CN101613627B - Catalytic deoxidation process of oxygen-contained coal bed gas - Google Patents
Catalytic deoxidation process of oxygen-contained coal bed gas Download PDFInfo
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- CN101613627B CN101613627B CN200910012669A CN200910012669A CN101613627B CN 101613627 B CN101613627 B CN 101613627B CN 200910012669 A CN200910012669 A CN 200910012669A CN 200910012669 A CN200910012669 A CN 200910012669A CN 101613627 B CN101613627 B CN 101613627B
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Abstract
The invention relates to a catalytic deoxidation process of oxygen-contained coal bed gas. The oxygen-contained coal bed gas and coal bed gas product gas returned with a certain recycle ratio are mixed to go to a fixed bed adiabatic catalytic reactor, methane in the coal bed gas is reacted with oxygen to generate carbon dioxide and water, thereby the concentration of the oxygen in the coal bed gas product gas is reduced to be lower than 0.2 percent. The invention can effectively remove the oxygen in the oxygen-contained coal bed gas with the concentration of the oxygen of 1-15 percent, the recovery ratio of the methane is similar to theoretical recovery ratio obtained by calculation according to complete conversion of the methane and the oxygen, and security risk which exists in subsequent coal bed gas separation (liquification, pressure varying adsorption, barrier separation, and the like) technical process can be completely eliminated due to the low-concentration oxygen in the product gas.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of oxygen (O that contains
2) the coal-seam gas catalytic deoxidation process.
Background technology
Coal-seam gas is a kind of inflammable gas that is adsorbed in the coal seam, and major ingredient is high purity methane (CH
4).The existence of coal-seam gas has brought bigger potential safety hazard to the colliery safety in production, therefore, and must be with its extraction or dilution in mined Cheng Qian or coal mining process.Because coal-seam gas is sulfur-bearing not usually; Do not contain the Toxic that benzene, mercury, lead etc. can be carcinogenic yet; So coal-seam gas can substitute conventional gas as a kind of high heating value, free of contamination high-quality clean energy, as fuel used to generate electricity, industrial fuel, vehicle fuel, industrial chemicals and resident living fuel.At present, for CH
4Content is in the coal-seam gas more than 60%, and the utilization technology is relatively ripe; And CH
4The coal-seam gas of the relatively low and entrained air of concentration usually can only in-field use, and the overwhelming majority is by the burning emptying.Annual according to statistics China is from the CH of coal mining industry discharging
4Reach 19,400,000,000 m
3, caused the great wasting of resources like this.In addition, CH
4Greenhouse effect are CO
221 times.Therefore, if can with in this, the coalbed methane containing oxygen of lower concentration processes purification, transports and utilizes, and will have great economic benefit and environmental benefit.
The coal-seam gas purification techniques is meant N
2Or air and CH
4Separate, make the corresponding increase of methane content in the coal-seam gas, thereby can improve the calorific value of coal-seam gas and reduce the conveying cost.The coal-seam gas purification techniques mainly comprises three kinds of low-temperature deep separation, transformation absorption and membrane sepn etc.For pressure swing adsorption process and membrane separation process, high pressure helps the isolation of purified of gas.But high working pressure makes the blast limit of methane broaden, in this, the coalbed methane containing oxygen of lower concentration purifies, operational danger increases.Patent CN1952569A and CN1908559A disclose a kind of low temperature twin-stage rectifying liquefying separation process that contains the air coal-seam gas, and its liquefaction is carried out with separating all at low temperatures, and the product purity of natural gas liquids can reach more than 99%.Yet should technology in sepn process, along with the raising of methane concentration, the oxygen level of discharging waste gas is also concentrated to be improved, it just in time is the scope that belongs to the burning and the blast of methane that a stage is arranged inevitably, exists very big security risk.
Therefore, a kind of safer separation purification scheme is the O that removes earlier in the coal-seam gas
2Carry out purification processes again.Effectively deoxidation process is the safety control of back program process such as the pressurized liquefied separation of coal-seam gas.Present adoptable coal bed gas deoxidation mode mainly comprises catalytic deoxidation (ZL02113628.9, CN101139239A etc.), coke combustion method (ZL02113627.0, CN1919986A) etc.Though the O of coal bed gas coke combustion method deoxidization technique in can the effective elimination coalbed methane containing oxygen
2But this process using coke is done fuel and (is then brought SO as adopting replacing coke w anthracite
2Problems such as discharging), energy consumption is higher; Coke booster and dust collecting process are also relatively complicated; Higher temperature of reaction is not only had higher requirement to reactor material, possibly cause CH simultaneously
4Side reaction such as Pintsch process and reformation takes place, and makes CH in the coal-seam gas
4The recovery reduces.These have all increased the cost of coke combustion method deoxidization technique.
