CN102533367B - System and method for catalytic combustion deoxidation of methane gas - Google Patents
System and method for catalytic combustion deoxidation of methane gas Download PDFInfo
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- CN102533367B CN102533367B CN201110440862.2A CN201110440862A CN102533367B CN 102533367 B CN102533367 B CN 102533367B CN 201110440862 A CN201110440862 A CN 201110440862A CN 102533367 B CN102533367 B CN 102533367B
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Abstract
The invention provides a system and method for catalytic combustion deoxidation of methane gas. The system mainly comprises a methane gas deoxidation reaction reactor, a device for supplying water vapour to the methane gas deoxidation reaction reactor and a fine deoxidation tower; the methane gas deoxidation reaction reactor is used for carrying out the methane gas deoxidation reaction; the methane gas deoxidation reaction reactor establishes a circulating ring through a circulator; the communication state of a circulating compressor and the system is adjustable; the fine deoxidation tower is connected behind the circulating ring and used for removing supplemented oxygen. The system and the process are easy to operate and easy to control. By supplementing water vapour to the system or supplementing both water vapour and circulating gas to the system, the content of oxygen at the inlet of the methane gas deoxidation reaction reactor can be improved, the use amount of the circulating gas can be reduced, and hereby the equipment size, the investment, the power consumption, the byproduct steam and the like can be reduced.
Description
Technical field
The present invention relates to coal mine gas process field and field of energy utilization, relate in particular to a kind of system and method for catalytic combustion deoxidation of methane gas.
Background technology
Coal mine gas refers in progress of coal mining, for coal mining security consideration, adopts down-hole extraction technology, extraction coal-seam gas out from mine.Owing to mixing into large quantity of air in pump drainage process, general methane volumetric concentration≤40%, and carrier of oxygen volume concentrations can reach 15% left and right.The products of combustion of coal mine gas is water and carbonic acid gas, can be to environment, by universally acknowledged for being a kind of clean energy of high-quality.
In China, most coal mine gas can only be used as domestic fuel on the spot, and most burned emptying, according to statistics, nearly 20,000,000,000 m of coal mine gas that China gives off due to coal mining every year
3, account for global coal mining to airborne release CH
41/3 of total amount, causes great energy dissipation; Meanwhile, the methane in coal mine gas is as a kind of important greenhouse gases, and its Greenhouse effect are 21 times of carbonic acid gas, and it directly enters aerial greatly degree aggravation Global Greenhouse Effect.Therefore, rationally utilize coal mine gas be solve China energy shortage and distribute uneven, alleviate environmental stress, slow down the important means of Greenhouse effect.
The key of coal mine gas utilization is exactly deoxidation, be about to scope that oxygen content in coal mine gas is removed to a safety after (volumetric concentration≤0.5%) fully utilize again.But because coal mine gas is the inflammable gas methane of high density and the gas mixture of high-concentration oxygen, adopt physical method deoxidation to there is very large danger.At present, more safe and effective deoxidation mode is exactly the combustion deoxidizing of coal mine gas, especially catalyticcombustion deoxidation, and under catalyst for catalytic combustion effect, the reaction of the methane non-flaming combustion that the methane in coal mine gas and oxygen occur.
The principal reaction of this reaction is CH
4+ 2O
2→ CO
2+ 2H
2o Δ H
Θ=-890.31KJ/mol, can learn from thermodynamic process, this reaction belongs to strong exothermal reaction.According to calculating, the coal mine gas of carrier of oxygen volume concentrations 10% left and right, the oxygen of every reaction 1% volumetric concentration, its system thermal insulation warming is 85 ℃ of left and right.In order to prevent that beds and reactor are at high temperature burned, simultaneously also in order to limit the cracking of methane under hot conditions, when doing catalytic combustion deoxidation of methane gas reaction, general requirement ingress oxygen level≤4% (volume %).For the coal mine gas higher than 4% oxygen level, general employing mixed in unstripped gas gas product as circulation gas, reaches the object that reduces oxygen level.For coal mine gas deoxidation, the energy consumption in working cycle is the main energy consumption source of whole technique.In coal mine gas, oxygen level is higher, and recycle ratio is larger, and circulating flow rate is also larger, and recycle compressor energy consumption is just larger; Simultaneously large-minded, also cause the size of circulator, interchanger and pipeline to strengthen, increased investment.
Therefore, chemists are being devoted to seek a kind of novel process and system that is suitable for the coal mine gas deoxidation of processing elevated oxygen level coal mine gas always.
