CN107987907A - It is a kind of that the method rich in methane gas is prepared by synthesis gas - Google Patents
It is a kind of that the method rich in methane gas is prepared by synthesis gas Download PDFInfo
- Publication number
- CN107987907A CN107987907A CN201610950692.5A CN201610950692A CN107987907A CN 107987907 A CN107987907 A CN 107987907A CN 201610950692 A CN201610950692 A CN 201610950692A CN 107987907 A CN107987907 A CN 107987907A
- Authority
- CN
- China
- Prior art keywords
- gas
- catalyst
- synthesis gas
- methanation
- methane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The method rich in methane gas is prepared by synthesis gas the present invention provides a kind of, is comprised the following steps：By net synthesis gas and the first methanation catalyst, haptoreaction obtains methanation unstripped gas in the first methanator；Methanation unstripped gas and the second methanation catalyst haptoreaction in the second methanator, obtain gas stream one；First methanation catalyst is drawn from the first methanator, and is divided into three parts；Gas stream one and Part III catalyst and/or regenerated first methanation catalyst haptoreaction in front three alkylation reactors, obtain the gaseous product rich in methane.The methanation catalyst of the present invention undertakes heat carrier function in moving bed, and can carry out effective recycling to reaction heat with on-line regeneration and recycling.
Description
Technical field
The present invention is to prepare the method rich in methane gas by synthesis gas on a kind of, more specifically, being a kind of carbon containing
Material conversion is synthesis gas, and synthesis gas prepares the method rich in methane gas by methanation group technology.
Background technology
With the rapid growth of China's economic, traditional natural gas, petroleum resources are far from meeting social production and people
The demand that the people's livelihood is lived.It is expected that the natural gas notch to the year two thousand twenty China every year will be more than 1000 billion cubic meters (standard).It is based on
The energy natural endowment of China and the consideration of energy security, it is necessary to coal, biomass etc. are converted into domestic gas, communications and transportation is fired
Material, basic chemical industry raw material etc..Wherein, natural gas from coal technology, is then converted by gasification preparing synthetic gas with low order lignite
For methane, the process as gaseous fuel.Natural gas from coal process efficiency is high, water consume is low, technology relative maturity, in exploitation
The coal of the western remote districts of state, the living standard for improving the people, reduction polluted gas discharge are significant.In addition, focusing
Producer gas is utilized, and methane is produced, also as new technology and industry growth point.
Methanation device is one of core apparatus of natural gas from coal technique and coke-stove gas methane technology.Existing first
Alkanisation process more using fixed bed reactors (CN200810099464, CN200910054761, CN2010800399242,
CN2011102686680、CN2011104182734、CN201210121649、CN201210150228、CN2012102193086
Deng), a few patents disclose using fluidized-bed reactor (CN101817716A, CN2011100236913,
CN2012102545935, CN2013102017159, CN201010123120.2) and paste state bed reactor
(CN2011104136098).In practical application, the characteristics of being strongly exothermic process with reference to methanation and heat energy recycle
Principle, one or two high-temperature methanation reactor is usually set first, the CO of major part is converted into CH4, recycling is instead
Heat release is answered, high steam occurs, one or two low temperature methanator (also known as supplementing methanator) is then set
Remaining CO is completely converted into CH4。
Different from fixed bed or fluidized-bed reactor, moving-burden bed reactor is another type of reactor routinely used.
During using moving-burden bed reactor, graininess or coccoid catalyst are continuously added to from reactor head, catalyst is made by gravity
With gradually moving down, last autoreactor bottom is continuously drawn off.Reaction mass is connect in the form of adverse current, cocurrent or cross-flow with catalyst
Touch reaction.Due to there is no relative motion between solid particle, but overall solid particle layer constantly moves down, catalyst
It can be moved in reactor, continuously pass in and out reactor, therefore, can also be regarded as a kind of fixed bed reaction of movement
Device.The operating characteristics of moving bed and requirement to catalyst are suitable for catalyst inactivation between fixed bed and fluid bed
Speed is medium, but still needs to the reaction of circular regeneration.So far, there is not yet moving bed methanator patent disclose or
Research report.
