CN101139239A - Sulfur-resistant catalytic deoxidization process for methane-rich gas - Google Patents
Sulfur-resistant catalytic deoxidization process for methane-rich gas Download PDFInfo
- Publication number
- CN101139239A CN101139239A CN 200710049962 CN200710049962A CN101139239A CN 101139239 A CN101139239 A CN 101139239A CN 200710049962 CN200710049962 CN 200710049962 CN 200710049962 A CN200710049962 A CN 200710049962A CN 101139239 A CN101139239 A CN 101139239A
- Authority
- CN
- China
- Prior art keywords
- deoxidation
- sulfur
- gas
- rich
- methane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The present invention discloses a sulfur wearable and catalyzing and oxidizing method for gas abundant of firedamp; the raw material gas abundant of firedamp such as coal bed gas firstly passes through a preheater for preheating, and then enters a oxidizing reaction device; under the condition of 0-0.5MPa of pressure, 500-750 DEG C of reaction temperature, 1000-3000h<SUP>-1</SUP>of reaction air speed, the firedamp in the air is reacted with oxygen to produce carbon dioxide and water in manganese base sulfur wearable and catalyzing and oxidizing bed; at the same time, a small quantity of firedamp is decomposed to produce carbon and hydrogen gas; the carbon and the hydrogen after being decomposed are also reacted with oxygen so as to reach the purpose of getting rid of oxygen in the airs abundant of firedamp effectively. The present invention adopts much newer and more economical new catalyzer, which does not need to desulfurize firstly for the air; the air can directly enter the oxidization reaction device for oxidization. So the present invention can decrease the cost and simplify the technics process.
Description
Technical field
The invention belongs to gas deoxy technology field, particularly a kind of sulfur-resistant catalytic deoxidization process that is rich in methane gas.
Background technology
The gas that is rich in methane mainly contains coal-seam gas (being commonly called as gas), refuse embedded gas etc., and its main component is methane.
Coal-seam gas is present in the coal seam in a large number, belongs to unconventional Sweet natural gas; It is the one of the main reasons that causes the colliery down-hole accident.In fact coal-seam gas is a kind of calorific value height, and free of contamination new forms of energy can be used as fuel used to generate electricity, process fuel, industrial chemicals and resident living fuel etc.China causes the huge environmental stress and the wasting of resources to about 300 billion cubic meters of airborne release coal-seam gas every year.Coal-seam gas is rationally fully utilized, can remedy China's energy shortage.The recycling of coal-seam gas simultaneously also helps the guard ring border, and the Greenhouse effect of methane are CO
2More than 20 times, a large amount of coal-seam gas enters atmosphere and has aggravated Global Greenhouse Effect.Therefore, the poor efficiency of coal-seam gas had both caused the significant wastage of resource, had increased the weight of environmental pollution again.
Southnest China Chemical Engineering Inst., Ministry of Chemical Industry discloses a kind of method of utilizing pressure swing adsorption process separation and concentration methane from coal-seam gas in the Chinese patent ZL85103557 " methane in the pressure swing adsorption process enrichment coal mine mash gas " of application in 1985.Generally speaking, the oxygen level of methane discharging waste gas in concentrating purification process also is concentrated raising, owing to inevitably contain 5～15% methane in the waste gas, cause exhaust gas discharged to be in the limits of explosion scope of methane, in the discharging waste gas pipe, all the time exist the danger of blast, this makes this The Application of Technology be restricted, thereby to carry out deoxidation treatment before coal-seam gas comprehensive utilization be very necessary.
Present adoptable coal bed gas deoxidation method mainly contains catalytic deoxidation method (ZL02113628.9) and coke deoxidization method (ZL02113627.0,200610021720.1) etc., these two kinds of methods all can effectively be reduced to the oxygen level in the coal-seam gas below 0.5%, propose the safety operation of dense process to guarantee subsequent technique.
Employed catalyzer was noble metal catalysts such as Pt or Pd during Chinese patent ZL02113628.9 " produced the catalyticcombustion deoxidization process of methyl alcohol with coal mine mash gas ", the advantage of this type of catalyzer is the catalytic activity height, temperature of reaction is lower, oxygen after the deoxidation in the gas can eliminate substantially, technological operation is easy, equipment is simple, is convenient to automatic control.Weak point is that catalyzer costs an arm and a leg, contain sulfide in the methane gas owing to being rich in simultaneously, thereby toxic effect causes catalyst deactivation and sulphur is to precious metal, therefore will carry out desulfurization before deoxidation earlier carries out deoxygenation again, cause the deoxidation cost to increase like this, caused the processing costs of coal-seam gas catalytic deoxidation higher.