Summary of the invention
The object of this invention is to provide a kind of new system and method that is suitable for the coal mine gas deoxidation of processing elevated oxygen level coal mine gas.For this reason, the present inventor conducts in-depth research and provides following all respects:
<1>. the system for catalytic combustion deoxidation of methane gas, described system comprises: for carrying out the deoxidation reactor of coal mine gas deoxygenation, described deoxidation reactor is set up circulating ring by recycle compressor, and the state that wherein recycle compressor and system are connected is adjustable;
For described deoxidation reactor being supplied with to the device of water vapour; With
Be connected to the smart deoxidation tower after described circulating ring, for supplementing, carry out oxygen and remove.
<2>. according to the system described in <1>, wherein said system also comprises: connecting recycle compressor in the situation that, to the mechanism of replenishment cycles gas in gas unstripped gas.
<3>. according to the system described in above-mentioned any one, wherein said circulation gas is incorporated into deoxidation reactor entrance by following process: from gas process waste heat boiler and the feed gas heater heat exchange of deoxidation reactor outlet, after below cooling the temperature to 300 ℃, after de-salted water preheater and recycle gas cooler heat exchange, cool the temperature to below 40 ℃, gas, after water separation tank carbonated drink separates, is sent into deoxidation reactor entrance by circulator.
<4>. according to the system described in above-mentioned any one, wherein said system also comprises: be connected to the one or more of the vapor superheater for waste heat recovery, waste heat boiler and preheater in described system.
<5>. according to the system described in above-mentioned any one, wherein said deoxidation reactor consists of 2 deoxidation reactors that are connected in series.
<6>. according to the system described in above-mentioned any one, wherein saidly for the device of described deoxidation reactor being supplied with to water vapour, the first deoxidation reactor of the deoxidation reactor in the upstream of technique is supplied with to water vapour.
<7>. for a method for catalytic combustion deoxidation of methane gas, described method comprises: to make up water steam in deoxidation reactor as rare gas element; In deoxidation reactor, coal mine gas is carried out to deoxidation, at this, remove a large amount of oxygen; In smart deoxidation reactor, carrying out supplemental oxygen removes.
<8>. according to method described in <7>, wherein, with respect to described gas unstripped gas cumulative volume, as the add-on of the water vapour of rare gas element, be 10～100 volume %, preferably 20～60 volume %.
<9>. according to the method described in any one in <7> to <8>, wherein, described method also comprises: to replenishment cycles gas in gas unstripped gas.
<10>. according to method described in any one in <7> to <9>, wherein, under the condition that oxygen level is 8～15% in coal mine gas, the size of circulating flow rate is 10～150 volume % of gas material gas quantity, wherein preferred 20～80 volume %.
<11>. according to the method described in any one in <7> to <10>, described method comprises: by the one or more heat to produce in recycling technological process in vapor superheater, waste heat boiler and preheater is set.
<12>. according to the method described in any one in <7> to <11>, described method comprises uses the coal mine gas dehydrogenation catalyst of preparing by following process to carry out deoxidation:
(1) choose suitable inert support material as catalyst backbone,
(2) cerium zirconium compound oxide and aluminium hydroxide are mixed according to the ratio of mol ratio 0.5～5, add dilute nitric acid solution, the volume that adds rare nitric acid is cerium zirconium compound oxide and aluminium hydroxide mixed volume 2～20 times, wet ball grinding form slurry,
(3) by the slurry coating making to inert catalyst carrier, dry after, at 500～900 ℃, roasting 2～6 hours, obtains required support of the catalyst,
(4) adopt pickling process, the impregnation of catalyst carriers making in (3), to containing in molybdenum solution, obtained to catalyst precursor A after being dried,
(5) by pickling process, catalyst precursor A is impregnated in rare earth nitrate solution, after being dried, obtains required catalyst precursor B,
(6) then, by catalyst precursor B, at 500～900 ℃, roasting 1～4 hour, obtains catalyst precursor C,
(7) adopt pickling process, will make catalyst precursor C and be impregnated in platiniferous solution, then dry,
(8), then at 900～1200 ℃, roasting 1～4 hour, obtains required dehydrogenation catalyst.
Technique of the present invention and system operation are easy, are easy to control, and can improve reactor inlet oxygen level, improve the treatment capacity of separate unit deoxidation reactor; Reduce circulation gas consumption simultaneously, thereby can reduce equipment size, reduce investment, reduce power consumption; Meanwhile, the present invention also takes full advantage of the heat energy in coal mine gas combustion processes, by the form of superheated vapour, has realized energy recovery.
Accompanying drawing explanation
Fig. 1 is a kind of process flow sheet that is suitable for the deoxidation of processing elevated oxygen level coal mine gas of the present invention.
Fig. 2 is the another kind of process flow sheet that is suitable for the deoxidation of processing elevated oxygen level coal mine gas of the present invention.
