is the 3rd gas mixture (29) of 200 ~ 400 ℃ that the second strand of second segment gas product (21) step d) being obtained and described the 3rd strand of unstripped gas (6), the 3rd steam (41) are mixed to get temperature, the 3rd gas mixture (29) is passed in the 3rd section of methanator (30) and reacted, obtain temperature and be the 3rd section of gas product (31) of 300 ~ 550 ℃, the three section gas product (32) of the 3rd section of gas product (31) after the first heat-exchange equipment (2) is cooled to 60 ~ 350 ℃ of coolings that obtain;
F) it is the 4th gas mixture (33) of 60 ~ 200 ℃ that the 3rd section of gas product (32) after cooling step e) being obtained and described the 4th strand of unstripped gas (7), the 4th steam (42) are mixed to get temperature, described the 4th gas mixture (33) passes in the 4th section of methanator (36) and reacts after the 6th heat-exchange equipment (34) is warming up to 200 ~ 350 ℃, obtains temperature and be the 4th section of gas product (37) of 250 ~ 450 ℃;
G) it is the gas product (38) of 20 ~ 80 ℃ that the 4th section of gas product (37) step f) being obtained obtains temperature after the 6th heat-exchange equipment (34) is lowered the temperature and carried out gas-liquid separation.
Preferably, the molar percentage of described unstripped gas (1) is composed as follows: carbon monoxide 5 ~ 50%, carbonic acid gas 0 ~ 30%, hydrogen 20 ~ 80%, methane 0 ~ 20%.
Preferably, in described step a), the volume ratio of first strand of unstripped gas (4) that described unstripped gas (1) is divided into, second strand of unstripped gas (5), the 3rd strand of unstripped gas (6) and the 4th strand of unstripped gas (7) can be 1:(0.5 ~ 2): (0 ~ 0.3): (0 ~ 0.3).
Preferably, in described step d), the circulation gas (20) that described second segment gas product (19) is divided into and the volume ratio of second strand of second segment gas product (21) can be (0.3 ~ 3): 1.
Preferably, in described step d), first strand of circulation gas (27) that described circulation gas (20) is divided into and the volume ratio of second strand of circulation gas (28) can be (0.7 ~ 1): (0 ~ 0.3).
In a kind of preferred embodiment of the present invention, described method also comprises utilizes methanation reaction heat release in the following manner: make the oiler feed (43 from battery limit (BL), 43 ') enter drum (44, 44 '), make from drum (44, 44 ') the first oiler feed (45, 45 ') enter the second heat-exchange equipment (11, 11 ') or the 3rd heat-exchange equipment (13, 13 ') produce the first saturation steam (46 of 3 ~ 10MPa, 46 '), make from drum (44, 44 ') the second oiler feed (47, 47 ') enter the 4th heat-exchange equipment (18, 18 ') produce the second saturation steam (48 of 3 ~ 10MPa, 48 '), from drum (44, 44 ') the 3rd saturation steam (49, 49 ') through the 3rd heat-exchange equipment (13, 13 ') or the second heat-exchange equipment (11, 11 ') heat up, obtain temperature and be the superheated vapour (50 of 300 ~ 550 ℃, 50 ').
In the above-mentioned mode of utilizing methanation reaction heat release, when the first oiler feed (45,45 ') enters the second heat-exchange equipment (11,11 '), the 3rd saturation steam (49,49 ') heats up through the 3rd heat-exchange equipment (13,13 '); When the first oiler feed (45,45 ') enters the 3rd heat-exchange equipment (13,13 '), the 3rd saturation steam (49,49 ') heats up through the second heat-exchange equipment (11,11 ').
According to the method for production synthetic natural gas provided by the invention, it is raw material that the method be take coal or gasifying biomass product, production synthetic natural gas, and the molar percentage that contains methane in the synthetic natural gas product of gained is more than 94%.
On the other hand, the present invention also provides the device for above-mentioned production synthesis of natural gas method provided by the invention, and this device comprises:
Methanator, comprises first paragraph methanator (9), second segment methanator (16), the 3rd section of methanator (30) and the 4th section of methanator (36) for carrying out methanation reaction;
Heat-exchange equipment, comprise for heating and/or the first heat-exchange equipment (2), second heat-exchange equipment (11 of cooling gas, 11 '), the 3rd heat-exchange equipment (13,13 '), the 4th heat-exchange equipment (18,18 '), the 5th heat-exchange equipment (22) and the 6th heat-exchange equipment (34);
Recycle compressor, comprises for by the recycle compressor of circulation gas supercharging (24).
In the preferred embodiment of present device, described first paragraph methanator (9), second segment methanator (16), the 3rd section of methanator (30) and the 4th section of methanator (36) are insulation fix bed methanator.
