CN102899112A - Method and device for producing synthetic natural gas - Google Patents
Method and device for producing synthetic natural gas Download PDFInfo
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- CN102899112A CN102899112A CN2012104210264A CN201210421026A CN102899112A CN 102899112 A CN102899112 A CN 102899112A CN 2012104210264 A CN2012104210264 A CN 2012104210264A CN 201210421026 A CN201210421026 A CN 201210421026A CN 102899112 A CN102899112 A CN 102899112A
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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 take coal or gasifying biomass product as method and the device of raw material production synthetic natural gas, belong to the 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.
Coal hydrogenation gasification is given birth to methanogenic subject matter to be had: efficiency of carbon conversion is low, the 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 finished 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 characteristics 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, to utilize coal production city coal gas as purpose, set up ripe coal gas part methanation technology in last century: researched and developed " Partial-methanation of Water-coal Gas At Atmospheric Pressure methanation production city coal gas " technology such as Dalian Chemiclophysics Inst., Chinese Academy of Sciences; The RHM-266 type nickel that chemical fertilizer institute of the Ministry of Chemical Industry has developed take the normal pressure semi-water gas as unstripped gas is methanation catalyst and technique; Coal Mining Research Institute has developed the 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, the wide temperature range type methanation catalyst, high temperature, high pressure full methanation technology have become the development trend of current methanation technology.A methanation commercialization of big plain in u.s.a factory is only arranged at present in the world, and in being, the low temperature methanation technology, for high temperature, the high pressure full methanation technology of methanation development trend, still do not have the precedent of industrial applications.Domestic methanation technology only stays in the part methanation at present, and catalyzer adaptive temperature narrow range, has greatly limited the comprehensive utilization ratio of energy; The part methanation technology that carries out under the normal pressure in addition is 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 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 the step a) and the first steam (37) and the supercharging being mixed to get temperature is the first gas mixture (8) of 250 ~ 400 ℃, the first gas mixture (8) passed in the first paragraph methanator (9) react, obtain temperature and be 450 ~ 750 ℃ first paragraph gas product (10), this first paragraph gas product (10) is cooled to 250 ~ 400 ℃ of first paragraph gas products (12) after obtaining lowering the temperature through the second heat-exchange equipment (11,11 ');
C) the first paragraph gas product (12) after the cooling that step b) is 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 100 ~ 350 ℃ circulation gas 16, the circulation gas (18) of circulation gas 16 after recycle compressor (17) supercharging obtains supercharging, circulation gas after the supercharging (18) heats up through the 3rd heat-exchange equipment (15), obtains temperature and be the circulation gas (19) after 250 ~ 350 ℃ the described supercharging;
D) the second strand of first paragraph gas product (14) after the cooling that step c) is obtained and described second strand of unstripped gas (5), it is the second gas mixture (20) of 250 ~ 400 ℃ that the second steam (38) is mixed to get temperature, the second gas mixture (20) passed in the second segment methanator (21) react, obtain temperature and be 450 ~ 700 ℃ second segment gas product (22), 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 the cooling, 24 ') be cooled to 200 ~ 400 ℃ of second segment gas products (26) after obtaining lowering the temperature through the 5th heat-exchange equipment (25,25 ');
E) it is 200 ~ 400 ℃ the 3rd gas mixture (27) that the second segment gas product (26) after the cooling that step d) is obtained and described the 3rd strand of unstripped gas (6), the 3rd steam (39) are mixed to get temperature, the 3rd gas mixture (27) passed in the 3rd section methanator (28) react, obtain temperature and be 300 ~ 550 ℃ the 3rd section gas product (29), the three section gas product (30) of the 3rd section gas product (29) after described the first heat-exchange equipment (2) is cooled to 60 ~ 350 ℃ of coolings that obtain;
F) it is 60 ~ 200 ℃ the 4th gas mixture (31) that the 3rd section gas product (30) after the cooling that step e) is 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) and obtains the 4th gas mixture 33 after temperature is 200 ~ 350 ℃ intensification, the 4th gas mixture 33 after the intensification passes in the 4th section methanator (34) and reacts, and obtains temperature and be 250 ~ 450 ℃ the 4th section gas product (35);
G) the 4th section gas product (35) that step f) is obtained gone forward side by side through the 6th heat-exchange equipment (32) cooling, and to obtain temperature after promoting the circulation of qi liquid separates be 20 ~ 80 ℃ gas product (36).