Coal bed gas coke method deoxidation (ZL02113627.0,200610021720.1) is under hot conditions, is rich in oxygen and coke gasification reaction in the methane gas, thereby while part methane and oxygen reaction reach the purpose of deoxidation.The advantage of coke method deoxidation is about 70% oxygen and coke gasification reaction, 30% oxygen and methane reaction, so the loss of methane is less.The processing costs of this method is lower than precious metal catalyst deoxidation method.But shortcoming is this method and wants the coke resource of consume valuable that the consuming cost of coke is about about 50% of whole service expense.In addition the deoxidation of coke method its add Jiao, the labour intensity of slagging tap is big, ambient dust is bigger, and has the sulfide of variform in the coke.
Refuse embedded gas etc. also are the gas that is rich in methane, and the methane content in its methane content and the coal-seam gas is close, and its sulphur content is then also different because of the sulphur content that the landfill waste difference is produced, but general sulphur content is no more than 40mg/m
3In the comprehensive recycling that refuse embedded gas etc. is rich in methane gas utilizes, also need to carry out deoxidation treatment, because its composition is close with coal-seam gas, its deoxidation treatment is close with coal bed gas deoxidation technology.
Summary of the invention
The purpose of this invention is to provide a kind of new catalytic deoxidation process that is rich in methane gas, promptly be rich in the sulfur-resistant catalytic deoxidization process of methane gas, this method adopts more economic raw catalyst, make and be rich in methane gas and need not to carry out first desulfurization, can directly enter deoxidation in the deoxidation reactor, thereby the reduction processing costs, and simplify processing step.
The technical solution adopted for the present invention to solve the technical problems is:
Be rich in the sulfur-resistant catalytic deoxidization process of methane gas: the unstripped gas that coal-seam gas etc. is rich in methane gas directly enters after by the preheater preheating and (does not need pre-desulfurization) in the deoxidation reactor, (under normal pressure～0.5Mp) and 500～750 ℃ of temperature condition, reaction velocity is 1000～3000h in normal pressure or low pressure
-1In beds, the methane and the oxygen reaction of being rich in the methane gas generate carbonic acid gas and water, and simultaneously a spot of methane generation cracking produces charcoal and hydrogen, charcoal that cracking produces and hydrogen react with oxygen again, effectively remove the purpose that is rich in oxygen in the methane gas thereby reach.
Used catalyzer is that manganese is sulfur-tolerance deoxidation catalyst in the deoxidation process, is made up of active ingredient, support carrier and binding agent; Active ingredient wherein is the oxide compound of manganese, can be selected from Manganse Dioxide, manganous carbonate, the manganous oxalate etc. any one or a few; Supporting carrier is molecular sieve or activated alumina, and molecular sieve can be selected from any one or a few in A type molecular sieve, X type molecular sieve, Y zeolite, the phosphate aluminium molecular sieve etc.; Binding agent is high-alumina cement or clay, and clay can be selected from any one or a few in kaolin, attapulgite, diatomite, the sweet soil of sheep etc.
Above-mentioned manganese is in the sulfur-tolerance deoxidation catalyst, is 100% in active ingredient, support carrier and binding agent gross weight, and the weight percent of each component can be preferably: active ingredient 20～80%, support monomer 0～50%, binding agent 20～50%.
Above-mentioned manganese is can also contain the organic or inorganic expanding agent in the sulfur-tolerance deoxidation catalyst, can be selected from starch, graphite, xylogen, carboxymethyl cellulose, the ethylene glycol etc. any one or a few; Its consumption is advisable to account for 0～20% of active ingredient, support carrier and binding agent gross weight.
Above-mentioned manganese is the preparation of sulfur-tolerance deoxidation catalyst, only needs each component is mixed in proportion moulding after sinter the finished catalyst of desired shape into and get final product; Can make multiple shapes such as spherical, strip, column, sheet, ring-type.
Be rich in that principal reaction is in the deoxidation process of methane gas:
CH
4+2O
2→CO
2+2H
2O
A small amount of methane generation cracking under the high temperature:
CH
4→C+2H
2
Following reaction further takes place again in charcoal and hydrogen that methane cracking produces:
2C+O
2→2CO
2CO+O
2→2CO
2
2H
2+O
2→2H
2O
Because methane and oxygen reaction are strong exothermal reactions, can be rich in methane gas being rich in the methane feed gas to the deoxidation by the cyclic part deoxidation is cooled, adjusting enters the oxygen level of reactor to optimum range, be generally 1～7%, with 2.5～5.5% is excellent, can effectively temperature of reaction be controlled in the optimum range, the sulfur-resistant catalytic deoxidization range of reaction temperature is 500～750 ℃.