The essence of catalytic deoxidation process is CH under the rich combustion oxygen-lean atmosphere
4Catalyticcombustion, the principal reaction that this process takes place is CH
4(g)+2O
2(g)=CO
2(g)+2H
2O (g)-802.32kJ/mol is strong exothermal reaction; Can know simultaneously CH when temperature of reaction surpasses 650 ℃ by the reaction system thermomechanical analysis
4The possibility that takes place of steam reforming reaction and cracking carbon distribution reaction bigger.Therefore, how to remove a large amount of heat of emitting in the reaction process and control catalyst bed temperature in relatively low level (in) as 650 ℃ to reduce the generation of side reaction, be the key point of this catalytic deoxidation process.The isothermal bed bioreactor that employing has inner member can make the reactor apparatus cost sharply raise; As adopt the adiabatic reactor reactor drum, then recirculation reactor and the portioned product gas circulation technology selection that is inevitable.Patent CN101139239A discloses a kind of sulfur-resistant catalytic deoxidization process that is rich in methane gas, reduces the oxygen concn control reaction temperature through the cooled gas of cyclic part deoxidation.But this process using manganese is sulfur-tolerance deoxidation catalyst, for keeping catalyst activity to meet the requirements of the deoxidation degree of depth, must adopt higher temperature of reaction and lower reaction velocity.Higher temperature of reaction can increase CH
4The chance of side reaction takes place, and has reduced CH
4The recovery; Lower reaction velocity can make reactor apparatus bulky, increases the coal bed gas deoxidation cost.In addition, the use of non-precious metal catalyst can make the ignition start of catalytic deoxidation reaction become difficult; The granule type catalyzer has then increased the resistance drop of bed, is unfavorable for the coal bed gas deoxidation technology that inlet pressure is lower.The problems referred to above all make the feasibility of this catalytic deoxidation process technical scheme reduce.
Given this, big to the coal-seam gas treatment capacity, pressure head is low, oxygen concentration changes frequent process characteristic such as violent, is necessary to develop the more coal-seam gas catalytic deoxidation circulation technology of highly effective, the feasibility that further develops skill with reduce the deoxidation cost.
Summary of the invention
The purpose of this invention is to provide a kind of coalbed methane containing oxygen catalytic deoxidation process, solved in coal gas gasification, the storage and transport process because O
2Existence and the potential safety hazard that causes, can be applicable to the catalytic deoxidation process of coalbed methane containing oxygen catalytic deoxidation and other oxygen-containing gas.
The invention provides a kind of coalbed methane containing oxygen catalytic deoxidation process, comprise system hypothermia starting process, technical process and process operation parameter;
Specific as follows:
Be preheating to 25-50 ℃ shallow bid hydrogen through in the coalbed methane containing oxygen virgin gas, introducing, with oxygen reaction, burning heat release preheating catalyst bed reaches the combustion initiation temperature of methane catalytic combustion on dehydrogenation catalyst; During steady state operation; Initial coalbed methane containing oxygen is mixed into the fixed bed adiabatic deoxidation reactor that the precious metal integer structure catalyst is housed with the coal-seam gas product gas that circulation is returned; Methane in the coal-seam gas and oxygen react under catalyst action and generate carbonic acid gas and water; Product gas to lower the temperature and to remove its contained moisture, obtains qualified coal-seam gas product gas through heat exchange/cooling; Portioned product gas is back to the deoxidation reactor inlet with certain recycle ratio and mixes the coal-seam gas oxygen concn with control deoxidation reactor inlet with initial coalbed methane containing oxygen; Wherein:
(1-1) concentration of volume percent of oxygen is 1%-15% in the coalbed methane containing oxygen;
(1-2) in the qualified coal-seam gas product gas oxygen concentration of volume percent less than 0.2% (being preferably 0.1%);
(1-3) working pressure of deoxidation reactor (gauge pressure) is 0-10MPa, and the temperature in of beds is 250-450 ℃ during steady state operation, and the temperature out of beds is 450-650 ℃, and the volumetric reaction air speed is 1,000-80,000hr
-1Optimum condition is that the working pressure (gauge pressure) of deoxidation reactor is 0.01-0.03MPa, and the temperature in of beds is 285-325 ℃ during steady state operation, and the temperature out of beds is 550-650 ℃, and the volumetric reaction air speed is 30,000-50,000hr
-1
(1-4) coal-seam gas product gas makes its temperature reduce to 30-50 ℃ and remove its contained moisture through two-stage heat exchange at least/cooling;
(1-5) the coal-seam gas product gas that returns of circulation is 0: 1 to 6: 1 with the ratio of the volumetric flow rate of initial coalbed methane containing oxygen.