Embodiment
The object of the present invention is to provide a kind of novel method and system that is suitable for the deoxidation of processing elevated oxygen level coal mine gas.Described elevated oxygen level typically refers to oxygen level in charging coal mine gas higher than 4 volume %, such as the gas unstripped gas of oxygen level in the scope of 4～15 volume %.As pointed in background technology, the in the situation that of this elevated oxygen level, general employing mixed in unstripped gas gas product as circulation gas, reaches and reduces the object of ingress oxygen level and implementing process.In the present invention, proposed a kind ofly by filling into water vapour to reach the object that reduces ingress oxygen level in system, can also using gas product as circulation gas, mix the processing mode in unstripped gas in conjunction with employing simultaneously.
Therefore, the invention provides a kind of new system for coal mine gas deoxidation, described system mainly comprises: multiple deoxidation reactors, and described reactor sets up circulating ring by recycle compressor, and wherein recycle compressor is adjustable with the state of system connection; For described reactor being supplied with to the device of water vapour; And be connected to the smart deoxidation tower after circulating ring, for supplemental oxygen, remove.
System of the present invention also comprises: connecting circulator in the situation that, to the mechanism of replenishment cycles gas in gas unstripped gas.This mechanism can adopt any being suitable for to the mechanism of replenishment cycles gas in system in the prior art.
In system of the present invention, described multiple deoxidation reactors can be the coexist reactors of form of multiple series, parallel or series-parallel connection.The deoxidation reactor that is multiple series connection at deoxidation reactor, normally, only the first deoxidation reactor of the deoxidation reactor in the upstream of technique is carried out to supplementing of water vapour.In addition,, in the present invention, also comprise the scheme of using single deoxidation reactor.
In system of the present invention, described recycle compressor and the connection state of system are determined by oxygen level in gas unstripped gas.For the gas unstripped gas of oxygen level 4～8 volume %, by make up water steam in system, can complete deoxidation requirement, recycle compressor is not opened; For the gas unstripped gas of oxygen level 8～15 volume %, only depend on moisturizing steam can not meet deoxidation requirement, need ON cycle compressor, in system, supplement part circulation gas.
For being the device that can realize water supplement function of knowing in association area to the device of deoxidation reactor make up water steam, for example, can use drum.
It is worthy of note, in system of the present invention, used the method that fills into water vapour to regulate the oxygen level of the coal mine gas that enters deoxidation reactor, therefore normally, need the quantity of the deoxidation reactor using relatively less.The inventor, by test repeatedly, finds for oxygen level the coal mine gas at 4-15%, conventionally only needs 2 series-parallel deoxidation reactors can complete the present invention.And in prior art, be all the deoxidation process that need to complete more than the deoxidation reactor of 2 conventionally, even have reported in literature to use nearly 27 deoxidation reactors, thereby system of the present invention can also be saved the process costs of this step.
Therefore, in system of the present invention, technique mainly comprises: according to the difference of oxygen level in coal mine gas, in deoxidation reactor, supplement appropriate water vapour, improve the deoxidizing capacity of each section of reactor, and realize the temperature control to each deoxygenation; In deoxidation reactor, carry out deoxidation process, at this, remove a large amount of oxygen; In smart deoxidation reactor, carrying out supplemental oxygen removes.
Coal mine gas deoxidation reactor of the present invention can be used multiple deoxidation reactors, but normally, only adopts two series-parallel high temperature deoxidation reactor groups, and these two reactors are connected by recycle compressor, sets up circulating ring.
In theory, technique of the present invention and system are applicable to the deoxidation of the coal mine gas of any oxygen level, but consider process costs, and the present invention is normally greater than 4% coal mine gas for oxygen level and carries out, for example, the coal mine gas of 4%～15% oxygen level is carried out.Above-mentioned deoxygenation in use, according to the oxygen level difference in coal mine gas, determine in deoxygenation process that water vapour fills into number.Normally, filling into steam vapour amount is 10～100% of gas material gas quantity, preferably 20～60%.
In addition,, for the high coal mine gas of oxygen level, such as oxygen level is in 8～15% coal mine gas, the present invention also adopts to the processing mode that fills into water vapour and the combination of replenishment cycles gas phase in gas unstripped gas.That is,, in coal mine gas deoxidization technique of the present invention, also comprise to the operation that fills into circulation gas in gas unstripped gas.Circulation gas is normally sent into deoxidation reactor entrance as circulation gas using a part of gas from deoxidation reactor by recycle compressor.Normally, from a part of gas in deoxidation reactor optionally after preheater and recycle gas cooler heat exchange, the gas after gas-liquid separation.Normally, in this case, depending on according to the oxygen level difference in gas unstripped gas, is 10～150% of gas material gas quantity to the amount that fills into circulation gas in gas unstripped gas, preferably 20～80%.