Reaction velocity in the above-mentioned deoxidation reactor can be preferably 1500～2500h
-1
The present invention is not only applicable to the deoxidation of coal-seam gas, is applicable to that simultaneously refuse embedded gas etc. is rich in the deoxidization technique in the comprehensive recycling of methane gas yet.The methane content of refuse embedded gas is close with the methane content in the coal-seam gas, but the sulphur content difference that its sulphur content is produced because of the landfill waste difference, but general sulphur content is no more than 40mg/m
3, this is that the anti-sulphur of sulfur-tolerance deoxidation catalyst can bear for manganese of the present invention.In addition, the oxygen level of refuse embedded gas is lower, generally can not surpass 5%, so just more is applicable to that anti-sulphur deoxidization technique of the present invention removes the oxygen in the refuse embedded gas, and its processing costs is very low.
Compared with prior art, the invention has the beneficial effects as follows:
(1), compare, sulfur-resistant catalytic deoxidization process of the present invention is owing to select non-precious metal catalyst for use, and the catalyzer price declines to a great extent with noble metal catalyst catalytic deoxidation method; The used manganese of the present invention simultaneously is that sulfur resistant catalyst has certain sulfur tolerance, the coal-seam gas sulphur content≤10mg/m in general colliery
3, can be with this method without pre-desulfurization, thereby saved the expense of pre-desulfurization link.
(2), compare, sulfur-resistant catalytic deoxidization process of the present invention is not because the methane reaction in oxygen and the coal-seam gas needs to consume coke resource with the coke deoxidization method, but save energy; And technical process of the present invention is easier, and easy and simple to handle, equipment is simple, is convenient to automatic control, and its running cost descends about 1/3rd than coke method.
(3), compare with the coke deoxidization method, though sulfur-resistant catalytic deoxidization process of the present invention will consume a small amount of methane, thereby the methane total amount slightly reduces after making deoxidation, but the oxygen level after the deoxidation in the coal-seam gas has reduced to below 0.5%, the total gas volume in back that dewaters reduces to some extent, thus after the deoxidation in the gaseous fraction relative content of methane change little; Simultaneously, though methane is lost, generate CO owing to behind the methane oxidation
2And H
2O can obtain heat, produces the part waste hot steam, can make other purposes.
In addition, sulfur-resistant catalytic deoxidization process of the present invention is applicable to that also refuse embedded gas etc. is rich in the deoxidization technique in the comprehensive recycling of methane gas.
Description of drawings
Fig. 1 is the sulfur-resistant catalytic deoxidization process schematic flow sheet that methane gas is rich in the present invention.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.
Embodiment 1
Present embodiment is the sulfur-resistant catalytic deoxidization process of coal-seam gas:
The raw material coal-seam gas is directly entered in the deoxidation reactor after by the preheater preheating, under normal pressure and 500～550 ℃ of temperature condition, air speed 2500h
-1, in beds, methane in the coal-seam gas and oxygen react and generate carbonic acid gas and water, and simultaneously a spot of methane generation cracking produces charcoal and hydrogen, and charcoal that cracking produces and hydrogen react with oxygen again, thereby reach the purpose of effectively removing oxygen in the coal-seam gas; In addition by in the raw material coal-seam gas of the cooled coal-seam gas of cyclic part deoxidation to the deoxidation, regulate enter reactor oxygen level to optimum range 1～1.5%, temperature of reaction is controlled in 500～550 ℃ of scopes.
Used catalyzer is that spherical manganese is sulfur-tolerance deoxidation catalyst in the present embodiment deoxidation process, is made up of active ingredient 80% and binding agent 20%; Active ingredient wherein is a Manganse Dioxide, and binding agent is a high-alumina cement.
Gas after present embodiment unstripped gas and the deoxidation (deoxidation gas) composition tabulates 1 as follows, and sulphur content wherein is a total sulfur, comprises organosulfur and inorganic sulfur (following each embodiment is all identical):
Table 1 embodiment 1 unstripped gas and deoxidation gas are formed
| H 2％ | O 2％ | N 2％ | CO％ | CO 2％ | CH 4％ | S mg/m 3 | |
| Unstripped gas is formed | 0.08 | 1.06 | 5.56 | 0.93 | 92.37 | 8.54 | |
| Deoxidation gas is formed | 0.09 | 0.05 | 5.72 | 0.15 | 1.78 | 92.21 |
Embodiment 2
Present embodiment is the sulfur-resistant catalytic deoxidization process of coal-seam gas:
The raw material coal-seam gas is directly entered in the deoxidation reactor after by the preheater preheating, under normal pressure and 500～550 ℃ of temperature condition, air speed 1000h
-1, in beds, methane in the coal-seam gas and oxygen react and generate carbonic acid gas and water, and simultaneously a spot of methane generation cracking produces charcoal and hydrogen, and charcoal that cracking produces and hydrogen react with oxygen again, thereby reach the purpose of effectively removing oxygen in the coal-seam gas; In addition by in the raw material coal-seam gas of the cooled coal-seam gas of cyclic part deoxidation to the deoxidation, regulate enter reactor oxygen level to optimum range 2.5～3%, temperature of reaction is controlled in 500～550 ℃ of scopes.