Preferably, described device also comprises drum (44,44 '), is used to heat-exchange equipment that oiler feed is provided and accepts the saturation steam that heat-exchange equipment produces, and saturation steam is delivered to heat-exchange equipment simultaneously.Particularly, described drum (44, 44 ') be used to the second heat-exchange equipment (11, 11 ') or the 3rd heat-exchange equipment (13, 13 ') the first oiler feed (45 is provided, 45 '), it is the 4th heat-exchange equipment (18, 18 ') the second oiler feed (47 is provided, 47 '), and accept the second heat-exchange equipment (11, 11 ') or the 3rd heat-exchange equipment (13, 13 ') the first saturation steam (46 of producing, 46 ') and the 4th heat-exchange equipment (18, 18 ') the second saturation steam (48 of producing, 48 '), simultaneously by the 3rd saturation steam (49, 49 ') be delivered to the 3rd heat-exchange equipment (13, 13 ') or the second heat-exchange equipment (11, 11 ').
Preferably, described heat-exchange equipment is selected from useless pot and vapor superheater.
Preferably, described device also comprises desulphurization reactor, for unstripped gas is carried out to deep desulfuration.
Preferably, described device also comprises deoxidation reactor, for unstripped gas is carried out to degree of depth deoxidation.
Preferably, described device also comprises gas-liquid separator, for separating of the water of condensation in process gas.
The invention provides a kind of continuous processing flow process and device of take coal or the synthetic natural gas of gasifying biomass product more than raw material production contains methane 94mol%.Technical process provided by the invention is as follows: unstripped gas is divided into four strands after preheating, and wherein first strand of unstripped gas enters first paragraph methanator after mixing with steam, first strand of circulation gas and react; Second strand of unstripped gas enters second segment methanator after mixing and reacts with first paragraph gas product, steam, second strand of circulation gas, second segment gas product is divided into two strands, after the first stock-traders' know-how recycle compressor supercharging, enter first paragraph methanator, after second strand of second segment gas product and the 3rd strand of unstripped gas, vapor mixing, enter the 3rd section of methanator and react; After the 3rd section of gas product and the 4th strand of unstripped gas, vapor mixing, enter the 4th section of methanator and react, the 4th section of gas product obtains gas product after gas-liquid separation.
In technique of the present invention, contain independent steam system, steam is mixed into corresponding methanator with unstripped gas respectively, can control preferably reactor outlet temperature; the flow of this steam can modulation, mixes on the one hand CO content in reduction unstripped gas with unstripped gas; control temperature of reaction; on the other hand can Optimization Technology, reduce circulating flow rate, reduce system energy consumption; improve energy utilization efficiency; also can, under the condition of unstripped gas fluctuation, control temperature of reaction, guard catalyst.Steam at least a portion derives from the steam of heat-exchange equipment by-product.
In technique of the present invention, contain the production of steam system of utilizing methanation reaction heat, can produce according to actual needs saturation steam and the superheated vapour of different grades.Oiler feed enters drum, and drum is that heat-exchange equipment is carried oiler feed and collected by riser the saturation steam that heat-exchange equipment produces by downtake, and saturation steam is delivered to heat-exchange equipment intensification obtains superheated vapour.
If still contain a small amount of carbon monoxide and carbonic acid gas in gas product of the present invention, gas further can be reacted and obtains the finished product.
Compared with prior art, the present invention has realized the synthetic gas full methanation after purifying by coal or gasifying biomass product and has carried out production synthetic natural gas, has technical process reasonable, possesses operability; Capacity usage ratio is high, save energy, advantages of environment protection.
Accompanying drawing explanation
Below, describe by reference to the accompanying drawings embodiment of the present invention in detail, wherein:
Fig. 1 is the process flow sheet that the present invention produces a kind of embodiment of synthesis of natural gas method;
Fig. 2 is the process flow sheet that the present invention produces the another embodiment of synthesis of natural gas method;
Fig. 3 is low temperature methanation process schema in tradition, for contrasting with production synthesis of natural gas method provided by the invention.
Embodiment
Below in conjunction with embodiment, the present invention is further described in detail, the embodiment providing is only in order to illustrate the present invention, rather than in order to limit the scope of the invention.
The present embodiment is a kind of preferred implementation of the production method of synthetic natural gas provided by the invention, and the process flow sheet of the present embodiment as shown in Figure 1.
