CN102899112B - Method and device for producing synthetic natural gas - Google Patents
Method and device for producing synthetic natural gas Download PDFInfo
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- CN102899112B CN102899112B CN201210421026.4A CN201210421026A CN102899112B CN 102899112 B CN102899112 B CN 102899112B CN 201210421026 A CN201210421026 A CN 201210421026A CN 102899112 B CN102899112 B CN 102899112B
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Abstract
The invention provides a method and a device for producing a synthetic natural gas. The invention is a continuous process that coal or biomass gasification products are used as raw materials to produce a methane-rich gas containing methane with the molar percent of more than 94%. According to the production process provided by the invention, the operating temperature of a methanation reactor can be better controlled, and the temperature runaway sintering problem of catalysts caused by larger raw material fluctuation or accidents is avoided; and a methanation reaction exothermic utilization system is provided, and the comprehensive energy utilization efficiency is improved.
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 ~ 350 ℃): (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) circulation gas (19) after the first strand of unstripped gas (4) in step a) and the first steam (37) and supercharging 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 cooled to 250 ~ 400 ℃ of first paragraph gas products (12) after being lowered the temperature through the second heat-exchange equipment (11,11 ');
C) the first paragraph gas product (12) after cooling step b) being obtained is (0.3 ~ 5) by volume: 1 is divided into circulation gas (13) and second strand of first paragraph gas product (14), described circulation gas (13) is lowered the temperature through the 3rd heat-exchange equipment (15), obtain temperature and be the circulation gas 16 of 100 ~ 350 ℃, circulation gas 16 obtains the circulation gas (18) after supercharging through recycle compressor (17) supercharging, circulation gas after supercharging (18) heats up through the 3rd heat-exchange equipment (15), obtains temperature and be the circulation gas (19) after the described supercharging of 250 ~ 350 ℃;
D) the second strand of first paragraph gas product (14) after cooling step c) being obtained and described second strand of unstripped gas (5), it is second gas mixture (20) of 250 ~ 400 ℃ that the second steam (38) is mixed to get temperature, the second gas mixture (20) is passed in second segment methanator (21) and reacted, obtain temperature and be the second segment gas product (22) of 450 ~ 700 ℃, this second segment gas product (22) is through the 4th heat-exchange equipment (23, 23 ') cooling, obtain the second segment gas product (24 after the cooling of 350 ~ 550 ℃ of temperature, 24 '), second segment gas product (24 after cooling, 24 ') through the 5th heat-exchange equipment (25, 25 ') be cooled to 200 ~ 400 ℃ of second segment gas products (26) after being lowered the temperature,
E) it is the 3rd gas mixture (27) of 200 ~ 400 ℃ that the second segment gas product (26) after cooling step d) being obtained and described the 3rd strand of unstripped gas (6), the 3rd steam (39) are mixed to get temperature, the 3rd gas mixture (27) is passed in the 3rd section of methanator (28) and reacted, obtain temperature and be the 3rd section of gas product (29) of 300 ~ 550 ℃, the three section gas product (30) of the 3rd section of gas product (29) after described the first heat-exchange equipment (2) is cooled to 60 ~ 350 ℃ of coolings that obtain;
F) it is the 4th gas mixture (31) of 60 ~ 200 ℃ that the 3rd section of gas product (30) after cooling step e) being obtained and described the 4th strand of unstripped gas (7), the 4th steam (40) are mixed to get temperature, described the 4th gas mixture (31) heats up and to obtain the 4th gas mixture 33 after temperature is the intensification of 200 ~ 350 ℃ through the 6th heat-exchange equipment (32), the 4th gas mixture 33 after intensification passes in the 4th section of methanator (34) and reacts, and obtains temperature and be the 4th section of gas product (35) of 250 ~ 450 ℃;
G) it is the gas product (36) of 20 ~ 80 ℃ that the 4th section of gas product (35) step f) being obtained obtains temperature after the 6th heat-exchange equipment (32) 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 c), the circulation gas (13) that the first paragraph gas product (12) after described cooling is divided into and the volume ratio of second strand of first paragraph gas product (14) can be (0.3 ~ 3): 1.
