CN104910988B - A kind of Methane Resources diversification utilization technique of environmental protection - Google Patents
A kind of Methane Resources diversification utilization technique of environmental protection Download PDFInfo
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- CN104910988B CN104910988B CN201510252998.9A CN201510252998A CN104910988B CN 104910988 B CN104910988 B CN 104910988B CN 201510252998 A CN201510252998 A CN 201510252998A CN 104910988 B CN104910988 B CN 104910988B
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000007613 environmental effect Effects 0.000 title claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 30
- 239000012528 membrane Substances 0.000 claims abstract description 22
- 238000007084 catalytic combustion reaction Methods 0.000 claims abstract description 13
- 239000003345 natural gas Substances 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 239000000047 product Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000011084 recovery Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 239000012466 permeate Substances 0.000 claims description 6
- 239000012465 retentate Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- -1 GB18047-2000 index Substances 0.000 claims description 2
- 238000006477 desulfuration reaction Methods 0.000 claims description 2
- 230000023556 desulfurization Effects 0.000 claims description 2
- 230000008676 import Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000003595 mist Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 4
- 230000006835 compression Effects 0.000 abstract description 3
- 238000007906 compression Methods 0.000 abstract description 3
- 239000005431 greenhouse gas Substances 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 238000012423 maintenance Methods 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 238000000746 purification Methods 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a kind of Methane Resources diversification utilization technique of environmental protection, belong to petrochemical industry, membrane separation technique, catalytic combustion technology and heat recovery system are integrated into an organic whole, by the low-grade gas of one-level two-segment film separation joint-product and automobile-used high end compression natural gas, by being catalyzed burning conversion residual methane, reduce greenhouse gas emission, by heat recovery system by-product hot water and middle pressure steam, it is achieved that the environmental protection diversification utilization of Methane Resources.The technique that the present invention is provided; methane yield is more than 95%; comprehensive utilization ratio is more than 98%; the production cost of product is less than 0.7 yuan/mark side; the utilization technique of a kind of flexible, efficient, inexpensive, easy to operate maintenance and environmental protection is provided for the small towns Methane Resources of small-scale, great fluctuation process and distributed production, industrialization, scale and the commercialization to promoting China's biogas utilization is significant.
Description
Technical field
The present invention relates to a kind of Methane Resources diversification utilization technique of environmental protection, belongs to petrochemical industry.This point
Separating process is fired using catalysis using the low-grade gas of one-level two-segment film separative element coproduction and automobile-used high end compression natural gas
Remaining methane in device conversion tail gas is burnt, and by heat recovery system by-product hot water and middle pressure steam, so as to environmental protection
Achieve the diversification utilization of Methane Resources.
Background technology
Due to sharply increasing for energy consumption, and the optimizing and revising of energy resource structure, natural gas is in China's energy-consuming
In proportion constantly rise.2009, proportion of the natural gas in China's energy-consuming only had 3.8%, according to " 12 "
Energy consumption structure adjusts target, and this proportion will be improved to 8.3% within 2015.Find the substitute gas in non-fossil source
Product, are to realize this target urgent problem.At present, the municipal refuse of China's discharge every year is more than 300,000,000 tons, human and animal excreta
About 4,000,000,000 tons of (aqueous), the crop material for wasting is burned more than 300,000,000 tons.These biomass efficient conversions can be obtained about 200,000,000,000
Cubic meter biological methane, is 2 times of China's gas production in 2010.Obviously, rational exploitation and utilization biomass resource, by which
Biological methane is converted into, is the important power-assisted of China's propulsion energy structure optimizing adjustment.Additionally, according to Copenhagen agreement, non-
Fossil energy accounts for the proportion of China's primary energy consumption, also will be improved to the 15.0% of the year two thousand twenty by 8.3% in 2009.Biological
The reasonable utilization of mass-energy will also play the part of very important role in the process.
The new century is entered, China puts into the fund of biogas engineering every year on average more than 5,000,000,000 yuan.By the end of the year 2011, agriculture
Village's domestic methane tank more than 4,000 ten thousand, medium-and-large-sized biogas engineering more than 2.7 ten thousand sets, and respectively with annual 15% and 27%
Growth rate continues development.Generally, the production capacity of China's biogas engineering has reached the huge size of hundred billion cubes/year, if it is possible to
Rationally using these projects, the structure optimization to AND ENERGY RESOURCES CONSUMPTION IN CHINA is adjusted with important function.
