CN102453564B - Carbon emission-free one-step method and equipment for synthesizing artificial natural gas - Google Patents
Carbon emission-free one-step method and equipment for synthesizing artificial natural gas Download PDFInfo
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- CN102453564B CN102453564B CN201010519763.9A CN201010519763A CN102453564B CN 102453564 B CN102453564 B CN 102453564B CN 201010519763 A CN201010519763 A CN 201010519763A CN 102453564 B CN102453564 B CN 102453564B
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Abstract
The invention discloses a method for preparing synthetic natural gas from coal-formed gas, coke-oven gas and the like through methanation one-step reaction. The method is characterized in that: in the production of the synthetic artificial natural gas, CO2 emission is avoided, namely the artificial natural gas is synthesized at zero carbon emission, the flow is simple, a few pieces of equipment is arranged, the temperature resistance requirement of a methanation catalyst is low, no recycle or a low recycle ratio is achieved, and electricity is saved.
Description
Technical field
The present invention relates to the method and apparatus of a kind of carbon emission-free one-step synthesis Artificial Natural Gas, belong to field of chemical engineering.
Background technology
Synthetic gas is obtained, by H wherein by gasification
2, CO, CO
2carry out methanation reaction and can produce various Artificial Natural Gas, reaction formula is as follows:
CO+3H
2＝CH
4+H
2O +206KJ/mol (1)
CO
2+4H
2＝CH
4+2H
2O +165KJ/mol (2)
Because methanation reaction (1) and (2) are strong exothermal reaction, therefore the temperature in synthetic gas methanation in methanator must be controlled, to prevent the overheated of catalyst reactor.And owing to being conducive to the formation of methane under low temperature, viewed from the viewpoint of balance, high temperature is disadvantageous, and high temperature decreases Synthetic holography and becomes methane.The ordinary method of prior art control temperature in methanation reaction process needs to use the complex appts comprising multiple heat exchanger and gas circulator, the overheated of methanator is prevented with cooling flow effluent gas, as the Chinese patent CN101560423A of disclosed Casale company application recently, application number 200910135203 (see accompanying drawing 1), pass into adiabatic reactor by parallel for virgin gas synthesis simultaneously, adopt adiabatic reactor and tower external heat exchanger, multiple stage series connection carries out methanation reaction, due to CO or CO
2add H
2methanation reaction heat very large, therefore one is adopt reaction-heat exchange cooling-react the way hocketed, and this is increase equipment number of units just, even if like this, exhaust gas temperature is also up to 600 DEG C; Two is adopt circulation gas to reduce CO content into methanation reaction gas to control reaction heat, this adds increased power consumption.
At publication CN101508922A, in application number 200910058611, with in the applying for a patent of preparing synthesis gas from coke oven gas, by CO+CO in dilution inlet gas
2< 3.5%, drops to < 450 DEG C by Outlet Gas Temperature.
Existing coal is in raw material Artificial Natural Gas method, no matter use which kind of gasification process, in the synthetic gas of gained, oxycarbide compares H
2many, and in synthesizing methane preparing natural gas, H
2by (H with oxycarbide
2-CO
2)/(CO+CO
2)=3 consume, when having O in synthetic gas
2in time, also can react H
2+ 1/2O
2=H
2o, therefore has a large amount of CO in obtained Artificial Natural Gas
2discharge, such as big plain in u.s.a preparing methane from coal factory daily output 3890km
35660km need be discharged during (2064 tons) synthesizing methane gas
3/ day (11118 tons) CO
2(see blue or green favorable to the people engineering---the preparing methane from coal of Tang Hong, " nitrogenous fertilizer and methyl alcohol ", November the 6th in 2009 phase P120), and China has the discharge of a large amount of coke(oven)gas to utilize in coal coking, and coke(oven)gas is hydrogen rich gas, when with then there being a large amount of hydrogen superfluous during coke(oven)gas synthesizing methane Artificial Natural Gas, such as, under 1MPa pressure, methanation synthesizes each composition as table 1, i.e. CH in methane synthetic gas in 100mol exhaust gas
4be 52%, excessive H in working off one's feeling vent one's spleen
243% (Chinese publication, publication number CN1919985A, application number 200610021836) nearly, this does not meet the national standard of China's natural gas and compressed natural gas, also needs to be separated H through pressure-variable adsorption
2and methane.