A) coal or biomass are met the unstripped gas of requirement through gasification unit, converter unit and clean unit.Unstripped gas 1 is warming up to the unstripped gas 3 after being heated up after 190 ~ 210 ℃ through the first heat-exchange equipment 2.Unstripped gas 3 after intensification is divided into four bursts of logistics, that is: first strand of unstripped gas 4, second strand of unstripped gas 5, the 3rd strand of unstripped gas 6 and the 4th strand of unstripped gas 7.
B) first strand of unstripped gas 4 mixed with the first steam 39, first strand of circulation gas 27, obtain temperature and be first gas mixture 8 of 290 ~ 310 ℃, passed in first paragraph methanator 9 and carried out methanation reaction, obtained temperature and be the first paragraph gas product 10 of 640 ~ 660 ℃.First paragraph gas product 10 is through the second heat-exchange equipment 11 and the cooling of the 3rd heat-exchange equipment 13, obtains temperature and be the first paragraph gas product 14 after the cooling of 270 ~ 290 ℃, simultaneously by-product saturation steam and superheated vapour.
C) first paragraph gas product 14 and second strand of unstripped gas after cooling 5, the second steam 40, second strand of circulation gas 28 are mixed, obtain temperature and be second gas mixture 15 of 290 ~ 310 ℃, passed in second segment methanator 16 and carried out methanation reaction, obtained temperature and be the second segment gas product 17 of 600 ~ 620 ℃.Second segment gas product 17 is cooled to the second segment gas product 19 after being lowered the temperature after 270 ~ 290 ℃ through the 4th heat-exchange equipment 18.
D) the second segment gas product 19 after cooling is divided into two strands: first strand of second segment gas product 20 and second strand of second segment gas product 21.First strand of second segment gas product 20 is cooled to first strand of second segment gas product 23 after being lowered the temperature after 160 ~ 180 ℃ through the 5th heat-exchange equipment 22.First strand of second segment gas product 23 after cooling enters recycle compressor 24 superchargings, obtains circulation gas 25, and loop compression acc power is 1163kW.Circulation gas 25 heats up through the 5th heat-exchange equipment 22, obtains temperature and be the circulation gas 26 after the intensification of 250 ~ 270 ℃.Circulation gas 26 after heating up is divided into two strands, that is: first strand of circulation gas 27 and second strand of circulation gas 28.First strand of circulation gas 27 and second strand of circulation gas 28 enter respectively in first paragraph and second segment methanator and react.
E) second strand of second segment gas product 21 mixes with the 3rd strand of unstripped gas 6 and the 3rd steam 41, obtain temperature and be the 3rd gas mixture 29 of 270 ~ 290 ℃, sent in the 3rd section of methanator 30 and carried out methanation reaction, obtained temperature and be the 3rd section of gas product 31 of 470 ~ 490 ℃.The 3rd section of gas product 31 through the first heat-exchange equipment 2 be cooled to 90 ~ 110 ℃ lowered the temperature after the 3rd section of gas product 32.
F) after cooling, the 3rd section of gas product 32 and the 4th strand of unstripped gas 7, the 4th steam 42 are mixed to get the 4th gas mixture 33.The 4th gas mixture 33 is heated up and obtains the 4th gas mixture 35 after temperature is the intensification of 240 ~ 260 ℃ through the 6th heat-exchange equipment 34, sent in the 4th section of methanator 36 and carry out methanation reaction, obtain temperature and be the 4th section of gas product 37 of 350 ~ 370 ℃.
G) the 4th section of gas product 37 be through the 6th heat-exchange equipment 34 coolings, then through gas-liquid separation, to obtain temperature be the gas product 38(SNG of 30 ~ 50 ℃).
Wherein, the technique of utilizing of methanation reaction heat release comprises: drum 44 is sent in the oiler feed 43 from battery limit (BL) after preheating, from the first oiler feed 45 in drum 44 and the second oiler feed 47, by downtake, enter respectively the second heat-exchange equipment 11 and the 4th heat-exchange equipment 18 production the first saturation steam 46 and the second saturation steams 48, the first saturation steam 46 and the second saturation steam 48 enter drum 44 through riser, the 3rd saturation steam 49 that drum 44 produces heats up through the 3rd heat-exchange equipment 13, and the superheated vapour 50 that obtains temperature and be 440 ~ 460 ℃ is sent battery limit (BL).
Wherein, the volume ratio of first strand of unstripped gas 4, second strand of unstripped gas 5, the 3rd strand of unstripped gas 6 and the 4th strand of unstripped gas 7 is 1:1.22:0.11:0, the volume ratio of first strand of second segment gas product 20 and second strand of second segment gas product 21 is 0.9:1, and the volume ratio of first strand of circulation gas 27 and second strand of circulation gas 28 is 0.9:0.1.
