CN101665395A - Fluidized bed process and device for preparing methane by synthetic gas - Google Patents
Fluidized bed process and device for preparing methane by synthetic gas Download PDFInfo
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- CN101665395A CN101665395A CN200910093101A CN200910093101A CN101665395A CN 101665395 A CN101665395 A CN 101665395A CN 200910093101 A CN200910093101 A CN 200910093101A CN 200910093101 A CN200910093101 A CN 200910093101A CN 101665395 A CN101665395 A CN 101665395A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 238000000034 method Methods 0.000 title claims abstract description 58
- 230000008569 process Effects 0.000 title claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- 238000005516 engineering process Methods 0.000 claims abstract description 21
- 239000003085 diluting agent Substances 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 174
- 239000000203 mixture Substances 0.000 claims description 27
- 230000009467 reduction Effects 0.000 claims description 17
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000004480 active ingredient Substances 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 6
- 230000002093 peripheral effect Effects 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 230000002779 inactivation Effects 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000002826 coolant Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 239000003245 coal Substances 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The invention relates to fluidized bed process and device for preparing methane by a synthetic gas, belonging to the field of chemical industry technologies and equipment. The process comprises the following steps: adding catalyst and diluent into a fluidized bed reaction vessel; heating and reducing the catalyst; charging the synthetic gas into the fluidized bed reaction vessel; charging a cooling medium into a reaction vessel heat exchange component to remove reaction heat; separating to obtain a methane product; and selectively containing the online replacement of the catalyst according tothe service life of the catalyst. The fluidized bed device comprises a reaction vessel simplified body, a raw gas inlet, a gas distributor, a heat exchange component, an expanding section, a cyclone separator, a catalyst feed opening and a gas outlet and selectively comprises a catalyst recovering machine and a gas stripping machine, and the reaction vessel can be divided into at least two stages.The invention has the advantages of good heat removing ability, uniform bed layer temperature, online replacement of the catalyst, high conversion rate and selectivity, long continuous running time of the catalyst, and the like.
Description
Technical field
The present invention relates to a kind of technology and device that utilizes preparing methane by synthetic gas, relate in particular to a kind of Processes and apparatus that adopts fluidized-bed process system methane, belong to chemical industry technology and equipment technical field.
Background technology
Up to now, 1,145 hundred million tons of coal in China economically recoverables account for 13.9% of the similar reserves in the world, and coal also is the main body of primary energy source consumption in China's energy consumption structure, accounts for 70.2%.But coal resources in China concentrates on the remote districts, Midwest, and the economy of transportcapacity and process is the factor that restriction coal directly utilizes.So, have important economic implications by coal high-efficiency being converted into chemical industry novel process and the technology that is easy to by the derived energy chemical product of pipeline transportation.The coal preparing natural gas is compared with other coal chemical technologies has the flow process weak point, the capacity usage ratio height, and the water consumption is less relatively, invests characteristics such as less, while heating value of natural gas height, products of combustion pollutes little, is the clean energy that generally adopts.Coal preparing natural gas process comprises that mainly gasification obtains the process of synthetic gas: C+H
2O-CO+H
2And synthetic gas methanation: CO+3H
2-H
2O+CH
4At present, the coal gasification course in the coal preparing natural gas process has had sophisticated relatively Technology, and the full methanation process has only big plain in u.s.a company to carry out the industrial application of fixed-bed process, the domestic laboratory development that still is in abroad.Therefore, the novel process and the technology of exploitation preparing methane by synthetic gas have important application prospects.
The oil crisis of the seventies in last century has caused the research of the world to coal system synthesizing methane, and the methanation process technology of formation mainly contains: one, the methanation process of big plain in u.s.a company, H
2/ CO is adjusted to stoichiometric ratio and enters methanator after 3: 1 and carry out methanation, adopts multistage circulation insulation fix bed reactor, 30 normal atmosphere of pressure, 250～550 ℃ of temperature.Two, the methanation technology of company of Centrica, 30～60 normal atmosphere of reaction pressure, 230～700 ℃ of temperature are used the circulating fixed bed reactor of multistage.Three, rope company of Denmark Top methanation technology adopts three placed in-line insulation fix bed reactors.And domestic correlative study and industrial technology exploitation mainly are at water-gas (25%CO, 40%H
2, 10%CO
2, 25%N
2) in the part methanation of carbon monoxide: remove the deleterious CO of part, generate methane simultaneously, improve the calorific value of coal gas, this technology is used fixed bed device, adopts nickel catalyst carriedly, and carrier is Al
2O
3, TiO
2Deng, 300～350 ℃ of temperature of reaction, in the process only part, about 15% CO be converted into methane, simultaneously because methanation reaction is a strong exothermal reaction, the thermal insulation warming height, bed temperature is difficult to control, process temperature runaway problem is more outstanding.