Subordinate list 1
| Title | H 2 | CO | CO 2 | O 2 | CH 4 | N 2 | H 2O |
| Raw coke oven gas | 56.8 | 7 | 2 | 0.4 | 28 | 4 | 2 |
| Methanation inlet gas | 50.4 | 3.5 | 1 | 0.2 | 40 | 4.8 | 2.46 |
| Methanation is worked off one's feeling vent one's spleen | 42.76 | 0.16 | 0.12 | 0.12 | 51.76 | 5.2 |
Summary of the invention
The present invention, for overcoming the deficiencies in the prior art, provides a kind of energy-conserving and environment-protective without CO
2discharge, flow process is simple, and equipment is few, and methanation catalyst heatproof requires the method for low methanation synthesis Artificial Natural Gas.
The present invention adopts the ratio allotment of coke(oven)gas and producing synthesis gas from coal synthesizing methane on demand, realizes without CO
2the Artificial Natural Gas synthetic technology of discharge.
Now divide rate than using with the mol of composition each in coke(oven)gas
y
cO,
represent, producing synthesis gas from coal respectively forms use
, Y
cO',
represent, for realizing without CO
2the Artificial Natural Gas synthetic method of discharge, supposes that 1000mol coke(oven)gas need be equipped with Xmol producing synthesis gas from coal, the following reaction of main generation in the methanation of mixing raw material gas:
3H
2+CO=CH
4+H
2O
4H
2+CO
2=CH
4+2H
2O
2H
2+O
2=2H
2O
The hydrogen-carbon ratio obtaining methanation reaction process in gas mixture is thus by (H
2-CO
2-2O
2)/(CO+CO
2)=3 consume.
Can be obtained by above-mentioned chemical equilibrium relational expression:
The invention provides a kind of by the raw material such as producing synthesis gas from coal and coke(oven)gas, through the method for methanation single stage method reaction synthetic natural gas processed, mainly synthesize in the production of Artificial Natural Gas without CO
2discharge, namely realizes the zero release synthesis Artificial Natural Gas of carbon.
The invention provides the method for a kind of carbon emission-free one-step synthesis Artificial Natural Gas, mainly adopt coke(oven)gas and producing synthesis gas from coal usage ratio according to hydrogen-carbon ratio (H in gas mixture
2-CO
2-2O
2)/(CO+CO
2) mol molecule number ratio be 3 to be made into.
The invention provides the method for a kind of carbon emission-free one-step synthesis Artificial Natural Gas, mainly gas mixture can in the mol number ratio of the tolerance mol number of producing synthesis gas from coal and coke(oven)gas
calculate, in formula
y
cO,
for the mol of composition each in distribution coke(oven)gas divides rate,
, Y
cO',
for the mol of composition each in distribution producing synthesis gas from coal divides rate.
The invention provides the method for a kind of carbon emission-free one-step synthesis Artificial Natural Gas, the gas mixture being mainly used for being made into, through gas sweetening, removes H
2s etc. are to after the harmful gas of catalyzer, CO conversion is not carried out separately through entering after exhaust gas heat exchange heats up, next footwork of methanation catalyst effect such as nickel system synthesis Artificial Natural Gas in water-cooled reactor 105, exhaust gas with enter after the heat exchange of tower gas lowers the temperature, again through air-cooler or watercooler 107 to about 30 DEG C of condensation separation liquid phase moisture, obtain Artificial Natural Gas.