The content of the invention
The object of the present invention is to provide a kind of fixed-bed process and moving bed process combination, movable bed catalyst to be recycled again
Raw, thermal energy organic efficiency height and the combined technical method that methane gas is rich in by synthesis gas preparation of simple operation.
The present inventor researchs and analyses discovery, and in moving-burden bed reactor, catalyst bed is connected with certain speed
Continuous movement, after reactor bottom discharge, can pass through regeneration or without regeneration treatment, then recycle.Moving bed
Reactor, is suitable for that catalyst deactivation rate is medium, but still needs to the reaction process of circular regeneration.Therefore, with moving-burden bed reactor
When matching, it is desirable to which catalyst has higher catalytic activity and target product selectivity, and also allows catalyst to have one
Fixed invertibity deactivation rate.Also, moving-burden bed reactor is also used as heat exchanger, realize that gas phase and the direct of solid phase connect
Heat exchange is touched, has the characteristics that heat transfer efficiency is high, easy to operate.
Based on above-mentioned discovery, to realize the object defined above of the present invention, the present invention provides prepared to be rich in methane by synthesis gas
The method of gas, comprises the following steps：
(1) by net synthesis gas and the first methanation catalyst in the first methanator haptoreaction, obtain methane
Change unstripped gas；
(2) the methanation unstripped gas and the second methanation catalyst obtained step (1) is in the second methanator
Haptoreaction, carries out heat exchange cooling by the high-temperature gas logistics that reaction obtains, obtains gas stream one；Between the heat exchange cooling is
Heat exchange is connect, heat exchange cooling is carried out to the high-temperature gas logistics after haptoreaction using heat exchanger known to those skilled in the art, is used
Heat transferring medium be water, low-pressure steam etc., preferred lower pressure steam is as heat transferring medium, high-grade steam occurs；
Second methanation catalyst is the methanation catalyst of commercial grades G1-86HT, CRG-LH or MCR-2X, or
Person and other catalyst of above-mentioned same type.
(3) the first methanation catalyst in step (1) is drawn from the first methanator, and is divided into three
Point：Part I catalyst is sent into regeneration reactor and carries out regeneration treatment, obtains regenerated first methanation catalyst and is sent into
Front three alkanisation reactor cycles use；Part II catalyst discharges reaction system as dead catalyst；Part III is catalyzed
Agent is routed directly to the use of front three alkanisation reactor cycles.
(4) gas stream one for obtaining step (2) is catalyzed with the first fresh methanation catalyst and Part III
Agent and/or regenerated first methanation catalyst haptoreaction in front three alkylation reactors, the gas that will be obtained after reaction
Product is cooled down, and obtains the gaseous product rich in methane；First methanator and the front three alkylation reaction
Device is moving-burden bed reactor, and second methanator is fixed bed reactors.Wherein, between the mode of the cooling is
Heat exchange is connect, is exchanged heat using heat exchanger known to those skilled in the art to the gas after haptoreaction, is dropped gaseous product
Temperature, and moisture is isolated, obtain the gaseous product rich in methane.Wherein, the heat transferring medium of use is preferably water, low-pressure steam,
And the steam that the grade obtained after exchanging heat improves further is sent to the outlet of the first methanator and the High Temperature Gas
Body logistics exchanges heat, so that high-grade steam occur.
It is of the present invention that the method rich in methane gas, in step (1), the catalytic bar are prepared by synthesis gas
Part is preferably：5-100 absolute atmosphere, 40-400 DEG C, gas space velocity 50-80000h-1, catalyst residence times 24h-
10 days；The catalytic condition is more preferably：10-70 absolute atmosphere, 100-350 DEG C, gas space velocity is
1000-50000h-1, catalyst residence times are 72h-5 days；In step (2), the catalytic condition is preferably：15-
100 absolute atmospheres, 330-800 DEG C, gas space velocity 7500-120000h-1；In step (4), the catalytic condition
Preferably：2-100 absolute atmosphere, 250-700 DEG C, gas space velocity 50-80000h-1, catalyst residence times 24h-
100 days；The catalytic condition is more preferably：10-70 absolute atmosphere, 310-620 DEG C, gas space velocity is
1000-50000h-1, catalyst residence times are 72h-30 days.