Can learn from above analysis:
One, existing water gas methanation technology is that normal pressure and temperature of reaction are lower, is 300～350 ℃.Because methane turns to strong exothermal reaction, reaction heat is up to 206kJ/mol, and therefore effectively shifting out reaction heat is one of key issue of reactor design.When temperature of reaction was low, heat transfer temperature difference was also less, and same heat needs bigger heat interchanging area.And the synthetic gas methanation, because reactant concn height, speed of response are fast, the exothermic heat of reaction amount is big, if temperature of reaction is low, then can be little owing to heat transfer temperature difference, bed temperature is restive.In addition, because temperature is low, can not produce high-quality steam, the utilization of reaction heat is restricted.
Two, use fixed-bed reactor, exchange capability of heat is poor, and methanation still can be satisfied the heat exchange requirement to the water-gas part, but for synthetic gas full methanation process, because thermal discharge is very big, fixed bed is difficult to effectively to withdraw from reaction heat and to control bed temperature, and industry that can't experimental reactor is amplified, and carries out methanation and connect by multistage fixed bed reactor, complex process, energy utilizes low, exists facility investment big, the shortcoming that efficiency is low.
Summary of the invention
The objective of the invention is at the preparing methane by synthetic gas process type of reactor, the requirement of aspects such as heat exchange design provides a kind of fluidized-bed process and device that is applicable to preparing methane by synthetic gas.
Above-mentioned purpose of the present invention is to be achieved through the following technical solutions: a kind of fluidized-bed process of preparing methane by synthetic gas, and described technology comprises following steps:
(1) catalyzer adds formation beds in the fluidized-bed reactor, feeds gas in the inert gas replacement reactor;
(2) heatable catalyst bed temperature to 200～600 ℃ add reducing gas simultaneously and make the reduction of catalyzer original position in rare gas element;
(3) synthetic gas enters fluidized-bed reactor from the fluidized-bed reactor bottom via gas distributor, in the fluidized-bed reactor cylindrical shell or in the fluidized-bed reactor cylindrical shell heat exchange component is set;
(4) under 200～700 ℃ of temperature of reaction and 1～70 normal atmosphere, react, and heat-eliminating medium is fed heat exchange component shift out reaction heat;
(5) reacted gas flows out from the fluidized-bed reactor top, enters centrifugal station and separates, and obtains methane product.
Can carry out online replacing to decaying catalyst.Described catalyzer replacing process comprises to be exported the catalyzer of part inactivation in the fluidized-bed reactor by the decaying catalyst delivery line, simultaneously by catalyst charge pipe enter catalyst, make the catalyzer in the fluidized-bed reactor maintain a stable activity level, thereby realize the long-play of fluidized-bed reactor.
Described catalyzer is a loaded catalyst.Wherein the catalyst activity component is one or more the combination among Pd, Pt, Co, Ni, Ru, Ag, Fe, Rh and the Cu, is preferably the one or more combination among Co, Ni and the Fe, and charge capacity is 0.1～60.0%, is preferably 2～40%; More preferably 5～35%, more preferably 10～30%; Support of the catalyst is Al
2O
3, SiO
2, TiO
2, ZnO, ZrO
2, in MgO and the molecular sieve one or both, be preferably Al
2O
3Or/and SiO
2, particle diameter is 20～200 μ m, is preferably 50～100 μ m.
Can also add auxiliary agent in described loaded catalyst, auxiliary agent is oxide compound, oxyhydroxide or the salt of any metal among Na, K, Cs, Li, Mg, Zn and the Ca.
The mol ratio of carbon monoxide and hydrogen is 1: 1～1: 6 in the fluidized-bed reactor inlet synthetic gas, is preferably 1: 3～1: 5, more preferably 1: 3～1: 4.
The operation air speed is 1000～50000h
-1, be preferably 2000～30000h
-1,, 2000～20000h more preferably
-1
Temperature of reaction is 200～700 ℃, is preferably 300～600 ℃.Choosing of temperature of reaction is relevant with activity of such catalysts temperature and selectivity.
Reaction pressure is 1～70 normal atmosphere, is preferably 10～60 normal atmosphere, more preferably 20～50 normal atmosphere.