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), second strand of unstripped gas (5), the 3rd strand of unstripped gas (6) and the 4th strand of unstripped gas (7) that described unstripped gas (1) is divided into 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 the 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 the methanation reaction heat release in the following manner: make the oiler feed (41 from the 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 (44,44 ') of 3 ~ 10MPa, make from drum (42,42 ') the second oiler feed (45,45 ') enter the second saturation steam (46 that described the 4th heat-exchange equipment (23,23 ') or described the 5th heat-exchange equipment (25,25 ') produce 3 ~ 10MPa, 46 '), from the 3rd saturation steam (47,47 ') of drum (42,42 ') through described the 5th heat-exchange equipment (25,25 ') or described the 4th heat-exchange equipment (23,23 ') heat up, obtain temperature and be 300 ~ 550 ℃ superheated vapour (48,48 ').
In the above-mentioned mode of utilizing the methanation reaction heat release, when the second oiler feed (45,45 ') entered the 4th heat-exchange equipment (23,23 '), the 3rd saturation steam (47,47 ') heated up through the 5th heat-exchange equipment (25,25 '); When the second oiler feed (45,45 ') entered the 5th heat-exchange equipment (25,25 '), the 3rd saturation steam (47,49 ') heated up through the 4th heat-exchange equipment (23,23 ').
According to the method for production synthetic natural gas provided by the invention, the method is take coal or gasifying biomass product as raw material, the 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 that is used for aforesaid method provided by the invention, and this device comprises:
Methanator comprises be used to the first paragraph methanator (9) that carries out methanation reaction, second segment methanator (21), the 3rd section methanator (28) and the 4th section methanator (34);
Heat-exchange equipment, comprise the first heat-exchange equipment (2), the second heat-exchange equipment (11 for heating and/or 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 the recycle compressor (17) with the circulation gas supercharging.
In the preferred embodiment of present device, described first paragraph methanator (9), second segment methanator (21), the 3rd section methanator (28) and the 4th section 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 simultaneously saturation steam is delivered to heat-exchange equipment.Particularly, described drum (42,42 ') is used to the second heat-exchange equipment (11,11 ') that the first oiler feed (43 is provided, 43 '), and accept the first saturation steam (44,44 ') that the second heat-exchange equipment (11,11 ') produces, it is the 4th heat-exchange equipment (23,23 ') or the 5th heat-exchange equipment (25,25 ') the second oiler feed (45,45 ') is provided, and accept the 4th heat-exchange equipment (23,23 ') or the second saturation steam (46,46 ') of producing of the 5th heat-exchange equipment (25,25 '), simultaneously with 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, is used for unstripped gas is carried out deep desulfuration.
Preferably, described device also comprises deoxidation reactor, is used for unstripped gas is carried out degree of depth deoxidation.
Preferably, described device also comprises gas-liquid separator, for separating of the water of condensation in the process gas.
The invention provides a kind of continuous processing flow process and device that contains the synthetic natural gas more than the methane 94mol% take coal or gasifying biomass product as raw material production.Technical process provided by the invention is as follows: unstripped gas is divided into four strands after preheating, wherein first strand of unstripped gas with enter the first paragraph methanator after steam, circulation gas mix and react; First strand of gas product is divided into two strands, enter the first paragraph methanator after the first stock-traders' know-how recycle compressor supercharging, enter the second segment methanator after second strand of first paragraph gas product and second strand of unstripped gas and the vapor mixing and react, enter the 3rd section methanator after second segment gas product and the 3rd strand of unstripped gas, the vapor mixing and react; Enter the 4th section methanator after the 3rd section gas product and the 4th strand of unstripped gas, the vapor mixing and react, the 4th section gas product obtains gas product after gas-liquid separation.