Coal bed gas deoxidation catalyst provided by the invention, said precious metal integer structure catalyst is meant one or more catalytic active component that contain among platinum family precious metals pd, Pt, Ru, Rh, the Ir, carrier is cordierite honeycomb ceramic, mullite ceramic honey comb, Al
2O
3The catalyzer of compound with regular structure inert materials such as ceramic honey comb, metal beehive, metal foam.
Coal bed gas deoxidation catalyst provided by the invention, said heat exchange/refrigerating unit comprise at least one pyritous gas-gas heat exchanger or waste heat boiler, and at least one cryogenic gas-liquid heat-exchange; High temperature gas-gas heat exchanger or waste heat boiler can be cooled to 150-500 ℃ with the deoxidation reactor Outlet Gas Temperature; The low temperature gas-liquid heat-exchange can be cooled to 30-50 ℃ with high temperature gas-gas heat exchanger or waste heat boiler Outlet Gas Temperature.
The coal-seam gas product gas that coal bed gas deoxidation catalyst provided by the invention, said circulation return is 0: 1 to 4: 1 with the ratio of the volumetric flow rate of initial coalbed methane containing oxygen.Gas circulation can adopt multiple mode.The coal-seam gas product gas that returns like circulation is that this strand gas and high-temperature reacting gas heat exchange are mixed into reactor drum with the normal temperature virgin gas then to carry out preheating through the coal-seam gas product gas after heat exchange/cooled dehydrated.And for example, the coal-seam gas product gas that circulation is returned is the high-temperature gas of deoxidation reactor outlet, and this strand gas and normal temperature virgin gas are mixed into reactor drum.
Coal bed gas deoxidation catalyst provided by the invention, said cold-starting process has dual mode, and a kind of mode is through directly in initial coal-seam gas virgin gas, introducing the shallow bid H that accounts for coal-seam gas feed gas volume flow 4-10%
2, oxygen in the coal-seam gas and hydrogen burn heat release preheating bed to 250-450 ℃ on dehydrogenation catalyst, reach the combustion initiation temperature of the catalyticcombustion of methane; Another kind of mode is through to be preheating to 30-50 ℃ initial coal-seam gas virgin gas through well heater in, introducing the shallow bid H that accounts for coal-seam gas feed gas volume flow 4-10%
2, oxygen in the coal-seam gas and hydrogen burn heat release preheating bed to 250-450 ℃ on dehydrogenation catalyst, reach the combustion initiation temperature of the catalyticcombustion of methane.
Coal bed gas deoxidation catalyst provided by the invention; The coal-seam gas product gas that said circulation is returned is through the coal-seam gas product gas after heat exchange/cooled dehydrated; This strand gas and high-temperature reacting gas heat exchange are mixed into reactor drum with the normal temperature virgin gas then to carry out preheating; The coal-seam gas product gas that returns that perhaps circulates is the high-temperature gas of deoxidation reactor outlet, and this strand gas and normal temperature virgin gas are mixed into reactor drum.
Technology of the present invention can realize the ignition start of catalytic deoxidation reaction at low temperatures and can stablize in low pressure, high-speed with under less than 650 ℃ temperature condition, deoxygenation efficiently, the volume percent content of oxygen is removed to below 0.2% in the coalbed methane containing oxygen the most at last.High catalyst activity, reaction velocity and low catalyst bed stressor layer fall and have improved the treatment capacity of coalbed methane containing oxygen on the per volume of catalyst, thereby have reduced the catalytic deoxidation cost; The CH that low temperature of reaction has avoided non-precious metal catalyst temperature of reaction height to cause
4The generation of side reactions such as cracking knot carbon and steam reformation has improved CH in the coal-seam gas
4The recovery.Technology of the present invention is specially adapted to that treatment capacity is big, pressure head is low, O
2Concentration change is the catalytic deoxidation process of violent coalbed methane containing oxygen frequently.
Description of drawings
Accompanying drawing is depicted as coalbed methane containing oxygen circulation catalytic deoxidation process of the present invention, comprises two kinds of Recycle design.
Fig. 1 is a part coal-seam gas product gas cold cycle technology, and wherein: 1 is reactor drum; 2 is circularly-supercharged blower fan; 3 is waste heat boiler or high-temperature heat-exchanging; 4 is water cooling heat exchanger; 5 is water distributing can; The coal-seam gas product gas that circulation is returned is through the coal-seam gas product gas after heat exchange/cooled dehydrated, and this strand gas and high-temperature reacting gas heat exchange mix with the normal temperature virgin gas then and send into reactor drum by the cold cycle blower fan to carry out preheating; In some embodiment of coalbed methane containing oxygen catalytic deoxidation process of the present invention, the normal temperature virgin gas can also be in high-temperature heat-exchanging with the high-temperature reacting gas heat exchange to carry out preheating, be mixed into reactor drum with circulation product gas then;
Fig. 2 is a part coal-seam gas product gas high temperature circulation technology, and wherein: 1 is reactor drum; 2 is circularly-supercharged blower fan; 3 is waste heat boiler or high-temperature heat-exchanging; 4 is water cooling heat exchanger; 5 is water distributing can; The coal-seam gas product gas that circulation is returned is the high-temperature gas of deoxidation reactor outlet, and this strand gas and normal temperature virgin gas mix the back and send into reactor drum by the high temperature circulation blower fan.