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 (41 from battery limit (BL), 41 ') enter drum (42, 42 '), make from drum (42, 42 ') the first oiler feed (43, 43 ') enter described the second heat-exchange equipment (11, 11 ') produce the first saturation steam (44 of 3 ~ 10MPa, 44 '), make from drum (42, 42 ') the second oiler feed (45, 45 ') enter described the 4th heat-exchange equipment (23, 23 ') or described the 5th heat-exchange equipment (25, 25 ') produce the second saturation steam (46 of 3 ~ 10MPa, 46 '), from drum (42, 42 ') the 3rd saturation steam (47, 47 ') through described the 5th heat-exchange equipment (25, 25 ') or described the 4th heat-exchange equipment (23, 23 ') heat up, obtain temperature and be the superheated vapour (48 of 300 ~ 550 ℃, 48 ').
In the above-mentioned mode of utilizing methanation reaction heat release, when the second oiler feed (45,45 ') enters the 4th heat-exchange equipment (23,23 '), the 3rd saturation steam (47,47 ') heats up through the 5th heat-exchange equipment (25,25 '); When the second oiler feed (45,45 ') enters the 5th heat-exchange equipment (25,25 '), the 3rd saturation steam (47,49 ') heats up through the 4th heat-exchange equipment (23,23 ').
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 aforesaid method provided by the invention, and this device comprises:
Methanator, comprises first paragraph methanator (9), second segment methanator (21), the 3rd section of methanator (28) and the 4th section of methanator (34) 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 (15), the 4th heat-exchange equipment (23,23 '), the 5th heat-exchange equipment (25,25 ') and the 6th heat-exchange equipment (32);
Recycle compressor, comprises for by the recycle compressor of circulation gas supercharging (17).
In the preferred embodiment of present device, described first paragraph methanator (9), second segment methanator (21), the 3rd section of methanator (28) and the 4th section of methanator (34) are insulation fix bed methanator.
Preferably, described device also comprises drum (42,42 '), 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 (42, 42 ') be used to the second heat-exchange equipment (11, 11 ') the first oiler feed (43 is provided, 43 '), and accept the second heat-exchange equipment (11, 11 ') the first saturation steam (44 of producing, 44 '), it is the 4th heat-exchange equipment (23, 23 ') or the 5th heat-exchange equipment (25, 25 ') the second oiler feed (45 is provided, 45 '), and accept the 4th heat-exchange equipment (23, 23 ') or the 5th heat-exchange equipment (25, 25 ') the second saturation steam (46 of producing, 46 '), simultaneously by the 3rd saturation steam (47, 47 ') be delivered to the 4th heat-exchange equipment (23, 23 ') or the 5th heat-exchange equipment (25, 25 ').
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, circulation gas and react; First strand of 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 first paragraph gas product and second strand of unstripped gas and vapor mixing, enter second segment methanator and react, after 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 the tradition contrasting with production synthesis of natural gas method provided by the present 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.
embodiment 1
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 210 ~ 230 ℃ 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 circulation gas 19 after the first steam 37 and supercharging, obtain temperature and be first gas mixture 8 of 280 ~ 300 ℃, passed in first paragraph methanator 9 and carried out methanation reaction, obtained temperature and be the first paragraph gas product 10 of 660 ~ 680 ℃.First paragraph gas product 10 is cooled to 320 ~ 340 ℃ of first paragraph gas products 12 after being lowered the temperature, simultaneously by-product saturation steam through the second heat-exchange equipment 11.