Catalyzer used in the present embodiment deoxidation process is with embodiment 1.
Gas after present embodiment unstripped gas and the deoxidation (deoxidation gas) composition tabulates 2 as follows, and sulphur content wherein is a total sulfur, comprises organosulfur and inorganic sulfur (following each embodiment is all identical):
Table 2 embodiment 2 unstripped gass and deoxidation gas are formed
| H 2％ | O 2％ | N 2％ | CO％ | CO 2％ | CH 4％ | S mg/m 3 | |
| Unstripped gas is formed | 0.07 | 2.68 | 15.78 | 0 | 1.91 | 79.56 | 14.68 |
| Deoxidation gas is formed | 0.09 | 0.14 | 15.84 | 0.23 | 2.85 | 80.85 |
Embodiment 3
Present embodiment is the sulfur-resistant catalytic deoxidization process of coal-seam gas:
The raw material coal-seam gas is directly entered in the deoxidation reactor after by the preheater preheating, under normal pressure and 600～650 ℃ of temperature condition, air speed 2000h
-1, in beds, methane in the coal-seam gas and oxygen react and generate carbonic acid gas and water, and simultaneously a spot of methane generation cracking produces charcoal and hydrogen, and charcoal that cracking produces and hydrogen react with oxygen again, thereby reach the purpose of effectively removing oxygen in the coal-seam gas; In addition by in the raw material coal-seam gas of the cooled coal-seam gas of cyclic part deoxidation to the deoxidation, regulate enter reactor oxygen level to optimum range 3.5～4%, temperature of reaction is controlled in 600～650 ℃ of scopes.
Catalyzer used in the present embodiment deoxidation process is a sulfur-tolerance deoxidation catalyst for ring-type manganese, is made up of active ingredient 20%, support carrier 50% and binding agent 30%; Active ingredient wherein is a manganous oxalate, and supporting carrier is X type molecular sieve, and binding agent is an attapulgite, and other adds active ingredient, supports the carboxymethyl cellulose of carrier and binding agent gross weight 10% as expanding agent.
Present embodiment unstripped gas and deoxidation gas composition tabulate 3 as follows:
Table 3 embodiment 3 unstripped gass and deoxidation gas are formed
| H 2％ | O 2％ | N 2％ | CO％ | CO 2％ | CH 4％ | S mg/m 3 | |
| Unstripped gas is formed | 0.01 | 3.77 | 15.78 | 0 | 0.97 | 79.47 | 5.07 |
| Deoxidation gas is formed | 0.10 | 0.15 | 16.22 | 0.37 | 2.80 | 80.36 |
Embodiment 4
Present embodiment is the sulfur-resistant catalytic deoxidization process of coal-seam gas:
The raw material coal-seam gas is directly entered in the deoxidation reactor after by the preheater preheating, under normal pressure and 650～700 ℃ of temperature condition, air speed 2500h
-1, in beds, methane in the coal-seam gas and oxygen react and generate carbonic acid gas and water, and simultaneously a spot of methane generation cracking produces charcoal and hydrogen, and charcoal that cracking produces and hydrogen react with oxygen again, thereby reach the purpose of effectively removing oxygen in the coal-seam gas; In addition by in the raw material coal-seam gas of the cooled coal-seam gas of cyclic part deoxidation to the deoxidation, regulate enter reactor oxygen level to optimum range 4.5～5%, temperature of reaction is controlled in 650～700 ℃ of scopes.
Catalyzer used in the present embodiment deoxidation process is with embodiment 3.
Present embodiment unstripped gas and deoxidation gas composition tabulate 4 as follows:
Table 4 embodiment 4 unstripped gass and deoxidation gas are formed
| H 2％ | O 2％ | N 2％ | CO％ | CO 2％ | CH 4％ | S mg/m 3 | |
| Unstripped gas is formed | 0.05 | 4.66 | 23.40 | 0 | 0.20 | 71.69 | 11.33 |
| Deoxidation gas is formed | 0.08 | 0.06 | 23.60 | 0.35 | 3.35 | 72.56 |
Embodiment 5
Present embodiment is the sulfur-resistant catalytic deoxidization process of coal-seam gas:
The raw material coal-seam gas that is rich in methane is directly entered in the deoxidation reactor after by the preheater preheating, under normal pressure and 700～750 ℃ of temperature condition, air speed 2000h
-1, in beds, methane in the coal-seam gas and oxygen react and generate carbonic acid gas and water, and simultaneously a spot of methane generation cracking produces charcoal and hydrogen, and charcoal that cracking produces and hydrogen react with oxygen again, thereby reach the purpose of effectively removing oxygen in the coal-seam gas; In addition by in the raw material coal-seam gas of the cooled coal-seam gas of cyclic part deoxidation to the deoxidation, regulate enter reactor oxygen level to optimum range 5～5.5%, temperature of reaction is controlled in 700～750 ℃ of scopes.