Contain independent steam system in the technique of the present invention, steam is mixed into corresponding methanator with unstripped gas respectively, can control preferably the reactor outlet temperature; but the flow modulation of this steam mixes with unstripped gas on the one hand, reduces CO content in the unstripped gas; the control temperature of reaction; but Optimization Technology reduces circulating flow rate on the other hand, reduces system energy consumption; improve energy utilization efficiency; also can be 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.
Contain the production of steam system of utilizing methanation reaction heat in the technique of the present invention, 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 the saturation steam that heat-exchange equipment produces by riser by downtake, and saturation steam is delivered to heat-exchange equipment heats up and obtain superheated vapour.
If still contain a small amount of carbon monoxide and carbonic acid gas in the gas product of the present invention, the further reaction of gas can be obtained the finished product.
Compared with prior art, the present invention has realized coal or the gasifying biomass product synthetic gas full methanation after purifying is come the production synthetic natural gas, has a technical process reasonable, possesses operability; Capacity usage ratio is high, save energy, advantages of environment protection.
Description of drawings
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 that compares 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 that provides 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 unstripped gas 3 after obtaining heating up after 210 ~ 230 ℃ through the first heat-exchange equipment 2.Unstripped gas 3 after the 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 circulation gas 19 after the first steam 37 and the supercharging, obtain temperature and be the first gas mixture 8 of 280 ~ 300 ℃, it is passed into carry out methanation reaction in the first paragraph methanator 9, obtain temperature and be 660 ~ 680 ℃ first paragraph gas product 10.First paragraph gas product 10 is cooled to 320 ~ 340 ℃ of first paragraph gas products 12 after obtaining lowering the temperature, simultaneously by-product saturation steam through the second heat-exchange equipment 11.
C) the first paragraph gas product 12 after will lowering the temperature is divided into circulation gas 13 and second strand of first paragraph gas product 14, circulation gas 13 is through 15 coolings of the 3rd heat-exchange equipment, obtain temperature and be 170 ~ 190 ℃ circulation gas 16, the circulation gas 18 of circulation gas 16 after recycle compressor 17 superchargings obtain supercharging, the loop compression acc power is 896kW, circulation gas 18 after the supercharging heats up through the 3rd heat-exchange equipment 15, obtains temperature and be the circulation gas 19 after 290 ~ 310 ℃ the supercharging;
D) second segment first paragraph gas product 14 and second strand of unstripped gas 5, second steam 38 being mixed to get temperature is the second gas mixture 20 of 290 ~ 310 ℃, the second gas mixture 20 passed in the second segment methanator 21 react, obtain temperature and be 620 ~ 640 ℃ second segment gas product 22, this second segment gas product 22 is through 23 coolings of the 4th heat-exchange equipment, obtain the second segment gas product 24 after the cooling of 480 ~ 500 ℃ of temperature, the second segment gas product 24 after the cooling is cooled to 280 ~ 300 ℃ of second segment gas products 26 after obtaining lowering the temperature through the 5th heat-exchange equipment 25;
E) to be mixed to get temperature be 280 ~ 300 ℃ the 3rd gas mixture 27 for the second segment gas product 26 after will lowering the temperature and the 3rd strand of unstripped gas 6, the 3rd steam 39, the 3rd gas mixture 27 passed in the 3rd section methanator 28 react, obtain temperature and be 480 ~ 500 ℃ the three section gas product 30 of 29, the three sections gas products 29 of the 3rd section gas product after the first heat-exchange equipment 2 is cooled to 80 ~ 100 ℃ of coolings that obtain;
F) to be mixed to get temperature be 70 ~ 90 ℃ the 4th gas mixture 31 for the 3rd section gas product 30 after will lowering the temperature and the 4th strand of unstripped gas 7, the 4th steam 40, described the 4th gas mixture 31 heats up through the 6th heat-exchange equipment 32 and obtains the 4th gas mixture 33 after temperature is 250 ~ 270 ℃ intensification, the 4th gas mixture 33 after the intensification passes in the 4th section methanator 34 and reacts, and obtains temperature and be 370 ~ 390 ℃ the 4th section gas product 35;
G) the 4th section gas product 35 gone forward side by side through the cooling of the 6th heat-exchange equipment 32 to obtain temperature after promoting the circulation of qi liquid separates be 30 ~ 50 ℃ gas product 36.