It is of the present invention that the method rich in methane gas is prepared by synthesis gas, in step (1), it is preferred that described net
Synthesis gas forms at least one of group by producing synthesis gas from coal, biomass preparing synthetic gas and oven gas and is taken off by pretreatment
Except what is obtained after impurity and/or hydrosphere transformation.
It is of the present invention that the method rich in methane gas is prepared by synthesis gas, wherein, the type of the moving-burden bed reactor
Formula be preferably selected from by erect-type, inclined, horizontal type, erect it is telescopic and erect reducing type form in group at least one
Kind.
It is of the present invention that the method rich in methane gas is prepared by synthesis gas, wherein, the front three alkylation reactors
Quantity be preferably 2-4, be preferably serially connected between the front three alkylation reactors, in parallel, series-multiple connection or parallel-serial.
Of the present invention to prepare the method rich in methane gas by synthesis gas, in step (1), the contact process is preferred
Once pass through the catalyst bed of the first methanator in a manner of adverse current, cross-flow or cocurrent for the net synthesis gas.
It is of the present invention that the method rich in methane gas, in step (1), the methanation unstripped gas are prepared by synthesis gas
In (H2-CO2)/(CO+CO2) molar ratio is preferably 2.8-3.5, more preferably 2.9-3.3.
It is of the present invention that the method rich in methane gas is prepared by synthesis gas, in step (4), the gas stream one with
The way of contact of Part III catalyst is preferably adverse current, cross-flow or cocurrent.
It is of the present invention that the method rich in methane gas is prepared by synthesis gas, wherein, first methanation catalyst
Preferably coccoid catalyst, the particle size range of the coccoid catalyst is preferably 0.1-200mm；More preferably 0.4-
100mm；More preferably 0.7-30mm.
It is of the present invention that the method rich in methane gas is prepared by synthesis gas, it is preferred that first methanation is urged
Agent is made of active component, carrier, binding agent and modified additive, wherein, active component, carrier, binding agent and modified additive
Percetage by weight be respectively 5-90%, 6-64%, 3-45% and 10-6~2%.
It is of the present invention that the method rich in methane gas is prepared by synthesis gas, wherein, the active component is preferably selected
Free Ni, Mo, Fe, Co, Ru, Pt, Pd and Rh form at least one of group.
It is of the present invention that the method rich in methane gas is prepared by synthesis gas, wherein, the modified additive is preferably selected from
At least one of group is formed by rare earth element, transition metal and major element.
It is of the present invention by synthesis gas prepare rich in methane gas method, wherein, the rare earth element be preferably La,
Ce, Pr, Nd and Sm, the transition metal are preferably Zr, Y, Nb, Cr, Ti, Zn, Cu, Mn, Os and Ir, the major element
Preferably Si, Al, Mg, K and Rb.
It is of the present invention that the method rich in methane gas is prepared by synthesis gas, in step (3), the Part I catalysis
Agent, Part II catalyst and Part III catalyst account for the percetage by weight of total amount be preferably successively 20-60%, 0-20% and
30-80%.
Of the present invention to prepare the method rich in methane gas by synthesis gas, in step (3), the regeneration treatment is preferred
Including three removing carbon, chemical modification and reduction treatment steps.