The invention provides the method for a kind of carbon emission-free one-step synthesis Artificial Natural Gas, mainly methanator uses water as the reaction heat vaporization generation high pressure steam of heat-eliminating medium absorbing catalyst bed methanation, controls vaporization temperature and methanation reaction temperature with the drum pressure be communicated with.
The invention provides the method for a kind of carbon emission-free one-step synthesis Artificial Natural Gas, mainly methanator uses water as the reaction heat vaporization generation high pressure steam of the outer beds methanation of heat-eliminating medium water absorption tube of Bottomhole pressure, controls vaporization temperature and methanation reaction temperature with the drum pressure be communicated with.
The invention provides the method for a kind of carbon emission-free one-step synthesis Artificial Natural Gas, mainly methanator uses water as the reaction heat vaporization generation high pressure steam of the heat-eliminating medium water absorption tube inner catalyst bed methanation of flowing between pipe, controls vaporization temperature and methanation reaction temperature with the drum pressure be communicated with.
The invention provides the method for a kind of carbon emission-free one-step synthesis Artificial Natural Gas, mainly go out the gas temperature < 430 DEG C of methanator, more excellent is < 350 DEG C.
The invention provides the method for a kind of carbon emission-free one-step synthesis Artificial Natural Gas, mainly exhaust gas does not circulate after going out methanator heat exchange, goes refrigerated separation water to obtain gas product further.
The invention provides the method for a kind of carbon emission-free one-step synthesis Artificial Natural Gas, the mainly ratio < 1 of small portion of gas and unstripped gas, after circulator boosting, and material mixed gas converges the reaction of demethanization tower.
Accompanying drawing explanation
Fig. 1 is multiple stage adiabatic reactor series system substitute natural gas schematic flow sheet (documents: Chinese patent CN101560423A, application number 200910135203).
Fig. 2 is carbon emission-free one-step Artificial Natural Gas synthesis flow schematic diagram.
Fig. 3 is non-carbon-emitting band circulator single stage method Artificial Natural Gas synthesis flow schematic diagram.
Fig. 4 is the single stage method Artificial Natural Gas synthesis flow schematic diagram that non-carbon-emitting has two drums.
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is described in detail.
Fig. 1 is carbon emission-free one-step Artificial Natural Gas synthesis flow schematic diagram, the coke(oven)gas being generally normal pressure boosts to the methanation synthesis pressure of 0.5 ~ 7MPa through compressor 101, the synthesis pressure of methanation has generally been reached with the water-gas that the vapourizing furnaces such as Texco, Shell, GSP or Lurgi come, above-mentioned two kinds of gases send into distribution cylinder 102, and tolerance presses CO, CO in gas mixture
2the hydrogen-carbon ratio that whole hydrogenation generates required for methane is sent into, and the gas mixture of configuration sloughs H in scavenging tower 103
2s etc. are to the active prejudicial harmful gas of methanation catalyst, meet methanation requirement, gas mixture through purification is heated to the isothermal methanation of water inlet pipe heat exchange more than 260 DEG C reactor 105 through methanator turnover gas-gas heat exchanger 104 and carries out methanation reaction, heat-eliminating medium water absorption reaction heat in methanator, drum 106 byproduct steam be communicated with water-cooled reactor is removed in part water vapor, methanator temperature of reaction controls pressure for vaporization and temperature of reaction by the variable valve 110 on drum 106, after unstripped gas synthesizing methane, temperature is 296 DEG C, exhaust gas cools to < 100 DEG C through gas-gas heat exchanger, low temperature about 30 DEG C is further cooled to again through air-cooler or water cooler 107, in gas, moisture content is condensed, then through water separator 108 separating and condensing water, obtain CH
4the synthetic Sweet natural gas of > 80%.When needing to control milder methanation reaction temperature, the exhaust gas circulation after partial warm down converges to heat up into methanator through interchanger 104 heat exchange with the gas of scavenging tower 103 again and reacts by equipment circulator 109.
