CN101982448B - Production of enriched CH4System for gas and production of CH-enriched gas using the same4Method for producing gas - Google Patents
Production of enriched CH4System for gas and production of CH-enriched gas using the same4Method for producing gas Download PDFInfo
- Publication number
- CN101982448B CN101982448B CN201010516312.XA CN201010516312A CN101982448B CN 101982448 B CN101982448 B CN 101982448B CN 201010516312 A CN201010516312 A CN 201010516312A CN 101982448 B CN101982448 B CN 101982448B
- Authority
- CN
- China
- Prior art keywords
- adsorbent
- reactor
- zone
- gas
- synthetic 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.)
- Active
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000003463 adsorbent Substances 0.000 claims abstract description 155
- 239000003054 catalyst Substances 0.000 claims abstract description 68
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000007789 gas Substances 0.000 claims description 155
- 238000006243 chemical reaction Methods 0.000 claims description 101
- 239000002594 sorbent Substances 0.000 claims description 84
- 230000007420 reactivation Effects 0.000 claims description 35
- 239000005864 Sulphur Substances 0.000 claims description 22
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 238000001179 sorption measurement Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- 229920006395 saturated elastomer Polymers 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002250 absorbent Substances 0.000 claims description 9
- 230000002745 absorbent Effects 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 238000006477 desulfuration reaction Methods 0.000 claims description 8
- 230000023556 desulfurization Effects 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- 238000002203 pretreatment Methods 0.000 claims description 7
- 230000008929 regeneration Effects 0.000 claims description 7
- 238000011069 regeneration method Methods 0.000 claims description 7
- 230000004888 barrier function Effects 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 238000002360 preparation method Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 208000005374 Poisoning Diseases 0.000 description 5
- 235000011089 carbon dioxide Nutrition 0.000 description 5
- 231100000572 poisoning Toxicity 0.000 description 5
- 230000000607 poisoning effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 206010062717 Increased upper airway secretion Diseases 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009395 breeding Methods 0.000 description 2
- 230000001488 breeding effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 208000026435 phlegm Diseases 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance 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
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 239000002253 acid Substances 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
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 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
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000009719 regenerative response Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/005—Separating solid material from the gas/liquid stream
- B01J8/0055—Separating solid material from the gas/liquid stream using cyclones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0207—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly horizontal
- B01J8/0221—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly horizontal in a cylindrical shaped bed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/12—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by gravity in a downward flow
- B01J8/125—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by gravity in a downward flow with multiple sections one above the other separated by distribution aids, e.g. reaction and regeneration sections
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
- B01J8/26—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with two or more fluidised beds, e.g. reactor and regeneration installations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
- B01J8/32—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with introduction into the fluidised bed of more than one kind of moving particles
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00115—Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/02—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles
- B01J2208/023—Details
- B01J2208/024—Particulate material
- B01J2208/025—Two or more types of catalyst
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Gas Separation By Absorption (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for producing rich CH from synthesis gas4System for gas and production of CH-enriched gas using the same4A method of producing a gas. The system includes a reactor including a syngas inlet at one end thereof and a CH-rich adsorbent at the other end thereof, and at least one adsorbent regenerator4A gas outlet, at least one in the reactor, N at the syngas inlet and rich in CH4Between the gas outletsN +1 methanation catalyst regions are arranged crosswise with the methanation catalyst regions and can absorb CO2And an adsorbent zone for a sulfide gas, wherein N is an integer greater than or equal to 1, the adsorbent regenerator being connected to the reactor via a spent adsorbent transfer line and a regenerated adsorbent transfer line, wherein spent adsorbent produced in the reactor enters the adsorbent regenerator via the spent adsorbent transfer line and is regenerated in the adsorbent regenerator, and the regenerated adsorbent is then recycled back to the reactor via the regenerated adsorbent transfer line.
Description
Technical field
The present invention relates to be rich in CH
4The production of gas particularly relates to producing and is rich in CH
4The system of gas and use this system to produce to be rich in CH
4The method of gas.
Background technology
Methanation is that for example coal and Wood Adhesives from Biomass are synthetic natural gas (or instead of natural gas, key step SNG) with solid carbon-containing material.In this step, be rich in the coal of carbon monoxide, carbonic acid gas and hydrogen and gasifying biomass product stream (being commonly referred to synthetic gas) and be 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 direct methanation reaction is mainly based on reaction 2, and it requires H
2The mol ratio of/CO is 1: 1.Compare with conventional methanation reaction, direct methanation reaction possesses following advantage: 1) required H in the feed gas
2Still less, the unstripped gas pre-treatment that therefore needs also still less; 2) some direct methanation catalysts shows high sulfidation resistance, and therefore, pre-desulfurization can be omitted in some cases; And 3) the catalyst carbon fouling that occurs in the conventional methanation reaction can not occur, catalyst life is longer thus.
Methanation reaction is reversible reaction.According to thermodynamic argument, CO
2Existence will make molecular balance mobile to the left, thereby so that the direction that reaction is carried out is unfavorable for CH
4Generation.Therefore, CO
2CH
4The inhibitor that generates, it has reduced speed of reaction, has also reduced the peak rate of conversion of product.In conventional commercial run, along with CO
2Accumulation in the methanation reaction process, speed of response will slow down gradually, and the transformation efficiency of product will significantly reduce.
The CO that in the direct methanation reaction process, forms
2Not only bring restriction on the thermodynamics to system.The CO that produces in the methanation reaction process
2As by product and CH
4Be present in together in the system, therefore must remove, the method for removing known to persons of ordinary skill in the art comprises Rectisol, Seloxol, MDEA, lime absorption etc.This type of is CO independently
2Remove or CH
4Purify and also significantly increased the total cost that methanation reaction is produced.Such CO
2Removal is CH
4The part of product postprocessing, rather than the part of methanation reaction itself.
It is H that the synthetic gas that gasification produces contains principal mode
2The sulphur component of S and COS, this sulphur component can make the methanation reaction poisoning of catalyst, therefore must remove from the feeding material before methanation reaction carries out.Industrial, synthetic gas made sulphur content be reduced to 0.1ppm through the deep purifying unit before entering the methanation reaction process.This type of deep purifying is normally realized by one or more industrially desulfurized processes, such as Rectisol and Selexol etc.Preliminary cleaning has significantly increased capital contribution.In addition, this type of purifying method needs low temperature (room temperature or lower), so the hot synthesis gas that gasification unit is produced must lower the temperature, thereby causes reduction or the loss of energy efficiency.