It is of the present invention that the method rich in methane gas is prepared by synthesis gas, these, it is preferred to, the removing carbon
Process is will disappear carbon gas and Part I catalyst progress haptoreaction, and the carbon gas that disappears is selected from by O2/ vapor mixes
Gas, O2/N2Mixed gas, air, O2/CO2Mixed gas and H2/ vapor mixed gas forms at least one in group
Kind, the reaction condition of the removing carbon process is：180-450 DEG C, 1.0-50 absolute atmosphere, the carbon gas space velocity that disappears be
50-100000h-1。
It is of the present invention that the method rich in methane gas is prepared by synthesis gas, these, it is preferred to, the chemical modification
Process be by chemical modifier with eliminate carbon distribution Part I catalyst carry out haptoreaction, the chemical modifier be selected from by
HNO3、HCl、HBr、HI、Cl2、Br2、I2, HClO and NO2At least one of formed group, the chemical modification process it is anti-
The condition is answered to be：120-600 DEG C, 1.0-20 absolute atmosphere, gas volume air speed be 50-50000h-1。
It is of the present invention that the method rich in methane gas is prepared by synthesis gas, these, it is preferred to, the reduction treatment
Using H2The Part I catalyst for completing chemical modification is reduced as reducing gas, the reaction bar of the reduction treatment
Part is：300-650 DEG C, 1.0-20 absolute atmosphere, gas volume air speed be 50-50000h-1。
It is of the present invention that the method rich in methane gas is prepared by synthesis gas, in step (3), it is preferred that it is described again
Raw reactor is formed in group selected from fixed bed reactors, moving-burden bed reactor, fluidized-bed reactor and entrained-flow reactor
At least one, be serially connected between the regeneration reactor.
, can also be in order to control the temperature of catalyst bed in reaction process since methanation reaction is exothermic process
Among moving-burden bed reactor bed or reactor wall sets heat removing tube line, is preheated using process gas, water vapor takes heat, water steams
The measures such as gas heat exchange, prevent catalyst bed from producing hot localised points, cause catalyst structure to damage and produce permanent inactivation, shadow
Ring process reaction efficiency.
In the present invention, front three alkylation reactors can also use adiabatic operation pattern, according to reactor inlet gas
The conversion per pass of the factor controlling such as composition, catalyst property CO, so as to control the temperature of reaction process, reaction heat is by circulating
Catalyst and gas stream take reactor out of.When controlling the conversion per pass of CO, contain in the gas stream of reactor outlet
There are a certain number of synthesis gas not converted.At this time, the gas stream that total reactor exports should be subjected to heat exchange cooling,
Then compression is sent to next methanator gas access, participates in reaction again, most whole CO is converted into CH at last4。
The preparation method of first methanation catalyst be by active component, carrier component, modifying element component first
Solid powder is prepared into together, is then combined with binding agent, and coccoid catalyst is prepared into by rolling ball method.Wherein prepare solid
The methods of method of powder can be infusion process, coprecipitation, heat melting method, sol-gel process, mixed grinding method, Ran Houjing
Dry, roasting, pulverization process are crossed, obtains solid powder.In addition, the preparation method of coccoid catalyst can also be activearm
Point, carrier component be prepared into solid powder together first, then combined with binding agent, coccoid catalysis is prepared into by rolling ball method
Agent, is then modified processing to coccoid catalyst by the methods of dipping, chemical precipitation by modified additive element again, passes through
The processing steps such as dry, roasting, finally obtain globular first methanation catalyst.
The method according to the invention can be by carbonaceous material by gaseous product of the synthesis gas production rich in methane.Because move
Dynamic bed catalyst circulates in reactor, so catalyst granules can undertake the difunctional of methanation catalyst and heat carrier,
Effectively exothermic heat of reaction is recycled.Also, movable bed catalyst can pass through on-line regeneration and recycle, therefore reduce
Catalyst is intended for single use the requirement in service life.
More specifically, compared with prior art, the beneficial effects are mainly as follows following three aspects：
First, method provided by the invention, using fixed bed high-temperature reactor and moving bed post-reactor optimum organization
Methanation process, select suitable gas residence time, and flexible modulation can be carried out to it, can be recycled in maximum high
While warm methanator reaction heat, fixed bed reactors " hot spot " are controlled, thus are connected compared to fixed bed
Technique is easier to control temperature of reactor and the conversion ratio of reaction process.
Secondly, method provided by the invention, using two moving-burden bed reactor series connection as supplement methanator
Pattern, its used methanation catalyst recycle in two moving-burden bed reactors, while undertake catalyst and heat load
Two kinds of functions of body, carry out direct contact heat transfer, so as to improve the initial reaction of fixed bed reactors to methanation unstrpped gas
Temperature, and the gas from fixed bed reactors outlet is not recycled to reactor inlet, the production of whole fixed bed reaction system
Ability increases.
3rd, method provided by the invention, using moving-burden bed reactor as supplement methanator, can realize it
The on-line regeneration of used methanation catalyst and recycling, can significantly reduce the active lifetime cycle of catalyst
For a couple of days or some months, thus the development difficulty of catalyst is obviously reduced, and can improve the development efficiency of methanation catalyst.
Brief description of the drawings
Fig. 1 is the process flow chart that the present invention is prepared the method rich in methane gas by synthesis gas.
Embodiment
The present invention is described further for the following examples, but not thereby limiting the invention.
The method rich in methane gas is prepared by synthesis gas the present invention provides a kind of, is comprised the following steps：By carbon containing thing
The crude synthesis gas that material is obtained by conversion, continues pretreatment to remove the impurity in the crude synthesis gas, obtains net synthesis gas 1；
Net synthesis gas 1 is obtained into methanation gas original in the first methanator 9 with 6 counter current contacting of the first methanation catalyst
Material 8；By 8 and second methanation catalyst of methanation gas raw material in the second methanator 2 haptoreaction, and will contact
The product obtained afterwards carries out heat exchange cooling by First Heat Exchanger 3, obtains the gas stream 1 rich in methane；By the first methane
The first methanation catalyst 6 changed in reactor 9 is drawn, and is divided into two parts：Part I catalyst 11 continues to be divided into two parts,
A portion is sent into regeneration reactor and carries out regeneration treatment, and it is anti-to obtain regenerated methanation catalyst feeding front three alkanisation
Device 5 is answered to recycle, another part catalyst discharges reaction system as dead catalyst；Part II catalyst 10 is routed directly to
Front three alkylation reactors 5 recycle.By one 4 and first methanation catalyst of gas stream in front three alkylation reactors 5
Middle haptoreaction, the product obtained after contact is cooled down by the second heat exchanger 7, obtains the gas stream rich in methane
12, the method according to the invention can prepare the gas rich in methane by synthesis gas, and methanation catalyst undertakes in moving bed
Heat carrier function, and effective recycling can be carried out to reaction heat with on-line regeneration and recycling.
Embodiment 1
It regard lignite fragment (chemical composition is shown in Table 1) the oxygen/water steam that granular size is 5-50mm as gasifying agent, gas
Crude synthesis gas is turned to, gained crude synthesis gas obtains net synthesis gas (group after supercooling, detar, hydrosphere transformation, thick desulfurization successively
Into being shown in Table 2), wherein (CO+H2) content is 74.59 volume %, H2/ CO molar ratios are 3.07, H2S contents are 5ppm.
Table 1
Table 2
| Key component | (mole %) |
| H2 | 56.26 |
| CO | 18.33 |
| CO2 | 2.20 |
| CH4 | 20.87 |
| N2 | 1.14 |
| Ar | 0.57 |
| C2+ hydrocarbon | 0.63 |
| H2S | 5ppm |
First methanator is moving-burden bed reactor, and catalyst is that the coccoid methanation of average diameter 2.6mm is urged
Agent (composition：20.3 weight %NiO, 78.9 weight %Al2O3, 0.6 weight %Fe2O3, 0.2 weight %K2O), it is catalyzed in bed
Agent reserve is 0.8L.Temperature enters for the net synthesis gas of room temperature via the gas distributor positioned at the first methanator bottom
Reactor, directly contacts with the thermocatalyst moved down, carries out countercurrent flow, and catalyst temperature is reacted by entering in reactor head
500 DEG C during device are down to 312 DEG C.It it is 305 DEG C in the gas stream temperature that reactor head comes out, then gas stream is sent to the
In diformazan alkylation reactors.
Second methanator is fixed bed reactors, and catalyst is full methanation catalyst (commercial grades CRG),
Loadings are 0.2L.Methanation reaction condition is：303 DEG C, inlet pressure 3.35MPa, gas space velocity 20000h of inlet temperature-1。
Detect that maximum temperature point is 618 DEG C in reactor, and " hot spot " does not move down in 96h detection times.Gas stream
310 DEG C are cooled to after heat exchange, by gas-liquid separation, gas stream is sent into front three alkylation reactors.
The coccoid methanation catalyst for being moved to the first methanator bottom end outlet leaves the first methanation reaction
Device, is divided into equiponderant two parts, and wherein 0.4L catalyst directly sends the magazine of front three alkanisation reactor top back to, then
Continue to participate in methanation reaction in into reactor, in addition 0.4L catalyst, which is sent in fixed bed reactors, carries out regeneration treatment,
Successively O is passed through into regeneration fixed bed reactors2/ vapor mixed gas (O2Volume fraction 2%) the carbon processing that disappears is carried out, it is passed through
HCl/ vapor mixed gas (HCl contents 200mg/Nm3) chemical regeneration is carried out, it is passed through H2/N2(H2Volume fraction 5%) mixing
Gas carries out reduction treatment.Disappear carbon treatment conditions：285 DEG C, pressure 0.4MPa, gas space velocity 2400h of temperature-1, processing time
0.8h.Chemical regeneration treatment conditions：500 DEG C, pressure 0.4MPa, gas space velocity 2400h of temperature-1, processing time 6h.Also original place
Manage bar part：575 DEG C, pressure 0.4MPa, gas space velocity 2400h of temperature-1, processing time 20h.
Complete regeneration treatment catalyst leave fixed bed regenerator, after indirect heat exchange is cooled to 310 DEG C, also send to
The magazine of front three alkanisation reactor top, subsequently into continue in reactor participate in methanation reaction.
The gas stream come out from second reactor enters reactor by the 3rd reactor head, with coccoid catalysis
Current contacting reaction is done in agent, and coccoid catalyst is constantly moved down by gravity.Methanation reaction condition is：Inlet temperature
310 DEG C, inlet pressure 3.30MPa, gas space velocity 20000h-1.Detect that bed maximum temperature is 501 DEG C in reactor.From anti-
Answer the gas stream that device outlet at bottom comes out to be cooled to through well heat exchange is subcooled close to 0 DEG C, then adsorbed by mol sieve beds residual
Remaining moisture, the composition of the gas is detected using gas-chromatography in due course, and calculates CO conversion ratios XCO(being shown in Table 3).Catalyst is moving
The residence time is 144h in dynamic bed.
Take the catalyst sample 0.5g after leaving front three alkylation reactors and cooling down, take into catalyst regeneration process simultaneously
Catalyst sample 0.5g after cooling, evaluated respectively on the miniature fixed bed device of constant temperature its CO conversion ratio (use gas-chromatography,
TCD detectors.It is shown in Table 4).Evaluation response condition：305 DEG C of reaction temperature, gas H2/ CO molar ratios are 3.0, inlet pressure
3.0MPa, gas space velocity 35000h-1。
Comparative example 1
The preparation of net synthesis gas and composition are identical with embodiment.Net synthesis gas is introduced into the first methanator and catalysis
Agent contact heat-exchanging simultaneously reacts, and subsequently into the second methanator and catalyst haptoreaction, the is entered after heat exchange cooling
Front three alkylation reactors and catalyst haptoreaction.Detected using gas-chromatography and exported from front three alkanisation reactor bottom in due course
Gas composition (butt) and CO conversion ratios XCO(being shown in Table 3).
Wherein, three reactors are loaded using fixed bed, and catalyst does not move.
First methanator and front three alkylation reactors load the coccoid methane of 0.8L average diameters 2.6mm
Change catalyst (composition：20.3 weight %NiO, 78.9 weight %Al2O3, 0.6 weight %Fe2O3, 0.2 weight %K2O).First first
In alkylation reactors, reaction condition is：307 DEG C, inlet pressure 3.36MPa, gas space velocity 20000h of gas inlet temperature-1.The
In front three alkylation reactors, reaction condition is：302 DEG C, inlet pressure 3.31MPa, gas space velocity 20000h of inlet temperature-1。
The full methanation catalyst (commercial grades CRG) of second reaction filling 0.2L.Reaction condition is：Inlet temperature
305 DEG C, inlet pressure 3.33MPa, gas space velocity 20000h-1。
To the catalyst in three reactors apart from 1/3 bed height of top, 0.5g is sampled in due course, according to embodiment
The miniature fixed bed device of identical constant temperature, identical evaluation response condition, evaluate its CO conversion ratio and (use gas-chromatography, TCD inspections
Survey device.It is shown in Table 4).