Can also add catalyst diluent in fluidized-bed reactor, to reduce the thermal discharge in the unit volume, make temperature of reaction more easy to control, reaction bed temperature is more even.Thinner is any or several mixing in aluminum oxide, silica gel, pottery and the silicon carbide, and the weight proportion of thinner and catalyzer is 0.1: 1～50: 1, is preferably 1: 1～40: 1, more preferably 2: 1～15: 1.
Fluidized-bed process for the preparing methane by synthetic gas of realizing the invention described above, the invention provides a kind of fluidizer that is used for preparing methane by synthetic gas, this device comprises fluidized-bed reactor cylindrical shell 1, be positioned at the unstripped gas inlet 2 and the gas distributor 3 of fluidized-bed bottom, in the fluidized-bed reactor cylindrical shell or fluidized-bed reactor cylindrical shell peripheral hardware replace hot member 4, be positioned at fluidized-bed reactor cylindrical shell upper extension section 5, be positioned at the cyclonic separator 6 of expanding reach, and the pneumatic outlet 7 and the catalyzer charging opening 8 that are positioned at the expanding reach top.
Fluidized-bed process for the preparing methane by synthetic gas of realizing the invention described above, the invention provides the fluidizer of another kind of synthetic gas, this device comprises fluidized-bed reactor cylindrical shell 1, be positioned at the reaction gas inlet 2 and the gas distributor 3 of fluidized-bed reactor cylindrical shell bottom, be positioned at the fluidized-bed reactor cylindrical shell and/or be positioned at the outer heat exchange component 4 of fluidized-bed reactor cylindrical shell, be positioned at fluidized-bed reactor cylindrical shell upper extension section 5, be positioned at the cyclonic separator 6 of expanding reach, be positioned at the pneumatic outlet 7 and the catalyzer charging opening 8 at expanding reach top, the catalyst recovery device 10 gentle devices 11 of carrying; Described catalyst recovery device links to each other with decaying catalyst discharge nozzle 9, and described gas is carried device and linked to each other by catalyst charge pipe 12 with fluidized-bed reactor.
In the fluidizer of two kinds of preparing methane by synthetic gas provided by the present invention, can the intravital beds of fluidized-bed reactor tube be divided into two-stage at least in the fluidized-bed reactor cylindrical shell by one or more inter-stage multihole distributor 14 is set; Described multihole distributor percentage of open area is 1～40%, is preferably 0.5～10%; Upflow tube 13 in outer upflow tube 13a of catalyzer or the catalyzer is set between not at the same level, outer upflow tube 13a of catalyzer and interior upflow tube 13 perhaps are set simultaneously.
The present invention compared with prior art has the following advantages and technique effect:
1. compare with existing water-gas part methanation technology, present technique can realize co hydrogenation methanation system methane in the coal preparing natural gas process, has expanded the technological line of coal-based clean derived energy chemical.
2. compare with fixed bed, it is remarkable that fluidized-bed of the present invention is removed heat energy power, can satisfy the heat exchange requirement of preparing methane by synthetic gas.
3. fluidized-bed process of the present invention can be realized the online replacing of catalyzer, thereby realizes the operate continuously of fluidized-bed reactor, has greatly improved process efficiency and has reduced process cost.
4. technical scheme of the present invention adopts higher temperature of reaction, and reacting the temperature difference on the one hand increases, thereby heat interchanging area reduces, and the heat exchange scheme is easier realization in industry; On the other hand, can also produce high-temperature water vapor, reaction heat is utilized effectively, improve the economy of process.
5. technical scheme of the present invention can adopt higher reaction pressure, on the one hand helps improving the selectivity of reaction, can directly be connected with the coal gasification course of High Temperature High Pressure on the one hand and carry out the preparing methane from coal process and improved process efficiency greatly.
In a word, but technical scheme provided by the invention has that reactor removes that heat energy power is good, reaction bed temperature evenly, reaction conversion ratio and selectivity height, catalyzer can onlinely be changed, the long byproduct steam of reactor continuous operating time, can carry out advantage such as large-scale production and application.
Description of drawings
Fig. 1 is a kind of example structure synoptic diagram of realizing the preparing methane by synthetic gas device of fluidized-bed process provided by the invention.
Fig. 2 is second kind of example structure synoptic diagram of realizing the preparing methane by synthetic gas device of fluidized-bed process provided by the invention.
Fig. 3 is the example structure synoptic diagram of the preparing methane by synthetic gas device of another realization fluidized-bed process provided by the invention.