Embodiment
Following examples will further be explained the present invention, but therefore not limit the present invention.
Only if point out in addition; All numerals that in specification sheets of the present invention and claims, occur; The import and export TR of each unit equipment for example; Pressure range, the numerical value such as volume percent that the expression gaseous fraction constitutes all should not be understood that absolute exact value, this numerical value is the one of ordinary skilled in the art in the limit of error that understand, that known technology allowed.The accurate numerical value that in specification sheets of the present invention and claims, occurs should be understood that to constitute part embodiment of the present invention.Although in the instance that the present invention provides, try hard to be the particularity that guarantees numerical value, because the standard deviation of various measuring technologys, all there is certain error inevitably in any numerical value that measures.
Reaction velocity of the present invention is defined as reactant gases raw material (butt) and per hour gets into the volume of the volumetric flow rate of reactive system divided by catalyzer.Represent that with GHSV unit is hr
-1
Catalytic ignition combustion initiation temperature of the present invention is meant under the described reaction process condition of specification sheets of the present invention, and when beds reached a certain temperature, bed temperature sharply rose suddenly and finally can make the burning of catalyzer be steady state.Defining this temperature is the catalytic ignition combustion initiation temperature.
The O that takes off of the present invention
2Transformation efficiency is defined as O in the virgin gas
2The molar percentage that is transformed, i.e. O in virgin gas and the product gas
2The difference of mole number with respect to O in the virgin gas
2Molar percentage, unit is %.
Recycle ratio of the present invention is meant the ratio of the coal-seam gas product gas that returns of circulation and the volumetric flow rate of initial coalbed methane containing oxygen, representes with R.
The essence of coal-seam gas catalytic deoxidation process is CH under the rich combustion oxygen-lean atmosphere
4Catalyticcombustion.As everyone knows, CH
4Molecule has the positive tetrahedron structure, is a kind of more difficult activatory organism.Therefore, how under lower temperature, realizing the ignition start of coal-seam gas catalytic deoxidation reaction, is matter of utmost importance to be solved in the technical scheme of the present invention.Compare with various MOX types, perovskite typed and hexa-aluminate type methyl hydride combustion catalyst, loaded noble metal catalyst is owing to it has higher catalytic activity, lower combustion initiation temperature and better antitoxin performance is widely used in CH
4The low temperature ignition stage of catalyticing combustion process.
The principal reaction that coal-seam gas catalytic deoxidation process takes place is following:
CH
4(g)+2O
2(g)＝CO
2(g)+2H
2O(g) (A)
This reaction is strong exothermal reaction, and thermal discharge is 802.32kJ/mol.O in the coalbed methane containing oxygen
2Concentration can be known by calculation of thermodynamics up to 15% sometimes, if directly remove the O about 15%
2, about about 1000 ℃ of gas thermal insulation warming possibly cause reaction bed temperature to reach more than 1300 ℃ thus.So high temperature of reaction is that most catalyzer and reactor material institute are unaffordable.Therefore, how removing a large amount of heat of emitting in the reaction process, is another key issue to be solved in the technical scheme of the present invention.The isothermal bed bioreactor that employing has inner member can make the reactor apparatus cost sharply raise; As adopt the adiabatic reactor reactor drum, then recirculation reactor and the portioned product gas circulation technology selection that is inevitable.
Following side reaction (B)-(F) also possibly take place in coal-seam gas catalytic deoxidation process in certain TR except that above-mentioned principal reaction (A) takes place:
CH
4+ 0.5O
2=CO+2H
2(partial oxidation reaction of methane) (B)
CO+0.5O
2=CO
2(CO burning reaction) (C)
H
2+ 0.5O
2=H
2O (combustion of hydrogen reaction) (D)
CH
4=C+2H
2(methane cracking reaction) (E)
CH
4+ H
2O=CO+3H
2(methane steam reformation reaction) (F)
According to the standard thermodynamic data of above-mentioned each reaction, can calculate in 250-1450 ℃ TR CH
4Perfect combustion reaction (A) is occupied an leading position.When temperature is lower than 650 ℃, CO and H
2Combustion reactions (C) and (D) also account for certain ratio; CH
4Cracking carbon distribution reaction (E) and steam reforming reaction (F) can not react basically.When temperature is higher than 650 ℃, reaction (E) and (F) possibly take place, and the rich CH of technology of the present invention
4The chance that atmosphere has more increased reaction (E) and (F) taken place.Simultaneously, along with the increase of temperature, H
2Increase CH with the equilibrium concentration of CO
4Yield reduce.Hence one can see that, and lower temperature of reaction helps to suppress CH
4The generation of reaction of cracking carbon distribution and steam reforming reaction reduces the H in the deoxidation coal-seam gas product gas
2With CO content, improve the security of methane yield and operation.The control catalyst bed temperature to reduce the generation of side reaction, is another key point of catalytic deoxidation process of the present invention in relatively low level (in as 650 ℃).Catalytic deoxidation process of the present invention will adopt loaded noble metal catalyst to realize above-mentioned purpose.