Below by the gas composition parameter of each logistics in table 1, a situation arises to have described intuitively the reality of each workshop section's methanation reaction in the technical process shown in Fig. 1.
Table 1
The explanation of logistics numbering: 1 is unstripped gas; 8 is the first gas mixture; 10 is first paragraph gas product; 15 is the second gas mixture; 17 is second segment gas product; 29 is the 3rd gas mixture; 31 is the 3rd section of gas product; 35 is the 4th gas mixture; 37 is the 4th section of gas product; 23 is first strand of second segment gas product after cooling; 38 is gas product SNG; 50 is superheated vapour.
The present embodiment is a kind of preferred implementation of the production method of synthetic natural gas provided by the invention, and the process flow sheet of the present embodiment as shown in Figure 2.
A) coal or biomass are met the unstripped gas of requirement through gasification unit, converter unit and clean unit.Unstripped gas 1 is warming up to the unstripped gas 3 after being heated up after 170 ~ 190 ℃ through the first heat-exchange equipment 2.Unstripped gas 3 after intensification is divided into four bursts of logistics, that is: first strand of unstripped gas 4, second strand of unstripped gas 5, the 3rd strand of unstripped gas 6 and the 4th strand of unstripped gas 7.
B) first strand of unstripped gas 4 mixed with the first steam 39, first strand of circulation gas 27, obtain temperature and be first gas mixture 8 of 250 ~ 270 ℃, passed in first paragraph methanator 9 and carried out methanation reaction, obtained temperature and be the first paragraph gas product 10 of 610 ~ 630 ℃.First paragraph gas product 10 is through the second heat-exchange equipment 11 and the cooling of the 3rd heat-exchange equipment 13, obtains temperature and be the first paragraph gas product 14 after the cooling of 280 ~ 300 ℃, simultaneously by-product saturation steam and superheated vapour.
C) first paragraph gas product 14 and second strand of unstripped gas after cooling 5, the second steam 40, second strand of circulation gas 28 are mixed, obtain temperature and be second gas mixture 15 of 280 ~ 300 ℃, passed in second segment methanator 16 and carried out methanation reaction, obtained temperature and be the second segment gas product 17 of 610 ~ 630 ℃.Second segment gas product 17 is cooled to the second segment gas product 19 after being lowered the temperature after 280 ~ 300 ℃ through the 4th heat-exchange equipment 18.
D) the second segment gas product 19 after cooling is divided into two strands: first strand of second segment gas product 20 and second strand of second segment gas product 21.First strand of second segment gas product 20 is cooled to first strand of second segment gas product 23 after being lowered the temperature after 150 ~ 170 ℃ through the 5th heat-exchange equipment 22.First strand of second segment gas product 23 after cooling enters recycle compressor 24 superchargings, obtains circulation gas 25.Circulation gas 25 heats up through the 5th heat-exchange equipment 22, obtains temperature and be the circulation gas 26 after the intensification of 230 ~ 250 ℃.Circulation gas 26 after heating up is divided into two strands, that is: first strand of circulation gas 27 and second strand of circulation gas 28.First strand of circulation gas 27 and second strand of circulation gas 28 enter respectively in first paragraph and second segment methanator and react.
E) second strand of second segment gas product 21 mixes with the 3rd strand of unstripped gas 6 and the 3rd steam 41, obtain temperature and be the 3rd gas mixture 29 of 280 ~ 300 ℃, sent in the 3rd section of methanator 30 and carried out methanation reaction, obtained temperature and be the 3rd section of gas product 31 of 410 ~ 430 ℃.The 3rd section of gas product 31 through the first heat-exchange equipment 2 be cooled to 100 ~ 120 ℃ lowered the temperature after the 3rd section of gas product 32.
F) after cooling, the 3rd section of gas product 32 and the 4th strand of unstripped gas 7, the 4th steam 42 are mixed to get the 4th gas mixture 33.The 4th gas mixture 33 is heated up and obtains the 4th gas mixture 35 after temperature is the intensification of 240 ~ 260 ℃ through the 6th heat-exchange equipment 34, sent in the 4th section of methanator 36 and carry out methanation reaction, obtain temperature and be the 4th section of gas product 37 of 290 ~ 310 ℃.
G) the 4th section of gas product 37 be through the 6th heat-exchange equipment 34 coolings, then through gas-liquid separation, to obtain temperature be the gas product 38(SNG of 30 ~ 50 ℃).