US6610264 discloses a kind of method and system of removing sulphur from gaseous mixture, and this system can be used to separate sulfide gas from above-mentioned raw material of synthetic gas.Simultaneously, US7713421 discloses a kind of method for remove component from fluid mixture, and its sorbent structure can adsorb some gaseous fraction that comprises above-mentioned sulfide gas.
Although there is high methanation in presence of sulfur catalysts, for example comprise the catalyst for methanation in presence of sulfur of disclosed molybdenum and lanthanum element or actinium element among the US5141191, the price of this type of catalyzer is very high.In addition, owing to not comprising regenerative system in the system, fouled catalyst accumulates in system, can cause the reduction of catalyst activity and selectivity or loses.In addition, it is fully out of service that more catalyst changeout requires system, causes thus rolling up of cost.Therefore, need to find the method in extending catalyst life-span.
The method that US4774261 discloses a kind of sulfur resistant catalyst and use this catalyzer in the presence of sulphur.But, under these type of processing condition, produce excessive CO
2, and it accumulates with the methanation reaction process, thereby causes chemical equilibrium to shift to direction with the methanation opposite direction, has suppressed thus CH
4Generation, limited its maximum conversion rate.Therefore, a large amount of unconverted synthetic gas are left in the product, cause its calorific value to reduce.In the case, further purified product so that the product of production pipe stage quality.
Except CO
2Excessive accumulation in reactive system and methanation reaction catalyzer are because of outside sulfide gas poisons, and also there is following problem in the method for methanation reaction of the prior art.
Because exothermic heat of reaction, low temperature is for CH
4Generation be favourable.As a result, the restriction on the thermodynamics wishes to use approximately 300-400 ℃ temperature to obtain acceptable transformation efficiency.But the speed of reaction that obtains under such temperature is very low, therefore needs very large reactor and/or a large amount of recirculated water steam to finish reaction, thereby has significantly increased capital contribution.In addition, the anti-sulphur of catalyzer is lowered at a lower temperature, so catalyst life is shortened.
Also have, the height exothermic character of reaction has improved the requirement that heat is transmitted.The equipment that heat is spread out of in the reaction system for example multi-tubular heat exchanger or interstage cooler require must be well-designed, and this has increased complicacy and the capital contribution of operation.
In addition, in the system of being everlasting, use heat exchanger so that reaction heat is spread out of system in this area, thus control temperature of reaction and produce electric power or driving device equipment with the hot steam that obtains.Doing like this needs high reaction temperature, and still, as mentioned above, high reaction temperature but is disadvantageous for reaction.
Summary of the invention
The object of the invention is in the situation that overcome the direct methanation reaction process that above one or more even all problems is implemented synthetic gas.
Inventor's discovery, above-mentioned purpose of the present invention can be by removing CO with sorbent material fast from reactive system when methanation reaction carries out
2And sulfide gas (H for example
2S and COS) and sorbent material regenerated to realize.
By from the methanation reaction system, removing simultaneously CO
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 higher methane of quality, and/or reduction and the methane relevant cost of purifying.In addition, remove simultaneously CO
2Avoided poisoning of catalyst with sulfide gas, therefore can obtain higher catalyst activity, selectivity and/or longer catalyst life, and save the desulfurization pre-treatment of synthetic gas, and/or can in the methanation reaction system, use the catalyzer of non-anti-sulphur and/or low anti-sulphur.
At last, by the regeneration of sorbent material, the actual consumption amount of sorbent material can greatly reduce in the system, therefore can obtain lower cost.This enforcement for industrially scalable is especially favourable.
According to an aspect of the present invention, from the methanation reaction system, remove simultaneously CO
2Can realize by such system with sulfide gas, namely it comprises reactor and at least one adsorbent reactivation device, and described reactor at one end has the synthetic gas entrance, has the CH of being rich at the other end
4Pneumatic outlet is in described reactor, at described synthetic gas entrance and the described CH that is rich in
4Having N methanation reaction catalyst zone and N+1 and above-mentioned methanation catalyst district between the pneumatic outlet is and intersects arrangement, energy while CO absorption
2With the adsorbent zone of sulfide gas, wherein N is the integer more than or equal to 1; Described at least one adsorbent reactivation device is connected with described reactor by spent sorbents line of pipes and reproducing adsorbent line of pipes, the spent sorbents that wherein produces in described reactor enters in the described adsorbent reactivation device by the spent sorbents line of pipes, and be reproduced therein, the sorbent material that is reproduced subsequently is recycled in the described reactor by described reproducing adsorbent line of pipes.
In a preferred embodiment of the invention, the entrance that can have at least one described sorbent material on top or the top of a described N+1 adsorbent zone.The synthetic gas entrance can be positioned at reactor head or bottom, and is rich in CH
4Pneumatic outlet can be positioned at bottom or the top of reactor.Preferably, the number of described adsorbent reactivation device is N, and the reproducing adsorbent that forms in each described adsorbent reactivation device is admitted to one top in the above-mentioned N adsorbent zone, and the spent sorbents that produces in an above-mentioned N adsorbent zone is fed to the top that is arranged in the nethermost adsorbent zone of described reactor and enters the adsorbent reactivation device from its underpart through the spent sorbents line of pipes and regenerates.
In another preferred implementation of the present invention, described catalyst zone and adsorbent zone can comprise respectively fluidized-bed, moving-bed and/or the fixed bed of described granules of catalyst and described absorbent particles.
Preferably, described fluidized-bed, moving-bed and/or the fixed bed of above-mentioned adsorbent zone can comprise that it has installed the perforation plate of at least one overflow pipe in its bottom, the upper end of wherein said overflow pipe is positioned at the bottom of described adsorbent zone, the lower end of described overflow pipe is arranged in the top of the nethermost adsorbent zone of described reactor, so that saturated or spent sorbents arrives the top of nethermost adsorbent zone in the described reactor.
Equally preferably, described fluidized-bed, moving-bed and/or the fixed bed of above-mentioned adsorbent zone comprises that in its bottom it has installed the perforation plate of at least one vertical baffle, the upper end of wherein said vertical baffle is positioned at the bottom of described adsorbent zone, and the lower end of described vertical baffle is arranged in the top of the nethermost adsorbent zone of described reactor, and the inwall of described vertical baffle and described reactor forms slit or passage, so that saturated or spent sorbents arrives the top of nethermost adsorbent zone in the described reactor.More preferably, the upper end of above-mentioned vertical baffle has at least one side otch.