C) the first paragraph gas product 12 after cooling is divided into circulation gas 13 and second strand of first paragraph gas product 14, circulation gas 13 is through the 3rd heat-exchange equipment 15 coolings, obtain temperature and be the circulation gas 16 of 170 ~ 190 ℃, circulation gas 16 obtains the circulation gas 18 after supercharging through recycle compressor 17 superchargings, loop compression acc power is 896kW, circulation gas 18 after supercharging heats up through the 3rd heat-exchange equipment 15, obtains temperature and be the circulation gas 19 after the supercharging of 290 ~ 310 ℃;
D) second segment first paragraph gas product 14 and second strand of unstripped gas 5, second steam 38 being mixed to get to temperature is second gas mixture 20 of 290 ~ 310 ℃, the second gas mixture 20 is passed in second segment methanator 21 and reacted, obtain temperature and be the second segment gas product 22 of 620 ~ 640 ℃, this second segment gas product 22 is through the 4th heat-exchange equipment 23 coolings, obtain the second segment gas product 24 after the cooling of 480 ~ 500 ℃ of temperature, the second segment gas product 24 after cooling is cooled to 280 ~ 300 ℃ of second segment gas products 26 after being lowered the temperature through the 5th heat-exchange equipment 25;
E) the second segment gas product 26 after cooling and the 3rd strand of unstripped gas 6, the 3rd steam 39 being mixed to get to temperature is the 3rd gas mixture 27 of 280 ~ 300 ℃, the 3rd gas mixture 27 is passed in the 3rd section of methanator 28 and reacted, obtain temperature and be 29, the three sections of gas products 29 of the 3rd section of gas product of 480 ~ 500 ℃ the 3rd section of gas product 30 after the first heat-exchange equipment 2 is cooled to 80 ~ 100 ℃ of coolings that obtain;
F) the 3rd section of gas product 30 after cooling and the 4th strand of unstripped gas 7, the 4th steam 40 being mixed to get to temperature is the 4th gas mixture 31 of 70 ~ 90 ℃, described the 4th gas mixture 31 heats up and obtains the 4th gas mixture 33 after temperature is the intensification of 250 ~ 270 ℃ through the 6th heat-exchange equipment 32, the 4th gas mixture 33 after intensification passes in the 4th section of methanator 34 and reacts, and obtains temperature and be the 4th section of gas product 35 of 370 ~ 390 ℃;
G) the 4th section of gas product 35 being obtained after the 6th heat-exchange equipment 32 is lowered the temperature and carried out gas-liquid separation to temperature is the gas product 36 of 30 ~ 50 ℃.
Wherein, the technique of utilizing of methanation reaction heat release comprises: the oiler feed 41 from battery limit (BL) enters drum 42, the first oiler feed 43 from drum 42 enters the first saturation steam 44 that the second heat-exchange equipment 11 produces 3 ~ 10MPa, the second oiler feed 45 from drum 42 enters the second saturation steam 46 that the 4th heat-exchange equipment 23 produces 3 ~ 10MPa, from the 3rd saturation steam 47 of drum 42, through the 5th heat-exchange equipment 25, heat up, obtain temperature and be the superheated vapour 48 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 1:0.33:0.04:0, and the volume ratio of circulation gas 13 and second strand of first paragraph gas product 14 is 1:0.54.
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; 20 is the second gas mixture; 22 is second segment gas product; 27 is the 3rd gas mixture; 29 is the 3rd section of gas product; 33 is the 4th gas mixture after heating up; 35 is the 4th section of gas product; 13 is circulation gas; 36 is gas product SNG; 48 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 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 circulation gas 19 after the first steam 37 and supercharging, obtain temperature and be first gas mixture 8 of 280 ~ 300 ℃, passed in first paragraph methanator 9 and carried out methanation reaction, obtained temperature and be the first paragraph gas product 10 of 600 ~ 620 ℃.First paragraph gas product 10 is cooled to 310 ~ 330 ℃ of first paragraph gas products 12 after being lowered the temperature, simultaneously by-product saturation steam through the second heat-exchange equipment 11.