Wherein, the technique of utilizing of methanation reaction heat release comprises: the oiler feed 41 from the 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, heat up through the 5th heat-exchange equipment 25 from the 3rd saturation steam 47 of drum 42, obtain temperature and be 440 ~ 460 ℃ 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 1:0.33:0.04:0, 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 the table 1, a situation arises to have described intuitively the reality of each workshop section's methanation reaction in the technical process shown in Figure 1.
Table 1
The explanation of logistics numbering: 1 is unstripped gas; 8 is the first gas mixture; 10 is the first paragraph gas product; 20 is the second gas mixture; 22 is the second segment gas product; 27 is the 3rd gas mixture; 29 is the 3rd section gas product; 33 are the 4th gas mixture after heating up; 35 is the 4th section 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 unstripped gas 3 after obtaining heating up after 190 ~ 210 ℃ through the first heat-exchange equipment 2.Unstripped gas 3 after the 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 circulation gas 19 after the first steam 37 and the supercharging, obtain temperature and be the first gas mixture 8 of 280 ~ 300 ℃, it is passed into carry out methanation reaction in the first paragraph methanator 9, obtain temperature and be 600 ~ 620 ℃ first paragraph gas product 10.First paragraph gas product 10 is cooled to 310 ~ 330 ℃ of first paragraph gas products 12 after obtaining lowering the temperature, simultaneously by-product saturation steam through the second heat-exchange equipment 11.
C) the first paragraph gas product 12 after will lowering the temperature is divided into circulation gas 13 and second strand of first paragraph gas product 14, circulation gas 13 is through 15 coolings of the 3rd heat-exchange equipment, obtain temperature and be 190 ~ 210 ℃ circulation gas 16, the circulation gas 18 of circulation gas 16 after 17 superchargings obtain supercharging, circulation gas 18 after the supercharging heats up through the 3rd heat-exchange equipment 15, obtains temperature and be the circulation gas 19 after 270 ~ 290 ℃ the supercharging;
D) second strand of first paragraph gas product 14 and second strand of unstripped gas 5, second steam 38 being mixed to get temperature is the second gas mixture 20 of 280 ~ 300 ℃, the second gas mixture 20 passed in the second segment methanator 21 react, obtain temperature and be 600 ~ 620 ℃ second segment gas product 22, this second segment gas product 22 is through the 4th heat-exchange equipment 23 ' cooling, obtain after the cooling of 380 ~ 400 ℃ of temperature second segment gas product 24 ', the second segment gas product 26 of the second segment gas product 24 after the cooling ' after 280 ~ 300 ℃ of the 5th heat-exchange equipments 25 ' be cooled to obtain lowering the temperature;
E) to be mixed to get temperature be 280 ~ 300 ℃ the 3rd gas mixture 27 for the second segment gas product 26 after will lowering the temperature and the 3rd strand of unstripped gas 6, the 3rd steam 39, the 3rd gas mixture 27 passed in the 3rd section methanator 28 react, obtain temperature and be 420 ~ 440 ℃ the three section gas product 30 of 29, the three sections gas products 29 of the 3rd section gas product after the first heat-exchange equipment 2 is cooled to 80 ~ 100 ℃ of coolings that obtain;
F) to be mixed to get temperature be 70 ~ 90 ℃ the 4th gas mixture 31 for the 3rd section gas product 30 after will lowering the temperature and the 4th strand of unstripped gas 7, the 4th steam 40, described the 4th gas mixture 31 heats up through the 6th heat-exchange equipment 32 and obtains the 4th gas mixture 33 after temperature is 240 ~ 260 ℃ intensification, the 4th gas mixture 33 after the intensification passes in the 4th section methanator 34 and reacts, and obtains temperature and be 310 ~ 330 ℃ the 4th section gas product 35;
G) the 4th section gas product 35 gone forward side by side through the cooling of the 6th heat-exchange equipment 32 to obtain temperature after promoting the circulation of qi liquid separates be 30 ~ 50 ℃ gas product 36.