In addition, for adapting to the gas source condition of the big flow of coalbed methane containing oxygen, low head, beds also must have lower resistance drop.Compare with traditional pellet type catalyst; Catalyst structure such as honeycombed catalyst etc. with regular geometrical shape are obtaining to have advantage aspect the lower beds resistance drop; Make deoxygenation under higher volumetric reaction air speed, to operate; Improve the coalbed methane containing oxygen treatment capacity of per volume of catalyst, thereby reduced the deoxidation cost.
Based on above consideration, first aspect of the present invention provides a kind of catalytic deoxidation circulation technology flow process of coalbed methane containing oxygen, sees accompanying drawing 1 and accompanying drawing 2.Accompanying drawing 1 and accompanying drawing 2 be the simple synoptic diagram of technical process of the present invention just, only discloses the essential characteristic of technology of the present invention, has wherein omitted many details, for example automatic control system, senser element, valve or the like.The technician who is familiar with this area work can design more detailed integrated technique drawing according to the technical process basic characteristics that accompanying drawing discloses fully.
According to coalbed methane containing oxygen catalytic deoxidation circulation technology flow process provided by the invention, during steady state operation, coalbed methane containing oxygen virgin gas and be mixed into deoxidation reactor 1, the CH in the coal-seam gas by the coal-seam gas product gas that supercharging recirculation blower 2 is sent back to
4With O
2Reaction generates CO under catalyst action
2And H
2O, product gas makes its temperature reduce to 30-50 ℃ and remove its contained moisture through two-stage heat exchange at least/cooling, obtains O
2Concentration of volume percent is less than 0.2% qualified coal-seam gas product gas; Portioned product gas is back to deoxidation reactor 1 inlet with certain recycle ratio and mixes the coal-seam gas oxygen concn with control deoxidation reactor inlet with initial coalbed methane containing oxygen.In the embodiment of above-mentioned coalbed methane containing oxygen catalytic deoxidation process, heat exchange/refrigerating unit comprises at least one pyritous gas-gas heat exchanger or waste heat boiler 3, and at least one cryogenic gas-liquid heat-exchange 4.High temperature gas-gas heat exchanger or waste heat boiler 3 can be cooled to 150-500 ℃ with the deoxidation reactor Outlet Gas Temperature.Low temperature gas-liquid heat-exchange 4 can be cooled to 30-50 ℃ with the temperature of high temperature gas-gas heat exchanger or waste heat boiler 3 exit gass.Gas circulation can adopt dual mode; As in certain embodiments; The coal-seam gas product gas that circulation is returned is through the coal-seam gas product gas after heat exchange/cooled dehydrated; This strand gas and high-temperature reacting gas heat exchange are mixed into reactor drum with the normal temperature virgin gas, i.e. product gas cold cycle then to carry out preheating; In other embodiments, the coal-seam gas product gas that circulation is returned is the high-temperature gas of deoxidation reactor outlet, and this strand gas and normal temperature virgin gas are mixed into reactor drum, i.e. product gas high temperature circulation; In other embodiments, normal temperature virgin gas and mix with circulation product gas, with the high-temperature reacting gas heat exchange to carry out preheating, get into reactor drum then.
Second aspect of the present invention provides a cover to be applicable to the operating procedure parameter and the condition of above-mentioned coalbed methane containing oxygen catalytic deoxidation circulation technology.
In the embodiment of coalbed methane containing oxygen catalytic deoxidation circulation technology of the present invention; Deoxidation reactor is the fixed bed adiabatic reactor that the precious metal integer structure catalyst is housed, and wherein the precious metal integer structure catalyst is meant that one or more catalytic active component, the carrier that contain among platinum family precious metals pd, Pt, Ru, Rh, the Ir are cordierite honeycomb ceramic, mullite ceramic honey comb, Al
2O
3The catalyzer of compound with regular structure inert materials such as ceramic honey comb, metal beehive, metal foam.For example preferable carried noble metal integer catalyzer instance is to be main catalytic active component with the platinum family precious metals pd, with CeO
2-La
2O
3The double base composite oxides are catalyst aid, are physical support with the cordierite honeycomb ceramic.Yet; In deoxidization technique of the present invention; Catalyzer can but be not limited to adopt top preferred embodiments, any have higher low-temperature catalyzed deoxy activity under less than 650 ℃ temperature condition and all can in deoxidization technique of the present invention, use with the precious metal integer structure catalyst of stability.