C) the first paragraph gas product 12 after cooling is divided into circulation gas 13 and second strand of first paragraph gas product 14, circulation gas 13 is through the 3rd heat-exchange equipment 15 coolings, obtain temperature and be the circulation gas 16 of 190 ~ 210 ℃, circulation gas 16 obtains the circulation gas 18 after supercharging through 17 superchargings, circulation gas 18 after supercharging heats up through the 3rd heat-exchange equipment 15, obtains temperature and be the circulation gas 19 after the supercharging of 270 ~ 290 ℃;
D) second strand of first paragraph gas product 14 and second strand of unstripped gas 5, second steam 38 being mixed to get to temperature is second gas mixture 20 of 280 ~ 300 ℃, the second gas mixture 20 is passed in second segment methanator 21 and reacted, obtain temperature and be the second segment gas product 22 of 600 ~ 620 ℃, this second segment gas product 22 is through the 4th heat-exchange equipment 23 ' cooling, obtain second segment gas product 24 after the cooling of 380 ~ 400 ℃ of temperature ', the second segment gas product 26 of the second segment gas product 24 after cooling ' after 280 ~ 300 ℃ of the 5th heat-exchange equipments 25 ' be cooled to are lowered the temperature;
E) the second segment gas product 26 after cooling and the 3rd strand of unstripped gas 6, the 3rd steam 39 being mixed to get to temperature is the 3rd gas mixture 27 of 280 ~ 300 ℃, the 3rd gas mixture 27 is passed in the 3rd section of methanator 28 and reacted, obtain temperature and be 29, the three sections of gas products 29 of the 3rd section of gas product of 420 ~ 440 ℃ the 3rd section of gas product 30 after the first heat-exchange equipment 2 is cooled to 80 ~ 100 ℃ of coolings that obtain;
F) the 3rd section of gas product 30 after cooling and the 4th strand of unstripped gas 7, the 4th steam 40 being mixed to get to temperature is the 4th gas mixture 31 of 70 ~ 90 ℃, described the 4th gas mixture 31 heats up and obtains the 4th gas mixture 33 after temperature is the intensification of 240 ~ 260 ℃ through the 6th heat-exchange equipment 32, the 4th gas mixture 33 after intensification passes in the 4th section of methanator 34 and reacts, and obtains temperature and be the 4th section of gas product 35 of 310 ~ 330 ℃;
G) the 4th section of gas product 35 being obtained after the 6th heat-exchange equipment 32 is lowered the temperature and carried out gas-liquid separation to temperature is the gas product 36 of 30 ~ 50 ℃.
Wherein, the technique of utilizing of methanation reaction heat release comprises: from the oiler feed 41 of battery limit (BL) ' enter drum 42 ', from drum 42 ' the first oiler feed 43 ' enter the second heat-exchange equipment 11 ' produce 3 ~ 10MPa the first saturation steam 44 ', from drum 42 ' the second oiler feed 45 ' enter the 5th heat-exchange equipment 25 ' produce 3 ~ 10MPa the second saturation steam 46 ', from drum 42 ' the 3rd saturation steam 47 ' through the 4th heat-exchange equipment 23 ' intensification, obtain temperature and be 490 ~ 510 ℃ superheated vapour 48 '.
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 1:0.18:0.01:0, and the volume ratio of circulation gas 13 and second strand of first paragraph gas product 14 is 1:0.18.
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; 20 is the second gas mixture; 22 is second segment gas product; 27 is the 3rd gas mixture; 29 is the 3rd section of gas product; 33 is the 4th gas mixture after heating up; 35 is the 4th section of gas product; 13 is circulation gas; 36 is gas product SNG; 48 ' 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 210 ~ 230 ℃ 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 circulation gas 19 after the first steam 37 and supercharging, 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 670 ~ 690 ℃.First paragraph gas product 10 is cooled to 320 ~ 340 ℃ of first paragraph gas products 12 after being lowered the temperature, simultaneously by-product saturation steam through the second heat-exchange equipment 11.