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 ' generation 3 ~ 10MPa the first saturation steam 44 ', from drum 42 ' the second oiler feed 45 ' enter the 5th heat-exchange equipment 25 ' generation 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 the 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 the first paragraph gas product; 20 is the second gas mixture; 22 is the second segment gas product; 27 is the 3rd gas mixture; 29 is the 3rd section gas product; 33 are the 4th gas mixture after heating up; 35 is the 4th section 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 unstripped gas 3 after obtaining heating up after 210 ~ 230 ℃ through the first heat-exchange equipment 2.Unstripped gas 3 after the 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 circulation gas 19 after the first steam 37 and the supercharging, obtain temperature and be the first gas mixture 8 of 290 ~ 310 ℃, it is passed into carry out methanation reaction in the first paragraph methanator 9, obtain temperature and be 670 ~ 690 ℃ first paragraph gas product 10.First paragraph gas product 10 is cooled to 320 ~ 340 ℃ of first paragraph gas products 12 after obtaining lowering the temperature, simultaneously by-product saturation steam through the second heat-exchange equipment 11.
C) the first paragraph gas product 12 after will lowering the temperature is divided into circulation gas 13 and second strand of first paragraph gas product 14, circulation gas 13 is through 15 coolings of the 3rd heat-exchange equipment, obtain temperature and be 170 ~ 190 ℃ circulation gas 16, the circulation gas 18 of circulation gas 16 after recycle compressor 17 superchargings obtain supercharging, circulation gas 18 after the supercharging heats up through the 3rd heat-exchange equipment 15, obtains temperature and be the circulation gas 19 after 290 ~ 310 ℃ the supercharging;
D) second strand of first paragraph gas product 14 and second strand of unstripped gas 5, second steam 38 being mixed to get temperature is the second gas mixture 20 of 290 ~ 310 ℃, the second gas mixture 20 passed in the second segment methanator 21 react, obtain temperature and be 640 ~ 660 ℃ second segment gas product 22, this second segment gas product 22 is through 23 coolings of the 4th heat-exchange equipment, obtain the second segment gas product 24 after the cooling of 480 ~ 500 ℃ of temperature, the second segment gas product 24 after the cooling is cooled to 280 ~ 300 ℃ of second segment gas products 26 after obtaining lowering the temperature through the 5th heat-exchange equipment 25;
E) to be mixed to get temperature be 280 ~ 300 ℃ the 3rd gas mixture 27 for the second segment gas product 26 after will lowering the temperature and the 3rd strand of unstripped gas 6, the 3rd steam 39, the 3rd gas mixture 27 passed in the 3rd section methanator 28 react, obtain temperature and be 480 ~ 500 ℃ the three section gas product 30 of 29, the three sections gas products 29 of the 3rd section gas product after the first heat-exchange equipment 2 is cooled to 80 ~ 100 ℃ of coolings that obtain;
F) to be mixed to get temperature be 70 ~ 90 ℃ the 4th gas mixture 31 for the 3rd section gas product 30 after will lowering the temperature and the 4th strand of unstripped gas 7, the 4th steam 40, 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 250 ~ 270 ℃ the intensification, the 4th gas mixture 33 after the intensification passes in the 4th section methanator 34 and reacts, and obtains temperature and be 370 ~ 390 ℃ the 4th section gas product 35;
G) the 4th section gas product 35 gone forward side by side through the cooling of the 6th heat-exchange equipment 32 to obtain temperature after promoting the circulation of qi liquid separates be 30 ~ 50 ℃ gas product 36.
Wherein, the technique of utilizing of methanation reaction heat release comprises: the oiler feed 41 from the 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, heat up through the 5th heat-exchange equipment 25 from the 3rd saturation steam 47 of drum 42, obtain temperature and be 440 ~ 460 ℃ 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 1:0.41:0.04:0.01, 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 the 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 Examples 1
For comparing with embodiment 1, under identical design basis condition, adopt low temperature methanation technology production synthetic natural gas in the tradition, the 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 obtaining heating up after 140 ~ 160 ℃ through the first heat-exchange equipment 2 〞.Unstripped gas 3 〞 after the 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 the first gas mixture 7 〞 of 270 ~ 290 ℃, it is passed among first paragraph methanator 8 〞 carry out methanation reaction, obtain temperature and be 490 ~ 510 ℃ first paragraph gas product 9 〞.First paragraph gas product 9 〞 are through the second heat-exchange equipment 10 〞 and the 3rd heat-exchange equipment 12 〞 cooling, obtain temperature and be first paragraph gas product 13 〞 after 300 ~ 320 ℃ the cooling, simultaneously by-product saturation steam and superheated vapour.