Wherein, the technique of utilizing of methanation reaction heat release comprises: from the oiler feed 43 of battery limit (BL) ' send into after preheating drum 44 ', the first oiler feed 45 of drum 44 ' interior ' and the second oiler feed 47 ' by downtake enter respectively the 3rd heat-exchange equipment 13 ' and the 4th heat-exchange equipment 18 ' produce the first saturation steam 46 ' and the second saturation steam 48 ', the first saturation steam 46 ' and the second saturation steam 48 ' process riser enter drum 44 ', the 3rd saturation steam 49 that drum 44 produces ' through the second heat-exchange equipment 11 ' intensification, obtain temperature and be superheated vapour 50 ' the send battery limit (BL) of 440 ~ 460 ℃.
Wherein, the volume ratio of first strand of unstripped gas 4, second strand of unstripped gas 5, the 3rd strand of unstripped gas 6 and the 4th strand of unstripped gas 7 is 1:1.27:0:0, the volume ratio of first strand of second segment gas product 20 and second strand of second segment gas product 21 is 2.4:1, and the volume ratio of first strand of circulation gas 27 and second strand of circulation gas 28 is 0.95:0.05.
Below by the gas composition parameter of each logistics in table 2, a situation arises to have described intuitively the reality of each workshop section's methanation reaction in Fig. 2 technical process.
Table 2
The explanation of logistics numbering: 1 is unstripped gas; 8 is the first gas mixture; 10 is first paragraph gas product; 15 is the second gas mixture; 17 is second segment gas product; 29 is the 3rd gas mixture; 31 is the 3rd section of gas product; 35 is the 4th gas mixture; 37 is the 4th section of gas product; 23 is first strand of second segment gas product after cooling; 38 is gas product SNG; 50 ' be superheated vapour.
The present embodiment is a kind of preferred implementation of the production method of synthetic natural gas provided by the invention, and the process flow sheet of the present embodiment as shown in Figure 1.
A) coal or biomass are met the unstripped gas of requirement through gasification unit, converter unit and clean unit.Unstripped gas 1 is warming up to the unstripped gas 3 after being heated up after 200 ~ 220 ℃ through the first heat-exchange equipment 2.Unstripped gas 3 after intensification is divided into four bursts of logistics, that is: first strand of unstripped gas 4, second strand of unstripped gas 5, the 3rd strand of unstripped gas 6 and the 4th strand of unstripped gas 7.
B) first strand of unstripped gas 4 mixed with the first steam 39, first strand of circulation gas 27, obtain temperature and be the first gas mixture 8 of 290 ~ 310, passed in first paragraph methanator 9 and carried out methanation reaction, obtained temperature and be the first paragraph gas product 10 of 640 ~ 660 ℃.First paragraph gas product 10 is through the second heat-exchange equipment 11 and the cooling of the 3rd heat-exchange equipment 13, obtains temperature and be the first paragraph gas product 14 after the cooling of 300 ~ 320 ℃, simultaneously by-product saturation steam and superheated vapour.
C) first paragraph gas product 14 and second strand of unstripped gas after cooling 5, the second steam 40, second strand of circulation gas 28 are mixed, obtain temperature and be second gas mixture 15 of 290 ~ 310 ℃, passed in second segment methanator 16 and carried out methanation reaction, obtained temperature and be the second segment gas product 17 of 600 ~ 620 ℃.Second segment gas product 17 is cooled to the second segment gas product 19 after being lowered the temperature after 270 ~ 290 ℃ through the 4th heat-exchange equipment 18.
D) the second segment gas product 19 after cooling is divided into two strands: first strand of second segment gas product 20 and second strand of second segment gas product 21.First strand of second segment gas product 20 is cooled to first strand of second segment gas product 23 after being lowered the temperature after 150 ~ 170 ℃ through the 5th heat-exchange equipment 22.First strand of second segment gas product 23 after cooling enters recycle compressor 24 superchargings, obtains circulation gas 25.Circulation gas 25 heats up through the 5th heat-exchange equipment 22, obtains temperature and be the circulation gas 26 after the intensification of 250 ~ 270 ℃.Circulation gas 26 after heating up is divided into two strands, that is: first strand of circulation gas 27 and second strand of circulation gas 28.First strand of circulation gas 27 and second strand of circulation gas 28 enter respectively in first paragraph and second segment methanator and react.
E) second strand of second segment gas product 21 mixes with the 3rd strand of unstripped gas 6 and the 3rd steam 41, obtain temperature and be the 3rd gas mixture 29 of 280 ~ 300 ℃, sent in the 3rd section of methanator 30 and carried out methanation reaction, obtained temperature and be the 3rd section of gas product 31 of 460 ~ 480 ℃.The 3rd section of gas product 31 through the first heat-exchange equipment 2 be cooled to 80 ~ 100 ℃ lowered the temperature after the 3rd section of gas product 32.