1-fluidized-bed reactor cylindrical shell among the figure; 2-unstripped gas inlet; The 3-gas distributor; The 4-heat exchange component; 5-reactor expanding reach; The 6-cyclonic separator; The outlet of 7-gas reactor; 8-catalyzer charging opening; 9-decaying catalyst discharge nozzle; The 10-catalyst recovery phase; 11-gas is carried device; 12-catalyst charge pipe; Upflow tube in the 13-catalyzer; The outer upflow tube of 13a-catalyzer; Multihole distributor between the 14a-first step; Grid distributor between the 14b-second stage; 15-gas stripping gas inlet; 16-gas is put forward the device catalyst feeds
Embodiment
Describe the fluidized-bed process and the device of the preparing methane by synthetic gas of the preferred embodiment of the present invention in detail below in conjunction with accompanying drawing.
In first embodiment,, the invention provides a kind of fluidizer that is used for preparing methane by synthetic gas, as shown in Figure 1 for realizing the fluidized-bed process of preparing methane by synthetic gas of the present invention.This fluidizer comprises fluidized-bed reactor cylindrical shell 1, be positioned at the unstripped gas inlet 2 and the gas distributor 3 of fluidized-bed reactor cylindrical shell bottom, be positioned at fluidized-bed reactor upper extension section 5, be positioned at the cyclonic separator 6 of expanding reach, and the pneumatic outlet 7 and the catalyzer charging opening 8 that are positioned at the expanding reach top, and in the fluidized-bed reactor cylindrical shell or be positioned at outside the fluidized-bed reactor cylindrical shell heat exchange component 4 that is provided with.Gas distributor is used to make unstripped gas to distribute by certain mode on the fluidized-bed reactor cross section, is preferably uniform distribution on the cylindrical shell cross section.Gas distributor can adopt micropore template, porous template, blister-type, multitube type or sintering cast sparger, preferably adopts blister-type, porous template or multitube type sparger.The catalyzer cylindrical shell is used for loading catalyst.When fluidized-bed reactor operates in bubbling bed or turbulent bed zone, form the emulsion zone territory of catalyzer in the cylindrical shell bottom, the dilute phase region of catalyzer is formed at cylindrical shell top.Be positioned at 5 pairs of gas-solid two-phases of cylindrical shell upper extension section and carry out initial gross separation, the gas-solid mixture after the initial gross separation carries out further gas solid separation by cyclonic separator 6 again.The material pin of cyclonic separator inserts the emulsion zone territory of fluidized-bed, and isolated solid particulate is back in the fluidized-bed reactor cylindrical shell from the material pin of cyclonic separator, and isolated gas is from entering the centrifugal station of back after fluidized-bed reactor flows out.According to the actual needs of gas solid separation, cyclonic separator can be one-level, also can use for plural serial stage.
The technology of utilizing this fluidizer to carry out preparing methane by synthetic gas comprises following steps:
1. in fluidized-bed reactor cylindrical shell 1, add catalyzer by the catalyzer charging opening, the preferred thinner that adds, form beds, in fluidized-bed reactor, feed rare gas element by unstripped gas inlet 2 through gas distributor 3, displacement fluidized-bed reactor atmosphere also makes the catalyst bed laminarization, realizes the uniform mixing of catalyzer and thinner.Described rare gas element can be preferably nitrogen for nitrogen, helium etc.
2. in fluidized-bed reactor or the fluidized-bed reactor peripheral hardware replace hot member 4.In heat exchange component 4, feed heating medium, be preferably water vapour, beds is heated up.Feed reducing gas in the temperature-rise period in the rare gas element, reducing gas is preferably H
2, catalyzer is reduced gradually.The molar content of reducing gas in gas mixture is 1～50%, is preferably 5～20%.Temperature is brought up to final reduction temperature gradually in the reduction process, 5～50 ℃/h of heat-up rate, and final reduction temperature is 200～600 ℃.When steam temperature is lower than required Heating temperature, can on the synthetic gas feed-pipe, in addition the electric heater that goes into operation be set, be used on water vapour heating basis, further heating up.Also can be only add hot synthesis gas and make beds reach temperature required by being arranged on the electric heater that goes into operation on the synthetic gas feed-pipe.
3. after catalyst reduction finished, synthetic gas entered fluidized-bed reactor from fluidized-bed reactor bottom unstripped gas inlet 2 through gas distributor 3, makes beds be in fluidized state.Described synthetic gas is the gas mixture of CO and hydrogen, or contains CO in the gas mixture of CO and hydrogen
2, CH
4, N
2, H
2O and H
2Among the S any or several in them.
