CN101301611A - Sulfur-tolerance deoxidation catalyst and preparation and use thereof - Google Patents
Sulfur-tolerance deoxidation catalyst and preparation and use thereof Download PDFInfo
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Abstract
The invention discloses a sulfur-tolerant deoxidizing catalyst, preparation method and application thereof. The catalyst of the invention is composed of active components and porous carriers, the active components are one or more of compound of iron and/or copper, the porous carriers are selected from one or more of aluminium oxide, titanium oxide, zirconium oxide, zinc oxide, magnesium oxide, calcium oxide, silicon dioxide, aluminophosphate molecular sieves, A type molecular sieves, X type molecular sieves, Y type molecular sieves, mordenite, ZSM-5 zeolite, kieselguhr, kaoline, natural clay, aluminum silicate and magnesium silicate. Based on the oxide content, the active components loading amount is 1-95% by weight, the rest are porous carriers. The catalyst of the invention has definite sulfur-tolerant performance, is suitable for deoxidation treatment of coal seam gas with oxygen content of 3-6% (V/V), and can deoxidize the coal seam gas to make the oxygen content less than 0.5%.
Description
Technical field
The present invention relates to a kind of catalyst, particularly a kind of sulfur-tolerance deoxidation catalyst and preparation method thereof and the application in oxygen-containing coal bed gas deoxidation.
Background technology
Coal bed gas is present in the coal seam in a large number, belongs to unconventional natural gas; It is the one of the main reasons that causes the colliery down-hole accident.In fact coal bed 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 pressure and the wasting of resources to about 300 billion cubic meters of airborne release coal bed gas every year.Coal bed gas is rationally fully utilized, can remedy China's energy shortage.The recycling of coal bed gas simultaneously also helps the protection ring border, and the greenhouse effects of methane are CO
2More than 20 times, a large amount of coal bed gas enters atmosphere and has aggravated Global Greenhouse Effect.Therefore, the poor efficiency of coal bed 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 method separation and concentration methane from coal bed gas in the Chinese patent ZL85103557 " methane in the pressure swing adsorption method enrichment coal mine mash gas " of application in 1985.Generally speaking, the oxygen content 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 explosion limit 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 bed 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 content in the coal bed gas below 0.5%, propose the safety operation of dense process to guarantee subsequent technique.
Employed catalyst was noble metal catalysts such as Pt or Pd during Chinese patent ZL02113628.9 " produced the catalytic combustion deoxidization process of methyl alcohol with coal mine mash gas ", the advantage of this type of catalyst is the catalytic activity height, reaction temperature 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 catalyst costs an arm and a leg, contain sulfide in the coal bed gas simultaneously, thereby toxic effect causes catalysqt deactivation and sulphur is to noble metal, therefore will carry out desulfurization before deoxidation earlier carries out deoxygenation again, cause the deoxidation cost to increase like this, caused the disposal cost of coal bed 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 disposal cost 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.
In view of precious metal catalyst deoxidation and coke method deoxidation shortcoming separately, develop a kind of base metal sulfur-tolerance deoxidation catalyst and be undoubtedly a kind of optimal selection, have very big market prospects simultaneously.
Summary of the invention
The objective of the invention is in order to overcome above shortcomings in the prior art, a kind of new base metal sulfur-tolerance deoxidation catalyst is provided.
Another object of the present invention provides the preparation method of above-mentioned sulfur-tolerance deoxidation catalyst.
The 3rd purpose of the present invention provides the application of this sulfur-tolerance deoxidation catalyst in oxygen-containing coal bed gas deoxidation, makes coalbed methane containing oxygen need not to carry out earlier desulfurization and handles, and can directly enter deoxidation in the deoxidation reactor, thereby reduce disposal cost, and simplify processing step.
Sulfur-tolerance deoxidation catalyst of the present invention, form by active component and porous carrier, described active component is an iron or/and any one or a few in the compound of copper, and described porous carrier is selected from any one or a few in aluminium oxide, titanium oxide, zirconia, zinc oxide, magnesia, calcium oxide, silica, phosphate aluminium molecular sieve, A type molecular sieve, X type molecular sieve, Y zeolite, modenite, ZSM-5 zeolite, diatomite, kaolin, natural clay, alumina silicate, the magnesium silicate; Wherein, in oxide, the percentage by weight of active component is 1～95%, is preferably 5～70%, and all the other are porous carrier.
The preferred iron of described active component is or/and the oxide of copper or salt.
Described active component be preferably iron or/and copper soluble-salt such as chloride, nitrate or sulfate.