C) the first paragraph gas product 12 after cooling is divided into circulation gas 13 and second strand of first paragraph gas product 14, circulation gas 13 is through the 3rd heat-exchange equipment 15 coolings, obtain temperature and be the circulation gas 16 of 170 ~ 190 ℃, circulation gas 16 obtains the circulation gas 18 after supercharging through recycle compressor 17 superchargings, circulation gas 18 after supercharging heats up through the 3rd heat-exchange equipment 15, obtains temperature and be the circulation gas 19 after the supercharging of 290 ~ 310 ℃;
D) second strand of first paragraph gas product 14 and second strand of unstripped gas 5, second steam 38 being mixed to get to temperature is second gas mixture 20 of 290 ~ 310 ℃, the second gas mixture 20 is passed in second segment methanator 21 and reacted, obtain temperature and be the second segment gas product 22 of 640 ~ 660 ℃, this second segment gas product 22 is through the 4th heat-exchange equipment 23 coolings, obtain the second segment gas product 24 after the cooling of 480 ~ 500 ℃ of temperature, the second segment gas product 24 after cooling is cooled to 280 ~ 300 ℃ of second segment gas products 26 after being lowered the temperature through the 5th heat-exchange equipment 25;
E) the second segment gas product 26 after cooling and the 3rd strand of unstripped gas 6, the 3rd steam 39 being mixed to get to temperature is the 3rd gas mixture 27 of 280 ~ 300 ℃, the 3rd gas mixture 27 is passed in the 3rd section of methanator 28 and reacted, obtain temperature and be 29, the three sections of gas products 29 of the 3rd section of gas product of 480 ~ 500 ℃ the 3rd section of gas product 30 after the first heat-exchange equipment 2 is cooled to 80 ~ 100 ℃ of coolings that obtain;
F) the 3rd section of gas product 30 after cooling and the 4th strand of unstripped gas 7, the 4th steam 40 being mixed to get to temperature is the 4th gas mixture 31 of 70 ~ 90 ℃, described the 4th gas mixture 31 heats up through the 6th heat-exchange equipment 32, obtain temperature and be the 4th gas mixture 33 after the intensification of 250 ~ 270 ℃, the 4th gas mixture 33 after intensification passes in the 4th section of methanator 34 and reacts, and obtains temperature and be the 4th section of gas product 35 of 370 ~ 390 ℃;
G) the 4th section of gas product 35 being obtained after the 6th heat-exchange equipment 32 is lowered the temperature and carried out gas-liquid separation to temperature is the gas product 36 of 30 ~ 50 ℃.
Wherein, the technique of utilizing of methanation reaction heat release comprises: the oiler feed 41 from battery limit (BL) enters drum 42, the first oiler feed 43 from drum 42 enters the first saturation steam 44 that the second heat-exchange equipment 11 produces 3 ~ 10MPa, the second oiler feed 45 from drum 42 enters the second saturation steam 46 that the 4th heat-exchange equipment 23 produces 3 ~ 10MPa, from the 3rd saturation steam 47 of drum 42, through the 5th heat-exchange equipment 25, heat up, obtain temperature and be the superheated vapour 48 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 1:0.41:0.04:0.01, and the volume ratio of circulation gas 13 and second strand of first paragraph gas product 14 is 1:0.54.
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 unstripped gas 3 〞 after being heated up after 140 ~ 160 ℃ through the first heat-exchange equipment 2 〞.Unstripped gas 3 〞 after intensification are divided into three bursts of logistics, that is: first gang of unstripped gas 4 〞, second gang of unstripped gas 5 〞 and the 3rd unstripped gas 6 〞.
B) first gang of unstripped gas 4 〞 mixed with the first steam 32 〞, first gang of circulation gas 26 〞, obtain temperature and be first gas mixture 7 〞 of 270 ~ 290 ℃, passed in first paragraph methanator 8 〞 and carried out methanation reaction, obtained temperature and be first paragraph gas product 9 〞 of 490 ~ 510 ℃.First paragraph gas product 9 〞 are through the second heat-exchange equipment 10 〞 and the 3rd heat-exchange equipment 12 〞 coolings, obtain temperature and be first paragraph gas product 13 〞 after the cooling of 300 ~ 320 ℃, simultaneously by-product saturation steam and superheated vapour.