Catalyzer used in the present embodiment deoxidation process is a sulfur-tolerance deoxidation catalyst for column manganese, is made up of active ingredient 50%, support carrier 30% and binding agent 20%; Active ingredient wherein is manganous oxalate and manganous carbonate half and half, and the support carrier is a Y zeolite, and binding agent is a diatomite.
Present embodiment unstripped gas and deoxidation gas composition tabulate 5 as follows:
Table 5 embodiment 5 unstripped gass and deoxidation gas are formed
| H 2％ | O 2％ | N 2％ | CO％ | CO 2％ | CH 4％ | S mg/m 3 | |
| Unstripped gas is formed | 0.02 | 5.41 | 27.73 | 0.02 | 0.28 | 66.54 | 6.67 |
| Deoxidation gas is formed | 0.16 | Trace | 29.32 | 0.39 | 2.84 | 67.29 |
Embodiment 6
Present embodiment is the sulfur-resistant catalytic deoxidization process of coal-seam gas:
The raw material coal-seam gas is directly entered in the deoxidation reactor after by the preheater preheating, under normal pressure and 700～750 ℃ of temperature condition, air speed 1500h
-1, in beds, methane in the coal-seam gas and oxygen react and generate carbonic acid gas and water, and simultaneously a spot of methane generation cracking produces charcoal and hydrogen, and charcoal that cracking produces and hydrogen react with oxygen again, thereby reach the purpose of effectively removing oxygen in the coal-seam gas; In addition by in the raw material coal-seam gas of the cooled coal-seam gas of cyclic part deoxidation to the deoxidation, regulate enter reactor oxygen level to optimum range 6.5～7%, temperature of reaction is controlled in 700～750 ℃ of scopes.
Catalyzer used in the present embodiment deoxidation process is a sulfur-tolerance deoxidation catalyst for ring-type manganese, is made up of active ingredient 35%, support carrier 40% and binding agent 25%; Active ingredient wherein is a manganous oxalate, and the support carrier is a phosphate aluminium molecular sieve, and binding agent is an attapulgite, and other adds active ingredient, supports the graphite of carrier and binding agent gross weight 20%.
Present embodiment unstripped gas and deoxidation gas composition tabulate 6 as follows:
Table 6 embodiment 6 unstripped gass and deoxidation gas are formed
| H 2％ | O 2％ | N 2％ | CO％ | CO 2％ | CH 4％ | S mg/m 3 | |
| Unstripped gas is formed | 0.01 | 6.62 | 27.94 | 0 | 0.80 | 64.63 | 5.07 |
| Deoxidation gas is formed | 0.34 | 0.45 | 28.85 | 0.68 | 4.42 | 65.26 |
Embodiment 7
Present embodiment is the sulfur-resistant catalytic deoxidization process of coal-seam gas:
This embodiment is the continuity reaction, and the time is continuous operation 30 days; The raw material coal-seam gas is directly entered in the deoxidation reactor after by the preheater preheating, under normal pressure and 600～650 ℃ of temperature condition, air speed 1800h
-1, in beds, methane in the coal-seam gas and oxygen react and generate carbonic acid gas and water, and simultaneously a spot of methane generation cracking produces charcoal and hydrogen, and charcoal that cracking produces and hydrogen react with oxygen again, thereby reach the purpose of effectively removing oxygen in the coal-seam gas; In addition by in the raw material coal-seam gas of the cooled coal-seam gas of cyclic part deoxidation to the deoxidation, regulate enter reactor oxygen level to optimum range 3.5～4%, temperature of reaction is controlled in 600～650 ℃ of scopes.
Catalyzer used in the present embodiment deoxidation process is with embodiment 5.