F) after cooling, the 3rd section of gas product 32 and the 4th strand of unstripped gas 7, the 4th steam 42 are mixed to get the 4th gas mixture 33.The 4th gas mixture 33 is heated up and obtains the 4th gas mixture 35 after temperature is the intensification of 240 ~ 260 ℃ through the 6th heat-exchange equipment 34, sent in the 4th section of methanator 36 and carry out methanation reaction, obtain temperature and be the 4th section of gas product 37 of 380 ~ 400 ℃.
G) the 4th section of gas product 37 be through the 6th heat-exchange equipment 34 coolings, then through gas-liquid separation, to obtain temperature be the gas product 38(SNG of 30 ~ 50 ℃).
Wherein, the technique of utilizing of methanation reaction heat release comprises: drum 44 is sent in the oiler feed 43 from battery limit (BL) after preheating, from the first oiler feed 45 in drum 44 and the second oiler feed 47, by downtake, enter respectively the second heat-exchange equipment 11 and the 4th heat-exchange equipment 18 production the first saturation steam 46 and the second saturation steams 48, the first saturation steam 46 and the second saturation steam 48 enter drum 44 through riser, the 3rd saturation steam 49 that drum 44 produces heats up through the 3rd heat-exchange equipment 13, and the superheated vapour 50 that obtains temperature and be 440 ~ 460 ℃ is sent battery limit (BL).
Wherein, the volume ratio of first strand of unstripped gas 4, second strand of unstripped gas 5, the 3rd strand of unstripped gas 6 and the 4th strand of unstripped gas 7 is 1:0.94:0.13:0.09, the volume ratio of first strand of second segment gas product 20 and second strand of second segment gas product 21 is 0.9:1, and the volume ratio of first strand of circulation gas 27 and second strand of circulation gas 28 is 1:0.
Below by the gas composition parameter of each logistics in table 3, a situation arises to have described intuitively the reality of each workshop section's methanation reaction in Fig. 1 technical process.
Table 3
The explanation of logistics numbering is with table 1.
comparative example 1
For contrasting with embodiment 1, under identical design basis condition, adopt low temperature methanation technology production synthetic natural gas in tradition, concrete technology schema is as shown in Figure 3.
A) coal or biomass are met the unstripped gas of requirement through gasification unit, converter unit and clean unit.Unstripped gas 1 is warming up to the unstripped gas 3 after being heated up after 170 ~ 190 ℃ through the first heat-exchange equipment 2.Unstripped gas 3 after intensification is divided into two bursts of logistics, that is: first strand of unstripped gas 4, second strand of unstripped gas 5.
B) first strand of unstripped gas 4 mixed with the first steam 39, first strand of circulation gas 27, obtain temperature and be first gas mixture 8 of 270 ~ 290 ℃, passed in first paragraph methanator 9 and carried out methanation reaction, obtained temperature and be the first paragraph gas product 10 of 490 ~ 510 ℃.First paragraph gas product 10 is through the second heat-exchange equipment 11 ' and the 3rd heat-exchange equipment 13 ' cooling, obtains temperature and be the first paragraph gas product 14 after the cooling of 300 ~ 320 ℃, while by-product saturation steam and superheated vapour.
C) first paragraph gas product 14 and second strand of unstripped gas after cooling 5, the second steam 40, second strand of circulation gas 28 are mixed, obtain temperature and be second gas mixture 15 of 270 ~ 290 ℃, passed in second segment methanator 16 and carried out methanation reaction, obtained temperature and be the second segment gas product 17 of 490 ~ 510 ℃.Second segment gas product 17 is cooled to the second segment gas product 19 after being lowered the temperature after 240 ~ 260 ℃ through the 4th heat-exchange equipment 18.
D) the second segment gas product 19 after cooling is divided into two strands: first strand of second segment gas product 20 and second strand of second segment gas product 21.First strand of second segment gas product 20 is cooled to first strand of second segment gas product 23 after being lowered the temperature after 30 ~ 50 ℃ through the 5th heat-exchange equipment 22.First strand of second segment gas product 23 after cooling enters recycle compressor 24 superchargings, obtains circulation gas 25, and loop compression acc power is 1651kW.Circulation gas 25 heats up through the 5th heat-exchange equipment 22, obtains temperature and be the circulation gas 26 after the intensification of 210 ~ 230 ℃.Circulation gas 26 after heating up is divided into two strands, that is: first strand of circulation gas 27 and second strand of circulation gas 28.First strand of circulation gas 27 and second strand of circulation gas 28 enter respectively in first paragraph and second segment methanator and react.