Fig. 3 is non-carbon-emitting band circulator single stage method Artificial Natural Gas synthesis flow schematic diagram.Fig. 3 and Fig. 2 is different is that small portion exhaust gas enters after circulator 109 boosts, and converges with virgin gas, heat exchange demethanization reactor reaction again after heating up.
Fig. 4 is the single stage method Artificial Natural Gas synthesis flow schematic diagram that non-carbon-emitting has two drums.Fig. 4 is also the reactor adopting water-cooled in horizontal pipe, differently from Fig. 3 is that two drums are connected with the water cooling tube of bottom with the water cooling tube on methanator top respectively, is controlled the temperature of upper strata and lower floor by the pressure adjustment of two drums.
Methanator 105 in above-mentioned Fig. 2-Fig. 4 adopts Horizontal water cooling reactor, do not have water circulating pump, but also can add water circulating pump as required in figure.In figure, methanator also can adopt vertical water cold reactor.Can be in pipe be heat-eliminating medium water in vertical reactor, can be also pipe apparatus with catalyst inside, be heat-eliminating medium water between pipe.Heat-eliminating medium water can be natural circulation, does not need water circulating pump.
Embodiment 1: the gas composition composition obtained with the coke(oven)gas of sequence number 1 in following table 2 and Texaco's coal water slurry gas of sequence number 2, calculate 1000mol coke(oven)gas adapted Xmol water-gas obtains the gas mixture of 1000mol+Xmol sequence number 3 by above-mentioned formula, the methanator that this patent is equipped with nickel catalyzator air speed 4000 under 1.5MPa enters tower inlet temperature of stabilizer 260 DEG C, exhaust gas temperature 296 DEG C of methanation reactions obtain the Artificial Natural Gas 470mol of sequence number 4 through refrigerated separation, obtain 1.62 tons/km simultaneously
3byproduct steam.
Subordinate list 2
Gas product calorific value 31.4MJ/M
3, gas product specification composition meets China's natural gas and compressed natural gas standard GB/T 17820-1999 and GB18047-2000 requirement.
beneficial effect
Compared with the prior art the present invention has significant advantage, and one is by CO and CO in synthetic gas and coke(oven)gas
2whole synthetic generation of methane does not have to produce in methane process in existing coal Artificial Natural Gas technology to discharge a large amount of CO
2, really realize CO
2zero release, preserves the ecological environment; Two is that production process is simple, CO conversion, CO in not needing synthetic gas to prepare
2remove, also do not need methanation exhaust gas through methods such as pressure-variable adsorptions, excessive separation H
2etc. component, save process energy consumption; Three is achieve not circulate or low recycle ratio, has saved power consumption; Four is significantly reduce equipment and save facility investment; Five is reclaim reaction heat, pays producing steam.
Claims (9)
1., by producing synthesis gas from coal and a coke(oven)gas raw material, through the method for methanation single stage method reaction synthetic natural gas processed, it is characterized in that in the production of synthesis Artificial Natural Gas without CO
2discharge, namely realizes the zero release synthesis Artificial Natural Gas of carbon; Adopt coke(oven)gas and producing synthesis gas from coal usage ratio according to hydrogen-carbon ratio (H in gas mixture
2-CO
2-2O
2)/(CO+CO
2) mol molecule number ratio be 3 to be made into.
2. the method for carbon emission-free one-step synthesis Artificial Natural Gas according to claim 1, is characterized in that gas mixture can in the mol number ratio of the tolerance mol number of producing synthesis gas from coal and coke(oven)gas
calculate, in formula
for the mol of composition each in distribution coke(oven)gas divides rate,
for the mol of composition each in distribution producing synthesis gas from coal divides rate.