C) first paragraph gas product 13 〞 after will lowering the temperature mix with second gang of unstripped gas 5 〞, the second steam 33 〞, second gang of circulation gas 27 〞, obtain temperature and be the second gas mixture 14 〞 of 270 ~ 290 ℃, it is passed among second segment methanator 15 〞 carry out methanation reaction, obtain temperature and be 490 ~ 510 ℃ second segment gas product 16 〞.Second segment gas product 16 〞 are cooled to second segment gas product 18 〞 after obtaining lowering the temperature after 230 ~ 250 ℃ through the 4th heat-exchange equipment 17 〞.
D) second segment gas product 18 〞 after will lowering the temperature 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 obtaining lowering the temperature after 30 ~ 50 ℃ through the 5th heat-exchange equipment 21 〞.First gang of second segment gas product 22 〞 after the cooling enter recycle compressor 23 〞 superchargings, obtain circulation gas 24 〞, and the 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 190 ~ 210 ℃ the intensification.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 the 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 230 ~ 250 ℃ the 3rd gas mixture 28 〞, it is sent among the 3rd section methanator 29 〞 carry out methanation reaction, obtain temperature and be 290 ~ 310 ℃ the 3rd section gas product 30 〞.The 3rd section gas product 30 〞 are through the first heat-exchange equipment 2 〞 cooling and to obtain temperature after gas-liquid separation be 30 ~ 50 ℃ gas product 31 〞 (SNG).
Wherein, the technique of utilizing of methanation reaction heat release comprises: oiler feed 35 〞 from the 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 〞, and superheated vapour 42 〞 that obtain temperature and be 440 ~ 460 ℃ send the 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 the table 4, a situation arises to have described intuitively the reality of each workshop section's methanation reaction in the technical process shown in Figure 3.
Table 4
The explanation of logistics numbering: 1 〞 is unstripped gas; 7 〞 are the first gas mixture; 9 〞 are the first paragraph gas product; 14 〞 are the second gas mixture; 16 〞 are the second segment gas product; 28 〞 are the 3rd gas mixture; 30 〞 are the 3rd section gas product; 22 〞 are circulation gas; 31 〞 are gas product SNG; 42 〞 are superheated vapour.
Compare with Comparative Examples 1, under identical design basis, embodiment 1 is higher than heat utilization ratio, consumption is low: embodiment 1 loop compression acc power is 896kW, and Comparative Examples 1 is 1115kW, and the energy consumption of embodiment 1 is than Comparative Examples 1 low 19.6%; Embodiment 1 by-product superheated vapour 171.2t/h, Comparative Examples 1 by-product superheated vapour 158.6t/h, the by-product superheated vapour amount of embodiment 1 is higher by 7.9% than Comparative Examples 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 (10)
1. 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);
B) circulation gas (19) after the first strand of unstripped gas (4) in the step a) and the first steam (37) and the supercharging being mixed to get temperature is the first gas mixture (8) of 250 ~ 400 ℃, the first gas mixture (8) passed in the first paragraph methanator (9) react, obtain temperature and be 450 ~ 750 ℃ first paragraph gas product (10), this first paragraph gas product (10) is cooled to 250 ~ 400 ℃ of first paragraph gas products (12) after obtaining lowering the temperature through the second heat-exchange equipment (11,11 ');
C) the first paragraph gas product (12) after the cooling that step b) is 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 100 ~ 350 ℃ circulation gas (16), the circulation gas (18) of circulation gas (16) after recycle compressor (17) supercharging obtains supercharging, circulation gas after the supercharging (18) heats up through the 3rd heat-exchange equipment (15), obtains temperature and be the circulation gas (19) after 250 ~ 350 ℃ the described supercharging;
D) step c) is obtained second strand of first paragraph gas product (14) and described second strand of unstripped gas (5), it is the second gas mixture (20) of 250 ~ 400 ℃ that the second steam (38) is mixed to get temperature, the second gas mixture (20) passed in the second segment methanator (21) react, obtain temperature and be 450 ~ 700 ℃ second segment gas product (22), 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 the cooling, 24 ') be cooled to 200 ~ 400 ℃ of second segment gas products (26) after obtaining lowering the temperature through the 5th heat-exchange equipment (25,25 ');