Above-mentioned N methanation reaction catalyst zone can be identical or different; A described N+1 adsorbent zone also can be identical or different.In described reactor and/or described adsorbent reactivation device, at least one cyclone cluster, cyclone cluster cascade, barrier film and/or strainer can be installed so that gas is separated with solid particulate.Described overflow pipe and/or described at least one vertical baffle can be staggered.At least one heat exchanger also can be installed in described reactor and/or described adsorbent reactivation device to be passed out in reactor and/or the adsorbent reactivation device will react the heat that produces.Especially, heat exchanger is installed in the temperature that adsorbent zone in the reactor has reduced sorbent material, the temperature of also having regulated catalyst zone simultaneously.Described sorbent material can be selected from the mixture of metal oxide or metal oxide, and wherein metal is selected from Ca, Zn, Cu, Fe, Mg, Al, alkali and alkaline earth metal ions; And described catalyzer is low anti-sulphur or non-catalyst for methanation in presence of sulfur, especially low anti-sulphur or the non-high reactivity of anti-sulphur methanation catalyst.
According to another aspect of the present invention, provide a kind of and be rich in CH with aforementioned system production
4The method of gas, described method may further comprise the steps in order:
To contain CO, CO
2, H
2, sulfide gas and optional water vapor synthetic gas send in the described reactor (100) by described synthetic gas entrance (101);
The synthetic gas that is admitted in the described reactor (100) passes through first described adsorbent zone (105 '), from the CO of synthetic gas
2Be removed by the sorbent material quick adsorption in the described adsorbent zone (105 ') with sulfide gas or reduce, subsequently;
Described synthetic gas passes through first described methanation reaction catalyst zone (105), and produces CH therein under the katalysis of methanation catalyst
4, CO
2And H
2O;
Described synthetic gas is subsequently by second described adsorbent zone (105 '), from the remaining CO of synthetic gas
2With the CO that produces in sulfide gas and/or the reaction
2Be removed by the sorbent material quick adsorption in the described adsorbent zone (105 ') or reduce, then again by second described methanation reaction catalyst zone (105), and under the katalysis of methanation catalyst, produce CH therein
4And CO
2And H
2O, described synthetic gas intersect so successively by N methanation reaction catalyst zone (105) and N+1 adsorbent zone (105 ');
By absorption and CO
2Be rich in the CH that generates with sulfide gas is separated
4Gas is by the described CH that is rich in
4Pneumatic outlet (102) leaves described reactor (100);
Spent sorbents leaves reactor (100) by spent sorbents line of pipes (103), enters in the described adsorbent reactivation device (200),
Enter described spent sorbents and oxygen flow reaction under 500-1200 ℃ in the described adsorbent reactivation device (200), thereby be converted into reproducing adsorbent;
Described reproducing adsorbent is recycled in the described reactor (100) by reproducing adsorbent line of pipes (104).
In the invention described above method, raw material of synthetic gas can be without the desulfurization pre-treatment before entering reactor, and the described reproducing adsorbent that is recycled simultaneously in the described reactor can carry out preheating to described synthetic gas charging
Said system of the present invention and method have the following advantages: because methanation reaction is reversible, if comprise CH
4, CO
2Removed fast from reactive system with the reaction product of sulfide gas, speed of reaction will improve; Sulfide gas in the synthetic gas is harmful to catalyst activity usually, if this type of gas can not be removed from reactive system at short notice, catalyst efficiency will be lowered, even lose fully, like this, the synthetic gas charging must be desulfurized, and perhaps uses sulfur resistant catalyst, but sulfur resistant catalyst is expensive.System and a method according to the invention.Not only can use low anti-sulphur even non-sulfur resistant catalyst, and not need raw material of synthetic gas is carried out the desulfurization pre-treatment; By using the sorbent material CO absorption
2And sulfide gas, CH
4With CO
2Be separated with sulfide gas, be rich in CH
4Gas can be purer, so so that be rich in CH
4The aftertreatment of gas is very easy to carry out, and significantly CH is rich in reduction
4The cost of gas aftertreatment; Because the sorbent material consumption is very large during the methanation reaction, if spent sorbents is not regenerated and is recycled, the sorbent material 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, the consumption of sorbent material is greatly diminished, and has also significantly reduced thus the use cost of sorbent material, and this is very favorable for plant-scale application.By with adsorbent reactivation and circulation, guaranteed that the sorbent material in the reactor is always fresh, and almost do not have spent sorbents to stop for a long time and be accumulated in the reactor, the activity of sorbent material is improved greatly thus, this is for the transformation of finishing methanation reaction and avoid catalyzer highly beneficial because of the sulfide gas poisoning, because CO
2From reactive system, removed rapidly before methanation reaction carries out with sulfide gas.In addition, owing to the sorbent material that needn't change in the reactor, the productivity of reactor is improved greatly, and this has also significantly reduced the operation and maintenance cost.Simultaneously, the reproducing adsorbent that enters in the reactor is higher owing to temperature, when it contacts with the synthetic gas charging, can carry out preheating to it, has so also improved the thermo-efficiency of reactive system.
Description of drawings
Fig. 1 is the schematic diagram of explanation system operation principles of the present invention.Wherein, reactor comprises a methanation reaction catalyst zone and two adsorbent zone.
Fig. 2 is another schematic diagram of explanation system operation principles of the present invention.Wherein, reactor comprises two methanation reaction catalyst zones and three adsorbent zone.
Fig. 3 has shown methanation reaction catalyst zone that the present invention is adjacent and a preferred structure of adsorbent zone, and wherein, adsorbent zone has overflow pipe.
Fig. 4 has shown methanation reaction catalyst zone that the present invention is adjacent and another preferred structure of adsorbent zone, and wherein, adsorbent zone has vertical baffle.
Fig. 5 is the schematic diagram of an optimal technical scheme of explanation system operation principles of the present invention.Wherein, reactor comprises two methanation reaction catalyst zones, three adsorbent zone, and simultaneity factor also comprises three heat exchangers and two cyclone clusters or cyclone cluster cascade.
Embodiment
As a generality embodiment of the present invention, with the method that comprises the system implementation methanation reaction of the present invention of reactor 100 and at least one adsorbent reactivation device 200 shown in Figure 1.Reactor 100 is for the methanation reaction that carries out the synthetic gas charging, simultaneously by removing fast CO with adsorbent zone from reactor 100
2And sulfide gas.And adsorbent reactivation device 200 is converted into reproducing adsorbent with spent sorbents, and it is looped back in the reactor 100.
Synthetic gas can enter in the space on first adsorption zone 105 ' in the reactor 100 as charging by entrance 101, and enters subsequently in first adsorption zone 105 '.On the other hand, the sorbent material of fresh/regeneration is added in first adsorbent zone 105 ' by reproducing adsorbent line of pipes 104, at this and CO
2React to catch CO with sulfide gas
2And sulfide gas, flow into subsequently in the methanation reaction catalyst zone 105 under first adsorbent zone 105 ', synthetic gas is under the katalysis of methanation reaction catalyzer therebetween, methanation reaction occurs generate methane, carbonic acid gas and water, synthetic gas enters second adsorbent zone 105 ' more afterwards, is adsorbed on the carbonic acid gas that forms in the methanation reaction catalyst zone and from the remaining CO of synthetic gas pan feeding at this
2And sulfide gas.Enter afterwards in second space of adsorbent zone below 105 ', and finally leave reactor 100 by spent sorbents line of pipes 103.In the invention described above system, the thickness of the first and second adsorbent zone can be different, also can be identical, and this depends on the concentration of carbonic acid gas and sulfide gas in the synthetic gas.
Before carrying out under the katalysis of methanation reaction at catalyzer of synthetic gas, the sorbent material quick adsorption CO of fresh/regeneration
2And sulfide gas, thereby so that they removed fast.Like this, the balance of methanation reaction is moved toward generation CH
4Direction so that the process of methanation reaction can reach transformation efficiency almost completely.Simultaneously, sulfide gas was removed through absorption before catalyzer is realized its catalysis, the anti-sulphur requirement of catalyzer is reduced greatly, can use thus the catalyzer (such catalyzer usually compared with corresponding sulfur resistant catalyst is more cheap but activity is higher) of non-anti-sulphur or low anti-sulphur in system.In addition, by 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 is rich in CH
4The purification of gaseous product will become and be more prone to, even no longer need to be rich in CH
4The purification of gaseous product.After through adsorbent zone 105 ' and methanation catalyst district 105, synthetic gas can reach the unidirectional transformation efficiency of reaction almost completely, so downstream CH
4The burden of purifying reduces greatly.
As discussing in detail below with reference to Fig. 2, can have a plurality of methanation catalysts district 105 and a plurality of adsorbent zone 105 ' in the reactor 100.In the case, each described catalyst zone 105 and adsorbent zone 105 ' can comprise be used to identical or different catalyzer and/or the absorbent particles of realizing identical or different function.This depends on the quality of synthetic gas, the type of sorbent material and the type of catalyzer, can adjust the distribution in these districts to obtain desired adsorption strength and catalytic effect.
Other parts (not shown) also can be installed in the reactor 100 to realize its separately function.For example, one or more coil pipes or multi tube heat exchanger can be installed, wherein the high-duty boiler feed water is by wherein and produce high pressure steam, thereby remove and utilize the reaction heat that produces, and can or cyclone cluster, cyclone cluster cascade, barrier film and/or strainer wherein be installed near pipeline outlet (for example pipeline outlet 102), thereby gas and solid particulate are separated.
In adsorption zone 105 ', the CO in the synthetic gas
2Be removed by the absorption of wherein sorbent material with sulfide gas, and through the synthetic gas of above-mentioned adsorption treatment then by methanation catalyst district 105, and under the katalysis of catalyzer, be converted into CH
4And CO
2In above-mentioned adsorption process, CO
2With by H
2The sulfide gas of S representative is removed fast by following reaction:
(reaction 5)
Wherein, M can be one or more suitable metals, for example Ca, Zn, Cu, Fe, Mg, Al, basic metal, alkaline-earth metal and/or its mixture.As the result of reaction 4 and 5, from the CO that produces in raw material of synthetic gas and the reaction process
2Reduced rapidly with sulfide gas, particularly the amount of sulfide gas reduces to the ppm level, and sorbent material is finally by saturated and be converted into spent sorbents.
Depend on upstream process, the synthetic gas charging can obtain by the gasification of coal, coke, biomass or other carbonaceous materials, perhaps produces CO and H by known to persons of ordinary skill in the art other
2The process of mixture obtain.One preferred embodiment in, in dry gas, synthetic gas contains the CO of 20-70 volume %, the H of 10-60 volume %
2, maximum 60 volume % CO
2And the H of 0.1-10 volume %
2S etc.The raw material of synthetic gas that system and method for the present invention uses need not to carry out the desulfurization pre-treatment before charging.
Of the present invention one preferred embodiment in, the pressure of reactor 100 can be 1 normal atmosphere to 100 bar, temperature of reaction can be 100 to 900 ℃.
Employed methanation reaction catalyzer can be any methanation catalyst that is purchased of industrial use among the present invention.This type of catalyzer is known to persons of ordinary skill in the art.For example, preferred catalyzer can be the mixture of Mo, Ni or Mo and Ni.More preferably, employed catalyzer can be low anti-sulphur or non-methanation in presence of sulfur catalysts among the present invention.
Among the present invention employed sorbent material can be selected from those can with CO
2And/or thereby the sulfide gas reaction produces solid matter reduction CO
2And/or the material of the content of sulfide gas in reactive system.Preferred sorbent material is selected from CaO, ZnO, Fe
2O
3And composition thereof.This type of sorbent material is known to persons of ordinary skill in the art.
Sorbent material and/or catalyzer can mix with inert substance and/or be shaped to specified shape, for example have the particle of specified particle size.From the explanation of the following Fig. 3 of relating to and Fig. 4, can know, the character of particle, for example granularity is important for implementing the present invention and obtaining good effect.Concrete which kind of character is the important self property that depends on sorbent material and catalyzer.
Preferably, as shown in Figure 1, spent sorbents leaves reactor 100 by spent sorbents line of pipes 103 and enters the bottom of the riser tube 201 of adsorbent reactivation device 200 by its entrance 202, and its oxygen flow by heat rises in the breeding blanket 203 that preferred form is fluidized-bed.In breeding blanket 203, under 600 to 1200 ℃, spent sorbents is regenerated as fresh adsorbent, and by refrigerating device inside (not shown), for example high-duty boiler feed water by wherein to be cooled to suitable temperature except the coil pipe or the multi tube heat exchanger that reduce phlegm and internal heat and produce high pressure steam.Reproducing adsorbent is recycled in the reactor 200 by reproducing adsorbent line of pipes 104.The waste acid gas that produces in the regenerative process leaves adsorbent reactivation device 200 by pipeline 204 and can mode known to persons of ordinary skill in the art process.
The regeneration of spent sorbents can realize by any mode known to persons of ordinary skill in the art.Usually, regenerative response carries out in adsorbent reactivation district 203 in the following manner:
(reaction 7)
As reaction 6,7 result, spent sorbents is reproduced and again becomes metal oxide; CO
2And SO
2After gating in office is crossed cyclone cluster, cyclone cluster cascade, barrier film and/or strainer (not shown) and solid particulate is separated, leave adsorbent reactivation device 200 by its pipeline 204, and further process for example recovery of sulphur and/or carbon and separating treatment by any mode known to persons of ordinary skill in the art.Reproducing adsorbent is recycled in the reactor 100 as fresh adsorbent by reproducing adsorbent line of pipes 104.
The air-flow that enters 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 degree of finishing. can use oxygen level to be the air-flow of 5-50%, the mixture of air or oxygen and rare gas element is as said flow. one preferred embodiment in, use the mixture of oxygen and carbonic acid gas as said flow, in order to contain the suitable easier high-purity carbon dioxide of catching carbon of pouncing in the downstream through above-mentioned pipeline 204 expellant gas.Depend on the temperature of composition and the reactor 100 of said flow, the temperature of said flow is generally 300-1000 ℃.
As shown in Fig. 3 and 4, methanation reaction catalyst zone 105 and adsorbent zone 105 ' can possess different structures.For example, they can comprise fixed bed, moving-bed, vibrating bed and/or the fluidized-bed of catalyzer or sorbent material.Of the present invention one preferred embodiment in, use the fluidized-bed of catalyzer and absorbent particles.
Fig. 3 has shown methanation reaction catalyst zone 105 among Fig. 1 and a kind of preferred implementation of adsorbent zone 105 ' structure, wherein they comprise fluidized-bed, spouted bed for example, the fluidized-bed of described adsorbent zone 105 ' has perforation plate 106 or similarly installs in the bottom, for example bubble deck or valve tray, it has one or more upwards overflow pipes 107 of flare openings.The top of overflow pipe 107 is preferably horn opening, and be positioned at bottom or the bottom of adsorbent zone 105 ', to hold by saturated or near saturated absorbent particles, enter overflow pipe 107 absorbent particles can by under lead next adsorbent zone 105 ' or reactor 100 nethermost adsorbent zone 105 ', and enter in the revivifier 200 regeneration finally by spent sorbents transport pipe 103.
Need to prove: in some cases, so-called spent sorbents is not complete saturated sorbent material, because each adsorbent zone 105 ' may there are differences in thickness, structure and sorbent material kind, synthetic gas also may be different in the time that each adsorbent zone stops simultaneously, therefore, final spent sorbents may be fully saturated sorbent material and approach fully saturated sorbent material or the mixture of half saturated sorbent material.
Have as shown in Figure 3 adsorbent zone 105 ' and catalyst zone 105 structures, as shown in Figure 1 system in carry out the methanation reaction process before, before methanation method of the present invention is implemented, the methanation reaction catalyzer is packed in the catalyst zone 105, and sorbent material is packed in the adsorbent zone 105 '.Once you begin operation, synthetic gas (can choose wantonly pretreated, as such as preheating, precharge, pre-desulfurization, to show among the figure) at first enters in the fluidized-bed of the first adsorbent zone 105 ' by the hole on the perforation plate 106.Simultaneously, absorbent particles is fluidized therein, and quick adsorption is from the CO in the raw material of synthetic gas
2With with H
2S is the sulfide gas of example.Afterwards through the first time adsorption treatment synthetic gas enter again catalyst zone 105, under the catalyst effect methanation reaction occurs at this synthetic gas, produce CH
4And CO
2, subsequently, synthetic gas enters the second adsorbent zone 105 ', methanation reaction generate with remnants from the CO in the raw material of synthetic gas
2With with H
2S is that the sulfide gas of example is by the quick adsorption again of the sorbent material in the second adsorbent zone 105 '.Because sulfide gas is removed by adsorbing rapidly, thereby avoided poisoning of catalyst in the catalyst zone 105.
In a preferred embodiment of the invention, the granularity of absorbent particles is generally 1 to 1000 micron, and the granularity of granules of catalyst is generally 0.1 millimeter to 1 centimetre.The temperature and pressure of reactor 100 within being fit to the zone of methanation reaction, for example 200-900 ℃, 1 normal atmosphere-100 bar.
Fig. 4 has shown methanation reaction catalyst zone 105 among Fig. 1 and another preferred implementation of adsorbent zone 105 ' structure.This embodiment and Fig. 3 are basic identical, and difference is the vertical baffle 107 ' that has used at least one preferably to have one or more side otch upper end, replace preferred upwards flare opening vertical overflow pipe 107 (being upflow tube).Those of ordinary skills obviously can recognize, identical among their principle of operation and Fig. 3.
As shown in Figure 4, the upper end that preferably has one or more side otch of vertical baffle 107 ' is positioned at bottom or the bottom of adsorbent zone 105 ', between the inner vertical walls of reactor 100 and above-mentioned at least one vertical baffle 107 ', there are slit or passage, the spent sorbents particle can be led next adsorbent zone 105 ' or reactor 100 nethermost adsorbent zone 105 ' by lower by above-mentioned slit or passage, and enters in the revivifier 200 finally by spent sorbents transport pipe 103 and to regenerate.
Fig. 5 has then shown a preferred embodiment of system of the present invention, it comprises reactor 100 and adsorbent reactivation device 200, and described reactor 100 comprises two catalyst zone 105, three adsorbent zone 105 ', three heat exchangers 110 and two cyclone cluster, cyclone cluster cascades 111 from wherein isolating solid particulate before gas leaves reactor 100 and adsorbent reactivation device 200 as shown in Figure 3.In catalyst zone 105, synthetic gas generation methanation reaction, and in adsorbent zone 105 ', the sorbent material CO absorption
2And sulfide gas, thereby from reactive system, remove CO
2And sulfide gas.Preferably, each adsorbent zone 105 ' and catalyst zone 105 are arranged with interlace mode as shown in Figure 5, and more preferably, overflow pipe 107 and vertical baffle 107 ' also can be arranged (not shown) by interlace mode, in order to remove fast CO
2And sulfide gas.Equally preferably, one of adsorbent zone 105 ' is positioned at bottom and/or the top of reactor 100, thereby so that just be removed before the catalyzer of most of sulfide gas in running into minimum and/or the highest catalyst zone 105, thereby more reduce the poisoning risk of methanation reaction catalyzer.This means and can use low anti-sulphur, the catalyzer of even not anti-sulphur, and/or some specific catalyst life is prolonged owing to the minimizing of poisoning of catalyst degree.In addition, the heat that produces because of absorption in the adsorbent zone 105 ' can be used as thermal source synthetic gas is preheated to the acceptable temperature of methanation reaction.
Although the catalyst zone among Fig. 5 105 and adsorbent zone 105 ' are designed to the structure among Fig. 3, obviously, they can possess other structure, for example structure shown in Figure 4, and each catalyst zone 105 and adsorbent zone 105 ' can and can have identical or different catalyzer and/or sorbent material by independent design.
Although 110 forms of the heat exchanger among Fig. 5 are the coil pipe of heat exchange medium (being preferably water) from wherein flowing through, obviously can use other forms 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 catalyst zone 105, will produce a large amount of reaction heat, 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 the reactor 100, and the temperature with catalyst zone 105 is controlled in the suitable scope thus.Particularly, when heat exchange medium is water, except reducing phlegm and internal heat, will produce a large amount of water vapors with heat exchanger 110.Because methanation reaction can carry out under comparatively high temps, can produce high-quality water vapor in heat exchanger 110.
What form in catalyst zone is rich in CH
4Gas in the laggard inlet/outlet pipeline 102 of gas-solid separation.This type of separation can any mode known to persons of ordinary skill in the art be carried out, and for example uses strainer, cyclone cluster or cyclone cluster cascade 111 or even barrier film.
In a preferred embodiment of the present invention shown in Figure 5, the synthetic gas pan feeding can have the composition identical with embodiment shown in Figure 1, the temperature of raw material of synthetic gas is 80-120 ℃, pressure is the 16-24 bar, flow per hour is 10000-16000 times of catalyst volume, be about 80-120kg/hr, be preferably 100kg/hr.The temperature of reactor 100 is controlled as 550-650 ℃, and pressure is controlled as the 18-22 bar.Flow is 100-140, and the sorbent material that is preferably 120kg/hr circulates between reactor 100 and adsorbent reactivation device 200.80-120kg/hr is preferably 900-1100 ℃ of 100kg/hr, is preferably the bottom that 1000 ℃ warm air is blown into adsorbent reactivation device 200.
Purpose of the present invention is by removing fast CO from reaction system before synthetic gas carries out methanation reaction
2Regenerate and realize with sulfide gas with to sorbent material.When methanation reaction carries out in reactor 100, CO
2With sulfide gas from reaction system by fast, side by side remove, they are not accumulation in catalyst zone, thus as the CO of reaction suppressor
2Be eliminated with sulfide gas, reaction is carried out continuously and is not had an impact of thermodynamical restriction.As a result, reaction obtains higher transformation efficiency.In addition, owing to having eliminated thermodynamical restriction, can use up to 600 ℃ even 800 ℃ reaction high temperature, compare with conventional conditions, speed of response is accelerated greatly, so equipment size can reduce greatly.Owing to from reaction system, having removed CO
2And sulfide gas, and be rich in CH
4The relevant cost of gas purification has not existed yet.Owing to being easy to find non-methanation in presence of sulfur catalysts under the high temperature, therefore, the invention enables the Choice and design to catalyzer to be more prone to.In addition, sorbent material also can reduce sulphur content, and this will significantly reduce the requirement to the anti-sulphur of catalyzer, and can use low anti-sulfur materials, most of methanation reaction catalyzer of present industrial employing 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 higher-quality water vapor, and obtains thus high energy efficiency.At last, the fluidized bed type system has guaranteed that more uniform temperature distributes in reactor, and the easier temperature control and the heat management that obtain thus, because a large amount of heat releases of reaction, this is very difficult for traditional fixed-bed reactor.
Embodiment
Use system implementation methanation method of the present invention as shown in Figure 5.Catalyzer is 1: 1 weight ratio mixture of Mo and Ni, and 90 % by weight particles are greater than 1mm.Sorbent material is 1: 10 the mixture of weight ratio of ZnO and CaO, granularity be 1 micron to 1mm, wherein 90% particle is less than 100 microns.The granularity of catalyzer and absorbent particles is determined with method of sieving or specific surface area method.
Ingress synthetic gas flow per hour is 10000 times of catalyst volume, is about 100kg/hr.Described ingress synthetic gas does not pass through the desulfurization pre-treatment.Ingress synthetic gas temperature is 100 ℃, and pressure is 20 bar.The mole of synthetic gas is composed as follows:
Table 1
| H 2 | CO | CO 2 | H 2O | H 2S |
| 28％ | 42％ | 11％ | 17％ | 2％ |
The synthetic gas pan feeding by the adsorbent zone 105 ' of bottom shown in Fig. 5 after, the sulfide gas that the overwhelming majority is derived from synthetic gas is removed through absorption, thereby so that its concentration be reduced near 1ppm.The thickness of catalyst zone 105 and adsorbent zone 105 ' is 0.8-1.2 rice independently, and it depends on that synthetic gas passes through the speed of catalyst zone 105 and adsorbent zone 105 '.
The charging of every 100mol synthetic gas finally can produce the approximately usefulness sorbent material Adsorption CO of 26.25mol
2The product gas that is rich in methane.When leaving reactor 100, be rich in CH
4Gaseous product is composed as follows:
Table 2
| H 2 | CO | CH 4 | CO 2 | H 2O | H 2S |
| 0.35％ | 7.68％ | 62.9％ | 0.02％ | 29.5％ | Trace |
The total conversion rate of CO has reached 95.2%.Methane purity (butt) has surpassed 90% in the gas in exit.Known under this type of condition, in conventional methanation method, the CO peak rate of conversion only reaches approximately 70%.
Even the temperature in the reactor 100 brought up to 700 ℃, and other conditions remain unchanged, and the CO total conversion rate is still near 91%.