In the embodiment of coalbed methane containing oxygen catalytic deoxidation process of the present invention, O in the coalbed methane containing oxygen raw material
2Concentration of volume percent can between 1-15%, change, adapt to O in the coal-seam gas
2The characteristics that the concentration change amplitude is bigger.The working pressure of deoxidation reactor (gauge pressure) is 0-10MPa, and the temperature in of beds is 250-450 ℃ during steady state operation, and the temperature out of beds is 450-650 ℃, and the volumetric reaction air speed is 1,000-80,000hr
-1, low pressure and high-speed adapt to characteristics such as coal-seam gas virgin gas treatment capacity is big, pressure head is low, can carry out high load operation to reduce the deoxidation cost; And CH can be effectively eliminated in operation below 650 ℃
4Side reaction such as cracking and steam reformation improves CH
4The recovery.In the preferable embodiment of patent of the present invention, the working pressure of deoxidation reactor (gauge pressure) is 0.01-0.03MPa, and the temperature in of beds is 285-325 ℃ during steady state operation; The temperature out of beds is 550-650 ℃; The volumetric reaction air speed is 30,000-50,000hr
-1
In the embodiment of coalbed methane containing oxygen catalytic deoxidation process of the present invention, the coal-seam gas product gas that circulation is returned is 0: 1 to 6: 1 with the ratio of the volumetric flow rate of initial coalbed methane containing oxygen.In the preferable embodiment of coalbed methane containing oxygen catalytic deoxidation process of the present invention; The coal-seam gas product gas that circulation is returned is 0: 1 to 4: 1 with the ratio of the volumetric flow rate of initial coalbed methane containing oxygen, should under the prerequisite that satisfies the catalyzer working conditions, reduce recycle ratio to reduce the booster fan energy consumption as far as possible.
The 3rd aspect of the present invention provides a kind of method that realizes coalbed methane containing oxygen catalytic deoxidation process system hypothermia starting according to the invention.
For realizing the cold-starting of whole coalbed methane containing oxygen catalytic deoxidation process system, the present invention utilizes the low characteristics of hydrogen-oxygen catalyst combustion reaction combustion initiation temperature, through in the coalbed methane containing oxygen virgin gas, introducing shallow bid hydrogen (H
2), make H
2On dehydrogenation catalyst with coal-seam gas in O
2Reaction, burning heat release preheating catalyst bed reaches CH
4The combustion initiation temperature of catalyticcombustion starts whole deoxygenation system smoothly, stops to infeed H during system stable operation
2In some embodiment of coalbed methane containing oxygen catalytic deoxidation process of the present invention, the starting of catalytic deoxidation low temperature reaction is through directly in the coalbed methane containing oxygen virgin gas, introducing the shallow bid H that accounts for coal-seam gas feed gas volume flow 4-10%
2, the O in the coal-seam gas
2And H
2Burning heat release preheating bed reaches the catalyticcombustion combustion initiation temperature of methane to 250-450 ℃ on dehydrogenation catalyst.In other embodiments, catalytic deoxidation low temperature reaction starting is through in being preheating to 30-50 ℃ initial coal-seam gas virgin gas, introducing the shallow bid H that accounts for coal-seam gas feed gas volume flow 4-10%
2, oxygen in the coal-seam gas and hydrogen burn heat release preheating bed to 250-450 ℃ on dehydrogenation catalyst, reach the combustion initiation temperature of the catalyticcombustion of methane.
Embodiment 1-embodiment 8
Embodiment 1-embodiment 8 has provided coal-seam gas product gas Recycle design different in the technology of the present invention and different coal gas virgin gas O
2The influence that operating procedure parameters such as concentration, reaction bed temperature in, temperature out, inlet pressure, recycle ratio R, reaction velocity are formed deoxidation coal-seam gas product gas, wherein embodiment 6 is a comparative example with embodiment 8, not at the row of the present invention's protection.
The experiment catalyst system therefor all is weight percentage and consists of 0.2%Pd/15%CeO among the embodiment 1-embodiment 8
2-5%La
2O
3The honeycomb ceramic integral catalyzer of/79.8% trichroite.CH in virgin gas and the product gas
4, N
2, CO
2, CO and H
2Detect through the gc thermal conductivity detector; O in virgin gas and the product
2Pass through PROLINE
The online detection of process mass spectrograph.