C) first paragraph gas product 13 〞 after cooling are mixed with second gang of unstripped gas 5 〞, the second steam 33 〞, second gang of circulation gas 27 〞, obtain temperature and be second gas mixture 14 〞 of 270 ~ 290 ℃, passed in second segment methanator 15 〞 and carried out methanation reaction, obtained temperature and be second segment gas product 16 〞 of 490 ~ 510 ℃.Second segment gas product 16 〞 are cooled to second segment gas product 18 〞 after being lowered the temperature after 230 ~ 250 ℃ through the 4th heat-exchange equipment 17 〞.
D) second segment gas product 18 〞 after cooling are divided into two strands: first gang of second segment gas product 19 〞 and second gang of second segment gas product 20 〞.First gang of second segment gas product 19 〞 are cooled to first gang of second segment gas product 22 〞 after being lowered the temperature after 30 ~ 50 ℃ through the 5th heat-exchange equipment 21 〞.First gang of second segment gas product 22 〞 after cooling enter recycle compressor 23 〞 superchargings, obtain circulation gas 24 〞, and loop compression acc power is 1651kW.Circulation gas 24 〞 heat up through the 5th heat-exchange equipment 21 〞, obtain temperature and be circulation gas 25 〞 after the intensification of 190 ~ 210 ℃.Circulation gas 25 〞 after heating up are divided into two strands, that is: first gang of circulation gas 26 〞 and second gang of circulation gas 27 〞.First gang of circulation gas 26 〞 and second gang of circulation gas 27 〞 enter respectively in first paragraph and second segment methanator and react.
E) second gang of second segment gas product 20 〞 mixes with the 3rd gang of unstripped gas 6 〞, the 3rd steam 34 〞, obtain temperature and be the 3rd gas mixture 28 〞 of 230 ~ 250 ℃, sent in the 3rd section of methanator 29 〞 and carried out methanation reaction, obtained temperature and be the 3rd section of gas product 30 〞 of 290 ~ 310 ℃.The 3rd section of gas product 30 〞 are through the first heat-exchange equipment 2 〞 coolings and after gas-liquid separation, to obtain temperature be gas product 31 〞 (SNG) of 30 ~ 50 ℃.
Wherein, the technique of utilizing of methanation reaction heat release comprises: oiler feed 35 〞 from battery limit (BL) send into drum 36 〞 after preheating, from the first oiler feed 37 〞 in drum 36 〞 with the second oiler feed 39 〞 enter respectively the 3rd heat-exchange equipment 12 〞 by downtake and the 4th heat-exchange equipment 17 〞 produce the first saturation steam 38 〞 and the second saturation steam 40 〞, the first saturation steam 38 〞 and the second saturation steam 40 〞 enter drum 36 〞 through riser, the 3rd saturation steam 41 〞 that drum 36 〞 produce heat up through the second heat-exchange equipment 10 〞, superheated vapour 42 〞 that obtain temperature and be 440 ~ 460 ℃ send battery limit (BL).
Wherein, the volume ratio of first gang of unstripped gas 4 〞, second gang of unstripped gas 5 〞, the 3rd gang of unstripped gas 6 〞 is 1:1.30:0.02, the volume ratio of first gang of second segment gas product 19 〞 and second gang of second segment gas product 20 〞 is 1:0.25, and the volume ratio of first gang of circulation gas 26 〞 and second gang of circulation gas 27 〞 is 1:0.05.
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
The explanation of logistics numbering: 1 〞 is unstripped gas; 7 〞 are the first gas mixture; 9 〞 are first paragraph gas product; 14 〞 are the second gas mixture; 16 〞 are second segment gas product; 28 〞 are the 3rd gas mixture; 30 〞 are the 3rd section of gas product; 22 〞 are circulation gas; 31 〞 are gas product SNG; 42 〞 are superheated vapour.