Although represented 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 synthetic gas preparation
4The system of gas, described system comprises
Reactor (100), described reactor (100) at one end has synthetic gas entrance (101), has the CH of being rich at the other end
4Pneumatic outlet (102) is in described reactor (100), at described synthetic gas entrance (101) and the described CH that is rich in
4Having N methanation reaction catalyst zone (105) and N+1 and above-mentioned methanation catalyst district between the pneumatic outlet (102) is and intersects arrangement, energy CO absorption
2With the adsorbent zone (105 ') of sulfide gas, wherein N is the integer more than or equal to 1; With
At least one adsorbent reactivation device (200), it is connected with described reactor (100) by spent sorbents line of pipes (103) and reproducing adsorbent line of pipes (104), the spent sorbents that wherein produces in described reactor (100) enters in the described adsorbent reactivation device (200) by spent sorbents line of pipes (103), and be reproduced therein, the sorbent material that is reproduced subsequently is recycled in the described reactor (100) by described reproducing adsorbent line of pipes (104).
2. system according to claim 1, the entrance that wherein has at least one described sorbent material on top or the top of described N+1 adsorbent zone (105 ').
3. system according to claim 1, wherein said synthetic gas entrance (101) is positioned at the top of reactor (100), is rich in CH
4Pneumatic outlet (102) is positioned at the bottom of reactor (100).
4. system according to claim 1, wherein said synthetic gas entrance (101) is positioned at the bottom of reactor (100), is rich in CH
4Pneumatic outlet (102) is positioned at the top of reactor (100).
5. system according to claim 1, the number of wherein said adsorbent reactivation device (200) is N, and the reproducing adsorbent that forms in each described adsorbent reactivation device (200) is admitted to one top in above-mentioned N the adsorbent zone (105 '), and the spent sorbents that produces in above-mentioned N adsorbent zone (105 ') is fed to the top that is arranged in described reactor (100) nethermost adsorbent zone (105 '), and enter the adsorbent reactivation device (200) regeneration from its underpart through spent sorbents line of pipes (103).
6. system according to claim 1, wherein said catalyst zone (105) and adsorbent zone (105 ') comprise respectively fluidized-bed, moving-bed and/or the fixed bed of described granules of catalyst and described absorbent particles.
7. system according to claim 6, the described fluidized-bed of wherein said adsorbent zone (105 '), moving-bed, and/or fixed bed comprises that in its bottom it has installed the perforation plate (106) of at least one overflow pipe (107), the upper end of wherein said overflow pipe (107) is positioned at the bottom of described adsorbent zone (105 '), the lower end of described overflow pipe (107) is arranged in nethermost adsorbent zone (the 105 ') top of described reactor (100), so that the saturated adsorption agent arrives nethermost adsorbent zone (105 ') top in the described reactor (100).
8. system according to claim 6, the described fluidized-bed of wherein said adsorbent zone (105 '), moving-bed, and/or fixed bed comprises that in its bottom it has installed the perforation plate (106) of at least one vertical baffle (107 '), the upper end of wherein said vertical baffle (107 ') is positioned at the bottom of described adsorbent zone (105 '), and the lower end of described vertical baffle (107 ') is arranged in described reactor (100) nethermost adsorbent zone (105 ') top, and described vertical baffle (107 ') forms slit or passage with the inwall of described reactor (100), so that the saturated adsorption agent arrives nethermost adsorbent zone (105 ') top in the described reactor (100).
9. system according to claim 8, the upper end of wherein said vertical baffle (107 ') has at least one side otch.
10. according to each described system of aforementioned claim 1-9, wherein said N methanation reaction catalyst zone (105) is identical or different.
11. according to each described system of aforementioned claim 1-9, wherein said N+1 adsorbent zone (105 ') is identical or different.
12. according to the described system of aforementioned claim 11, wherein said overflow pipe (107) and/or described at least one vertical baffle are staggered.
13. according to each described system of aforementioned claim 1-9, at least one heat exchanger (110) wherein is installed in described reactor (100) and/or described adsorbent reactivation device (200) is passed out in reactor (100) and/or the adsorbent reactivation device (200) will react the heat that produces.
14. according to each described system of aforementioned claim 1-9, at least one cyclone cluster, cyclone cluster cascade, barrier film and/or strainer (109) wherein are installed so that gas is separated with solid particulate in described reactor (100) and/or described adsorbent reactivation device (200).
15. according to each described system of aforementioned claim 1-9, wherein said catalyzer is low anti-sulphur or non-catalyst for methanation in presence of sulfur.
16. according to each described system of aforementioned claim 1-9, wherein said sorbent material is selected from the mixture of metal oxide or metal oxide, wherein metal is selected from Zn, Cu, Fe, Al, alkali and alkaline earth metal ions.
17. according to the described system of aforementioned claim 16, wherein alkaline-earth metal is Ca, Mg.
18. one kind with according to aforementioned claim 1-17 each described system production be rich in CH
4The method of gas, described method may further comprise the steps in order:
To contain CO, CO
2, H
2, sulfide gas and optional water vapor synthetic gas send in the described reactor (100) by described synthetic gas entrance (101);
The synthetic gas that is admitted in the described reactor (100) passes through first described adsorbent zone (105 '), from the CO of synthetic gas
2Be removed by the sorbent material quick adsorption in the described adsorbent zone (105 ') with sulfide gas or reduce, subsequently;
Described synthetic gas passes through first described methanation reaction catalyst zone (105), and produces CH therein under the katalysis of methanation catalyst
4, CO
2And H
2O;
Described synthetic gas is subsequently by second described adsorbent zone (105 '), from the remaining CO of synthetic gas
2With the CO that produces in sulfide gas and/or the reaction
2Be removed by the sorbent material quick adsorption in the described adsorbent zone (105 ') or reduce, then again by second described methanation reaction catalyst zone (105), and under the katalysis of methanation catalyst, produce CH therein
4And CO
2And H
2O, described synthetic gas intersect so successively by N methanation reaction catalyst zone (105) and N+1 adsorbent zone (105 ');
By absorption and CO
2Be rich in the CH that generates with sulfide gas is separated
4Gas is by the described CH that is rich in
4Pneumatic outlet (102) leaves described reactor (100);
Spent sorbents leaves reactor (100) by spent sorbents line of pipes (103), enters in the described adsorbent reactivation device (200),
Enter described spent sorbents and oxygen flow reaction under 500-1200 ℃ in the described adsorbent reactivation device (200), thereby be converted into reproducing adsorbent;
Described reproducing adsorbent is recycled in the described reactor (100) by reproducing adsorbent line of pipes (104).
19. method according to claim 18, wherein said synthetic gas is without the desulfurization pre-treatment.
20. method according to claim 18, the described reproducing adsorbent that wherein is recycled in the described reactor (100) carries out preheating as thermal medium to described synthetic gas charging.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010516312.XA CN101982448B (en) | 2010-10-19 | 2010-10-19 | Production of enriched CH4System for gas and production of CH-enriched gas using the same4Method for producing gas |
| PCT/CN2011/080845 WO2012051921A1 (en) | 2010-10-19 | 2011-10-17 | System for generating gas rich in ch4 and method for generating gas rich in ch4 by using said system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010516312.XA CN101982448B (en) | 2010-10-19 | 2010-10-19 | Production of enriched CH4System for gas and production of CH-enriched gas using the same4Method for producing gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101982448A CN101982448A (en) | 2011-03-02 |
| CN101982448B true CN101982448B (en) | 2013-02-27 |
Family
ID=43619362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010516312.XA Active CN101982448B (en) | 2010-10-19 | 2010-10-19 | Production of enriched CH4System for gas and production of CH-enriched gas using the same4Method for producing gas |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN101982448B (en) |
| WO (1) | WO2012051921A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101982448B (en) * | 2010-10-19 | 2013-02-27 | 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 |
| CN102040441B (en) * | 2010-10-20 | 2013-04-17 | 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 |
| CN103464059B (en) * | 2012-06-08 | 2015-05-13 | 北京低碳清洁能源研究所 | Methanation fluidization magnetron reactor system |
| WO2017064352A1 (en) * | 2015-10-12 | 2017-04-20 | Wärtsilä Finland Oy | Pressure vessel |
| CN110817801A (en) * | 2019-12-10 | 2020-02-21 | 太原理工大学 | Adsorption-enhanced methane steam reforming hydrogen production device and method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0089105A2 (en) * | 1982-03-12 | 1983-09-21 | British Gas Corporation | Multi stage methanation |
| EP0120590A1 (en) * | 1983-03-03 | 1984-10-03 | Gas Research Institute | Production of pipeline gas from sulfur containing raw or synthesis gas |
| CN101544527A (en) * | 2008-03-24 | 2009-09-30 | 通用电气公司 | Methods and systems for fischer tropsch reactor low product variation |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3967936A (en) * | 1975-01-02 | 1976-07-06 | The United States Of America As Represented By The United States Energy Research And Development Administration | Methanation process utilizing split cold gas recycle |
| US6610264B1 (en) * | 1992-04-15 | 2003-08-26 | Exxonmobil Oil Corporation | Process and system for desulfurizing a gas stream |
| CN101560134B (en) * | 2009-05-21 | 2014-01-15 | 新奥新能(北京)科技有限公司 | Novel process for preparing methane from high energy-efficiency synthetic gas |
| CN101982448B (en) * | 2010-10-19 | 2013-02-27 | 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 |
-
2010
- 2010-10-19 CN CN201010516312.XA patent/CN101982448B/en active Active
-
2011
- 2011-10-17 WO PCT/CN2011/080845 patent/WO2012051921A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0089105A2 (en) * | 1982-03-12 | 1983-09-21 | British Gas Corporation | Multi stage methanation |
| EP0120590A1 (en) * | 1983-03-03 | 1984-10-03 | Gas Research Institute | Production of pipeline gas from sulfur containing raw or synthesis gas |
| CN101544527A (en) * | 2008-03-24 | 2009-09-30 | 通用电气公司 | Methods and systems for fischer tropsch reactor low product variation |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012051921A1 (en) | 2012-04-26 |
| CN101982448A (en) | 2011-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102040441B (en) | System for producing CH4-rich gas and method for producing CH4-rich gas with system | |
| CN102021037B (en) | Method and apparatus for preparing methane by catalytic gasification of coal | |
| US20070283812A1 (en) | System and method for removing sulfur from fuel gas streams | |
| CN101774542B (en) | Biomass gasification hydrogen-producing system and method | |
| CN101982448B (en) | Production of enriched CH4System for gas and production of CH-enriched gas using the same4Method for producing gas | |
| RU2670761C9 (en) | Regulation of acid gas in process of liquid fuel production | |
| JP4757343B2 (en) | CO2 separation and recovery device including steam pretreatment machine | |
| CN103373706B (en) | A kind of methane reforming hydrogen production process and device | |
| JP5011127B2 (en) | Management of hydrogen in hydrogen-containing streams from hydrogen sources | |
| CN102371136B (en) | Production of enriched CH4Reactor system for gases with coaxial closed sandwich structure and method for using the same | |
| CN106629600B (en) | Crude synthesis gas adsoption catalysis process for making hydrogen and its equipment | |
| CN107698419B (en) | Chemical chain oxidative dehydrogenation of propane prepares the method and system of propylene | |
| CN104031703A (en) | Method and device for preparation of natural gas synthesis gas from coal | |
| CN103288048A (en) | Process for preparing hydrogen by strengthening chemical chain reforming in continuous catalytic adsorption manner via moving bed | |
| CN108698816A (en) | Produce the method and system of dimethyl ether | |
| CN103466546B (en) | Intermediate temperate pressure swing adsorption method for using bifunctional adsorbent in adsorption enhanced type vapor reforming and water-vapor transformation reactions | |
| CN102180757B (en) | Method for direct methanation of recirculating fluidized bed synthesis gas | |
| 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 | |
| CN103464059B (en) | Methanation fluidization magnetron reactor system | |
| CN102464299A (en) | Method for producing hydrogen through fluidized-bed methane steam reforming | |
| CN104003833A (en) | System for preparing low-carbon olefin by coal-based methanol | |
| CN100586840C (en) | Coke oven gas adsorption reinforced catalytic hydrogen producing process and apparatus | |
| JPH06191801A (en) | Production of hydrogen | |
| KR102173505B1 (en) | Method for synthetic methane using fluidized bed | |
| CN113122336B (en) | Method and system for preparing hydrogen by thermal conversion of biomass |
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: 20150623 Owner name: NATIONAL INSTITUTE OF CLEAN AND LOW CARBON ENERGY Effective date: 20150623 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20150623 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: Xinyi No. 1 building, 100011 Beijing city Chaoyang District Wai Street 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 |