The preparation method of above-mentioned sulfur-tolerance deoxidation catalyst can adopt mixing method.Mixing method prepares sulfur-tolerance deoxidation catalyst and may further comprise the steps:
(1) active constituent compound is mixed in proportion with porous carrier;
(2) with the mixture of step (1) by compressing tablet, spin or extruded moulding, 120 ℃ dry 1～2 hour down, 400～500 ℃ of following roastings 4～5 hours make sulfur-tolerance deoxidation catalyst.
The active component of above-mentioned sulfur-tolerance deoxidation catalyst is an iron or/and when the soluble-salt of copper such as chloride, nitrate or sulfate, can adopt immersion process for preparing, may further comprise the steps:
(1) the active component soluble-salt is made into the aqueous solution of any concentration;
(2) porous carrier is immersed in the active component solution of step (1) configuration, normal temperature flooded 6～12 hours down;
(3) with the mixture of step (2) by spin or extruded moulding, 120 ℃ dry 1～2 hour down, 400～500 ℃ of following roastings 4～5 hours can make sulfur-tolerance deoxidation catalyst of the present invention.
The moulding of above-mentioned sulfur-tolerance deoxidation catalyst can be made multiple shapes such as spherical, strip, column, sheet, ring-type.
Sulfur-tolerance deoxidation catalyst of the present invention is the deoxidation treatment of the coal bed gas of 1～12% (V/V) applicable to oxygen content, be specially adapted to oxygen content and be the deoxidation treatment of 3～6% coal bed gas, can regulate the oxygen content that enters reactor, unstripped gas air speed 1000～6000h by regulating circulating air
-1, reaction temperature is 200～750 ℃, reaction temperature is preferably 300～650 ℃, the oxygen in the coal bed gas can be taken off after the reaction to less than 0.5%.
Key reaction in the deoxidation process of coalbed methane containing oxygen is:
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 by in the unstripped gas of the cooled gas of cyclic part deoxidation to the deoxidation, adjusting enters the oxygen content of reactor to optimum range, can effectively reaction temperature be controlled in the optimum range, range of reaction temperature is 200～750 ℃, is preferably 300～650 ℃.
Reaction velocity in the above-mentioned deoxidation reactor can be preferably 1000～6000h
-1
Compared with prior art, the invention has the beneficial effects as follows:
(1) compare with noble metal catalyst catalytic deoxidation method, sulfur-resistant catalytic deoxidization process of the present invention is owing to select non-precious metal catalyst for use, and the catalyst price declines to a great extent; The used sulfur resistant catalyst of the present invention simultaneously has certain sulfur tolerance, the coal bed gas sulfur content≤10mg/m in general colliery
3, can be with the method without pre-desulfurization, thereby saved the expense of pre-desulfurization link.
(2) compare with the coke deoxidization method, sulfur-resistant catalytic deoxidization process of the present invention is not because the methane reaction in oxygen and the coal bed gas needs to consume coke resource, but energy savings; And technological process of the present invention is easier, and easy and simple to handle, equipment is simple, is convenient to automatic control, and its operating 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 content after the deoxidation in the coal bed gas has reduced to below 0.5%, the total gas flow in back that dewaters reduces to some extent, thus after the deoxidation in the gas component relative amount 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.
The specific embodiment
The present invention is described in further detail below in conjunction with the specific 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
The spherical sulfur-tolerance deoxidation catalyst of present embodiment, active component by 20% and 80% porous carrier are formed, and promptly are made up of the oxide of 20% copper, 40% magnesia and 40% titanium oxide, are named doc1.
The preparation method of the spherical sulfur-tolerance deoxidation catalyst of present embodiment is:
(1) 18g cuprous oxide (being equivalent to the 20g cupric oxide) and 40g magnesia and 40g titanium oxide are mixed;
(2) with the mixture of step (1) by roller forming, in 120 ℃ dry 1～2 hour down, 400～500 ℃ of following roastings 4～5 hours can make spherical sulfur-tolerance deoxidation catalyst.
Embodiment 2
The sheet sulfur-tolerance deoxidation catalyst of present embodiment, active component by 40% and 60% carrier are formed.58g ferrous carbonate (being equivalent to the 40g iron oxide), 10g zirconia, 30g aluminium oxide and 20g diatomite are mixed, compression molding, in 120 ℃ dry 1～2 hour down, 400～500 ℃ of following roastings 4～5 hours, can make the sulfur-tolerance deoxidation catalyst of sheet, be named doc2.
Embodiment 3
The strip sulfur-tolerance deoxidation catalyst of present embodiment, active component by 70% and 30% carrier are formed.42g basic copper carbonate (being equivalent to the 30g cupric oxide), 40g di-iron trioxide, 30g zinc oxide are mixed, extruded moulding, in 120 ℃ dry 1～2 hour down, 400～500 ℃ of following roastings 4～5 hours, can make the sulfur-tolerance deoxidation catalyst of strip, be named doc3.