In the tandem reaction sequence, carry out the deoxidation analysis stage by stage, each stage deoxidation result all can meet design requirement; Wherein, react the 1st day (635 ℃ of temperature of reaction) and the 30th day (650 ℃ of temperature of reaction), present embodiment unstripped gas and deoxidation gas are formed and are tabulated 7 and table 8 respectively as follows:
The 1st day unstripped gas of table 7 embodiment 7 and deoxidation gas are formed
| H 2％ | O 2％ | N 2％ | CO％ | CO 2％ | CH 4％ | S mg/m 3 | |
| Unstripped gas is formed | 0.01 | 3.87 | 17.90 | 0 | 1.15 | 77.07 | 48.56 |
| Deoxidation gas is formed | 0.42 | 0.07 | 18.17 | 0.19 | 3.04 | 78.11 |
The 30th day unstripped gas of table 8 embodiment 7 and deoxidation gas are formed
| H 2％ | O 2％ | N 2％ | CO％ | CO 2％ | CH 4％ | S mg/m 3 | |
| Unstripped gas is formed | 0.01 | 3.71 | 17.77 | 0 | 1.41 | 77.10 | 10.50 |
| Deoxidation gas is formed | 0.23 | Trace | 17.70 | 0.59 | 4.00 | 77.48 |
Embodiment 8
Present embodiment is the sulfur-resistant catalytic deoxidization process of refuse embedded gas:
The refuse embedded gas that is rich in methane is directly entered in the deoxidation reactor after by the preheater preheating, under 0.5MPa and 600～650 ℃ of temperature condition, air speed 3000h
-1In beds, methane in the refuse embedded gas and oxygen reaction generate carbonic acid gas and water, and simultaneously a spot of methane generation cracking produces charcoal and hydrogen, charcoal that cracking produces and hydrogen react with oxygen again, thereby reach the purpose of effectively removing oxygen in the refuse embedded gas.
Catalyzer used in the present embodiment deoxidation process is a sulfur-tolerance deoxidation catalyst for sheet manganese, is made up of active ingredient 40%, support carrier 10% and 50% binding agent; Active ingredient wherein is a Manganse Dioxide, and the support carrier is a phosphate aluminium molecular sieve, and binding agent is the sweet soil of sheep.
Present embodiment unstripped gas and deoxidation gas composition tabulate 9 as follows:
Table 9 embodiment 8 unstripped gass and deoxidation gas are formed
| H 2％ | O 2％ | N 2％ | CO％ | CO 2％ | CH 4％ | CnHm％ | S mg/m 3 | |
| Unstripped gas is formed | 2.62 | 14.69 | 1.57 | 81.11 | 0.01 | 30 | ||
| Deoxidation gas is formed | 0.2 | 0.2 | 15.05 | 0.3 | 2.85 | 81.40 | 30 |
Claims (10)
1. be rich in the sulfur-resistant catalytic deoxidization process of methane gas, in deoxidation reactor, under normal pressure or low pressure, the certain temperature condition, methane in the unstripped gas that is rich in methane gas and oxygen are reacted in beds and reach the deoxidation purpose, it is characterized in that:
Before carrying out deoxygenation, the unstripped gas that is rich in methane gas is directly entered deoxidation in the deoxidation reactor after by the preheater preheating;
Pressure in the deoxidation reactor is normal pressure～0.5Mp; Temperature is 500～750 ℃ of temperature; Reaction velocity is 1000～3000h
-1
Used catalyzer is that manganese is sulfur-tolerance deoxidation catalyst in the deoxidation process, is made up of active ingredient, support carrier and binding agent, and active ingredient wherein is the oxide compound of manganese.
2. the sulfur-resistant catalytic deoxidization process that is rich in methane gas according to claim 1 is characterized in that: described manganese is in the sulfur-tolerance deoxidation catalyst, is 100% in active ingredient, support carrier and binding agent gross weight, and each weight percentages of components is:
Active ingredient 20～80%, support carrier 0～50%, binding agent 20～50%.
3. the sulfur-resistant catalytic deoxidization process that is rich in methane gas according to claim 1 is characterized in that: the oxide compound of described manganese is selected from any one or a few in Manganse Dioxide, manganous carbonate, the manganous oxalate etc.
4. the sulfur-resistant catalytic deoxidization process that is rich in methane gas according to claim 1 is characterized in that: described support carrier is molecular sieve or activated alumina; Molecular screening any one or a few in A type molecular sieve, X type molecular sieve, Y zeolite, phosphate aluminium molecular sieve etc.
5. the sulfur-resistant catalytic deoxidization process that is rich in methane gas according to claim 1 is characterized in that: described binding agent is high-alumina cement or clay; Clay is selected from any one or a few in kaolin, attapulgite, diatomite, the sweet soil of sheep etc.
6. the sulfur-resistant catalytic deoxidization process that is rich in methane gas according to claim 1, it is characterized in that: described manganese is also to contain the organic or inorganic expanding agent in the sulfur-tolerance deoxidation catalyst, and its consumption accounts for active ingredient, supports 0～20% of carrier and binding agent gross weight.
7. the sulfur-resistant catalytic deoxidization process that is rich in methane gas according to claim 6 is characterized in that: described expanding agent is selected from any one or a few in starch, graphite, xylogen, carboxymethyl cellulose, the ethylene glycol.