4. reaction pressure is controlled to be 1～70 normal atmosphere, and temperature of reaction is controlled to be 200～700 ℃, and synthetic gas is at the beds generation methane that reacts under this reaction pressure and temperature.Temperature of reaction and pressure are preferably 300～600 ℃ and 20～50 normal atmosphere.
5. in reaction process, heat-eliminating medium is fed the heat exchange component of fluidized-bed reactor, shift out reaction heat.Heat-eliminating medium is water or oil, is preferably water.When making water as heat-eliminating medium, water gasifies in heat exchange component and is water vapour, with the form of vaporization heat reaction heat is shifted out fluidized-bed reactor.
6. reaction back gas flows out from fluidized-bed reactor top gas outlet 7, enters centrifugal station and separates, and obtains methane product.
Below be typical experimental results:
1. work as support of the catalyst and select SiO for use
2, particle diameter 200 μ m, active ingredient is Ru, and its quality percentage composition is 0.1%, and thinner is selected silicon carbide for use, and the mass ratio of itself and catalyzer is 0.1: 1, and rare gas element uses He, and it is 20% H that reducing gas is used the hydrogen molar content
2/ He gas mixture, 300 ℃ of reduction temperatures, the percentage composition of synthetic gas mole is: 67%H
2, 22%CO, 5%CO
2, 6%H
2O, temperature of reaction is 200 ℃, when pressure is 70 normal atmosphere, air speed 5000h
-1The time, the transformation efficiency 95% of carbon monoxide, the selectivity of methane is about 100%; 2. work as carrier and select Al for use
2O
3, particle diameter 50 μ m, active ingredient is a nickel, and active ingredient quality percentage composition is 30%, and auxiliary agent is K
2CO
3, thinner is selected pottery for use, and the mass ratio of itself and catalyzer is 15: 1, and rare gas element uses N
2, reducing gas is used the H of molar percentage 5%
2/ N
2Gas mixture, 600 ℃ of reduction temperatures, the percentage composition of synthetic gas mole is: 75%H
2, 25%CO, 700 ℃ of temperature of reaction, 1 normal atmosphere of pressure, air speed 2000h
-1The time, CO transformation efficiency 99%, methane selectively 100%; 3. work as carrier and select Al for use
2O
3And SiO
2Mixture, particle diameter 20 μ m, active ingredient is a nickel, and active ingredient quality percentage composition is 60%, and auxiliary agent is MgO, and thinner is selected aluminum oxide for use, and the mass ratio of itself and catalyzer is 0.1: 1, and rare gas element uses N
2, reducing gas is used the H of molar percentage 50%
2/ N
2Gas mixture, 600 ℃ of reduction temperatures, the percentage composition of synthetic gas mole is: 50%H
2, 50%CO, 450 ℃ of temperature of reaction, normal atmosphere of pressure, air speed 30000h
-1The time, CO transformation efficiency 100%, methane selectively 50%; 4. work as carrier and select Al for use
2O
3, particle diameter 50 μ m, active ingredient is a nickel, and active ingredient quality percentage composition is 20%, and auxiliary agent is K
2O, rare gas element uses N
2, reducing gas is used the H of molar percentage 20%
2/ N
2Gas mixture, 400 ℃ of reduction temperatures, the percentage composition of synthetic gas mole is: 75%H
2, 25%CO, temperature of reaction is 450 ℃, when pressure is 30 normal atmosphere, air speed 10000h
-1The time, CO transformation efficiency 100%, methane selectively 96%.
According to another preferred embodiment of the present invention, one or more inter-stage multihole distributor 14 is set in the described fluidized-bed reactor cylindrical shell, the intravital beds of fluidized-bed reactor tube is divided into two-stage at least; In the present embodiment, grid distributor 14b between multihole distributor 14a and the second stage is set in the fluidized-bed reactor cylindrical shell between the first step, divides two-stage the intravital beds of fluidized-bed reactor tube.Described multihole distributor percentage of open area is 1～40%, is preferably 0.5～10%; Upflow tube 13a or interior upflow tube 13 outside the catalyzer are set between not at the same level, outer upflow tube 13a of catalyzer and interior upflow tube 13 perhaps are set simultaneously, as shown in Figure 2.Compare with the single-stage fluidized bed device, the multistage fluidized bed device can effectively reduce the axial backmixing of gas phase, helps reducing side reaction, improves the selectivity of reaction.