Above-mentioned deoxygenation process, pressure is 0.5～3MPa.
In addition, in the system for coal mine gas deoxidation of the present invention, can also in any suitable technical process, connect such as devices such as vapor superheater, waste heat boiler, preheaters, to make full use of the heat of process treatment process.
As an example of technique of the present invention, as shown in Figure 1, the present invention can carry out in accordance with the following steps: the coal mine gas that mining area is come purifies rear by feed preheater E104 and from gas Bing Cheng mono-tunnel after smart deoxidation reactor R103, and after mixing with the part water vapour of drum V102, guarantee that combi inlet port temperature is 280～300 ℃, enter the first deoxidation reactor R101, reactor outlet temperature is 500～700 ℃, the gas of deoxidation reactor R101 outlet is through vapor superheater E101, after waste heat boiler E102 heat exchange, after being down to 280～300 ℃, gas temperature enters the second deoxidation reactor R102, the temperature out of deoxidation reactor R102 is 300～700 ℃, deoxidation reactor R102 exit gas is through waste heat boiler E103 and feed gas heater E104 heat exchange, cool the temperature to after 280～300 ℃, be divided into two-way: lead up to after de-salted water preheater E105 and recycle gas cooler E106 heat exchange, cool the temperature to below 40 ℃, after water separation tank V103 vapor-liquid separation, trade effluent discharger, gas is sent into deoxidation reactor R101 entrance as circulation gas by recycle compressor C101, an other road enters smart deoxidation reactor R103, and oxygen residual in gas is removed, and reactor outlet temperature is 300～400 ℃.Reacted gas, after circulating gas preheater E107 and de-salted water preheater E108 and gas product water cooler E109, cools the temperature to 40 ℃ of left and right, enters water separation tank V101 divided gas flow and water, and gas product enters next workshop section's operation, water discharge device.
De-salted water is divided into two-way access to plant, lead up to de-salted water interchanger E105 with from the portioned product gas heat exchange of deoxidation reactor R102; Lead up in addition de-salted water interchanger E108 with from the gas product heat exchange of smart deoxidation reactor R103, the de-salted water after heat exchange is preheated to after 100～250 ℃, enters drum V102.Gas in drum by waste heat boiler E102 and waste heat boiler E103 respectively with gas product heat exchange from deoxidation reactor R101 and R102 after, temperature is heated to 300～450 ℃, after part steam mixes with unstripped gas and circulation gas as inert substance, by deoxidation reactor, R101 enters reactive system, a part of steam forms superheated vapour through vapor superheater E101 in addition, and carrying device is used.
Fig. 2 is another example of technique of the present invention, and difference is: the deoxidation reactor in Fig. 2 is to adopt parallel form.
In above-mentioned deoxygenation process, by waste heat boiler and interchanger, a large amount of heat energy that produce in deoxidation process have been carried out to efficient recovery, improved the efficiency of whole system.
In addition, it is worthy of note, the gas dehydrogenation catalyst using in above-mentioned deoxygenation can be any catalyzer can with better hydrothermal, the preferably catalyticcombustion dehydrogenation catalyst of request for utilization people independent development, and described catalyst loading is in each deoxidation reactor.
The preparation method of the catalyticcombustion dehydrogenation catalyst of applicant's independent development comprises the steps:
(1) choose suitable inert support material as catalyst backbone,
(2) aluminium hydroxide and cerium zirconium compound oxide are mixed according to the ratio of mol ratio 0.5～5, add appropriate dilute nitric acid solution, the dilute nitric acid solution that for example volumetric concentration is 0.1～2%, the volume that adds rare nitric acid is cerium zirconium compound oxide and aluminium hydroxide mixed volume 2～20 times, wet ball grinding form slurry
(3) by the slurry coating making to inert catalyst carrier, dry, at 500～900 ℃, roasting 2～6 hours, obtains required support of the catalyst,
(4) adopt pickling process, by the impregnation of catalyst carriers making, to containing in the solution of molybdenum, the ammonium molybdate solution of for example 0.1～1g/ml, is then dried, and obtains catalyst precursor A,
(5) by pickling process, the catalyst precursor A making is impregnated in rare earth nitrate solution, for example 0.1～1g/ml rare earth nitrate solution, dipping time is 2～6 hours, after being dried, makes catalyst precursor B,
(6) then by catalyst precursor B at 500～900 ℃, roasting 1～4 hour,
(7) adopt pickling process, by making catalyst precursor, be impregnated in the solution of platiniferous, the platinum acid chloride solution that for example concentration is 10～50mg/ml, dipping time is 20～40 minutes, dry, obtains catalyst precursor C,
(8) then,, 900～1200 ℃ of roastings 1～4 hour, obtain required dehydrogenation catalyst.
For example, prepare example for one that catalyzer is described below.