Compare with comparative example 1, under identical design basis, embodiment 1 is higher than heat utilization ratio, it is low to consume: embodiment 1 loop compression acc power is 896kW, and comparative example 1 is 1115kW, and the energy consumption of embodiment 1 is lower by 19.6% than comparative example 1; Embodiment 1 by-product superheated vapour 171.2t/h, comparative example 1 by-product superheated vapour 158.6t/h, the by-product superheated vapour amount of embodiment 1 is higher by 7.9% than comparative example 1.To sum up, can illustrate that the method capacity usage ratio of production synthetic natural gas provided by the invention is high, consume low.
Claims (13)
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 150～350 ℃): (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, described unstripped gas (1) is the gasification product of coal or biomass, when the volume of described the 3rd strand of unstripped gas (6) and the 4th strand of unstripped gas (7) is different, is 0;
B) circulation gas (19) after the first strand of unstripped gas (4) in step a) and the first steam (37) and supercharging 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 cooled to 250～400 ℃ of first paragraph gas products (12) after being lowered the temperature through the second heat-exchange equipment (11,11 ');
C) the first paragraph gas product (12) after cooling step b) being obtained is (0.3～5) by volume: 1 is divided into circulation gas (13) and second strand of first paragraph gas product (14), described circulation gas (13) is lowered the temperature through the 3rd heat-exchange equipment (15), obtain temperature and be the circulation gas (16) of 100～350 ℃, circulation gas (16) obtains the circulation gas (18) after supercharging through recycle compressor (17) supercharging, circulation gas after supercharging (18) heats up through the 3rd heat-exchange equipment (15), obtains temperature and be the circulation gas (19) after the described supercharging of 250～350 ℃;
D) step c) is obtained to second strand of first paragraph gas product (14) and described second strand of unstripped gas (5), it is second gas mixture (20) of 250～400 ℃ that the second steam (38) is mixed to get temperature, the second gas mixture (20) is passed in second segment methanator (21) and reacted, obtain temperature and be the second segment gas product (22) of 450～700 ℃, this second segment gas product (22) is through the 4th heat-exchange equipment (23, 23 ') cooling, obtain the second segment gas product (24 after the cooling of 350～550 ℃ of temperature, 24 '), second segment gas product (24 after cooling, 24 ') through the 5th heat-exchange equipment (25, 25 ') be cooled to 200～400 ℃ of second segment gas products (26) after being lowered the temperature,
E) it is the 3rd gas mixture (27) of 200～400 ℃ that the second segment gas product (26) after cooling step d) being obtained and described the 3rd strand of unstripped gas (6), the 3rd steam (39) are mixed to get temperature, the 3rd gas mixture (27) is passed in the 3rd section of methanator (28) and reacted, obtain temperature and be the 3rd section of gas product (29) of 300～550 ℃, the three section gas product (30) of the 3rd section of gas product (29) after described the first heat-exchange equipment (2) is cooled to 60～350 ℃ of coolings that obtain;
F) it is the 4th gas mixture (31) of 60～200 ℃ that the 3rd section of gas product (30) after cooling step e) being obtained and described the 4th strand of unstripped gas (7), the 4th steam (40) are mixed to get temperature, described the 4th gas mixture (31) heats up through the 6th heat-exchange equipment (32), obtain temperature and be the 4th gas mixture (33) after the intensification of 200～350 ℃, the 4th gas mixture (33) after intensification passes in the 4th section of methanator (34) and reacts, and obtains temperature and be the 4th section of gas product (35) of 250～450 ℃;
G) it is the gas product (36) of 20～80 ℃ that the 4th section of gas product (35) step f) being obtained obtains temperature after the 6th heat-exchange equipment (32) 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 (41 from battery limit (BL), 41 ') enter drum (42, 42 '), make from drum (42, 42 ') the first oiler feed (43, 43 ') enter described the second heat-exchange equipment (11, 11 ') produce the first saturation steam (44 of 3～10MPa, 44 '), make from drum (42, 42 ') the second oiler feed (45, 45 ') enter described the 4th heat-exchange equipment (23, 23 ') or described the 5th heat-exchange equipment (25, 25 ') produce the second saturation steam (46 of 3～10MPa, 46 '), from drum (42, 42 ') the 3rd saturation steam (47, 47 ') through described the 5th heat-exchange equipment (25, 25 ') or described the 4th heat-exchange equipment (23, 23 ') heat up, obtain temperature and be the superheated vapour (48 of 300～550 ℃, 48 ').