The technology of utilizing this fluidizer to carry out preparing methane by synthetic gas comprises following steps:
1. in fluidized-bed reactor cylindrical shell 1, add catalyzer by the catalyzer charging opening, the preferred thinner that adds, form beds, in fluidized-bed reactor, feed rare gas element by unstripped gas inlet 2 through gas distributor 3, displacement fluidized-bed reactor atmosphere also makes the catalyst bed laminarization, realizes the uniform mixing of catalyzer and thinner.Described rare gas element can be preferably nitrogen for nitrogen, helium etc.
2. in fluidized-bed reactor or the fluidized-bed reactor peripheral hardware replace hot member 4.In heat exchange component 4, feed heating medium, be preferably water vapour, beds is heated up.Feed reducing gas in the temperature-rise period in the rare gas element, reducing gas is preferably H
2, catalyzer is reduced gradually.The molar content of reducing gas in gas mixture is 1～50%, is preferably 5～20%.Temperature is brought up to final reduction temperature gradually in the reduction process, 5～50 ℃/h of heat-up rate, and final reduction temperature is 200～600 ℃.When steam temperature is lower than required Heating temperature, can on the synthetic gas feed-pipe, in addition the electric heater that goes into operation be set, be used on water vapour heating basis, further heating up.Also can be only add hot synthesis gas and make beds reach temperature required by being arranged on the electric heater that goes into operation on the synthetic gas feed-pipe.
3. after catalyst reduction finished, synthetic gas entered fluidized-bed reactor from fluidized-bed reactor bottom unstripped gas inlet 2 through gas distributor 3, makes beds be in fluidized state.
4. reaction pressure is controlled to be 1～70 normal atmosphere, and temperature of reaction is controlled to be 200～700 ℃, and synthetic gas is at the beds generation methane that reacts under this reaction pressure and temperature.Temperature of reaction and pressure are preferably 300～600 ℃ and 20～50 normal atmosphere.
5. in reaction process, heat-eliminating medium is fed the heat exchange component of fluidized-bed reactor, shift out reaction heat.Heat-eliminating medium is water or oil, is preferably water.When making water as heat-eliminating medium, water gasifies in heat exchange component and is water vapour, with the form of vaporization heat reaction heat is shifted out fluidized-bed reactor.
6. reaction back gas flows out from fluidized-bed reactor top gas outlet 7, enters centrifugal station and separates, and obtains methane product.
Concrete experimental result is as follows:
When carrier is selected Al for use
2O
3, particle diameter 50 μ m, active ingredient is a nickel, and active ingredient quality percentage composition is 20%, and auxiliary agent is K
2O, rare gas element uses N
2, reducing gas is used the H of molar percentage 20%
2/ N
2Gas mixture, 400 ℃ of reduction temperatures, the percentage composition of synthetic gas mole is: 75%H
2, 25%CO, temperature of reaction is 450 ℃, when pressure is 30 normal atmosphere, air speed 10000h
-1The time, the transformation efficiency of CO is near 100%, and the selectivity of methane is 98%.
According to another preferred embodiment of the invention, the fluidizer that is provided also comprises catalyst recovery device 10 and is used to carry the gas of catalyzer to carry device 11, as shown in Figure 3 except that comprising above-mentioned single-stage or multistage fluidized bed reactor.Described catalyst stripper comprises that gas carries the device cylindrical shell, the gas stripping gas 15 gentle device catalyst feeds 16 of carrying that enter the mouth.This fluidizer also comprises the decaying catalyst discharge nozzle 9 that links to each other with withdrawer with fluidized-bed reactor, the gentle catalyst charge pipe 12 that device links to each other with fluidized-bed reactor, the strength flow valve or the mechanical valve that can also be provided for regulating catalyst flow on the decaying catalyst discharge nozzle put forward.Fluidized-bed reactor, gentle device and connecting pipeline and the valve etc. carried of withdrawer are formed complete reactive system.Utilize the preparing methane by synthetic gas technology of this fluidizer to comprise that also catalyzer is carried out online replacing to be handled, make the catalyzer in the fluidized-bed reactor maintain a stable activity level, thereby realize fluidized-bed reactor operation for a long time continuously.Described catalyzer replacing process comprises that the catalyzer with part inactivation in the fluidized-bed reactor is transported to withdrawer by the decaying catalyst output tube, catalyzer is carried device catalyst feeds input gas by gas and is carried device, feeds gas stripping gas by the gas stripping gas inlet catalyzer is transported to fluidized-bed reactor by the catalyst charge pipe.