(1) taking 100g alumina globule is catalyzer inert support.
(2) take respectively zirconium oxychloride 64.4g and cerous nitrate 86.8g, and be dissolved in respectively in 500ml deionized water, after dissolving completely, two kinds of solution are mixed.Under agitation condition, the ammonia soln that is 25% to mixed solution and dripping volumetric concentration, controlling titration end point pH value is 9.5～10, titration finishes, standing 12 hours of throw out, suction filtration washing precipitate, be washed till pH value and be 7,100 ℃ and be dried, grind into powder.Within 3 hours, internal program is warming up to 900 ℃, roasting 4 hours, and making structural formula is CeZrO
4cerium zirconium compound oxide 57.89g standby.
(3) take 30g cerium zirconium compound oxide and 16g aluminium hydroxide, fully mix, adding volumetric concentration is rare nitric acid 150ml of 0.5%, and wet ball grinding 12 hours, obtains the slurry that contains cerium zirconium aluminium.Measure 50ml slurry, alumina globule is impregnated in the slurry measuring, flood 20 minutes, at 100 ℃ dry 12 hours, will support the alumina globule of cerium zirconium aluminium, within 3 hours, internal program is warming up to 500 ℃, roasting 2 hours.Repeat again above-mentioned experiment once, obtain supporting the support of the catalyst of cerium zirconium aluminum oxide.
(4) take 20g ammonium dimolybdate, be dissolved in 15% the ammonia soln of 100ml, be made into ammonium dimolybdate solution.By the impregnation of catalyst carriers making wherein, flood 3 hours, at 80 ℃ dry 12 hours, then repeat twice of above-mentioned experiment.
(5) take 10g lanthanum nitrate, be dissolved in 100ml deionized water, be made into lanthanum nitrate hexahydrate, the catalyst precursor that supports ammonium dimolybdate is flooded wherein, flood 3 hours, at 80 ℃ dry 12 hours.
(6) by the catalyst precursor supporting after molybdenum and lanthanum, within 3 hours, internal program is warming up to 500 ℃, and roasting 2 hours obtains supporting molybdic oxide and lanthanum oxide catalyst precursor.
(7) adopt above-mentioned same method to support precious metals pt.Pt strength of solution is 1mg/L, and dipping time is 30 minutes.
Within (8) 3 hours, internal program is warming up to 900 ℃, roasting 2 hours.Make catalyzer DX-1.It specifically consists of (quality %):
0.4 ‰ Pt/3.98%MoO
3/ 0.45%La
2o
3/ 2.79% γ-Al
2o
3/ 4.70%CeO
2/ 3.36%ZrO
2, surplus is alumina globule.
Deoxidation reactor R103 filling independent development catalyticcombustion essence dehydrogenation catalyst in above-mentioned smart deoxygenation.Its preparation process is basic identical with said process.Difference is that the preparation of this catalyzer does not have (2) process of above-mentioned preparation, only supports aluminium hydroxide slurry on alumina globule.Successor operation is identical.Make catalyzer DX-2, it specifically consists of (quality %): 0.3 ‰ Pt/5.33%MoO
3/ 0.70%La
2o
3/ 11.92% γ-Al
2o
3, surplus is alumina globule.
Compared with prior art, the invention has the beneficial effects as follows: in catalyticing combustion process, make up water steam can absorb as heat storage material the amount of heat that methane and oxygen produce in combustion processes, thereby reduce the thermal insulation warming of system, improve the deoxidizing capacity of separate unit reactor; Meanwhile, cause the molecular balance of methane and oxygen combustion to move to the left side a large amount of adding of water vapour, thereby suppress the severe degree of combustion reactions, reaches the object of reduction system temperature rise; Water vapour exists as inert material in system, does not participate in the process of reaction, after reaction finishes, is easy to separate; Meanwhile, for methane and oxygen mix system, have good effectiveness of explosion suppression a large amount of adding of water vapour.For the deoxidation process of elevated oxygen level, adding of water vapour can reduce circulation gas consumption greatly, reduces the energy consumption of deoxidation, simultaneously the reduction of circulating flow rate, the size that also can significantly reduce circulator, interchanger and pipe valve, reduces production costs and fixed investment.The present invention is directed to the difference of oxygen level in coal mine gas, by adjusting the amount of filling into of water vapour and the size of circulating flow rate, applicable to the oxygen of the coal mine gas of various different oxygens, remove.The present invention simultaneously makes full use of the heat producing in coal mine gas deoxidation process, has reclaimed energy and has reduced energy consumption.
Embodiment
Below in conjunction with accompanying drawing, by embodiment, the present invention will be described in more detail, but the present invention is not limited to these embodiment.