3. the method for carbon emission-free one-step synthesis Artificial Natural Gas according to claim 1, is characterized in that gas mixture for being made into is through gas sweetening, removing H
2s etc. are to after the harmful gas of catalyzer, CO conversion is not carried out separately through entering after exhaust gas heat exchange heats up, at next footwork of methanation catalyst effect synthesis Artificial Natural Gas such as the middle nickel systems of water-cooled reactor (105), exhaust gas with enter after the heat exchange of tower gas lowers the temperature, arrive about 30 DEG C of condensation separation liquid phase moisture through air-cooler or watercooler (107) again, obtain Artificial Natural Gas.
4. carbon emission-free one-step synthesizes the method for Artificial Natural Gas according to claim 1, it is characterized in that methanator uses water as the reaction heat vaporization generation high pressure steam of heat-eliminating medium absorbing catalyst bed methanation, control vaporization temperature and methanation reaction temperature with the drum pressure be communicated with.
5. carbon emission-free one-step synthesizes the method for Artificial Natural Gas according to claim 1, it is characterized in that methanator uses water as the reaction heat vaporization generation high pressure steam of the outer beds methanation of heat-eliminating medium water absorption tube of Bottomhole pressure, control vaporization temperature and methanation reaction temperature with the drum pressure be communicated with.
6. carbon emission-free one-step synthesizes the method for Artificial Natural Gas according to claim 1, it is characterized in that methanator uses water as the reaction heat vaporization generation high pressure steam of the heat-eliminating medium water absorption tube inner catalyst bed methanation of flowing between pipe, control vaporization temperature and methanation reaction temperature with the drum pressure be communicated with.
7. carbon emission-free one-step synthesizes the method for Artificial Natural Gas according to claim 1, and it is characterized in that the gas temperature < 430 DEG C of methanator, more excellent is < 350 DEG C.
8., according to the method for claim 1 carbon emission-free one-step synthesis Artificial Natural Gas, it is characterized in that exhaust gas does not circulate after going out methanator heat exchange, go refrigerated separation water to obtain gas product further.
9. according to the method for claim 1 carbon emission-free one-step synthesis Artificial Natural Gas, it is characterized in that the ratio < 1 of small portion of gas and unstripped gas, after circulator boosting, and material mixed gas converges the reaction of demethanization tower.
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| CN201010519763.9A CN102453564B (en) | 2010-10-17 | 2010-10-17 | Carbon emission-free one-step method and equipment for synthesizing artificial natural gas |
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|---|---|---|---|---|
| CN102942972B (en) * | 2012-11-14 | 2014-10-15 | 中国电子工程设计院 | Method for producing liquefied natural gas by coke oven gas |
| CN104152200A (en) * | 2014-08-20 | 2014-11-19 | 北京创时能源技术有限公司 | Water-saving type compressed natural gas production system and production method thereof |
| CN109266413B (en) * | 2018-10-30 | 2021-09-07 | 青岛联信催化材料有限公司 | Method for producing synthetic natural gas by utilizing hydrogen to recover non-permeate gas |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1033764A (en) * | 1963-09-23 | 1966-06-22 | Gas Council | Improvements in or relating to the production of methane gases |
| US5935544A (en) * | 1996-06-06 | 1999-08-10 | Brown & Root, Inc. | Moderate excess nitrogen Braun Purifier™ process and method for retrofitting non-Braun Purifier™ ammonia plants |
| CN101074397A (en) * | 2007-06-22 | 2007-11-21 | 清华大学 | Combined system and process for producing electric-substituted natural gas based on coal gasification and methanation |
-
2010
- 2010-10-17 CN CN201010519763.9A patent/CN102453564B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1033764A (en) * | 1963-09-23 | 1966-06-22 | Gas Council | Improvements in or relating to the production of methane gases |
| US5935544A (en) * | 1996-06-06 | 1999-08-10 | Brown & Root, Inc. | Moderate excess nitrogen Braun Purifier™ process and method for retrofitting non-Braun Purifier™ ammonia plants |
| CN101074397A (en) * | 2007-06-22 | 2007-11-21 | 清华大学 | Combined system and process for producing electric-substituted natural gas based on coal gasification and methanation |
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