E) second strand of second segment gas product 21 mixes with the 3rd steam 41, obtains temperature and be the 3rd gas mixture 29 of 240 ~ 260 ℃, sent in the 3rd section of methanator 30 and carries out methanation reaction, obtains temperature and be the 3rd section of gas product 31 of 300 ~ 320 ℃.The 3rd section of gas product 31 lowered the temperature and passes through gas-liquid separation to obtain temperature be the gas product 38 ' (SNG) of 30 ~ 50 ℃ through the first heat-exchange equipment 2.
Wherein, the technique of utilizing of methanation reaction heat release comprises: from the oiler feed 43 of battery limit (BL) ' send into after preheating drum 44 ', from the first oiler feed 45 of drum 44 ' interior ' and the second oiler feed 47 ' by downtake enter respectively the 3rd heat-exchange equipment 13 ' and the 4th heat-exchange equipment 18 ' produce the first saturation steam 46 ' and the second saturation steam 48 ', the first saturation steam 46 ' and the second saturation steam 48 ' process riser enter drum 44 ', the 3rd saturation steam 49 of drum 44 ' generation ' through the second heat-exchange equipment 11 ' intensification, obtain temperature and be superheated vapour 50 ' the send battery limit (BL) of 440 ~ 460 ℃.
Wherein, the volume ratio of first strand of unstripped gas 4, second strand of unstripped gas 5 is 1:1.33, the volume ratio of first strand of second segment gas product 20 and second strand of second segment gas product 21 is 1:0.26, and the volume ratio of first strand of circulation gas 27 and second strand of circulation gas 28 is 0.95:0.05.
Below by the gas composition parameter of each logistics in table 4, a situation arises to have described intuitively the reality of each workshop section's methanation reaction in the technical process shown in Fig. 3.
Table 4
Compare with comparative example 1, under identical design basis, embodiment 1 heat utilization ratio is high, it is low to consume: embodiment 1 loop compression acc power is 1163kW, and comparative example 1 is 1651kW, and the energy consumption of embodiment 1 is lower by 29.7% than comparative example 1; Embodiment 1 by-product superheated vapour 252.3t/h, comparative example 1 by-product superheated vapour 234.7t/h, the heat utilization ratio of embodiment 1 is higher by 7.5% than comparative example 1.
Claims (12)
1. a method of producing synthetic natural gas, said method comprising the steps of:
A) unstripped gas (1) 1:(0.5～5 by volume after the first heat-exchange equipment (2) is warming up to 150～400 ℃): (0～0.5): (0～0.5) is divided into first strand of unstripped gas (4), second strand of unstripped gas (5), the 3rd strand of unstripped gas (6) and the 4th strand of unstripped gas (7), wherein said the 3rd strand of unstripped gas (6) and the 4th strand of unstripped gas (7) are not 0, wherein, described unstripped gas is coal or gasifying biomass product;
B) the first strand of unstripped gas (4) in step a) and the first steam (39) and first strand of circulation gas (27) being mixed to get to temperature is first gas mixture (8) of 250～400 ℃, the first gas mixture (8) is passed in first paragraph methanator (9) and reacted, obtain temperature and be the first paragraph gas product (10) of 450～750 ℃, this first paragraph gas product (10) is through the second heat-exchange equipment (11,11 ') and the 3rd heat-exchange equipment (13,13 ') be cooled to 250～400 ℃ of first paragraph gas products (14) after being lowered the temperature;
C) it is second gas mixture (15) of 250～400 ℃ that the first paragraph gas product (14) after cooling step b) being obtained and described second strand of unstripped gas (5), the second steam (40), second strand of circulation gas (28) are mixed to get temperature, the second gas mixture (15) is passed in second segment methanator (16) and reacted, obtain temperature and be the second segment gas product (17) of 450～700 ℃, this second segment gas product (17) is cooled to 200～400 ℃ of second segment gas products (19) after the cooling obtaining through the 4th heat-exchange equipment (18,18 ');
D) the second segment gas product (19) after cooling step c) being obtained is (0.3～5) by volume: 1 is divided into circulation gas (20) and second strand of second segment gas product (21), described circulation gas (20) is cooled to and after 100～350 ℃, sends into recycle compressor (24) supercharging and obtain the circulation gas (25) after supercharging through the 5th heat-exchange equipment (22), circulation gas after supercharging (25) is warmed up to 200～350 ℃ through the 5th heat-exchange equipment (22), then by its (0.5～1) by volume: (0～0.5) is divided into described first strand of circulation gas (27) and second strand of circulation gas (28), wherein said second strand of circulation gas (28) is not 0,