Embodiment 1
The present embodiment deoxidization technique as shown in Figure 1, but ON cycle system not in experiment.
Gas unstripped gas consists of (volume %): CH
440.7%, N
245.6%, CO
25.9%, O
27.8%.Tolerance is 100Nm
3/ h, 300 ℃ of temperature, pressure 0.6MPa.
In experimentation, in system, fill into the water vapour that is equivalent to gas feed gas volume 20%, the volume ratio of the gas composition after make up water steam is: CH
434%, N
238%, CO
24.9%, O
26.4%, H
2o 16.7%.
Deoxidation reactor R101 temperature in is 300 ℃, 620 ℃ of temperature outs.Reacted mixed gas is after heat exchange, and temperature is down to 300 ℃, passes into deoxidation reactor R102, and reactor outlet temperature is 540 ℃.From deoxidation reactor R102 gas out, through useless pot E103 and feed gas chiller E104, be cooled to after 300 ℃, pass into smart deoxidation reactor R103,300 ℃ of temperature outs, oxygen content < 0.1 volume %.After de-salted water water cooler E108 and gas product water cooler E109, gas temperature is down to 40 ℃, and through a point flow container V102 separatory gas, the volume ratio of the final composition of gas product is: CH
439.9%, N
249.5%, CO
210.6%.
Filling self-control dehydrogenation catalyst in deoxidation reactor R101 and R102, adopt on alumina globule and support cerium zirconium compound oxide and pseudo-boehmite slurry, after roasting, flood Pt, Mo, La isoreactivity component makes, it consists of (quality %): 0.4 ‰ Pt/3.98%MoO
3/ 0.45%La
2o
3/ 2.79% γ-Al
2o
3/ 4.70%CeO
2/ 3.36%ZrO
2/ 84.68% alumina globule.
Method for preparing catalyst in essence deoxidation reactor R103 is identical with above-mentioned method for preparing catalyst, and it specifically consists of (quality %): 0.3 ‰ Pt/5.33%MoO
3/ 0.70%La
2o
3/ 11.92% γ-Al
2o
3/ 82.02% alumina globule.
Comparative example 1
The deoxidization technique of the present embodiment as shown in Figure 1, is not still used moisturizing technique.
Gas unstripped gas gas composition adopts the coal mine gas identical with embodiment 1, and it consists of: CH
440.7%, N
245.6%, CO
25.9%, O
27.8%.Tolerance is 100Nm
3/ h, 300 ℃ of temperature, pressure 0.6MPa.
Experiment replenishes deoxidation reactor R101 using the portioned product gas after E104 heat exchange as circulation gas, and recycle ratio is 1.2, is equivalent to the tolerance of gas unstripped gas 120% as circulation gas.The gas composition that enters deoxidation reactor R101 after replenishment cycles gas is (volume %): CH
440.3%, N
247.7%, CO
28.5%, O
23.5%.Tolerance is 220Nm
3/ h.
Deoxidation reactor R101 temperature in is 300 ℃, 650 ℃ of temperature outs.By reacted mixed gas, after heat exchange, temperature is down to 300 ℃, passes into deoxidation reactor R102, and reactor outlet temperature is 440 ℃.By from deoxidation reactor R102 gas out, through useless pot E103 and feed gas chiller E104, be cooled to after 300 ℃, pass into smart deoxidation reactor R103,300 ℃ of temperature outs.After de-salted water water cooler E108 and gas product water cooler E109, gas temperature is down to 40 ℃, and through a point flow container V102 separatory gas, the volume ratio of the final composition of gas product is: CH
439.1%, N
249.9%, CO
211%.
The catalyzer using in the present embodiment is identical with the catalyzer using in embodiment 1.
Known with the comparing result of embodiment 1 by this comparative example, moisturizing can reduce circulation gas ratio greatly, thereby reduces the energy consumption in deoxidation process, and reduces processing unit volume, reduces cost.
Embodiment 2
The present embodiment deoxidization technique is as shown in Figure 1:
Gas unstripped gas consists of (volume %): CH
435.6%, N
247.8%, CO
23.2%, O
213.4%.Tolerance is 100Nm
3/ h, 300 ℃ of temperature, pressure 0.6MPa.
In experimentation, in system, fill into the water vapour that is equivalent to feed gas volume 50%, and by the gas of deoxidation reactor R102 outlet, after mixing with water vapour with unstripped gas as circulation gas, enter deoxidation reactor R101, internal circulating load is 0.5 times, is equivalent to the tolerance of unstripped gas 50% as circulation gas.After make up water steam and circulation gas, gas composition is (volume %): CH
426.2%, N
237.7%, CO
24.4%, O
26.7%, H
2o 25%, tolerance is 200Nm
3/ h.