8. the sulfur-resistant catalytic deoxidization process that is rich in methane gas according to claim 1 is characterized in that: the reaction velocity in the described deoxidation reactor is 1500～2500h
-1
9. the sulfur-resistant catalytic deoxidization process that is rich in methane gas according to claim 1, it is characterized in that: in described deoxidation process, be rich in the unstripped gas of methane gas to the deoxidation by the cyclic part deoxidation is cooled, regulate oxygen level to 1～7% that enters reactant gases in the deoxidation reactor.
10. the sulfur-resistant catalytic deoxidization process that is rich in methane gas according to claim 9, it is characterized in that: in described deoxidation process, be rich in the unstripped gas of methane gas to the deoxidation by the cyclic part deoxidation is cooled, regulate oxygen level to 2.5～5.5% that enters reactant gases in the reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100499626A CN101139239B (en) | 2007-09-06 | 2007-09-06 | Sulfur-resistant catalytic deoxidization process for methane-rich gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100499626A CN101139239B (en) | 2007-09-06 | 2007-09-06 | Sulfur-resistant catalytic deoxidization process for methane-rich gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101139239A true CN101139239A (en) | 2008-03-12 |
| CN101139239B CN101139239B (en) | 2010-04-14 |
Family
ID=39191373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100499626A Expired - Fee Related CN101139239B (en) | 2007-09-06 | 2007-09-06 | Sulfur-resistant catalytic deoxidization process for methane-rich gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101139239B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321494A (en) * | 2011-05-24 | 2012-01-18 | 北京惟泰安全设备有限公司 | Coal bed gas separating system and process |
| CN102321493A (en) * | 2011-05-24 | 2012-01-18 | 北京惟泰安全设备有限公司 | Coal bed gas separating system and process utilizing catalyst to deoxidize |
| CN102430367A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Coal-bed gas deoxidization method applying tube array fixed bed reactor |
| CN102533367A (en) * | 2011-12-23 | 2012-07-04 | 新地能源工程技术有限公司 | System and method for catalytic combustion deoxidation of methane gas |
| CN102600815A (en) * | 2012-03-31 | 2012-07-25 | 太原理工大学 | Preparation method of deoxidant used for deoxidation of coalbed methane |
| CN101613627B (en) * | 2009-07-23 | 2012-10-03 | 中国科学院大连化学物理研究所 | Catalytic deoxidation process of oxygen-contained coal bed gas |
| CN101508924B (en) * | 2009-03-16 | 2012-10-03 | 西南化工研究设计院 | Catalysis deoxidization process for coal bed gas of coal mine zone |
| CN103131491A (en) * | 2012-05-21 | 2013-06-05 | 太原理工大学 | Method for treating oxygen-bearing coalbed methane by using coal gangue |
| CN103159580A (en) * | 2011-12-19 | 2013-06-19 | 西南化工研究设计院 | Method of purifying and extracting methane in waste landfill gas |
| CN105764598A (en) * | 2013-07-11 | 2016-07-13 | 纽卡斯尔创新有限公司 | Mineral carbonate looping reactor for ventilation air methane mitigation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1330739C (en) * | 2002-04-18 | 2007-08-08 | 西南化工研究设计院 | Catalytic combusticon dehydrogenation process of mine gas for producing methyl alcohol |
-
2007
- 2007-09-06 CN CN2007100499626A patent/CN101139239B/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508924B (en) * | 2009-03-16 | 2012-10-03 | 西南化工研究设计院 | Catalysis deoxidization process for coal bed gas of coal mine zone |
| CN101613627B (en) * | 2009-07-23 | 2012-10-03 | 中国科学院大连化学物理研究所 | Catalytic deoxidation process of oxygen-contained coal bed gas |
| CN102430367B (en) * | 2010-09-29 | 2013-11-06 | 中国石油化工股份有限公司 | Coal-bed gas deoxidization method applying tube array fixed bed reactor |
| CN102430367A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Coal-bed gas deoxidization method applying tube array fixed bed reactor |
| CN102321493A (en) * | 2011-05-24 | 2012-01-18 | 北京惟泰安全设备有限公司 | Coal bed gas separating system and process utilizing catalyst to deoxidize |
| CN102321494A (en) * | 2011-05-24 | 2012-01-18 | 北京惟泰安全设备有限公司 | Coal bed gas separating system and process |
| CN102321493B (en) * | 2011-05-24 | 2013-11-27 | 北京惟泰安全设备有限公司 | Coal bed gas separating system and process utilizing catalyst to deoxidize |
| CN103159580A (en) * | 2011-12-19 | 2013-06-19 | 西南化工研究设计院 | Method of purifying and extracting methane in waste landfill gas |
| CN103159580B (en) * | 2011-12-19 | 2015-06-17 | 西南化工研究设计院有限公司 | Method of purifying and extracting methane in waste landfill gas |
| CN102533367A (en) * | 2011-12-23 | 2012-07-04 | 新地能源工程技术有限公司 | System and method for catalytic combustion deoxidation of methane gas |