E) it is 200 ~ 400 ℃ the 3rd gas mixture (27) that the second segment gas product (26) after the cooling that step d) is obtained and described the 3rd strand of unstripped gas (6), the 3rd steam (39) are mixed to get temperature, the 3rd gas mixture (27) passed in the 3rd section methanator (28) react, obtain temperature and be 300 ~ 550 ℃ the 3rd section gas product (29), the three section gas product (30) of the 3rd section gas product (29) after described the first heat-exchange equipment (2) is cooled to 60 ~ 350 ℃ of coolings that obtain;
F) it is 60 ~ 200 ℃ the 4th gas mixture (31) that the 3rd section gas product (30) after the cooling that step e) is 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 200 ~ 350 ℃ the intensification, the 4th gas mixture (33) after the intensification passes in the 4th section methanator (34) and reacts, and obtains temperature and be 250 ~ 450 ℃ the 4th section gas product (35);
G) the 4th section gas product (35) that step f) is obtained gone forward side by side through the 6th heat-exchange equipment (32) cooling, and to obtain temperature after promoting the circulation of qi liquid separates be 20 ~ 80 ℃ gas product (36).
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), second strand of unstripped gas (5), the 3rd strand of unstripped gas (6) and the 4th strand of unstripped gas (7) that described unstripped gas (1) is divided into is 1:(0.5 ~ 2): (0 ~ 0.3): (0 ~ 0.3).
4. each described method in 3 according to claim 1, in described step c), the circulation gas (13) that the first paragraph gas product (12) after the described cooling is divided into and the volume ratio of second strand of first paragraph gas product (14) are (0.3 ~ 3): 1.
5. each described method in 4 according to claim 1, described method also comprises utilizes the methanation reaction heat release in the following manner: make the oiler feed (41 from the 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 (44,44 ') of 3 ~ 10MPa, make from drum (42,42 ') the second oiler feed (45,45 ') enter the second saturation steam (46 that described the 4th heat-exchange equipment (23,23 ') or described the 5th heat-exchange equipment (25,25 ') produce 3 ~ 10MPa, 46 '), from the 3rd saturation steam (47,47 ') of drum (42,42 ') through described the 5th heat-exchange equipment (25,25 ') or described the 4th heat-exchange equipment (23,23 ') heat up, obtain temperature and be 300 ~ 550 ℃ superheated vapour (48,48 ').
6. be used for the device of each described method of claim 1 to 5, it comprises:
Methanator comprises be used to the first paragraph methanator (9) that carries out methanation reaction, second segment methanator (21), the 3rd section methanator (28) and the 4th section methanator (34);
Heat-exchange equipment, comprise the first heat-exchange equipment (2), the second heat-exchange equipment (11 for heating and/or 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 the recycle compressor (17) with the circulation gas supercharging.
7. device according to claim 6, wherein, described first paragraph methanator (9), second segment methanator (21), the 3rd section methanator (28) and the 4th section methanator (34) are insulation fix bed methanator.
8. according to claim 6 or the device described in 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 simultaneously saturation steam is delivered to heat-exchange equipment.
9. each described device in 8 according to claim 6, wherein, described heat-exchange equipment is selected from useless pot and vapor superheater.
10. each described device in 9 according to claim 6, wherein, described device also comprises desulphurization reactor, is used for unstripped gas is carried out deep desulfuration;
Preferably, described device also comprises deoxidation reactor, is used for unstripped gas is carried out degree of depth deoxidation;
Preferably, described device also comprises gas-liquid separator, for separating of the water of condensation in the process gas.
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| CN105385478A (en) * | 2015-12-08 | 2016-03-09 | 大唐国际化工技术研究院有限公司 | Method and apparatus for producing synthetic natural gas |
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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. |