The gas unstripped gas that mining area is come is by feed preheater E104 and from circulation gas Bing Cheng mono-tunnel after smart deoxidation reactor R103, and after mixing with the water vapour of drum V102, total flux is 200Nm
3/ h, after mixing, gas temperature is 300 ℃, enters deoxidation reactor R101 and carries out deoxygenation, reactor outlet temperature is 650 ℃.The gas of deoxidation reactor R101 outlet is after vapor superheater E101, waste heat boiler E102 heat exchange, and gas temperature is down to 300 ℃, enters deoxidation reactor R102 deoxidation.The temperature out of deoxidation reactor R102 is 540 ℃.Deoxidation reactor R102 exit gas is through waste heat boiler E103 and feed gas heater E104 heat exchange, cool the temperature to after 300 ℃, be divided into two-way: lead up to after de-salted water preheater E105 and recycle gas cooler E106 heat exchange, cool the temperature to below 40 ℃, after water separation tank V103 carbonated drink separates, gas is sent into deoxidation reactor R101 entrance as circulation gas by circulator C101,50 volume % of circulating flow rate gas material gas quantity; Smart deoxidation reactor R103 is sent on an other road, and oxygen residual in gas is removed, and reactor outlet temperature is 410 ℃.Reacted gas is after circulating gas preheater E107 and de-salted water preheater E108 and gas product water cooler E109, cool the temperature to 40 ℃ of left and right, enter water separation tank V101 divided gas flow and water, gas product enters next workshop section's operation, after water treatment, recycles.
De-salted water is divided into two-way access to plant, lead up to de-salted water interchanger 1E105 with from the portioned product gas heat exchange of deoxidation reactor R102; Lead up in addition de-salted water interchanger 2E108 with from the gas product heat exchange of smart deoxidation reactor R103, the de-salted water after heat exchange is preheated to after 220 ℃, enters drum V102.Gas in drum by waste heat boiler E102 and waste heat boiler E103 respectively with gas product heat exchange from deoxidation reactor R101 and R102 after, temperature is heated to 300 ℃, part steam enters reactive system as inert substance by deoxidation reactor R101, a part of steam forms superheated vapour through vapor superheater E101 in addition, and carrying device is used.
The volume ratio of the final composition of gas product is: CH
433.4%, N
255.3%, CO
211.3%.
The catalyzer using in the present embodiment is identical with the catalyzer using in embodiment 1.
In the present embodiment, if do not adopt the mode of moisturizing, only adopt gas product to reduce the oxygen level in the coal mine gas of ingress as the mode of circulation gas, required circulating flow rate is 3～4 times of gas material gas quantity, is far longer than 0.5 times of internal circulating load of the present embodiment.
Embodiment 3
The deoxidization technique of the present embodiment is as shown in Figure 1:
Gas unstripped gas adopts the coal mine gas identical with embodiment 2, and it consists of (volume %): CH
435.6%, N
247.8%, CO
23.2%, O
213.4%.Tolerance is 100Nm
3/ h, 300 ℃ of temperature, pressure 0.6MPa.
In experiment, deoxidation reactor R101 and R102 all load the 506HT type dehydrogenation catalyst that commercially available Dalian Ke Lian new technology development company produces, and load the 506HL type dehydrogenation catalyst that commercially available Dalian Ke Lian new technology development company produces in smart deoxidation reactor R103.
Experiment adopts the control step identical with embodiment 2, in system, fill into the water vapour that is equivalent to gas feed gas volume 50%, and the R102 exit gas that fills into the tolerance that is equivalent to unstripped gas 50% is as circulation gas.
The volume ratio of the final composition of gas product is: CH
433.9%, N
255.0%, CO
211.1%.
Industrial applicability
Due to system of the present invention and technological operation easy, be easy to control, by fill into water vapour in system, or adopt the mode combining to filling into water vapour and circulation gas in system, can improve reactor inlet oxygen level, reduce circulation gas consumption, thereby can reduce equipment size, reduce investment, reduce power consumption and byproduct steam etc., therefore industrial, have broad application prospects.
Claims (13)
1. for a system for catalytic combustion deoxidation of methane gas, described system comprises:
For carrying out the deoxidation reactor of coal mine gas deoxygenation, described deoxidation reactor is set up circulating ring by recycle compressor, and the state that wherein recycle compressor and system are connected is adjustable;
For described deoxidation reactor being supplied with to the device of water vapour; With
Be connected to the smart deoxidation tower after described circulating ring, for supplementing, carry out oxygen and remove, wherein said system also comprises: in the situation that connecting recycle compressor, to the mechanism of replenishment cycles gas in gas unstripped gas.