| CN102533367B (en) * | 2011-12-23 | 2014-04-30 | 新地能源工程技术有限公司 | System and method for catalytic combustion deoxidation of methane gas |
| CN102600815A (en) * | 2012-03-31 | 2012-07-25 | 太原理工大学 | Preparation method of deoxidant used for deoxidation of coalbed methane |
| CN103131491A (en) * | 2012-05-21 | 2013-06-05 | 太原理工大学 | Method for treating oxygen-bearing coalbed methane by using coal gangue |
| CN105764598A (en) * | 2013-07-11 | 2016-07-13 | 纽卡斯尔创新有限公司 | Mineral carbonate looping reactor for ventilation air methane mitigation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101139239B (en) | 2010-04-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101139239B (en) | Sulfur-resistant catalytic deoxidization process for methane-rich gas | |
| CN101322942B (en) | Oxygen-containing coal bed gas deoxidation catalyst and preparation thereof as well as applications | |
| CN101301611A (en) | Sulfur-tolerance deoxidation catalyst and preparation and use thereof | |
| CN101245262B (en) | Gas-steam combined cycle system and technique based on coal gasification and methanation | |
| CN103204470B (en) | Gas transformation deep purifying technique for separating and purifying CO and H2 of calcium carbide furnace | |
| CN102703108B (en) | Technical method for Fischer-Tropsch synthesis and tail gas utilization | |
| CN106629600B (en) | Crude synthesis gas adsoption catalysis process for making hydrogen and its equipment | |
| CN104445196B (en) | Method for purifying and separating calcium carbide furnace exhaust and application thereof in ethylene glycol production | |
| Sun et al. | One step upcycling CO2 from flue gas into CO using natural stone in an integrated CO2 capture and utilisation system | |
| CN101450790A (en) | Method and apparatus for preparing synthesis gas by natural gas-carbon dioxide reforming | |
| CN101239702A (en) | High temperature coke oven crude gas hydrogen generating system device and technique | |
| WO2012174968A1 (en) | Novel process for purifying and refining crude synthetic gas based on molten salt properties | |
| CN105883851B (en) | A kind of Novel gasification and pyrolysis coupling coal gas multi-production process | |
| CN105255531B (en) | A kind of system and method for low temperature distillation coal gas preparing natural gas parallel connection hydrogen producing | |
| CN111925837A (en) | Converter gas purification treatment method | |
| CN104447195B (en) | Method for producing chemical product methanol, natural gas or synthetic oil by using calcium carbide furnace tail gas | |
| CN111348622A (en) | Preparation system and preparation method for preparing synthesis gas from carbon-rich natural gas | |
| CN210261105U (en) | Device for preparing various synthesis gases by using yellow phosphorus tail gas | |
| CN101624186B (en) | Method for synthesizing carbon monoxide by selective hydrogenation of carbon dioxide | |
| CN101717074A (en) | Double selectivity efficient sulfur recovery device | |
| CN212403458U (en) | Device for preparing hydrogen for fuel cell from yellow phosphorus tail gas | |
| CN205347354U (en) | Device of low temperature pyrolysis coal gas system natural gas and coproduction hydrogen | |
| CN213326721U (en) | Natural gas hydrogen production product purification system | |
| CN210934478U (en) | System for flue gas desulfurization and denitration are carried out with methane | |
| CN1330739C (en) | Catalytic combusticon dehydrogenation process of mine gas for producing methyl alcohol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: SOUTHWEST RESEARCH + DESIGN INSTITUTE OF CHEMICAL Free format text: FORMER NAME: SOUTHWEST RESEARCH + DESIGN INSTITUTE OF CHEMICAL INDUSTRY |
|
| CP01 | Change in the name or title of a patent holder |
Address after: No. 5 high tech Zone Gaopeng road in Chengdu city of Sichuan Province in 610041 Patentee after: SOUTHWEST RESEARCH & DESIGN INSTITUTE OF CHEMICAL INDUSTRY Address before: No. 5 high tech Zone Gaopeng road in Chengdu city of Sichuan Province in 610041 Patentee before: THE SOUTHWEST RESEARCH & DESIGN INSTITUTE OF CHEMICAL INDUSTRY |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20191224 Address after: 611430 No.777, Xinghua 10th Road, dengshuang Town, Xinjin County, Chengdu City, Sichuan Province (Industrial Park) Patentee after: HAO HUA (CHENGDU) TECHNOLOGY Co.,Ltd. Address before: No. 5 high tech Zone Gaopeng road in Chengdu city of Sichuan Province in 610041 Patentee before: SOUTHWEST RESEARCH & DESIGN INSTITUTE OF CHEMICAL INDUSTRY |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100414 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |