CN103464059A - Methanation fluidization magnetron reactor system - Google Patents
Methanation fluidization magnetron reactor system Download PDFInfo
- Publication number
- CN103464059A CN103464059A CN2012101875872A CN201210187587A CN103464059A CN 103464059 A CN103464059 A CN 103464059A CN 2012101875872 A CN2012101875872 A CN 2012101875872A CN 201210187587 A CN201210187587 A CN 201210187587A CN 103464059 A CN103464059 A CN 103464059A
- Authority
- CN
- China
- Prior art keywords
- reaction
- reactor
- adsorbent
- adsorption zone
- gas
- 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
- 238000005243 fluidization Methods 0.000 title claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 184
- 238000001179 sorption measurement Methods 0.000 claims abstract description 129
- 239000003463 adsorbent Substances 0.000 claims abstract description 107
- 239000002245 particle Substances 0.000 claims abstract description 76
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 37
- 230000003068 static effect Effects 0.000 claims abstract description 18
- 239000000376 reactant Substances 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims description 154
- 238000006243 chemical reaction Methods 0.000 claims description 128
- 239000007787 solid Substances 0.000 claims description 54
- 230000015572 biosynthetic process Effects 0.000 claims description 49
- 238000003786 synthesis reaction Methods 0.000 claims description 49
- 239000002594 sorbent Substances 0.000 claims description 36
- 230000007420 reactivation Effects 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 27
- 238000010521 absorption reaction Methods 0.000 claims description 25
- 239000012530 fluid Substances 0.000 claims description 22
- 239000005864 Sulphur Substances 0.000 claims description 19
- 239000002250 absorbent Substances 0.000 claims description 19
- 230000002745 absorbent Effects 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- 230000000694 effects Effects 0.000 claims description 15
- 239000000696 magnetic material Substances 0.000 claims description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910001566 austenite Inorganic materials 0.000 claims description 8
- 238000006477 desulfuration reaction Methods 0.000 claims description 8
- 230000023556 desulfurization Effects 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000011246 composite particle Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910003321 CoFe Inorganic materials 0.000 claims description 2
- 229910017061 Fe Co Inorganic materials 0.000 claims description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 2
- 229910003271 Ni-Fe Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims description 2
- 239000003863 metallic catalyst Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002699 waste material Substances 0.000 abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 4
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- 239000008187 granular material Substances 0.000 description 59
- 239000000047 product Substances 0.000 description 27
- 230000002051 biphasic effect Effects 0.000 description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 19
- 229910052717 sulfur Inorganic materials 0.000 description 15
- 239000011593 sulfur Substances 0.000 description 15
- 238000009826 distribution Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 208000005374 Poisoning Diseases 0.000 description 6
- 230000005307 ferromagnetism Effects 0.000 description 6
- 231100000572 poisoning Toxicity 0.000 description 6
- 230000000607 poisoning effect Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002309 gasification Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000012805 post-processing Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 206010062717 Increased upper airway secretion Diseases 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 208000026435 phlegm Diseases 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- 206010017740 Gas poisoning Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 229910052767 actinium Inorganic materials 0.000 description 1
- QQINRWTZWGJFDB-UHFFFAOYSA-N actinium atom Chemical compound [Ac] QQINRWTZWGJFDB-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005426 magnetic field effect Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000009719 regenerative response Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003469 silicate cement Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Images
Landscapes
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Separation Of Gases By Adsorption (AREA)
Abstract
The invention discloses a reactor system for producing a methane-abundant gas from a synthetic gas, and a method for using the system to produce the methane-abundant gas. The reactor system comprises: a fluidization reactor which is provided with a synthetic gas inlet at one end and a methane product abundant gas outlet at the other end, at least one reaction-adsorption zone between the synthetic gas inlet and the methane product abundant gas outlet, an adsorbent regenerator communicated with the above reactor by a waste adsorbent conveying pipeline and a regenerated adsorbent conveying pipeline; and the reaction-adsorption zone comprises a methanation catalyst and an adsorbent for adsorbing or absorbing carbon dioxide and/or a sulfide gas. By applying magnetic field, the methanation catalyst is in a basically static state relative to other flowing reactants. Waste adsorbent particles enters into the adsorbent regenerator via the waste adsorbent conveying pipeline and are regenerated in the adsorbent regenerator, and the regenerated adsorbent particles are again cycled to the reactor via the regenerated adsorbent conveying pipeline.
Description
Technical field
The present invention relates to a kind ofly by synthesis gas preparation, be rich in CH
4cH is rich in this reactor assembly production of the reactor assembly of gas and a kind of use
4the method of gas, particularly relate to a kind of wherein catalyst granules and realize with absorbent particles the methanation fluidisation magnetic control reactor assembly automatically separated.
Background technology
Methanation is to be synthetic natural gas (or instead of natural gas, key step SNG) by solid carbonaceous material, for example coal and biomass conversion.In this step, the coal and the gasification of biomass product stream (being commonly referred to synthesis gas) that are rich in carbon monoxide, carbon dioxide and hydrogen are converted into the CH that is rich in as pipe stage quality product by following reversible reaction
4gas:
Conventional methanation is based on reaction 1, and it requires H
2the mol ratio of/CO is about 3:1, and acid methanation mainly based on the reaction 2, it requires H
2the mol ratio of/CO is 1:1.With conventional methanation, compare, acid methanation possesses following advantage: 1) required H in feed gas
2still less, the unstrpped gas pretreatment therefore needed also still less; 2) some acid methanation catalyst shows high sulfidation resistance, and therefore, pre-desulfurization can be omitted in some cases; And 3) the catalyst carbon fouling that occurs in conventional methanation can not occur, catalyst life is longer thus.
Methanation reaction is reversible reaction.According to Thermodynamic Law, CO
2existence will make molecular balance move to the left, thereby make the reaction direction of carrying out be unfavorable for CH
4generation.Therefore, CO
2cH
4the inhibitor generated, it has reduced reaction rate, has also reduced the maximum conversion of product.In conventional commercial run, along with CO
2accumulation in methanation, reaction speed will slow down gradually, and the conversion ratio of product will significantly reduce.
The CO formed in acid methanation
2not only to system, bring the restriction on thermodynamics.The CO produced in methanation
2as accessory substance and CH
4be present in together in system, therefore must remove, the method for removing well known by persons skilled in the art comprises Seloxol, MDEA, lime absorption etc.This type of is CO independently
2remove or CH
4purification process has also significantly increased the totle drilling cost of methanation.Such CO
2removal is CH
4the part of product postprocessing, rather than the part of methanation itself.
It is H that the synthesis gas that gasification produces contains principal mode
2the sulphur component of S and COS, this sulphur component can make methanation catalyst poisoning, therefore must before methanation, from charging, remove.Industrial, synthesis gas has passed through the deep purifying cell processing before entering methanation, makes sulfur content be reduced to 0.1ppm.This type of deep purifying normally passes through one or more industrially desulfurized process implementations, such as Rectisol and Selexol etc.Preliminary clearning has significantly increased capital input.In addition, this type of purification method needs low temperature (room temperature or lower), so the hot synthesis gas that gasification unit is produced must lower the temperature, and this will cause energy efficiency to reduce.
US6610264 discloses a kind of method and system of removing sulphur from admixture of gas, and this system can be used to separate sulfide gas from above-mentioned raw material of synthetic gas.Simultaneously, US7713421 discloses a kind of for remove the method for some component from fluid mixture, and wherein sorbent structure can adsorb the gas component that some comprises above-mentioned sulfide gas.
Although there is high catalyst for methanation in presence of sulfur, for example comprise the catalyst for methanation in presence of sulfur of disclosed molybdenum and lanthanum element or actinium element in US5141191, the price of this type of catalyst is very high.In addition, owing to not comprising regenerative system in system, fouled catalyst accumulates in system, can cause reduction or the loss of catalyst activity and selectivity.In addition, it is fully out of service that more catalyst changeout requires system, causes thus cost to roll up.Therefore, need to find the method in extending catalyst life-span.
A kind of method that US4774261 discloses sulfur resistant catalyst and use this catalyst under the existence of sulphur.But, under these type of process conditions, excessive CO
2produce and accumulate with methanation, thereby cause chemical balance to shift to the direction with the methanation opposite direction, suppressed thus CH
4generation, limited CH
4maximum conversion rate.Therefore, in product, a large amount of unconverted synthesis gas be left behind, and calorific value reduces.In the case, necessary further purified product, so that the product of production pipe stage quality.
Except CO
2excessive accumulation and catalyst because of sulfide gas poisoning outside, also there is following problem in methanation method of the prior art.
Due to exothermic heat of reaction, low temperature is for CH
4production be favourable.As a result, for fear of the restriction on thermodynamics, wish to use the operating temperature of about 300-400 ℃ to obtain acceptable conversion ratio.But the reaction rate obtained at such temperature is lower, therefore need very large reactor and/or a large amount of recirculated water steam to complete reaction, this will significantly increase capital input.In addition, the anti-sulphur of catalyst is lowered at a lower temperature, and catalyst life is shortened thus.
Also have, the height exothermic character of reaction has improved the requirement that heat is transmitted.From equipment, for example multi-tubular heat exchanger or interstage cooler heat spread out of in reaction system, requiring must be well-designed, and this has increased complexity and the capital input of operation.
In addition, in this area, in the system of being everlasting, use heat exchanger so that reaction heat is spread out of to system, thereby control reaction temperature and produce electric power or driving device equipment by the vapours obtained.Do like this and need high reaction temperature, still, as mentioned above, high reaction temperature is but disadvantageous for reaction.
CN102040441, CN101982448, CN102371136 and CN102126906 disclose a kind of production and have been rich in CH
4the system of gas and produce and be rich in CH by this system
4the method of gas.Although said method has all been taked methanation reaction and CO
2and sulfide gas adsorbs the technical thought of simultaneously carrying out, but, aspect methanation catalyst and spent sorbents physical separation, but adopted respectively the poor use of the fluid height descending funnel that relies on methanation catalyst and spent sorbents or down pipe is separated, the method for by interlaced sandwich, being separated or being separated with monolithic structure.These separation methods have been obtained technique effect preferably, but the abrasion of methanation catalyst or loss, methanation reaction and CO
2and still may life period between sulfide gas absorption poor and methanation catalyst is non-exchange or be difficult to change and be still technical problem very important when reality is used.
All disclosures of above-mentioned document are introduced with for referencial use in full at this.
The object of the invention is in the situation that overcome the acid methanation that above one or more even all problems is implemented synthesis gas.
Summary of the invention
Inventor's discovery, above-mentioned purpose of the present invention can be by removing fast CO when methanation reaction carries out from reaction system with adsorbent
2with sulfide gas, for example H
2s and COS, and adsorbent is regenerated to realize, wherein by by modern coating technology or hybrid technology, giving methanation catalyst particle magnetic, and realize that methanation catalyst and the automatic of spent sorbents separate in the situation that apply magnetic field.
By remove CO from the methanation reaction system simultaneously
2and sulfide gas, the balance of methanation reaction is pushed to and forms CH
4an end, can obtain higher CH thus
4productive rate.This type of removal methane production of can also purifying, thereby can obtain the methane that quality is higher, and/or reduction and the methane relevant cost of purifying.In addition, remove CO simultaneously
2avoided catalyst poisoning with sulfide gas, therefore can obtain higher catalyst activity, selectively and/or longer catalyst life, and save the desulfurization pretreatment of synthesis gas, and/or can in the methanation reaction system, use the catalyst of non-anti-sulphur or low anti-sulphur.
Finally, by adsorbent reactivation, in system, the actual consumption amount of adsorbent can greatly reduce, and therefore can obtain lower cost.This enforcement for industrially scalable is especially favourable.
Remove CO from the methanation reaction system simultaneously
2with sulfide gas, can realize by such reactor assembly, it comprises reactor and at least one adsorbent reactivation device, and described reactor retains methanation catalyst therein, allows CO simultaneously
2and/or the sulfide gas adsorbent passes through reactor.By CO
2and/or the saturated spent sorbents of sulfide gas can regenerate in the adsorbent reactivation device, the adsorbent of regeneration is recycled in reactor.Methanation catalyst and fresh adsorbent can be mixed together, and, by above-mentioned specific magnetic control separating mechanism, spent sorbents can be realized separating with methanation catalyst automatically.
Thus, first aspect present invention relates to and a kind ofly by synthesis gas preparation, is rich in CH
4the reactor assembly of gas, described system comprises:
Reactor (100), described reactor (100) at one end has synthesis gas entrance (101), at the other end, has the CH of being rich in
4product gas outlet (102), in described reactor (100), have at least one reaction-adsorption zone (105) between described synthesis gas entrance (101) and described product gas outlet (102), wherein said reaction-adsorption zone (105) comprises methanation catalyst and can adsorb and/or absorb CO
2and/or the adsorbent of sulfide gas;
At least one adsorbent reactivation device (200), it is connected with described reactor (100) by spent sorbents conveyance conduit (103) and reproducing adsorbent conveyance conduit (104), the spent sorbents wherein produced in described reactor (100) enters in described adsorbent reactivation device (200) by its conveyance conduit (103), and be reproduced therein, the adsorbent be reproduced is subsequently looped back in described reaction-adsorption zone (105) again by its conveyance conduit (104); With
Magnetic field generator, for making the inner direction magnetic field contrary with reaction mass fluidisation or flow direction that produces of described reaction-adsorption zone (105),
It is characterized in that: by applying above-mentioned magnetic field, make magnetic methanation catalyst particle produce the magnetic force that direction is contrary with its fluidisation force direction, offset its fluidisation power and other flowing reactive thing motive force to it, so that its reactant mobile with respect to other in described reaction-adsorption zone (105) in substantially static state, thereby realize automatically separating of methanation catalyst particle and mobile spent sorbents particle.
Preferably; above-mentioned magnetic field generator is direct current or alternating current through therebetween and surround at least one coil of described reaction-adsorption zone (105); described magnetic field intensity is transformable along described reaction-adsorption zone (105) longitudinal direction or reaction mass fluidisation or flow direction; more preferably; described magnetic field intensity exports an end maximum at described reaction-adsorption zone (105) adsorbent; for example, to export an end at described reaction-adsorption zone (105) adsorbent be 2000-7000A/m to described magnetic field intensity; And be 300-2000A/m in other zone.
Usually, described reaction logistics comprises reactant and product, but described magnetic methanation catalyst particle particles of magnetic material, the particle that contains magnetic material or the composite particles that the magnetic material of take is core, but described methanation catalyst metallic catalyst, metal oxide catalyst and/or metal carbide catalyst, wherein the catalyst activity component can be Mo, Ni, Ru, Fe, Co, Rh, Pd, Pt, Cr and/or their oxide or carbide, and described magnetic material can be selected from least one following material: γ-Fe
3o
4, Fe
3o
4, CoFe
2o
4, MnFe
2o
4, NiFe
2o
4, Ni, Co, Fe, Fe-Co and/or Ni-Fe, described methanation catalyst is low anti-sulphur or non-sulfur resistant catalyst preferably.
Preferably, described adsorbent is selected from Ca, Zn, Cu, Fe, Mg, the oxide of Al and alkaline-earth metal or its mixture, described reaction-adsorption zone (105) comprises the fluid bed of methanation catalyst and absorbent particles, described reactor (100) can have a plurality of described reaction-adsorption zones (105), each reaction-adsorption zone (105) can be identical or different, on described reaction-adsorption zone (105), between, or under can insert one or more adsorption zones (105 '), in described reactor (100) and/or described adsorbent reactivation device (200), at least one heat exchanger (110) can be installed, pass out reactor (100) and/or adsorbent reactivation device (200) in order to will react the heat produced, in described reactor (100) and/or described adsorbent reactivation device (200), at least one cyclone cluster can be installed, the cyclone cluster cascade, and/or filter (111), so that by gas and solid dust or particle separation.
Second aspect present invention relates to a kind ofly produces and to be rich in CH by previous reaction device system
4the method of gas, described method comprises the following steps in order:
(1) will be containing CO, CO
2, H
2, sulfide gas and optional steam synthesis gas by described synthesis gas entrance (101), send in described reactor (100);
(2) synthesis gas in described reactor (100) is by described reaction-adsorption zone (105), and carries out therein methanation reaction under the catalytic action of methanation catalyst, forms CH
4and CO
2, while CO
2and/or sulfide gas is by adsorbent quick adsorption and/or absorption in described reaction-adsorption zone (105);
(3) by absorption and/or absorption and CO
2and/or sulfide gas is realized the CH that is rich in separated
4product gas leaves described reactor (100) by its outlet (102);
(4) spent sorbents leaves reactor (100) by its conveyance conduit (103), enter in described adsorbent reactivation device (200),
(5) the described spent sorbents in described adsorbent reactivation device (200) reacts under 600-1200 ℃ with oxygen flow, thereby is converted into reproducing adsorbent;
(6) described reproducing adsorbent is recycled in described reaction-adsorption zone (105) by its conveyance conduit (104).
It is characterized in that: by applying magnetic field, make magnetic methanation catalyst particle produce the magnetic force that direction is contrary with its fluidisation force direction, offset its fluidisation power and other mobile reactant motive force to it, make its reactant mobile with respect to other in described reaction-adsorption zone (105) in substantially static state, thereby realize automatically separating of methanation catalyst particle and mobile spent sorbents particle.
Preferably, above-mentioned synthesis gas is to enter reactor (100) front without the desulfurization pretreatment.
Said system of the present invention and method have the following advantages: because methanation reaction is reversible, if comprise CH
4, CO
2with the product of sulfide gas, from reaction system, removed fast, reaction rate will improve; Sulfide gas in synthesis gas is harmful to catalyst activity usually, if this type of gas can not be removed at short notice from reaction system, catalyst efficiency will be lowered, lose even fully, therefore, the synthesis gas charging must be desulfurized, or uses sulfur resistant catalyst, but sulfur resistant catalyst is expensive.System and method of the present invention not only can be used low anti-sulphur, even non-sulfur resistant catalyst, and does not need raw material of synthetic gas is carried out to the desulfurization pretreatment; By using the adsorbent CO absorption
2and sulfide gas, CH
4with CO
2be separated with sulfide gas, be rich in CH
4gas can be purer, so just make and be rich in CH
4the post processing of gas is very easy to carry out, and significantly reduces and be rich in CH
4the cost of gas post processing; Because adsorbent consumption during methanation reaction is very large, if spent sorbents is not regenerated and is recycled, the adsorbent use cost will be very high, the adsorbent reactivation device of the application of the invention, the heated oxygen-containing gas of spent sorbents is converted into the fresh adsorbent of regeneration, and the consumption of adsorbent is greatly diminished, and has also significantly reduced thus the use cost of adsorbent, for plant-scale application, this is very favorable.By by adsorbent reactivation and circulation, guaranteed that the adsorbent in the reactor is always fresh, and almost do not have spent sorbents stop and be accumulated in reactor, the activity of adsorbent is improved greatly thus, this is for the transformation that completes methanation reaction and avoid catalyst poisoning highly beneficial because of sulfide gas, because CO
2carry out the while by the while from reaction system and remove rapidly at methanation reaction with sulfide gas.In addition, due to the adsorbent that needn't change in reactor, the productivity ratio of reactor is improved greatly, and this has also significantly reduced the operation and maintenance cost.
The accompanying drawing explanation
Fig. 1 is the schematic diagram of the operating principle of explanation reactor assembly of the present invention.
Fig. 2 realizes the structural representation of reaction-adsorption zone of automatically separating at additional magnetic fields magnetic methanation catalyst particle and absorbent particles.
Fig. 3 be magnetic methanation catalyst particle weak, in, distribution figure under strong magnetic field action in gas-solid two phase materials.
Fig. 4 has shown a preferred embodiment of reactor assembly of the present invention, and wherein system comprises two reaction-adsorption zones as shown in Figure 2, three adsorption zones, and three hot heat exchangers of recovery from reactor and adsorbent reactivation device.
Fig. 5 has shown another preferred embodiment of reactor assembly of the present invention, and the technical scheme shown in itself and Fig. 4 is similar, but the fluidisation opposite direction.
The specific embodiment
Be further explained in detail the present invention by the description below with reference to accompanying drawing, but following description is only for making the general technical staff of the technical field of the invention can more be expressly understood principle of the present invention and marrow, and do not mean that the present invention is carried out to any type of restriction.That be equal in accompanying drawing or corresponding parts or feature mean by identical reference numerals.
As a generality embodiment of the present invention, with the reactor assembly that comprises reactor 100 and at least one adsorbent reactivation device 200 shown in Fig. 1, implement methanation method of the present invention.Reactor 100 is for carrying out the methanation reaction of synthesis gas, simultaneously by remove fast CO from reactor 100 with adsorbent
2and sulfide gas.Adsorbent reactivation device 200 is converted into reproducing adsorbent by spent sorbents, and it is looped back in reactor 100.
Synthesis gas can enter in the space under the reaction-adsorption zone 105 in reactor 100 by entrance 101 as pan feeding, and enters subsequently in reaction-adsorption zone 105.On the other hand, the adsorbent of fresh/regeneration is added in reaction-adsorption zone 105 by its conveyance conduit 104, at this and CO
2with the sulfide gas reaction, to catch CO
2and sulfide gas, absorption reaches saturated spent sorbents subsequently under the effect of fluidisation power, enters in the space on reaction-adsorption zone 105, and finally by its conveyance conduit 103, leaves reactor 100.Reaction-adsorption zone 105 has held catalyst granules and absorbent particles simultaneously, thereby makes methanation reaction and the CO of synthesis gas
2with the removal of sulfide gas, can carry out simultaneously.In other words, in reaction-adsorption zone 105, synthesis gas is converted into CH under the existence of methanation catalyst
4and CO
2, while CO
2be adsorbed agent quick adsorption and/or absorption with sulfide gas.
While carrying out under the catalytic action of methanation reaction at catalyst of synthesis gas, once fresh/regeneration adsorbent stream around catalyst, CO
2with sulfide gas, just by absorption or absorption, removed fast.Like this, CO
2the reaction site that realizes its catalysis from catalyst is removed, and the balance of methanation reaction is moved toward generation CH
4direction, make methanation can reach conversion ratio almost completely.Simultaneously, sulfide gas realizes that from catalyst the reaction site of its catalysis is adsorbed and removes, the anti-sulphur requirement of catalyst is reduced greatly, can in system, use thus the catalyst without anti-sulphur or low anti-sulphur, such catalyst is wanted considerably cheaper usually compared with corresponding sulfur resistant catalyst.In addition, by absorption and/or absorption, CO
2with sulfide gas from being rich in CH
4gas in be removed, can obtain the highly purified CH of being rich in like this
4gas, be rich in CH
4the purification of gaseous product will become and be more prone to, and even no longer need to be rich in CH
4the purification of gaseous product.After reaction-adsorption zone 105, can reach the unidirectional conversion ratio of reaction almost completely, so downstream CH
4the burden of purifying reduces greatly.
As discussed in detail below with reference to Fig. 4 and Fig. 5, in a reactor 100, can there are a plurality of reaction-adsorption zones 105.In the case, each reaction-adsorption zone 105 can comprise for realizing identical or different catalyst and/or the absorbent particles of identical or different function.Simultaneously, also can be on reaction-adsorption zone 105, between and under insert one or more adsorption zones 105 '.Depend on the quality of synthesis gas, the type of adsorbent and the type of catalyst, can adjust the distribution in these districts to obtain desired adsorption strength.
Other parts also can be arranged in reactor 100 to realize its function separately.For example, one or more coil pipes or multi tube heat exchanger can be installed, wherein the high-pressure boiler feed water is by wherein and produce high steam, thereby remove and utilize produced reaction heat, and also can for example, or cyclone cluster or filter wherein be installed near pipeline outlet (pipeline outlet 102), thereby gas and solid particle are separated.For example, Fig. 1 has shown to be positioned at and has been rich in CH
4near cyclone cluster 111 gas vent 102, it will be rich in CH
4gas and and spent sorbents tiny solid particle separation.
In reaction-adsorption zone 105, pretreated (for example through preheating and/or pressurization) synthesis gas is converted into CH by above-mentioned reaction 2
4and CO
2, and CO
2with by H
2the sulfide gas of S representative carries out by following reaction, being removed fast at methanation reaction simultaneously:
(reacting 5)
M can be one or more suitable metals, for example Ca, Zn, Cu, Fe, Mg, Al, alkaline-earth metal and/or its mixture.As the result of reaction 4 and 5, from the CO produced in raw material of synthetic gas and course of reaction
2with sulfide gas, reduced rapidly, particularly the amount of sulfide gas reduces to the ppm level, and adsorbent is finally by saturated and be converted into spent sorbents.
Depend on upstream process, the synthesis gas charging can obtain by the gasification of coal, coke, living beings or other carbonaceous material, or produces CO and H by known to persons of ordinary skill in the art other
2the process of mixture obtain.In a preferred embodiment of the invention, based on dry gas, synthesis gas is containing 20-70 volume %CO, 10-60 volume %H
2, maximum 60 volume %CO
2, and 0.1-10 volume %H
2s etc.The raw material of synthetic gas that system and method for the present invention is used is without carry out the desulfurization pretreatment before entering reactor.
In a preferred embodiment of the invention, reactor pressure can be 1 atmospheric pressure to 100 bar, and reaction temperature can be 100 to 900 ° of C.
The methanation catalyst that the present invention uses can be any methanation catalyst that is purchased of industrial use.This type of catalyst is known to persons of ordinary skill in the art.For example, preferred catalyst can be mixture or their hopcalites of Mo and Ni.More preferably, the catalyst that the present invention uses can be low anti-sulphur or non-catalyst for methanation in presence of sulfur.
The adsorbent that the present invention uses can be selected from those can with CO
2thereby and/or sulfide gas reacts to produce solid matter reduction CO
2and/or the material of the content of sulfide gas in reaction-adsorption zone 105.Preferred adsorbent is selected from CaO, ZnO, Fe
2o
3and composition thereof.This type of adsorbent is known to persons of ordinary skill in the art.
Adsorbent and/or catalyst can mix with inert substance and/or be shaped to given shape, for example have the particle of specified particle size.From the explanation of the following Fig. 2 of relating to and Fig. 3, can know, the character of particle, for example granularity, proportion or to the susceptibility in magnetic field, be important for implementing the present invention and obtaining good effect.Concrete which kind of character is that the mechanism in reaction-adsorption zone 105 is removed, again catalyst is retained in to important depending on by adsorbent from reaction-adsorption zone 105 simultaneously.
Preferably, as shown in Figure 1, spent sorbents leaves reactor 100 by its conveyance conduit 103 and enters the bottom of the riser 201 of adsorbent reactivation device 200 by its entrance 202, and it is risen in the renewing zone 203 that preferred form is fluid bed by hot oxygen flow.In renewing zone 203, under 600-1200 ℃, spent sorbents is regenerated as fresh adsorbent, and by refrigerating device inside, for example high-pressure boiler feed water stream through therebetween except the coiled or the multi tube heat exchanger that reduce phlegm and internal heat and produce high steam, to be cooled to suitable temperature.Reproducing adsorbent is recycled in reactor 100 by its conveyance conduit 104.The waste acid gas that regenerative process produces leaves adsorbent reactivation device 200 by pipeline 204, and available mode known to persons of ordinary skill in the art is carried out subsequent treatment to above-mentioned waste acid gas.
Spent sorbents regeneration can realize by any mode known to persons of ordinary skill in the art.Usually, regenerative response carries out in the following manner in adsorbent reactivation district 203:
(reacting 7)
As reaction 6 and 7 result, spent sorbents is reproduced and again becomes metal oxide; CO
2and SO
2after gating in office is crossed cyclone cluster and/or filter and solid fine particle is separated, leave adsorbent reactivation device 200 by its pipeline 204, and carry out further post processing by any mode known to persons of ordinary skill in the art, for example recovery of sulphur and/or carbon and separating treatment.Reproducing adsorbent is recycled in reactor 100 as fresh adsorbent by its conveyance conduit 104.
The air-flow entered in above-mentioned entrance 202 should contain the required oxygen of above-mentioned reaction 7, and be heated to and be enough to order about above-mentioned reaction 6 and 7 temperature that complete. can use the air-flow that oxygen content is 5-50%, the mixture of air or oxygen and inert gas can be used as said flow.In a preferred embodiment of the invention, use oxygen and carbon dioxide mixture as said flow, so that containing, the gas of discharging through above-mentioned pipeline 204 more easily in downstream, flutters the high-purity carbon dioxide of catching carbon. depend on the temperature of composition and the reactor 100 of said flow, the temperature of said flow is generally 300-1000 ℃
Reaction-adsorption zone 105 can possess different structures.For example, reaction-adsorption zone 105 can comprise catalyst fixed bed, and adsorbent flows through from this fixed bed.But in a preferred embodiment of the invention, use the fluid bed of catalyst and absorbent particles in reaction-adsorption zone 105, wherein by applying magnetic field, make magnetic methanation catalyst particle produce the magnetic force that direction is contrary with its fluidisation force direction, offset its fluidisation power and other flowing reactive thing motive force to it so that its reactant mobile with respect to other in described reaction-adsorption zone 105 in substantially static state.Like this, the methanation catalyst particle is retained in reaction-adsorption zone 105 under magnetic fields, other fluidisation such as magnetic spent sorbents particle of tool or mobile reaction mass do not leave reaction-adsorption zone 105, and finally leave reactor 100, thereby, realize automatically separating of methanation catalyst particle and mobile spent sorbents particle.
Fig. 2 has shown a kind of preferred embodiment of the reaction-adsorption zone 105 in Fig. 1, wherein reaction-adsorption zone 105 comprises fluid bed 106, spouted bed for example, fresh/reproducing adsorbent enters the bottom of fluid bed 106 downwards by downcomer or hollow tube (not shown), be fluidized subsequently bed upwards fluidisation quick adsorption CO wherein
2and sulfide gas.In the process of the floating movement that makes progress by fluidisation, fresh/reproducing adsorbent completes adsorption process and due to the saturated spent sorbents that becomes of absorption, finally under the effect of fluidisation power, and mobile reactant, for example CH with other
4, H
2leave reaction-adsorption zone 105, and finally leave reactor 100, and the magnetic methanation catalyst particle of tool still rests in reaction-adsorption zone 105 owing to being subject to magnetic fields to keep relatively static, unless needed to change fresh catalyst.With being rich in CH
4and H
2the product gas spent sorbents particle that leaves reaction-adsorption zone 105 through gas-solid separator, for example cyclone cluster 111, realize separating with product gas, and enter regeneration in adsorbent reactivation device 200 through its conveyance conduit 103.
Key of the present invention is to realize that the methanation catalyst particle separates with the automatic of spent sorbents particle, and the key that reaches this purpose is to make the methanation catalyst particle have stronger magnetic, so that it can be retained in reaction-adsorption zone 105 under magnetic fields, and the spent sorbents particle is subject to the effect of fluidisation power to leave reaction-adsorption zone 105 owing to not possessing magnetic or magnetic a little less than.But well-known, conventional or known methanation catalyst or do not possess magnetic, or magnetic a little less than, for example be carried in oxide carrier, as Al
2o
3, SiO
2, or TiO
2on Mo, Ni, Co, Ru, Fe, Rh, Pd and/or Cr catalyst based.Yet, by the coating technology of present maturation, form and take the composite particles that magnetic material is core, can give above-mentioned methanation catalyst particle magnetic characteristic.Through great many of experiments and theory analysis, we find: can effectively offset gas-solid biphasic reaction logistics fluidisation or the external force that flows to the motive force that wherein catalyst granules produces is the direction magnetic force contrary with above-mentioned motive force that while applying external magnetic field, magnetic catalyst granule produces.
Above-mentioned technical Analysis is that catalyst granules of the present invention is realized the theoretical foundation of automatically separating with the spent sorbents particle, but the environment in the gas-solid biphasic reaction logistics of catalyst granules in flowing is complicated, biphasic reaction logistics fluidisation or flow to the motive force of catalyst granules may be in time, place is different and different, this magnetic force of with regard to needs, offsetting above-mentioned motive force also because of this in time, place is different, compares difference when particularly there is externally-applied magnetic field in catalyst granules being distributed in gas-solid biphasic reaction logistics and do not have externally-applied magnetic field; Weak, in, under strong magnetic field action, the distribution of magnetic solid catalyst particle in gas-solid two phase materials is also different.
Fig. 3 mean the magnetic solid granulates weak, in, distribution under strong magnetic field action in gas-solid two phase materials.As shown in Figure 3, (magnetic field intensity: H=532.38A/m) under the low-intensity magnetic field effect, the magnetic solid granulates, particularly particle diameter is less, for example particle diameter is less than the particle of 150 microns is all even homogeneous distribution in gas-solid two phase materials, be the shot state, for catalyst granules, this is optimal distribution, this state can guarantee catalyst granules equal even homogeneous distribution in gas-solid biphasic reaction material, being beneficial to catalytic reaction carries out, can guarantee again when gas-solid biphasic reaction material during in fluidisation or flow regime, it is relatively static that catalyst granules can keep, or faint drift only appears, because the resistance that now the catalyst granules flow produces is less.(magnetic field intensity: H=3194.26A/m) under middle magnetic fields, the magnetic solid granulates is directional profile in gas-solid biphasic reaction material, be the chain type state, now the magnetic solid granulates is non-homogeneous and inhomogeneous distribution in gas-solid two phase materials, when the magnetic solid granulates is catalyst granules, it is difficult at gas-solid biphasic reaction goods fluid or when mobile keep relatively static, because the resistance that now the catalyst granules flow produces is larger, again due to the catalyst granules skewness, this state also is unfavorable for that catalytic reaction carries out.(magnetic field intensity: H=6388.52A/m) under strong magnetic field action, the magnetic solid granulates is in gas-solid two phase materials assembles distribution, be the poly-state of magnetic, it is least even that this state distributes the magnetic solid granulates in gas-solid two phase materials, when the magnetic solid granulates is catalyst granules, it can't keep relatively static at gas-solid biphasic reaction goods fluid or when mobile, because the resistance maximum that now the catalyst granules flow produces, this state also is most disadvantageous in catalytic reaction to carry out.Therefore, in the present invention, except the adsorbent exit of absorption-reaction zone 105, the distribution of catalyst in gas-solid biphasic reaction material should as much as possible avoid occurring chain type state and the poly-state of magnetic, and makes it remain under the shot state as far as possible.
Certainly, when gas-solid biphasic reaction material during in fluidisation or flow regime, catalyst granules wants to realize relatively static, except magnetic field intensity, also need to consider other many-sided factor, for example, the size of catalyst granules, form and density, the flow velocity of reaction logistics, solid content, gas content, form that fluid is mobile etc., only have above-mentioned factor and externally-applied magnetic field intensity to combine, acting in conjunction, form one when just in time offsetting gas-solid biphasic reaction goods fluid or flowing the motive force that catalyst granules is produced, catalyst granules could be realized relatively static.
As shown in Figure 2, comprise CO, CO
2, H
2, the synthesis gas of sulfide gas and optional steam can enter fluid bed 106 from the bottom (or top) of reaction-adsorption zone 105, and with magnetic catalyst granule 503 wherein with absorbent particles 505 is fluidized or flow, wherein magnetic catalyst granule 503 is subject to one and just in time offsets fluidisation or the mobile gas-solid biphasic reaction material motive force to it under externally-applied magnetic field 501 effect, thereby make its maintenance relatively static, and in contrast, absorbent particles 505 is owing to not having magnetic not to be subject to the effect of externally-applied magnetic field, leave reaction-adsorption zone 105 with the vapor reaction material, thereby automatically realized the physical separation of catalyst granules 503 and absorbent particles 505.
In order farthest to make, catalyst granules 503 is basic in reaction-adsorption zone 105 keeps static, in the side of reaction-adsorption zone 105 surrounding, at least one externally-applied magnetic field 501 is set, comprehensive above-mentioned other factors, the intensity of externally-applied magnetic field should make catalyst granules 503 be evenly distributed in gas-solid biphasic reaction material, and gas-solid biphasic reaction goods fluid or when mobile in relatively static state, the most desirable is in the shot state shown in Fig. 3, so farthest make catalyst granules 503 keep transfixion, guaranteed again efficiently to carry out catalytic reaction in reaction-adsorption zone 105.Although strive making catalyst granules 503 gas-solid biphasic reaction goods fluid or when mobile in relative static conditions, but the complexity due to gas-solid biphasic reaction Flow of Goods and Materials in reaction-adsorption zone 105, the reaction logistics is in zones of different, even the same area different time may have different nowed formings and distribution situation, and this makes motion or the movement of sometimes definitely stopping catalyst granules 503 is impossible.
In order to make it is all, at least that most catalyst granules 503 is in relative static conditions or faint drift only occurs, externally-applied magnetic field intensity is preferably transformable along reaction-adsorption zone 105 longitudinal directions (axial direction) or the mobile direction of reaction mass, or at reaction-adsorption zone 105 some FX, Zone Full even, magnetic field intensity in time or the difference of reactor 100 running statuses also can change.The benefit of doing like this is: when motion or mobile sign appear in magnetic solid catalyst particle; serious drift for example appears; this explanation externally-applied magnetic field gives the magnetic force of catalyst granules and gas-solid biphasic reaction Flow of Goods and Materials to unbalance between the motive force of catalyst granules; in order again to reach balance; can increase or reduce the magnetic force that gives catalyst granules by variation magnetic field intensity, and make catalyst granules get back to former position.
Sometimes, if do not reach good coupling or coordination between reactor 100 each operational factors, have few partially catalyzed agent particle 503 and be entrained with reaction-adsorption zone 105, in order to prevent this situation, as shown in Figure 2, in reaction-adsorption zone 105 adsorbent exits, the intensity of externally-applied magnetic field is set to maximum, thereby make few partially catalyzed agent particle 503 when reaching herein, being subject to powerful magnetic field force pulls back, in order to stop it to leave reaction-adsorption zone 105, to prevent the loss of catalyst granules 503.
As everyone knows, any catalyst has certain service life, after catalyst granules 503 in reaction-adsorption zone 105 has reached the inactivation in service life, just need to change fresh catalyst, at this moment, need to cancel externally-applied magnetic field, after externally-applied magnetic field gives the magnetic force disappearance of catalyst granules, spent catalyst particles is under the gas-solid biphasic reaction logistics flowed promotes, leave reaction-adsorption zone 105, and finally leave reactor 100, and fresh catalyst granules through feed arrangement from reactor 100 bottoms or top enter reaction-adsorption zone 105, and again in gas-solid biphasic reaction material, be all even homogeneous distribution states, thereby realize the original dead catalyst of online updating.Like this, the renewal of catalyst will become and be very easy to simple.
In the present invention, the generator that produces externally-applied magnetic field is that direct current or alternating current are through therebetween, and surround the coil of described reaction-adsorption zone 105, one of such magnetic field generator, but preferably a plurality of, can be formed on so the different distribution of reaction-adsorption zone 105 zones of different magnetic field intensity, in order to determine different magnetic field intensities according to operational factor and liquid form or the state of gas-solid biphasic reaction material in reaction-adsorption zone 105 zoness of different of reactor 100, especially, near the 105 adsorbent outlets of reaction-adsorption zone, maximum magnetic field intensity can be set, like this, even certain movement or drift appear in catalyst granules 503 when gas-solid biphasic reaction Flow of Goods and Materials, but when it arrives the adsorbent exit, owing to being subject to the just in time magneticaction contrary with its moving direction of powerful direction, it can't leave reaction-adsorption zone 105 with absorbent particles 505 and gaseous reactant stream, absorbent particles 505 and gaseous reactant flow can leave reaction-adsorption zone 105 unobstructedly.And, as long as catalyst granules 503 does not leave reaction-adsorption zone 105, just can, by adjusting magnetic field intensity, make catalyst granules 503 come back to original position.
To achieve these goals, magnetic field intensity can be 1000-10000A/m near reaction-adsorption zone 105 adsorbent exits or its, but is preferably 2000-7000A/m; And can be 100-3000 in other zone, but be preferably 300-2000A/m.Final magnetic field intensity depends on the operational factor of reactor, the character of reactant and product and gas-solid biphasic reaction Flow of Goods and Materials form etc.
Amid all these factors, the intensity of externally-applied magnetic field should make catalyst granules 503 be evenly distributed in gas-solid biphasic reaction material, and gas-solid biphasic reaction goods fluid or when mobile in relatively static state, the most desirable in the shot state shown in Fig. 1, so, can farthest make catalyst granules 503 keep transfixion, guarantee again efficiently to carry out catalytic reaction in reaction-adsorption zone 105.
By coating technology form take the method for the composite particles that magnetic material is core have a variety of, for example silicate cement solution, sol-gel process, microemulsion method, the precipitation method, liquid phase deposition, spray drying process, infusion process etc.Relevantly with coating technology, to form and take the ins and outs of the catalyst composite particles that magnetic material is core and please refer to prior art US2005/0116195, in order saving space, at this, to save its detailed description.All disclosures of this patent documentation are introduced with for referencial use in full at this.
In fact, form by coating technology that to take the composite particles that magnetic material is core be only one of method of giving the catalyst granules magnetic characteristic.Can also use other method, for example, catalyst fines and magnetic material powder are mixed to form to compound particles, or to take the magnetic material of inertia be carrier, by the active principle of catalyst material or active constituent loading on magnetic carrier.
Carry out methanation reaction in the reactor assembly as shown in Figure 1 with reaction-adsorption zone 105 as shown in Figure 2 before, methanation catalyst is packed in reaction-adsorption zone 105.Once you begin operation, synthesis gas (can be optionally pretreated, as preheating, precharge, pre-desulfurization) enters in fluid bed by the hole on perforated plate gas distributor (not shown).Simultaneously, absorbent particles also enters in fluid bed, and is fluidized together with catalyst granules.Methanation reaction carries out under the catalyst effect, that simultaneous reactions generates and from the CO in raw material of synthetic gas
2with with H
2the sulfide gas that S is representative is adsorbed agent quick adsorption and/or absorption.Because sulfide gas is removed rapidly by absorption and/or absorption, thereby has avoided the catalyst sulfur poisoning.
In a preferred embodiment of the invention, the granularity of absorbent particles is the 1-1000 micron, and the granularity of catalyst granules is 0.1 millimeter-1 centimetre.The temperature and pressure of reactor 100 within being applicable to the scope that methanation reaction carries out, for example 200-900 ℃ and 1 atmospheric pressure-100 bar.
Fig. 4 has shown preferred embodiment of reactor assembly of the present invention, it comprises reactor 100 and adsorbent reactivation device 200, and described reactor 100 comprises two reaction-adsorption zones as shown in Figure 2 105, three adsorption zones 105 ', three heat exchangers 110 and two gas-solid separator, for example cyclone cluster or cyclone cluster cascades 111 from wherein isolating solid fine particle before gas leaves reactor 100 and adsorbent reactivation device 200.In reaction-adsorption zone 105, the methanation reaction of synthesis gas and to CO
2and the absorption of sulfide gas occurs simultaneously, and, in adsorption zone 105 ', CO only occurs
2with the absorption of sulfide gas, further to remove CO
2and sulfide gas.Preferably, reaction-adsorption zone 105 and adsorption zone 105 ' are arranged with interlace mode as shown in Figure 4 and Figure 5, thereby remove fast CO
2and sulfide gas.Under such arrangement mode, the absorbent particles longer distance of motion of having in the fluid bed of catalyst granules and absorbent particles, thus make mixing more effective, can obtain better adsorption effect thus.Equally preferably, one of adsorption zone 105 ' is positioned at the bottom of reactor 100, thereby just is removed before making the catalyst of most of sulfide gas in running into minimum reaction-adsorption zone 105, thereby more reduces the possibility of methanation catalyst sulfur poisoning.This means and can use low anti-sulphur, the catalyst of even not anti-sulphur, and/or some specific catalyst life is extended because the catalyst poisoning probability reduces.In addition, the heat produced because of absorption in adsorption zone 105 ' can be used as thermal source synthesis gas is preheated to the acceptable temperature of methanation reaction.
Fig. 5 has shown another preferred embodiment of reactor assembly of the present invention, and the technical scheme shown in itself and Fig. 4 is similar, but the fluidisation opposite direction.In the technical scheme shown in Fig. 4, the synthesis gas entrance is positioned at reactor 100 bottoms, is rich in CH
4the product gas outlet is positioned at reactor 100 tops, like this, comprises that the goods fluid of catalyst granules, absorbent particles, reactant and product or flow direction are from top to bottom; And in contrast, in the technical scheme shown in Fig. 5, the synthesis gas entrance is positioned at reactor 100 tops, be rich in CH
4the product gas outlet is positioned at reactor 100 bottoms, like this, comprises that the goods fluid of catalyst granules, absorbent particles, reactant and product or flow direction are from top to bottom.
Although the reaction-adsorption zone 105 in Fig. 4 and Fig. 5 can be designed as the structure in Fig. 2, obviously, each reaction-adsorption zone 105 can possess other structure, and each reaction-adsorption zone 105 can and can have identical or different catalyst and/or adsorbent by independent design.
Although heat exchanger 110 forms in Fig. 4 and Fig. 5 are heat exchange medium, are preferably water, the coil pipe from flowing through therebetween, obviously also can use other form known to persons of ordinary skill in the art.When using a plurality of heat exchanger, each heat exchanger can be identical or different.Along with methanation reaction carries out in reaction-adsorption zone 105, reaction heat produces in a large number, and the temperature of reactor 100 will rise thereupon.The heat exchange medium of heat exchanger 110 of flowing through is heated, thereby produces overheated medium, and heat is migrated out in reactor 100, and the temperature of will react thus-adsorption zone 105 is controlled in suitable scope.Particularly, when heat exchange medium is water, with heat exchanger 110, except reducing phlegm and internal heat, can produce water vapour.Because methanation reaction can carry out under higher temperature, in heat exchanger 110, can produce high quality water steam.
What in reaction-adsorption zone 105, form is rich in CH
4gas before or after gas-solid separation, enter in its outlet conduit 102.This type of gas-solid separation can any mode known to persons of ordinary skill in the art be carried out, and for example uses filter, cyclone cluster or cyclone cluster cascade.
In the present invention shown in Fig. 4 and Fig. 5 more preferably in embodiment, the synthesis gas pan feeding can have the composition identical with Fig. 1 illustrated embodiment, the temperature of raw material of synthetic gas is 80-120 ° of C, pressure is the 16-24 bar, flow is 10000-16000 times of per hour catalyst active principle volume, be about 80-120kg/hr, be preferably 100kg/hr.The temperature of reactor 100 is controlled as 450-650 ℃, and pressure is controlled as the 18-22 bar.Flow is 100-140, and the adsorbent that is preferably 120kg/hr circulates between reactor 100 and adsorbent reactivation device 200.Flow is 60-120, is preferably 80-90 cube m/h 700-1100 ℃, is preferably the bottom that the hot-air of 800-1000 ℃ is blown into adsorbent reactivation device 200.
The object of the invention by removing fast CO when the synthesis gas methanation reaction carries out from reaction system
2regenerated and realized with sulfide gas with to adsorbent.When methanation reaction carries out in reactor 100, CO
2with sulfide gas by from reaction system fast, side by side remove, they are not accumulation in reaction-adsorption zone 105, therefore, as the CO of reaction suppressor
2with sulfide gas, be eliminated, reaction is carried out continuously and be there is no an impact of thermodynamic limitation.As a result, can obtain higher conversion ratio.In addition, owing to having eliminated thermodynamic limitation, can use up to 600 ℃, the reaction high temperature of 800 ℃ even, compare with conventional conditions, reaction speed is accelerated greatly, so equipment size can reduce greatly.Owing to having removed CO from reaction system
2and sulfide gas, and be rich in CH
4the relevant cost of gas purification has not existed yet.Because be easy to find non-catalyst for methanation in presence of sulfur under high temperature, so the present invention is more prone to the Choice and design catalyst.In addition, adsorbent also can reduce sulfur content, and this will significantly reduce the requirement to the anti-sulphur of catalyst, and can use low anti-sulfur materials, most of methanation catalysts of present industrial use for example.Except the high sulfidation resistance that high reaction temperature brings, catalyst life has also obtained prolongation, and running cost has obtained reduction.High reaction temperature also can provide more high quality water steam, and the high energy efficiency obtained thus.Finally, the fluid bed-type of reactor system has guaranteed that more uniform temperature distributes in reactor, and the temperature more easily the realized control and the heat management that obtain thus, and due to a large amount of heat releases of reaction, this is very difficult for traditional fixed bed reactors.
Those of ordinary skills also can use the present invention's design that retains catalyst and remove product and/or catalyst poison from reaction system in other application.For example, the product, accessory substance and/or the catalyst poison that are not limited only to reaction removed.As long as remove specific components or composition, can impel reaction further to complete, just can use the present invention.For example, if reaction only has a kind of product, rather than in above-mentioned embodiment two kinds, be CO
2and CH
4, remove this product and also can impel reaction further to complete.
Embodiment
Embodiment 1
1, preparation ferromagnetism methanation catalyst particle
(1) micron order γ-Fe
3o
4the preparation of magnetic core
To analyze pure γ-Fe
3o
4solid (being purchased from Tianjin great Mao chemical reagent factory) grinds, and is sieved with 240 orders (63 microns), cleans with distilled water, ethanol respectively afterwards, then separates with magnet, under 100 ℃, dries, and makes micron order (being less than 63 microns) γ-Fe
3o
4the sealing of magnetic core is standby.
(2) prepare 15MoO
3-15NiO/100 γ-Fe
3o
4(parts by weight) core-shell type ferromagnetism methanation catalyst particle
Under room temperature, take in proportion a certain amount of (NH
4)
4mo
7o
244H
2o and Co (NO
3)
26H
2o(all is purchased the close europeanized reagent Co., Ltd from Tianjin section)) put into appropriate distilled water, be mixed with certain density solution; Then add load weighted above-mentioned γ-Fe in proportion in this solution
3o
4magnetic core, incipient impregnation, place 24h under room temperature, natural drying after, then under 120 ℃ dry 4 hours, 450 ℃ of lower roastings 9 hours, obtain 15MoO
3-15NiO/100 γ-Fe
3o
4core-shell type ferromagnetism catalyst, roasting, by compressing tablet, pulverizing, is sieved, and getting particle diameter, to be less than the catalyst granules of 300 microns standby.
After tested, the clad ratio of above-mentioned core-shell type ferromagnetism methanation catalyst composite particles is 82.3%, and its saturation magnetization is 28.5emu/g, and pore volume is 0.032cm
3/ g, aperture is 4.3nm.Above-mentioned core-shell type ferromagnetism methanation catalyst can be used being equal to or less than at the temperature of 500 ℃.
2, carry out methanation reaction process and CO
2and the absorption of sulfide gas
Use reactor assembly as shown in Figure 4 to implement methanation method of the present invention.Catalyst is the core-shell type ferromagnetism methanation catalyst of preparation in above-mentioned steps 1, and its granularity is the 100-300 micron, and wherein 95 % by weight particles are less than 150 microns.Adsorbent is ZnO/CaO(weight) than being the mixture of 1:10, granularity is 1 micron-1 millimeter, wherein 95% particle is less than 100 microns.The granularity of catalyst and absorbent particles is determined by sieve method or specific area method.
Place equally spacedly 4 DC currents through coil therebetween along each reaction-adsorption zone 105 vertical (axially) at its sidewall periphery, thereby produce the downward stabilizing magnetic field of direction in each reaction-adsorption zone 105.In above-mentioned 4 magnetic field generators (coil), be positioned at the magnetic field intensity maximum of the magnetic field generator generation in reaction-adsorption zone 105 adsorbent exits, be about 1973.89A/m; Other three magnetic field generators produce the magnetic field that intensity is about 629.21A/m, above-mentioned magnetic field intensity can be adjusted at any time with the variation of reactor operational factor and reaction logistics composition and the type of flow, always so that catalyst granules keeps shot state as shown in Figure 3 in gas-solid biphasic reaction logistics.
Porch synthesis gas flow per hour is 10000 times of catalyst active principle volume, is about 100kg/hr.Described porch synthesis gas does not pass through the desulfurization pretreatment.Porch synthesis gas temperature is 100 ° of C, and pressure is 20 bar.Synthesis gas composition (mole) as follows:
Table 1
| H 2 | CO | CO 2 | H 2O | H 2S |
| 30% | 40% | 10% | 18% | 2% |
After synthesis gas passes through the adsorption zone 105 ' of bottom shown in Fig. 4, the sulfide gas that major part is derived from synthesis gas is removed through absorption, and its concentration is reduced to and approaches 1ppm.The thickness of reaction-adsorption zone 105 and adsorption zone 105 ' is 0.8-1.2 rice independently, and it depends on that synthesis gas passes through the speed of reaction-adsorption zone 105 and adsorption zone 105 '.
The charging of every 100mol synthesis gas finally can produce about 26.24mol with the adsorbent Adsorption CO
2and H
2the product gas that is rich in methane of S.When leaving reactor 100, it is as follows that product gas forms (volume %):
Table 2
| H 2 | CO | CH 4 | CO 2 | H 2O | H 2S |
| 0.30% | 7.68% | 62.7% | 0.02% | 29.3% | Trace |
The total conversion of CO has reached 95.1%.In the gas in exit, methane purity (butt) has surpassed 90%.Known under this type of condition, in conventional methanation method, the CO maximum conversion only reaches approximately 70%.
The term that this specification is used and form of presentation only are used as descriptive and nonrestrictive term and form of presentation, the feature that when using these terms and form of presentation, will mean and describe unintentionally or any equivalent exclusion of its part.
Although meaned and described several embodiment of the present invention, the present invention is not restricted to described embodiment.On the contrary, those of ordinary skills should recognize can carry out any accommodation and improvement to these embodiments in the situation that do not break away from principle of the present invention and essence, and protection domain of the present invention is determined by appended claim and equivalent thereof.
Claims (20)
1. one kind is rich in CH by the synthesis gas preparation
4the reactor assembly of gas, described system comprises
Reactor (100), described reactor (100) at one end has synthesis gas entrance (101), at the other end, has the CH of being rich in
4product gas outlet (102), in described reactor (100), have at least one reaction-adsorption zone (105) between described synthesis gas entrance (101) and described product gas outlet (102), wherein said reaction-adsorption zone (105) comprises methanation catalyst and can adsorb and/or absorb CO
2and/or the adsorbent of sulfide gas;
At least one adsorbent reactivation device (200), it is connected with described reactor (100) by spent sorbents conveyance conduit (103) and reproducing adsorbent conveyance conduit (104), the spent sorbents wherein produced in described reactor (100) enters in described adsorbent reactivation device (200) by its conveyance conduit (103), and be reproduced therein, the adsorbent be reproduced is subsequently looped back in described reaction-adsorption zone (105) again by its conveyance conduit (104); With
Magnetic field generator, for making the inner direction magnetic field contrary with reaction mass fluidisation or flow direction that produces of described reaction-adsorption zone (105),
It is characterized in that: by applying above-mentioned magnetic field, make magnetic methanation catalyst particle produce the magnetic force that direction is contrary with its fluidisation force direction, offset its fluidisation power and other mobile reactant motive force to it, so that its reactant mobile with respect to other in described reaction-adsorption zone (105) in substantially static state, thereby realize automatically separating of methanation catalyst particle and mobile spent sorbents particle.
2. reactor assembly according to claim 1, wherein said magnetic field generator is direct current or alternating current through therebetween and surround at least one coil of described reaction-adsorption zone (105).
3. reactor assembly according to claim 1, the intensity in wherein said magnetic field changes along described reaction-adsorption zone (105) longitudinal direction or reaction mass fluidisation or flow direction.
4. reactor assembly according to claim 3, the intensity in wherein said magnetic field exports an end maximum at described reaction-adsorption zone (105) adsorbent.
5. reactor assembly according to claim 3, it is 2000-7000A/m that the intensity in wherein said magnetic field exports an end at described reaction-adsorption zone (105) adsorbent; And be 300-2000A/m in other zone.
6. magnetic strength reactor according to claim 1, wherein said reaction logistics comprises reactant and product.
7. according to one of any described reactor assembly of claim 1-6, wherein said magnetic methanation catalyst particle is particles of magnetic material, containing the particle of magnetic material or the composite particles that the magnetic material of take is core.
8. reactor assembly according to claim 7, wherein said methanation catalyst is metallic catalyst, metal oxide catalyst and/or metal carbide catalyst.
9. magnetic strength reactor according to claim 8, wherein said catalyst activity component is Mo, Ni, Ru, Fe, Co, Rh, Pd, Pt, Cr and/or their oxide or carbide.
10. reactor assembly according to claim 7, wherein said magnetic material is selected from least one following material: γ-Fe
3o
4, Fe
3o
4, CoFe
2o
4, MnFe
2o
4, NiFe
2o
4, Ni, Co, Fe, Fe-Co and/or Ni-Fe.
11. according to one of any described reactor assembly of claim 1-6, wherein said methanation catalyst is low anti-sulphur or non-anti-sulphur.
12., according to one of any described reactor assembly of aforementioned claim 1-6, wherein said adsorbent is selected from oxide or its mixture of Ca, Zn, Cu, Fe, Mg, Al and alkaline-earth metal.
13., according to one of any described reactor assembly of claim 1-6, wherein said reaction-adsorption zone (105) comprises the fluid bed of methanation catalyst and absorbent particles.
14., according to one of any described reactor assembly of claim 1-6, wherein said reactor (100) has a plurality of described reaction-adsorption zones (105), each reaction-adsorption zone (105) is identical or different.
15. according to one of any described reactor assembly of claim 1-6, wherein on described reaction-adsorption zone (105), between or under insert one or more adsorption zones (105 ').
16. according to one of any described reactor assembly of claim 1-6, at least one heat exchanger (110) wherein is installed in described reactor (100) and/or described adsorbent reactivation device (200), in order to will react the heat produced, is passed out reactor (100) and/or adsorbent reactivation device (200).
17. according to one of any described reactor assembly of claim 1-6, at least one cyclone cluster wherein is installed in described reactor (100) and/or described adsorbent reactivation device (200), the cyclone cluster cascade, and/or filter (111), so that by gas and solid dust or particle separation.
18. reactor assembly according to claim 17, wherein on described reaction-adsorption zone (105), between or under insert one or more adsorption zones (105 ').
19. one kind with according to aforementioned claim 1-18 any one described reactor assembly production be rich in the method for CH4 gas, described method comprises the following steps in order:
(1) will be containing CO, CO
2, H
2, sulfide gas and optional steam synthesis gas by described synthesis gas entrance (101), send in described reactor (100);
(2) synthesis gas in described reactor (100) is by described reaction-adsorption zone (105), and carries out therein methanation reaction under the catalytic action of methanation catalyst, forms CH
4and CO
2, while CO
2and/or sulfide gas is by adsorbent quick adsorption and/or absorption in described reaction-adsorption zone (105);
(3) by absorption and/or absorption and CO
2and/or sulfide gas is realized the CH that is rich in separated
4product gas leaves described reactor (100) by its outlet (102);
(4) spent sorbents leaves reactor (100) by its conveyance conduit (103), enter in described adsorbent reactivation device (200),
(5) the described spent sorbents in described adsorbent reactivation device (200) reacts under 600-1200 ℃ with oxygen flow, thereby is converted into reproducing adsorbent;
(6) described reproducing adsorbent is recycled in described reaction-adsorption zone (105) by its conveyance conduit (104).
It is characterized in that: by applying magnetic field, make magnetic methanation catalyst particle produce the magnetic force that direction is contrary with its fluidisation force direction, offset its fluidisation power and other flowing reactive thing motive force to it, make its reactant mobile with respect to other in described reaction-adsorption zone (105) in substantially static state, thereby realize automatically separating of methanation catalyst particle and mobile spent sorbents particle.
20. method according to claim 19, wherein said synthesis gas is front without the desulfurization pretreatment in entering reactor (100).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210187587.2A CN103464059B (en) | 2012-06-08 | 2012-06-08 | Methanation fluidization magnetron reactor system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210187587.2A CN103464059B (en) | 2012-06-08 | 2012-06-08 | Methanation fluidization magnetron reactor system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103464059A true CN103464059A (en) | 2013-12-25 |
| CN103464059B CN103464059B (en) | 2015-05-13 |
Family
ID=49789231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210187587.2A Active CN103464059B (en) | 2012-06-08 | 2012-06-08 | Methanation fluidization magnetron reactor system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103464059B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105381876A (en) * | 2015-12-09 | 2016-03-09 | 长沙矿冶研究院有限责任公司 | Coil magnetic system capable of generating gradient weak magnetic field |
| CN106390867A (en) * | 2016-08-29 | 2017-02-15 | 孟玲 | Maintenance system of methanation fluidization magnetron reactor system |
| CN113056326A (en) * | 2018-10-01 | 2021-06-29 | 日立造船爱诺瓦Eto气体有限公司 | Fixed bed device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1152605A (en) * | 1995-12-20 | 1997-06-25 | 中国石油化工总公司石油化工科学研究院 | Saturation hydrogenating process for removing olefines from reforming produced oil |
| CN101982448A (en) * | 2010-10-19 | 2011-03-02 | 北京低碳清洁能源研究所 | Production of enriched CH4System for gas and production of CH-enriched gas using the same4Method for producing gas |
| CN102040441A (en) * | 2010-10-20 | 2011-05-04 | 北京低碳清洁能源研究所 | System for producing CH4-rich gas and method for producing CH4-rich gas with system |
| CN102126906A (en) * | 2011-01-18 | 2011-07-20 | 北京低碳清洁能源研究所 | Production of enriched CH4Reactor system for gas with monolithic channel structure and production of CH-enriched gas using the same4Method for producing gas |
| CN102371136A (en) * | 2010-12-08 | 2012-03-14 | 北京低碳清洁能源研究所 | Production of enriched CH4Reactor system for gases with coaxial closed sandwich structure and method for using the same |
-
2012
- 2012-06-08 CN CN201210187587.2A patent/CN103464059B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1152605A (en) * | 1995-12-20 | 1997-06-25 | 中国石油化工总公司石油化工科学研究院 | Saturation hydrogenating process for removing olefines from reforming produced oil |
| CN101982448A (en) * | 2010-10-19 | 2011-03-02 | 北京低碳清洁能源研究所 | Production of enriched CH4System for gas and production of CH-enriched gas using the same4Method for producing gas |
| CN102040441A (en) * | 2010-10-20 | 2011-05-04 | 北京低碳清洁能源研究所 | System for producing CH4-rich gas and method for producing CH4-rich gas with system |
| CN102371136A (en) * | 2010-12-08 | 2012-03-14 | 北京低碳清洁能源研究所 | Production of enriched CH4Reactor system for gases with coaxial closed sandwich structure and method for using the same |
| CN102126906A (en) * | 2011-01-18 | 2011-07-20 | 北京低碳清洁能源研究所 | Production of enriched CH4Reactor system for gas with monolithic channel structure and production of CH-enriched gas using the same4Method for producing gas |
Non-Patent Citations (1)
| Title |
|---|
| ZHIYONG PAN ET AL.: "Zhiyong Pan et al.", 《CHEMICAL ENGINEERING SCIENCE》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105381876A (en) * | 2015-12-09 | 2016-03-09 | 长沙矿冶研究院有限责任公司 | Coil magnetic system capable of generating gradient weak magnetic field |
| CN106390867A (en) * | 2016-08-29 | 2017-02-15 | 孟玲 | Maintenance system of methanation fluidization magnetron reactor system |
| CN113056326A (en) * | 2018-10-01 | 2021-06-29 | 日立造船爱诺瓦Eto气体有限公司 | Fixed bed device |
| CN113056326B (en) * | 2018-10-01 | 2023-10-27 | 日立造船爱诺瓦公司 | Fixed bed device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103464059B (en) | 2015-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103373706B (en) | A kind of methane reforming hydrogen production process and device | |
| US20070283812A1 (en) | System and method for removing sulfur from fuel gas streams | |
| US9296672B2 (en) | Process and plant for the production of methanol from synthesis gas rich in inerts | |
| CN103170284B (en) | Fischer-Tropsch synthesis system and process of high-temperature and high-pressure slurry bed reactor | |
| CN102040441B (en) | System for producing CH4-rich gas and method for producing CH4-rich gas with system | |
| WO2012003806A1 (en) | A fischer-tropsch synthesis process and system | |
| CN107698419B (en) | Chemical chain oxidative dehydrogenation of propane prepares the method and system of propylene | |
| CN106629600B (en) | Crude synthesis gas adsoption catalysis process for making hydrogen and its equipment | |
| CN105073952A (en) | Process for utilizing blast furnace gases, associated gases and/or biogases | |
| CN103464059B (en) | Methanation fluidization magnetron reactor system | |
| CN102371136B (en) | Production of enriched CH4Reactor system for gases with coaxial closed sandwich structure and method for using the same | |
| CN101982448B (en) | Production of enriched CH4System for gas and production of CH-enriched gas using the same4Method for producing gas | |
| CN108698816A (en) | Produce the method and system of dimethyl ether | |
| CN104549566B (en) | Catalytic conversion catalyst regenerator and renovation process | |
| CN106588526A (en) | System for preparing olefin by taking coal and refinery dry gas as raw materials and method for preparing olefin | |
| CN102773051B (en) | Process and device of fluidized bed for synthesis gas methanation | |
| CN102180757B (en) | Method for direct methanation of recirculating fluidized bed synthesis gas | |
| US2583611A (en) | Method for the synthesis of hydrocarbons in the presence of a solid adsorbent | |
| CN102070125A (en) | Reaction device for making hydrogen by adsorption-enhanced methane steam reforming and method thereof | |
| CN102464299B (en) | Method for producing hydrogen through fluidized-bed methane steam reforming | |
| KR101632888B1 (en) | Energy reduction high efficiency water gas shift reaction system | |
| CN103332650B (en) | System and method for simultaneous dry-method hydrogen production from catalytic methane decomposition and carbon dioxide separation | |
| CN103508417B (en) | Method and apparatus for producing hydrogen from bio-oil in chained mode and separating CO2 | |
| CN102126906B (en) | Production of enriched CH4Reactor system for gas with monolithic channel structure and production of CH-enriched gas using the same4Method for producing gas | |
| CN103183318B (en) | A kind of moving-bed lighter hydrocarbons producing hydrogen from steam conversion method and apparatus |
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 | ||
| ASS | Succession or assignment of patent right |
Owner name: SHENHUA GROUP CO., LTD. Free format text: FORMER OWNER: NATIONAL INSTITUTE OF CLEAN AND LOW CARBON ENERGY Effective date: 20150626 Owner name: NATIONAL INSTITUTE OF CLEAN AND LOW CARBON ENERGY Effective date: 20150626 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20150626 Address after: 100011 Beijing city Dongcheng District Binhe West Road No. 22 Shenhua building Patentee after: Shenhua Group LLC Patentee after: National Institute of Clean and Low Carbon Energy Address before: 102209, Beijing, Changping District, Xiaotangshan future technology city Shenhua low carbon 001 mailbox Patentee before: National Institute of Clean and Low Carbon Energy |
|
| CP03 | Change of name, title or address |
Address after: No. 22, diazepam West Binhe Road, Dongcheng District, Beijing, Beijing Co-patentee after: National Institute of Clean and Low Carbon Energy Patentee after: National energy investment Refco Group Ltd Address before: 100011 Shenhua building 22, West Binhe Road, Dongcheng District, Beijing Co-patentee before: National Institute of Clean and Low Carbon Energy Patentee before: Shenhua Group LLC |
|
| CP03 | Change of name, title or address | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 100011 Beijing Dongcheng District, West Binhe Road, No. 22 Patentee after: CHINA ENERGY INVESTMENT Corp.,Ltd. Patentee after: Beijing low carbon clean energy research institute Address before: 100011 Beijing Dongcheng District, West Binhe Road, No. 22 Patentee before: CHINA ENERGY INVESTMENT Corp.,Ltd. Patentee before: Beijing low carbon clean energy research institute |
|
| CP01 | Change in the name or title of a patent holder |