Although prospect is very grand, the methane-generating pit for farm household of biogas engineering overwhelming majority production capacity is occupied to these resources
Reasonable using proposing challenge.At present, the application mode of the household biogas in China rural area and small-sized plant's biogas is mainly
Self-sufficient, domestic gas are provided.Although the serious biogas excess phenomenon of generally existing, due to these biogas production capacities have little
The feature of scale, great fluctuation process and distributed production, it is difficult to link directly with the demand of natural gas of industry.Moreover, methane is
A kind of very big gas of greenhouse gases effect, its GWP value are 25 times of carbon dioxide.The methane that the scattered methane-generating pit in the whole nation is wasted
Amount, is substantially all direct loss to air, equivalent to annual 3.6 hundred million tons of carbon dioxide of discharge.
The biogas obtained by fermenting, mainly contain methane (～50mol%), carbon dioxide (～45mol%), saturation
Water vapour (～3%) and a small amount of air (<, and hydrogen sulfide (50～1000ppm) 1%).The mistake of the scattered methane-generating pit in rural area
Surplus production capacity, by separating-purifying deep processing, every year can at least 7,000,000,000 cubes of output high-grade natural gas, such as vehicular compressed
Natural gas, its direct economic benefit is more than 2,000,000,000 yuan.Obviously, rational process for separating and purifying is to the industrialization of biological methane to pass
Important.
At present, common biogas process for separating and purifying has the conventional arts such as absorption and sorption and cryogenic separation, and emerging
Gas membrane Seperation Technology.Small-scale, great fluctuation process and the dispersion of household biogas and small-sized plant's biogas in view of China rural area
The feature of formula production, conventional art is due to scale adaptability and operating flexibility deficiency, it is difficult to adapt to this kind of biogas production pattern.
Gas membrane Seperation Technology has the advantages that easy to operate, energy consumption is low, occupation area of equipment is little, it is more suitable for scattered rural area family and uses
Firedamp gas equipment and middle-size and small-size evaluation of biogas project on husbandry farms.
Even so, developed at present and great majority are in the UF membrane methane purification technology that grinds, its productive target is past
Toward based on production high-grade natural gas such as, compressed natural gas used as vehicle fuel, on the one hand, the flexibility of production is inadequate, it is difficult to adapt to
Country Household Using Marsh Gas and the characteristic of small-sized plant's biogas, and be not suitable for small towns energy market to civilian low-grade gas with automobile-used
The demand characteristic of high-grade compressed natural gas；On the other hand, separation costs are higher, be unfavorable for small-scale production process investment and
Cash Flow pattern.Therefore, production chains are improved further, reduces biogas deep processing producing cost, become continuation development film
Separate the key point of methane purification technology.In addition, tail gas of the methane purification technology by-product containing a small amount of methane, according to technique not
With its content is fluctuated generally between 1～5mol%, avoids, by process modification, the unfavorable shadow that methane losses cause to environment
Ring, be also to continue with developing the problem that UF membrane methane purification technology must take into.
In sum, the deep processing and utilization of China's Country Household Using Marsh Gas and small-sized plant's biogas, needing exploitation badly can be real
The Methane Resources diversification utilization technique of existing environmental protection, is improving resource utilization, reduction separating energy consumption and separation costs
Simultaneously, it is to avoid environmental pollution.
Content of the invention
It is an object of the invention to provide a kind of Methane Resources diversification utilization technique of environmental protection.The technology utilization one
The level low-grade gas of two-segment film separative element coproduction and automobile-used high end compression natural gas, convert tail using catalytic combustion system
Remaining methane in gas, and by heat recovery system by-product hot water and middle pressure steam, so as to realize the green ring of Methane Resources
Poly is used and diversification utilization.Effectively prevent existing methane purifying technique problems faced：Production chains are low, energy consumption relatively
High, be unsatisfactory for small towns energy market demand, be not suitable for middle and small scale biogas engineering.
For achieving the above object, the technical scheme that the present invention is provided is as follows：
A kind of Methane Resources diversification utilization technique of environmental protection,
In pretreatment system 1, biogas is pressurized through compressor 1a, knot screen 1b removes solid particle and liquid mist, through changing
Hot device 1c is warming up to the operating condition of membrane module, enters film separation system 2；
In film separation system 2, the biogas that pretreatment system 1 is exported enters one section of membrane separator 2a, per-meate side be containing few
The carbon dioxide of amount methane, enters catalytic combustion system 3；The low-grade domestic gas of retentate side output, shunts through current divider 2b, one
Part output enters city gas pipe network as product, and remainder enters two-segment film separator 2c；In two-segment film separator 2c
Retentate side produces the product for meeting compressed natural gas used as vehicle fuel, index GB18047-2000, and per-meate side is that methane content is higher
Carbon dioxide enriched circulating air, returns the biogas in pretreatment system 1 through compressor 1a import.
In catalytic combustion system 3, the per-meate side gas of one section of membrane separator 2a enters devulcanizer 3a；Gas after desulfurization
Blender 3b is entered together with air, ignition point is warmed up to subsequently into heat exchanger 3c, be catalyzed in catalytic combustion reactor 3d
Conversion；The high-temperature tail gas of reactor 3d output, in heat exchanger 3f, recovery heat of high temperature, output 5.0MPa middle pressure steam, are changing
In hot device 3c, the raw material of heatable catalytic combustion reaction, temperature is improved to ignition point, reclaims low-temperature heat quantity in heat exchanger 3e, is produced
Go out 70～90 DEG C of hot water, low-temperature heat quantity is reclaimed in the heat exchanger 1c in pretreatment system 1, make biogas temperature reach 40～80
℃.
One section of membrane separator 2a oozes the methane content of residual air and oozes residual air for 80～90mol%, two-segment film separator 2c
Methane content is >=97%；
After in the catalytic combustion system 3, tail gas carries out harmless treatment, methane content is down to below 100ppm.
Advantages of the present invention and beneficial effect：
The invention provides a kind of Methane Resources diversification utilization technique of environmental protection, taken into full account raw material composition,
The features such as product actual demand and Energy distribution, by UF membrane is become an organic whole with process set such as catalysis burnings,
And the mutually promoting of multiple technologies, mutually improve, step purifying marsh gas and step heat recovery, it is achieved that economic and environment-friendly low energy
Consumption is while produce the civilian biological methane needed for small towns and automobile-used biological methane, pressure is steamed in 70 DEG C of hot water of co-production and 5.0MPa
Vapour, due to the technique coupled using membrane separation process and catalytic combustion method in the present invention, makes the technique divide with traditional biogas film
Compare from purifying technique, not only little with simple to operation and equipment volume, and also reduce separating-purifying energy
Consume, economic benefit is improve, and tail gas hazard-free is realized while producing the diversification natural pond for meeting small towns Gas Market characteristic
Gas product, the biogas separating-purifying being more suitably applied in small towns scattered household biogas project and evaluation of biogas project on husbandry farms.
Description of the drawings
Accompanying drawing is the principle flow chart of environmental type Methane Resources diversification utilization technique.
In figure：1 pretreatment system；1a compressor；1b knot screen；1c heat exchanger；2 film separation systems；Mono- section of film of 2a divides
From device；2b current divider；Mono- section of membrane separator of 2c；3 catalytic combustion system；3a devulcanizer；3b blender；3c heat exchanger；3d is catalyzed
Reactor；3e heat exchanger；3f heat exchanger.
Specific embodiment
Technical scheme is described below by way of instantiation.
Embodiment 1：
Process object：The biogas of large-scale plant that raises biogas engineering, gas production are 500Nm3/h.
Biogas constitutes mol%：
| CH4 | 53 | CO2 | 44 | H2O | 2 |
| O2 | 0.2 | N2 | 0.7 | H2S | 800ppm |
The operating condition of one section of membrane separator 2a is：Temperature 60 C, pressure are 2.5MPa, and membrane area is 116m2.
The operating condition of two-segment film separator 2c is：52 DEG C of temperature, pressure are 2.48MPa, and membrane area is 140m2.
Compressed air volume flow rate is：200Nm3/h
In this embodiment, civilian biological methane yield is 2.4 × 105Nm3/ a, automobile-used biological methane yield be 1.7 ×
106Nm3/ a, 70 DEG C of hot water yield are 315t/a for 3543t/a, 5.0MPa middle pressure steam yield, and economic benefit is 3,100,000 yuan/a,
The technique is capable of the biogas of abundant Multi-class propagation large-scale plant that raises biogas engineering.
Embodiment 2：
Process object：The biogas of the household biogas project of centralized recovery, yield are 1000Nm3/h.
Biogas constitutes mol%：
| CH4 | 50 | CO2 | 45 | H2O | 3 |
| O2 | 0.78 | N2 | 1.04 | H2S | 800ppm |
The operating condition of one section of membrane separator 2a is：Temperature 60 C, pressure are 2.5MPa, and membrane area is 240m2.
The operating condition of two-segment film separator 2c is：52 DEG C of temperature, pressure are 2.48MPa, and membrane area is 286m2.
Compressed air volume flow rate is：500Nm3/h
In this embodiment, civilian biological methane yield is 6.37 × 105Nm3/ a, automobile-used biological methane yield be 3.05 ×
106Nm3/ a, 70 DEG C of hot water yield are 670t/a for 9688t/a, 5.0MPa middle pressure steam yield, and economic benefit is 5,830,000 yuan/a,
The technique being capable of the superfluous biogas of effectively utilizes small towns household biogas project.
Claims (3)
1. the Methane Resources diversification utilization technique of a kind of environmental protection, it is characterised in that
In pretreatment system (1), biogas is pressurized through compressor (1a), knot screen (1b) removes solid particle and liquid mist, warp
Heat exchanger (1c) is warming up to the operating condition of membrane module, enters film separation system (2)；
In film separation system (2), biogas that pretreatment system (1) is exported enters one section of membrane separator (2a), per-meate side be containing
The carbon dioxide of a small amount of methane, enters catalytic combustion system (3)；The low-grade domestic gas of retentate side output, through current divider (2b)
Shunting, part output enter city gas pipe network as product, and remainder enters two-segment film separator (2c)；In two-segment film
Separator (2c) retentate side produces the product for meeting compressed natural gas used as vehicle fuel, GB18047-2000 index, and per-meate side is methane
The higher carbon dioxide enriched circulating air of content, returns the biogas in pretreatment system (1) through compressor (1a) import；
In catalytic combustion system (3), the per-meate side gas of one section of membrane separator (2a) enters devulcanizer (3a)；Gas after desulfurization
Body and air enter blender (3b) together, are warmed up to ignition point subsequently into heat exchanger (3c), in catalytic combustion reactor
(3d) catalyzed conversion in；The high-temperature tail gas that reactor (3d) is exported, reclaim heat of high temperature, output 5.0MPa in heat exchanger (3f)
Middle pressure steam, in heat exchanger (3c), the raw material of heatable catalytic combustion reaction, temperature is improved to ignition point, at heat exchanger (3e)
Middle recovery low-temperature heat quantity, 70～90 DEG C of hot water of output, low-temperature heat quantity is reclaimed in the heat exchanger (1c) in pretreatment system (1),
Biogas temperature is made to reach 40～80 DEG C.
2. Methane Resources diversification utilization technique according to claim 1, it is characterised in that one section of described membrane separator
(2a) methane content for oozing residual air is 80～90mol%, and two-segment film separator (2c) oozes residual air methane content for >=97%.
3. Methane Resources diversification utilization technique according to claim 1 and 2, it is characterised in that described catalysis burning
After in system (3), tail gas carries out harmless treatment, methane content is down to below 100ppm.
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| CN106281524A (en) * | 2016-08-31 | 2017-01-04 | 胜利油田孚瑞特石油装备有限责任公司 | A kind of recoverying and utilizing method of non-combustible oil field gas |
| CN106430864A (en) * | 2016-12-20 | 2017-02-22 | 大连爱特流体控制有限公司 | Sewage treatment device capable of generating hydrogen |
| CN107998841A (en) * | 2017-12-24 | 2018-05-08 | 杨正山 | A kind of rubbish landfill gas UF membrane couples microalgae carbon sequestration technique |
| CN109593582A (en) * | 2018-12-03 | 2019-04-09 | 中国船舶重工集团公司第七〇九研究所 | Biogas film purifies integrating device and its methane purification method |
| EP3705170A1 (en) * | 2019-03-08 | 2020-09-09 | Hitachi Zosen Inova AG | Biogas plant and biogas treatment |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101584960A (en) * | 2008-05-22 | 2009-11-25 | 青岛生物能源与过程研究所 | Separator and separation and purification method of gas-liquid phase absorbing membrane |
| CN101973523A (en) * | 2010-10-28 | 2011-02-16 | 四川亚联高科技股份有限公司 | Method for preparing hydrogen gas by taking marsh gas as raw material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101584960A (en) * | 2008-05-22 | 2009-11-25 | 青岛生物能源与过程研究所 | Separator and separation and purification method of gas-liquid phase absorbing membrane |
| CN101973523A (en) * | 2010-10-28 | 2011-02-16 | 四川亚联高科技股份有限公司 | Method for preparing hydrogen gas by taking marsh gas as raw material |
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