At first in the coal-seam gas virgin gas, introduce the H that accounts for above-mentioned raw materials gas total flux 6% during experiment
2, be 5000hr at the GHSV of all gas
-1(butt air speed) and reactor inlet temperature are under 25 ℃ the condition, H
2With the O in the coal-seam gas
2On catalyzer, begin to react, burning heat release preheating catalyst bed reaches CH
4The combustion initiation temperature of catalyticcombustion starts whole deoxygenation system smoothly, stops to infeed H during system stable operation
2The steady running experimental data is listed in the table below 1 under each different condition.Wherein, the product gas Recycle design of embodiment 1-embodiment 6 is a cold cycle, and the Recycle design of embodiment 7 and embodiment 8 is a high temperature circulation.
Visible by table 1, except that embodiment 6 (comparative example 6) and embodiment 8 (comparative example 8), the embodiment that operates according to processing parameter of the present invention has all obtained deoxidation effect preferably, the O in the coal-seam gas product gas
2Content promptly takes off O less than 1000ppm
2Transformation efficiency is greater than 98.5%; H in the while product gas
2Lower with CO content, CH
4The amount loss is less, and is approaching according to CH
4And O
2The theoretical recovery that complete conversion calculations obtains, thus higher CH guaranteed
4The recovery.Comparative examples 6 is visible with comparative example 8, though the O in the coal-seam gas product gas
2Content is also less than 1000ppm, but because the service temperature of deoxidation reactor is higher, makes CH
4Side reactions such as cracking carbon distribution and steam reformation aggravation has caused higher H in the coal-seam gas product gas
2With CO content, thereby increased the difficulty of follow-up coal gas gasification technological process.This shows, thereby the recycle ratio through regulating coal-seam gas product gas is controlled at the service temperature of deoxidation reactor in 650 ℃, is the key point of technology of the present invention.
Steady running experimental data under each different condition among the table 1 embodiment 1-embodiment 8
Embodiment 9-embodiment 12
Embodiment 9-embodiment 12 has provided the ignition start performance comparison of catalytic deoxidation reaction process system under the different condition.The experiment catalyst system therefor is weight percentage and consists of 0.2%Pd/15%CeO
2-5%La
2O
3The honeycomb ceramic integral catalyzer of/79.8% trichroite, the volume space velocity of igniting source of the gas is 5,000hr
-1Experimental data by table 2 is visible; Come (Comparative Examples 12) to say for the coalbed methane containing oxygen virgin gas; Under this experiment condition; Have only it is preheating to just to make deoxygenation begin to carry out more than 280 ℃, need before getting into deoxidation reactor, add preheater preheating reaction raw materials, this has increased the complexity of deoxidization technique undoubtedly.Through in the coal-seam gas virgin gas, introducing certain amount of H
2, H
2With the O in the coal-seam gas
2On catalyzer, begin to react, burning heat release preheating catalyst bed reaches CH
4The combustion initiation temperature of catalyticcombustion can make the starting smoothly under lower temperature of whole deoxygenation system.
The ignition start performance of catalytic deoxidation reaction process system under table 2 different condition
Claims (14)
1. a coalbed methane containing oxygen catalytic deoxidation process comprises system hypothermia starting process, technical process and process operation parameter;
Specific as follows:
Be preheating to 25-50 ℃ shallow bid hydrogen through in the coalbed methane containing oxygen virgin gas, introducing, with oxygen reaction, burning heat release preheating catalyst bed reaches the combustion initiation temperature of methane catalytic combustion on dehydrogenation catalyst; During steady state operation; Initial coalbed methane containing oxygen is mixed into the fixed bed adiabatic deoxidation reactor that the precious metal integer structure catalyst is housed with the coal-seam gas product gas that circulation is returned; Methane in the coal-seam gas and oxygen react under catalyst action and generate carbonic acid gas and water; Product gas to lower the temperature and to remove its contained moisture, obtains qualified coal-seam gas product gas through heat exchange/cooling; Portioned product gas is back to the deoxidation reactor inlet with certain recycle ratio and mixes the coal-seam gas oxygen concn with control deoxidation reactor inlet with initial coalbed methane containing oxygen; It is characterized in that:
(1-1) concentration of volume percent of oxygen is 1%-15% in the coalbed methane containing oxygen;
(1-2) in the qualified coal-seam gas product gas oxygen concentration of volume percent less than 0.2%;
(1-3) working pressure of deoxidation reactor is 0-10MPa, and the temperature in of beds is 250-450 ℃ during steady state operation, and the temperature out of beds is 450-650 ℃, and the volumetric reaction air speed is 1,000-80,000hr
-1
(1-4) coal-seam gas product gas makes its temperature reduce to 30-50 ℃ and remove its contained moisture through two-stage heat exchange at least/cooling;
(1-5) the coal-seam gas product gas that returns of circulation is 0: 1 to 6: 1 with the ratio of the volumetric flow rate of initial coalbed methane containing oxygen.
2. according to the said coalbed methane containing oxygen catalytic deoxidation process of claim 1, it is characterized in that: the oxygen concentration of volume percent is less than 0.1% in the said qualified coal-seam gas product gas.