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) is 0 when the volume of described the 3rd strand of unstripped gas (6) and the 4th strand of unstripped gas (7) is different.
4. method according to claim 1 and 2, in described step c), the circulation gas (13) that the first paragraph gas product (12) after described cooling is divided into and the volume ratio of second strand of first paragraph gas product (14) are (0.3～3): 1.
5. method according to claim 3, in described step c), the circulation gas (13) that the first paragraph gas product (12) after described cooling is divided into and the volume ratio of second strand of first paragraph gas product (14) are (0.3～3): 1.
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 (21), the 3rd section of methanator (28) and the 4th section of methanator (34) 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 (15), the 4th heat-exchange equipment (23,23 '), the 5th heat-exchange equipment (25,25 ') and the 6th heat-exchange equipment (32);
Recycle compressor, comprises for by the recycle compressor of circulation gas supercharging (17).
7. device according to claim 6, wherein, described first paragraph methanator (9), second segment methanator (21), the 3rd section of methanator (28) and the 4th section of methanator (34) are insulation fix bed methanator.
8. device according to claim 6, wherein, described device also comprises drum (42,42 '), 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. device according to claim 7, wherein, described device also comprises drum (42,42 '), 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.
10. according to the device described in any one in claim 6 to 9, wherein, described heat-exchange equipment is selected from useless pot and vapor superheater.
11. according to the device described in any one in claim 6 to 9, and wherein, described device also comprises desulphurization reactor, for unstripped gas is carried out to deep desulfuration.
12. according to the device described in any one in claim 6 to 9, and wherein, described device also comprises deoxidation reactor, for unstripped gas is carried out to degree of depth deoxidation.
13. according to the device described in any one in claim 6 to 9, and wherein, described device also comprises gas-liquid separator, for separating of the water of condensation in process gas.
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Owner name: SINOPEC LUOYANG PETROCHEMICAL ENGINEERING CORPORAT Effective date: 20140228 |
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Inventor after: Li Anxue Inventor after: Mei Changsong Inventor after: Kong Fangui Inventor after: Liu Jianan Inventor after: Wang Longyan Inventor after: Zhang Linqing Inventor after: Li Chunqi Inventor after: Zuo Yubang Inventor after: Liu Yongjian Inventor after: Ding Wanyou Inventor after: Yu Mingcheng Inventor after: Liu Xuewu Inventor before: Li Anxue Inventor before: Liu Jianan Inventor before: Li Chunqi Inventor before: Zuo Yubang Inventor before: Liu Yongjian Inventor before: Ding Wanyou Inventor before: Yu Mingcheng Inventor before: Liu Xuewu Inventor before: Mei Changsong Inventor before: Kong Fangui |
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Free format text: CORRECT: INVENTOR; FROM: LI ANXUE LI CHUNQI ZUO YUBANG LIU YONGJIAN DING WANYOU YU MINGCHENG LIU XUEWU MEI CHANGSONG KONG FANGUI LIU JIANAN TO: LI ANXUE WANG LONGYAN ZHANG LINQING LI CHUNQI ZUO YUBANG LIU YONGJIAN DING WANYOU YU MINGCHENG LIU XUEWU MEI CHANGSONG KONG FANGUI LIU JIANAN |
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Effective date of registration: 20140228 Address after: 100070, No. 20, No. 12, No. 188, South Fourth Ring Road, Fengtai District, Beijing Patentee after: Datang International Chemical Technology Institute Co., Ltd. Patentee after: Luoyang Petrochemical Engineering Corporation /SINOPEC Address before: 100070, No. 20, No. 12, No. 188, South Fourth Ring Road, Fengtai District, Beijing Patentee before: Datang International Chemical Technology Institute Co., Ltd. |