Embodiment 4
The column sulfur-tolerance deoxidation catalyst of present embodiment, active component by 95% and 5% carrier are formed.95g di-iron trioxide, 5g silica are mixed, are pressed into column, in 120 ℃ dry 1～2 hour down, 400～500 ℃ of following roastings 4～5 hours can make the sulfur-tolerance deoxidation catalyst of strip, are named doc4.
Embodiment 5
The ring-type sulfur-tolerance deoxidation catalyst of present embodiment, active component by 50% and 50% carrier are formed.20g iron oxide, 28g basic copper carbonate (being equivalent to the 20g cupric oxide) and 14.5g ferrous carbonate (being equivalent to the 10g iron oxide) and 50g phosphate aluminium molecular sieve are mixed, be pressed into ring-type, drying is 1～2 hour under 120 ℃, 400～500 ℃ of following roastings 4～5 hours, can make the sulfur-tolerance deoxidation catalyst of strip, be named doc5.
Embodiment 6
The strip sulfur-tolerance deoxidation catalyst of present embodiment is made up of the carrier of 1% active component and 99%, is that 1% ferric nitrate and 50% calcium oxide and 49% alumina silicate are formed by being equivalent to iron oxide promptly, is named doc6.
The preparation method of the sulfur-tolerance deoxidation catalyst of present embodiment is:
(1) 5.1g nine water ferric nitrates (being equivalent to the 1g iron oxide) is dissolved in the 98g water, is made into the aqueous solution;
(2) 50g calcium oxide and 49g alumina silicate carrier are immersed in the active component aqueous solution of step (1) configuration, normal temperature flooded 6～12 hours down;
(3) with the mixture extruded moulding of step (2), 120 ℃ dry 1～2 hour down, 400～500 ℃ of following roastings 4～5 hours can make the strip sulfur-tolerance deoxidation catalyst of present embodiment.
Embodiment 7
The sulfur-tolerance deoxidation catalyst of present embodiment is made up of the carrier of 5% active component and 95%, is that 5% nitrate trihydrate copper and 95% carrier are formed by being equivalent to cupric oxide promptly.15g nitrate trihydrate copper (being equivalent to the 5g cupric oxide) is mixed with the aqueous solution, the 95g modenite is immersed in the aqueous solution of active component, normal temperature flooded 6～12 hours down, compression moulding, drying is 1～2 hour under 120 ℃, 400～500 ℃ of following roastings 4～5 hours are made column with catalyst, are named doc7.
Embodiment 8
The sulfur-tolerance deoxidation catalyst of present embodiment is made up of the carrier of 18% active component and 82%, is 3% nine water ferric nitrates by being equivalent to iron oxide promptly, to be equivalent to cupric oxide be that 15% nitrate trihydrate copper, 52% aluminium oxide and 30% kaolin are formed.15.3g nine water ferric nitrates, 45g nitrate trihydrate copper are mixed with the aqueous solution, 52g aluminium oxide and 30g kaolin are immersed in the aqueous solution of active component, normal temperature flooded 6～12 hours down, can make after drying, the roasting after the compression moulding, was named doc8.
Embodiment 9
The sulfur-tolerance deoxidation catalyst of present embodiment, its preparation method is identical with embodiment 6, its active component is made up of 10g iron chloride, 10g ferrous sulfate and 10g copper chloride, carrier is made up of 40gSM-5 zeolite and 50g natural clay, carrier is immersed in the aqueous solution of active component and flooded 6～12 hours, be pressed into strip, can make after drying, the roasting, be named doc9.
Embodiment 10
The sulfur-tolerance deoxidation catalyst of present embodiment, its preparation method is identical with embodiment 6, and its active component is a 10g copper sulphate, and carrier is made up of 30g magnesium silicate, 30g A type molecular sieve and 30g X type molecular sieve, and catalyst is made strip, is named doc10.
Embodiment 11
Present embodiment is the application of sulfur-tolerance deoxidation catalyst of the present invention in the deoxidation treatment of coalbed methane containing oxygen.
Directly send in deoxidation reactor after by the preheater preheating raw material coalbed methane containing oxygen, under normal pressure, uniform temperature and air speed condition, in beds, methane in the coal bed gas and oxygen reaction generate carbon dioxide and water, 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 coal bed gas.