The technology of utilizing this fluidizer to carry out preparing methane by synthetic gas comprises following steps:
1. in fluidized-bed reactor cylindrical shell 1, add catalyzer by the catalyzer charging opening, the preferred thinner that adds, form beds, in fluidized-bed reactor, feed rare gas element by unstripped gas inlet 2 through gas distributor 3, displacement fluidized-bed reactor atmosphere also makes the catalyst bed laminarization, realizes the uniform mixing of catalyzer and thinner.Described rare gas element can be preferably nitrogen for nitrogen, helium etc.
2. in fluidized-bed reactor or the fluidized-bed reactor peripheral hardware replace hot member 4.In heat exchange component 4, feed heating medium, be preferably water vapour, beds is heated up.Feed reducing gas in the temperature-rise period in the rare gas element, reducing gas is preferably H
2, catalyzer is reduced gradually.The molar content of reducing gas in gas mixture is 1～50%, is preferably 5～20%.Temperature is brought up to final reduction temperature gradually in the reduction process, 5～50 ℃/h of heat-up rate, and final reduction temperature is 200～600 ℃.When steam temperature is lower than required Heating temperature, can on the synthetic gas feed-pipe, in addition the electric heater that goes into operation be set, be used on water vapour heating basis, further heating up.Also can be only add hot synthesis gas and make beds reach temperature required by being arranged on the electric heater that goes into operation on the synthetic gas feed-pipe.
3. after catalyst reduction finished, synthetic gas entered fluidized-bed reactor from fluidized-bed reactor bottom unstripped gas inlet 2 through gas distributor 3, makes beds be in fluidized state.
4. reaction pressure is controlled to be 1～70 normal atmosphere, and temperature of reaction is controlled to be 200～700 ℃, and synthetic gas is at the beds generation methane that reacts under this reaction pressure and temperature.Temperature of reaction and pressure are preferably 300～600 ℃ and 20～50 normal atmosphere.
5. in reaction process, heat-eliminating medium is fed the heat exchange component of fluidized-bed reactor, shift out reaction heat.Heat-eliminating medium is water or oil, is preferably water.When making water as heat-eliminating medium, water gasifies in heat exchange component and is water vapour, with the form of vaporization heat reaction heat is shifted out fluidized-bed reactor.
6. reaction back gas flows out from fluidized-bed reactor top gas outlet 7, enters centrifugal station and separates, and obtains methane product.
7. decaying catalyst is transported to withdrawer 10 by decaying catalyst output tube 9, and gas is carried in the device 11 catalyzer by catalyst charge pipe 12 input reactors simultaneously, guarantees the carrying out that reaction is continual and steady.
Concrete experimental result is as follows:
When carrier is selected Al for use
2O
3, particle diameter 50 μ m, active ingredient is a nickel, and active ingredient quality percentage composition is 20%, and rare gas element uses N
2, reducing gas is used the H of molar percentage 20%
2/ N
2Gas mixture, 400 ℃ of reduction temperatures, the percentage composition of synthetic gas mole is: 75%H
2, 25%CO, temperature of reaction is 450 ℃, when pressure is 30 normal atmosphere, air speed 10000h
-1, by the online replacing of catalyzer, move 1000h continuously simultaneously, the transformation efficiency 100% of CO, the selectivity of methane is 98%.
The present invention is not limited to above embodiment.
Claims (10)
1. the fluidized-bed process method of a preparing methane by synthetic gas is characterized in that described technology carries out as follows:
(1) catalyzer is added forms beds in the fluidized-bed reactor, feed gas in the inert gas replacement reactor;
(2) heatable catalyst bed temperature to 200～600 ℃ add reducing gas simultaneously and make the reduction of catalyzer original position in rare gas element;
(3) synthetic gas enters fluidized-bed reactor from the fluidized-bed reactor bottom via gas distributor, in the fluidized-bed reactor cylindrical shell or fluidized-bed reactor cylindrical shell peripheral hardware replace hot member, described synthetic gas is the gas mixture of CO and hydrogen, or contains CO in the gas mixture of CO and hydrogen
2, CH
4, N
2, H
2O and H
2Among the S any or several in them.
(4) under 200～700 ℃ of temperature of reaction and 1～70 normal atmosphere, react, and heat-eliminating medium fed shift out reaction heat in the heat exchange component;
(5) reacted gas flows out from the fluidized-bed reactor top, enters centrifugal station and separates, and obtains methane product.