E) it is the 3rd gas mixture (29) of 200～400 ℃ that the second strand of second segment gas product (21) step d) being obtained and described the 3rd strand of unstripped gas (6), the 3rd steam (41) are mixed to get temperature, the 3rd gas mixture (29) is passed in the 3rd section of methanator (30) and reacted, obtain temperature and be the 3rd section of gas product (31) of 300～550 ℃, the three section gas product (32) of the 3rd section of gas product (31) after the first heat-exchange equipment (2) is cooled to 60～350 ℃ of coolings that obtain;
F) it is the 4th gas mixture (33) of 60～200 ℃ that the 3rd section of gas product (32) after cooling step e) being obtained and described the 4th strand of unstripped gas (7), the 4th steam (42) are mixed to get temperature, described the 4th gas mixture (33) passes in the 4th section of methanator (36) and reacts after the 6th heat-exchange equipment (34) is warming up to 200～350 ℃, obtains temperature and be the 4th section of gas product (37) of 250～450 ℃;
G) it is the gas product (38) of 20～80 ℃ that the 4th section of gas product (37) step f) being obtained obtains temperature after the 6th heat-exchange equipment (34) is lowered the temperature and carried out gas-liquid separation,
Wherein, described method also comprises utilizes methanation reaction heat release in the following manner: make the oiler feed (43 from battery limit (BL), 43 ') enter drum (44, 44 '), make from drum (44, 44 ') the first oiler feed (45, 45 ') enter the second heat-exchange equipment (11, 11 ') or the 3rd heat-exchange equipment (13, 13 ') produce the first saturation steam (46 of 3～10MPa, 46 '), make from drum (44, 44 ') the second oiler feed (47, 47 ') enter the 4th heat-exchange equipment (18, 18 ') produce the second saturation steam (48 of 3～10MPa, 48 '), from drum (44, 44 ') the 3rd saturation steam (49, 49 ') through the 3rd heat-exchange equipment (13, 13 ') or the second heat-exchange equipment (11, 11 ') heat up, obtain temperature and be the superheated vapour (50 of 300～550 ℃, 50 ').
2. method according to claim 1, wherein, the molar percentage of described unstripped gas is composed as follows: carbon monoxide 5～50%, carbonic acid gas 0～30%, hydrogen 20～80%, methane 0～20%.
3. method according to claim 1 and 2, in described step a), the volume ratio of first strand of unstripped gas (4) that described unstripped gas (1) is divided into, second strand of unstripped gas (5), the 3rd strand of unstripped gas (6) and the 4th strand of unstripped gas (7) is 1:(0.5～2): (0～0.3): (0～0.3), wherein said the 3rd strand of unstripped gas (6) and the 4th strand of unstripped gas (7) they are not 0.
4. method according to claim 1, in described step d), the circulation gas (20) that described second segment gas product (19) is divided into and the volume ratio of second strand of second segment gas product (21) are (0.3～3): 1.
5. method according to claim 1, in described step d), first strand of circulation gas (27) that described circulation gas (20) is divided into and the volume ratio of second strand of circulation gas (28) are (0.7～1): (0～0.3), wherein said second strand of circulation gas (28) is not 0.
6. for the device of method described in claim 1 to 5 any one, it comprises:
Methanator, comprises first paragraph methanator (9), second segment methanator (16), the 3rd section of methanator (30) and the 4th section of methanator (36) for carrying out methanation reaction;
Heat-exchange equipment, comprise for heating and/or the first heat-exchange equipment (2), second heat-exchange equipment (11 of cooling gas, 11 '), the 3rd heat-exchange equipment (13,13 '), the 4th heat-exchange equipment (18,18 '), the 5th heat-exchange equipment (22) and the 6th heat-exchange equipment (34);
Recycle compressor, comprises for by the recycle compressor of circulation gas supercharging (24).
7. device according to claim 6, wherein, described first paragraph methanator (9), second segment methanator (16), the 3rd section of methanator (30) and the 4th section of methanator (36) are insulation fix bed methanator.
8. device according to claim 6, wherein, described device also comprises drum (44,44 '), is used to heat-exchange equipment that oiler feed is provided and accepts the saturation steam that heat-exchange equipment produces, and saturation steam is delivered to heat-exchange equipment simultaneously.
9. according to the device described in any one in claim 6 to 8, wherein, described heat-exchange equipment is selected from useless pot and vapor superheater.
10. according to the device described in any one in claim 6 to 8, wherein, described device also comprises desulphurization reactor, for unstripped gas is carried out to deep desulfuration.
11. according to the device described in any one in claim 6 to 8, and wherein, described device also comprises deoxidation reactor, for unstripped gas is carried out to degree of depth deoxidation.
12. according to the device described in any one in claim 6 to 8, and wherein, described device also comprises gas-liquid separator, for separating of the water of condensation in process gas.
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