2. system according to claim 1, wherein said circulation gas is incorporated into deoxidation reactor entrance by following process: from gas process waste heat boiler and the feed gas heater heat exchange of deoxidation reactor outlet, after below cooling the temperature to 300 ℃, after de-salted water preheater and recycle gas cooler heat exchange, cool the temperature to below 40 ℃, gas, after water separation tank carbonated drink separates, is sent into deoxidation reactor entrance by circulator.
3. system according to claim 1, wherein said system also comprises: be connected to the one or more of the vapor superheater for waste heat recovery, waste heat boiler and preheater in described system.
4. system according to claim 1, wherein said deoxidation reactor consists of 2 deoxidation reactors that are connected in series.
5. system according to claim 4, wherein saidly supplies with water vapour for the device of described deoxidation reactor being supplied with to water vapour to the first deoxidation reactor of the deoxidation reactor in the upstream of technique.
6. right to use requires the method for catalytic combustion deoxidation of methane gas of the system described in 1, and described method comprises: to make up water steam in deoxidation reactor as rare gas element; In deoxidation reactor, coal mine gas is carried out to deoxidation, at this, remove a large amount of oxygen; In smart deoxidation reactor, carrying out supplemental oxygen removes.
7. method according to claim 6 wherein, with respect to described gas unstripped gas cumulative volume, is 10～100 volume % as the add-on of the water vapour of rare gas element.
8. method according to claim 7 wherein, with respect to described gas unstripped gas cumulative volume, is preferred 20～60 volume % as the add-on of the water vapour of rare gas element.
9. method according to claim 6, wherein, described method also comprises: to replenishment cycles gas in gas unstripped gas.
10. method according to claim 8, wherein, under the condition that oxygen level is 8～15% in coal mine gas, the size of circulating flow rate is 10～150 volume % of gas material gas quantity.
11. methods according to claim 10, wherein, under the condition that oxygen level is 8～15% in coal mine gas, the size of circulating flow rate is 20～80 volume % of gas material gas quantity.
12. according to the method described in any one in claim 6-9, and described method comprises: by the one or more heat to produce in recycling technological process in vapor superheater, waste heat boiler and preheater is set.
13. according to the method described in any one in claim 6-9, and described method comprises uses the coal mine gas dehydrogenation catalyst of preparing by following process to carry out deoxidation:
(1) choose suitable inert support material as catalyst backbone,
(2) aluminium hydroxide and cerium zirconium compound oxide are mixed according to the ratio of mol ratio 0.5～5, add dilute nitric acid solution, the volume that adds rare nitric acid is cerium zirconium compound oxide and aluminium hydroxide mixed volume 2～20 times, wet ball grinding form slurry,
(3) by the slurry coating making to inert catalyst carrier, dry after, at 500～900 ℃, roasting 2～6 hours, obtains required support of the catalyst,
(4) adopt pickling process, the impregnation of catalyst carriers making in (3), to containing in molybdenum solution, obtained to catalyst precursor A after being dried,
(5) by pickling process, catalyst precursor A is impregnated in rare earth nitrate solution, after being dried, obtains required catalyst precursor B,
(6) then, by catalyst precursor B, at 500～900 ℃, roasting 1～4 hour, obtains catalyst precursor C,
(7) adopt pickling process, will make catalyst precursor C and be impregnated in platiniferous solution, then dry,
(8), then at 900～1200 ℃, roasting 1～4 hour, obtains required dehydrogenation catalyst.
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| CN101139239A (en) * | 2007-09-06 | 2008-03-12 | 西南化工研究设计院 | Sulfur-resistant catalytic deoxidization process for methane-rich gas |
| CN101508924A (en) * | 2009-03-16 | 2009-08-19 | 西南化工研究设计院 | Catalysis deoxidization process for coal bed gas of coal mine zone |
| CN101664679A (en) * | 2009-11-17 | 2010-03-10 | 中国科学院大连化学物理研究所 | Coal bed gas deoxidation catalyst as well as preparation method and application thereof |
| CN102031170A (en) * | 2010-12-30 | 2011-04-27 | 新奥新能(北京)科技有限公司 | Novel method for preparing urban gas from coal mine gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101139239A (en) * | 2007-09-06 | 2008-03-12 | 西南化工研究设计院 | Sulfur-resistant catalytic deoxidization process for methane-rich gas |
| CN101508924A (en) * | 2009-03-16 | 2009-08-19 | 西南化工研究设计院 | Catalysis deoxidization process for coal bed gas of coal mine zone |
| CN101664679A (en) * | 2009-11-17 | 2010-03-10 | 中国科学院大连化学物理研究所 | Coal bed gas deoxidation catalyst as well as preparation method and application thereof |
| CN102031170A (en) * | 2010-12-30 | 2011-04-27 | 新奥新能(北京)科技有限公司 | Novel method for preparing urban gas from coal mine gas |
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