2. the fluidized-bed process method of a kind of preparing methane by synthetic gas according to claim 1 is characterized in that: described fluidized-bed process also comprises to be handled the online replacing of catalyzer; Described catalyzer replacing process comprises that the catalyzer with part inactivation in the fluidized-bed reactor is transported to withdrawer by the decaying catalyst delivery line, and catalyzer is transported to fluidized-bed reactor by the catalyst charge pipe.
3. the fluidized-bed process method of a kind of preparing methane by synthetic gas according to claim 1, it is characterized in that: described catalyzer is a loaded catalyst, wherein the catalyst activity component is one or more the combination among Pd, Pt, Co, Ni, Ru, Ag, Fe, Rh and the Cu, and the quality percentage composition of active ingredient is 0.1～60.0%; Support of the catalyst is Al
2O
3, SiO
2, TiO
2, ZnO, ZrO
2, in MgO and the molecular sieve one or both, the support of the catalyst particle diameter is 20～200 μ m.
4. the fluidized-bed process method of a kind of preparing methane by synthetic gas according to claim 3, it is characterized in that: add auxiliary agent in described loaded catalyst, auxiliary agent is oxide compound, oxyhydroxide or the salt of any one or two kinds of metals among Na, K, Cs, Li, Mg, Zn and the Ca.
5. the fluidized-bed process of a kind of preparing methane by synthetic gas according to claim 1, it is characterized in that: the mole proportioning of carbon monoxide and hydrogen is 1: 1～1: 6 in the described synthetic gas, the operation air speed is 1000～50000h
-1
6. the fluidized-bed process of a kind of preparing methane by synthetic gas according to claim 1, it is characterized in that: in fluidized-bed reactor, also add catalyst diluent, the weight proportion of thinner and catalyzer is 0.1: 1～50: 1, and thinner is any or several mixing in aluminum oxide, silica gel, pottery and the silicon carbide.
7. realize the fluidizer of the preparing methane by synthetic gas of fluidized-bed process according to claim 1 for one kind, it is characterized in that: this device comprises fluidized-bed reactor cylindrical shell (1), be positioned at unstripped gas inlet (2) and the gas distributor (3) of fluidized-bed bottom, in the fluidized-bed reactor cylindrical shell or fluidized-bed reactor cylindrical shell peripheral hardware replace hot member (4), be positioned at fluidized-bed reactor cylindrical shell upper extension section (5), be positioned at the cyclonic separator (6) of expanding reach, and the pneumatic outlet (7) and the catalyzer charging opening (8) that are positioned at the expanding reach top.
8. according to the fluidizer of the preparing methane by synthetic gas of the described fluidized-bed process of claim 7, it is characterized in that: one or more inter-stage multihole distributor (14) is set in the described fluidized-bed reactor cylindrical shell, the intravital beds of fluidized-bed reactor tube is divided into two-stage at least; Described multihole distributor percentage of open area is 1～40%; Upflow tube (13) in outer upflow tube (13a) of catalyzer or the catalyzer is set between not at the same level, outer upflow tube (13a) of catalyzer and interior upflow tube (13) perhaps are set simultaneously.
9. a realization is as the fluidizer of the preparing methane by synthetic gas of fluidized-bed process as described in the claim 2, it is characterized in that: this device comprises fluidized-bed reactor cylindrical shell (1), be positioned at unstripped gas inlet (2) and the gas distributor (3) of fluidized-bed reactor cylindrical shell bottom, the heat exchange component (4) that is provided with in the fluidized-bed reactor cylindrical shell or outside the fluidized-bed reactor cylindrical shell, be positioned at fluidized-bed reactor cylindrical shell upper extension section (5), be positioned at the cyclonic separator (6) of expanding reach, be positioned at the pneumatic outlet (7) and the catalyzer charging opening (8) at expanding reach top, and the gentle device (11) of carrying of catalyst recovery device (10); Described catalyst recovery device links to each other with the fluidized-bed reactor cylindrical shell by decaying catalyst output tube (9), and described gas is carried device and linked to each other by catalyst charge pipe (12) with the fluidized-bed reactor cylindrical shell.
10. according to the fluidizer of the preparing methane by synthetic gas of the described fluidized-bed process of claim 9, it is characterized in that: one or polylith inter-stage multihole distributor (14a are set in the described fluidized-bed reactor cylindrical shell, 14b), the intravital beds of fluidized-bed reactor tube is divided at least two sections; The percentage of open area of described inter-stage multihole distributor is 1～40%; Upflow tube outside the catalyzer (13a) or interior upflow tube (13) are set between not at the same level, outer upflow tube (13a) of catalyzer and interior upflow tube (13) perhaps are set simultaneously.
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