Methane and oxygen reaction are strong exothermal reaction, and per 1% oxygen and methane reaction liberated heat adiabatic temperature rise are 95～100 ℃, therefore, for the unlikely too high methane cracking loss that causes of control reaction temperature, need the unstripped gas Control for Oxygen Content 3～6%.When raw material coal bed gas oxygen content is higher than 6%, can be by in the raw material coal bed gas of the cooled coal bed gas of cyclic part deoxidation to the deoxidation, regulate enter reactor oxygen content to optimum range, thereby reach the purpose of deoxidation and temperature control.
Different model catalyst activity property testing concrete outcome sees Table 1, and the unstripped gas oxygen content is 3～6%, sulfur content 15～20mg/m
3, methane content is 70～85%, all the other are nitrogen, unstripped gas air speed 1000～6000h
-1, the catalytic deoxidation reaction temperature is 300～650 ℃, loaded catalyst 100ml.
Table 1
| The catalyst numbering | Unstripped gas oxygen content % | Unstripped gas total sulfur content mg/m 3 | Deoxidation temperature ℃ | Unstripped gas air speed h -1 | Tail gas oxygen content % |
| doc1 | 6.01 | 18.83 | 445 | 2000 | 0.17 |
| doc2 | 4.14 | 15.64 | 504 | 3800 | 0.35 |
| doc3 | 5.53 | 8.61 | 300 | 1800 | 0.09 |
| doc4 | 4.07 | 5.79 | 390 | 2500 | 0.14 |
| doc5 | 3.70 | 10.21 | 563 | 6000 | 0.26 |
| doc6 | 3.01 | 6.42 | 650 | 1000 | 0.38 |
| doc7 | 3.98 | 13.55 | 479 | 1500 | 0.32 |
| doc8 | 5.25 | 9.67 | 587 | 4500 | 0.26 |
| doc9 | 4.34 | 10.51 | 629 | 3700 | 0.12 |
| doc10 | 4.66 | 7.65 | 569 | 1800 | 0.21 |
Claims (7)
1, a kind of sulfur-tolerance deoxidation catalyst, form by active component and porous carrier, it is characterized in that: described active component is that iron is or/and one or more in the compound of copper, described porous carrier is selected from aluminium oxide, titanium oxide, zirconia, zinc oxide, magnesia, calcium oxide, silica, phosphate aluminium molecular sieve, A type molecular sieve, X type molecular sieve, Y zeolite, modenite, the ZSM-5 zeolite, diatomite, kaolin, natural clay, alumina silicate, in the magnesium silicate one or more, in oxide, the weight percentage of active component is 1～95%, and all the other are carrier.
2, sulfur-tolerance deoxidation catalyst according to claim 1 is characterized in that: the weight percentage of described active component is 5～70%.
3, sulfur-tolerance deoxidation catalyst according to claim 1 is characterized in that: described active component is an iron or/and the oxide of copper or in the salt one or more.
4, sulfur-tolerance deoxidation catalyst according to claim 3 is characterized in that: described active component is that iron is or/and one or more in the chloride of copper, nitrate or the sulfate.
5, the preparation method of the described sulfur-tolerance deoxidation catalyst of a kind of claim 4 is characterized in that this method may further comprise the steps:
(1) active component is mixed with the aqueous solution of any concentration;
(2) porous carrier is immersed in the active component solution of step (1) preparation, normal temperature flooded 6～12 hours down;
(3) with the mixture of step (2) by spin or extruded moulding, in 120 ℃ dry 1～2 hour down, 400～500 ℃ of following roastings 4～5 hours can make sulfur-tolerance deoxidation catalyst of the present invention.
6, the preparation method of the described sulfur-tolerance deoxidation catalyst of a kind of claim 1～4 is characterized in that may further comprise the steps:
(1) active constituent compound is mixed in proportion with porous carrier;
(2) with the mixture of step (1) by compressing tablet, spin or extruded moulding, 120 ℃ dry 1～2 hour down, 400～500 ℃ of following roastings 4～5 hours make sulfur-tolerance deoxidation catalyst.
7, according to the application of the described sulfur-tolerance deoxidation catalyst of claim 1～4 in coalbed methane containing oxygen, it is characterized in that: described sulfur-tolerance deoxidation catalyst is applied to the deoxidation treatment that oxygen content is 3～6% coal bed gas, and the unstripped gas air speed is 1000～6000h
-1, the temperature of catalytic deoxidation reaction is 300～650 ℃.
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| CN115301246A (en) * | 2022-09-06 | 2022-11-08 | 中晶环境科技股份有限公司 | Method for removing oxygen in hydrogen sulfide-containing gas and application of catalyst |
| CN115301246B (en) * | 2022-09-06 | 2024-08-30 | 中晶环境科技股份有限公司 | Method for removing oxygen in gas containing hydrogen sulfide and application of catalyst |
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