3. according to the said coalbed methane containing oxygen catalytic deoxidation process of claim 1; It is characterized in that: said precious metal integer structure catalyst is meant one or more catalytic active component that contain among platinum family precious metals pd, Pt, Ru, Rh, the Ir, and carrier is cordierite honeycomb ceramic, mullite ceramic honey comb, Al
2O
3The catalyzer of ceramic honey comb, metal beehive, some compound with regular structure inert materials of metal foam.
4. according to the said coalbed methane containing oxygen catalytic deoxidation process of claim 1; It is characterized in that: the working pressure of said deoxidation reactor is 0.01-0.03MPa; The temperature in of beds is 285-325 ℃ during steady state operation, and the temperature out of beds is 550-650 ℃, and the volumetric reaction air speed is 30; 000-50,000hr
-1
5. according to the said coalbed methane containing oxygen catalytic deoxidation process of claim 1, it is characterized in that: said heat exchange/refrigerating unit comprises at least one pyritous gas-gas heat exchanger or waste heat boiler, and at least one cryogenic gas-liquid heat-exchange.
6. according to the said coalbed methane containing oxygen catalytic deoxidation process of claim 1, it is characterized in that: the coal-seam gas product gas that said circulation is returned is 0: 1 to 4: 1 with the ratio of the volumetric flow rate of initial coalbed methane containing oxygen.
7. according to the said coalbed methane containing oxygen catalytic deoxidation process of claim 1; It is characterized in that: said cold-starting process is through directly in initial coal-seam gas virgin gas, introducing shallow bid hydrogen; Oxygen in the coal-seam gas and hydrogen burn heat release preheating bed to 250-450 ℃ on dehydrogenation catalyst, reach the combustion initiation temperature of the catalyticcombustion of methane.
8. according to the said coalbed methane containing oxygen catalytic deoxidation process of claim 1; It is characterized in that: said cold-starting process is through in through the initial coal-seam gas virgin gas of well heater preheating, introducing shallow bid hydrogen; Oxygen in the coal-seam gas and hydrogen burn heat release preheating bed to 250-450 ℃ on dehydrogenation catalyst, reach the combustion initiation temperature of the catalyticcombustion of methane.
9. according to the said coalbed methane containing oxygen catalytic deoxidation process of claim 1; It is characterized in that: the coal-seam gas product gas that said circulation is returned is through the coal-seam gas product gas after heat exchange/cooled dehydrated; This strand gas and high-temperature reacting gas heat exchange are mixed into reactor drum with the normal temperature virgin gas then to carry out preheating.
10. according to the said coalbed methane containing oxygen catalytic deoxidation process of claim 1, it is characterized in that: the coal-seam gas product gas that said circulation is returned is the high-temperature gas of deoxidation reactor outlet, and this strand gas and normal temperature virgin gas are mixed into reactor drum.
11. according to the said coalbed methane containing oxygen catalytic deoxidation process of claim 5, it is characterized in that: said high temperature gas-gas heat exchanger or waste heat boiler are that the deoxidation reactor Outlet Gas Temperature is cooled to 150-500 ℃.
12. according to the said coalbed methane containing oxygen catalytic deoxidation process of claim 5, it is characterized in that: said low temperature gas-liquid heat-exchange is that high temperature gas-gas heat exchanger or waste heat boiler Outlet Gas Temperature are cooled to 30-50 ℃.
13. according to claim 7 or 8 said coalbed methane containing oxygen catalytic deoxidation process, it is characterized in that: the said amounts of hydrogen that infeeds is the 4-10% of initial coal-seam gas feed gas volume flow.
14. according to the said coalbed methane containing oxygen catalytic deoxidation process of claim 8, it is characterized in that: the preheating temperature of said initial coal-seam gas virgin gas is 30-50 ℃.
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| CN200910012669A CN101613627B (en) | 2009-07-23 | 2009-07-23 | Catalytic deoxidation process of oxygen-contained coal bed gas |
| PCT/CN2010/000528 WO2011009283A1 (en) | 2009-07-23 | 2010-04-19 | Catalyst for deoxidation of coalbed gas, preparation method and use thereof |
| US12/737,342 US20120003132A1 (en) | 2009-07-23 | 2010-04-19 | Process for catalytic deoxygenation of coal mine methane |
| AU2010249248A AU2010249248B2 (en) | 2009-07-23 | 2010-04-19 | Process of catalytic deoxygenation of coal mine methane |
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| WO2011009283A1 (en) * | 2009-07-23 | 2011-01-27 | 中国科学院大连化学物理研究所 | Catalyst for deoxidation of coalbed gas, preparation method and use thereof |
| CN102433185A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Catalytic deoxidation method for coalbed gas in coal mine area |
| CN102433182A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Catalytic deoxidation method for coalbed gas in coal mine area |
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