Table 3
Note：
Wherein：
Table 4
Note：
For the ratio between CO and Ar peak areas in former TCD calibrating gas
From embodiment 1 and the result of comparative example 1, comparative example 1 is compared to, can using method provided by the invention
Effectively to convert synthesis gas to methane, without setting fine de-sulfur tower before methanator, therefore it can reduce and set
Standby investment and sorbent consumption.3rd moving-burden bed reactor undertakes the function of desulfurization at the same time, and catalyst is exempted from the reaction of protection first
It is poisoned, the methanation catalyst of the factors such as sulfur poisoning and activity reduction is subject in front three alkylation reactors, by the present invention
After the catalyst regeneration process method processing of offer, the initial activity of catalyst can be returned to, so as to ensure the second methane
Change catalyst in reactor and maintain higher activity always, improve the production efficiency of reactor.It is additionally, since the second methane
Changing catalyst can be with cyclic regeneration, therefore uses method provided by the invention, can be required to avoid using fixed bed reactors
Catalyst has the rigors of long-life, embodies the advantage using moving-burden bed reactor.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
Protection scope of the present invention should all be belonged to.
Claims (15)
1. a kind of prepare the method rich in methane gas by synthesis gas, it is characterised in that comprises the following steps：
(1) by net synthesis gas and the first methanation catalyst in the first methanator haptoreaction, obtain methanation original
Expect gas；
(2) the methanation unstripped gas that step (1) obtains is contacted with the second methanation catalyst in the second methanator
Reaction, carries out heat exchange cooling by the high-temperature gas logistics that reaction obtains, obtains gas stream one；
(3) the first methanation catalyst in step (1) is drawn from the first methanator, and is divided into three parts：The
A part of catalyst is sent into regeneration reactor and carries out regeneration treatment, obtains regenerated first methanation catalyst and is sent into front three
Alkylation reactors recycle；Part II catalyst discharges reaction system as dead catalyst；Part III catalyst is direct
It is sent to the use of front three alkanisation reactor cycles；
(4) gas stream one for obtaining step (2) exists with Part III catalyst and/or regenerated first methanation catalyst
Haptoreaction in front three alkylation reactors, the gaseous product obtained after reaction is cooled down, and obtains the gas rich in methane
Product；
First methanator and the front three alkylation reactors are moving-burden bed reactor, second methanation
Reactor is fixed bed reactors.
2. according to claim 1 prepare the method rich in methane gas by synthesis gas, it is characterised in that in step (1),
The catalytic condition is：5-100 absolute atmosphere, 40-400 DEG C, gas space velocity 50-80000h-1, catalyst stops
It is 24h-10 days to stay the time；In step (2), the catalytic condition is：15-100 absolute atmosphere, 330-800 DEG C,
Gas space velocity 7500-120000h-1；In step (4), the catalytic condition is：2-100 absolute atmosphere, 250-
700 DEG C, gas space velocity 50-80000h-1, catalyst residence times be 24h-100 days.
3. according to claim 1 prepare the method rich in methane gas by synthesis gas, it is characterised in that in step (1),
The net synthesis gas forms at least one of group by pre- by producing synthesis gas from coal, biomass preparing synthetic gas and oven gas
Obtained after processing imurity-removal and/or hydrosphere transformation.
4. according to claim 1 prepare the method rich in methane gas by synthesis gas, it is characterised in that the moving bed
The pattern of reactor selected from by erect-type, inclined, horizontal type, erect it is telescopic and erect reducing type form in group extremely
Few one kind.
5. according to claim 1 prepare the method rich in methane gas by synthesis gas, it is characterised in that the front three
The quantity of alkylation reactors is 2-4, is serially connected between the front three alkylation reactors, in parallel, series-multiple connection or simultaneously-string
Connection.
6. according to claim 1 prepare the method rich in methane gas by synthesis gas, it is characterised in that in step (1),
The contact process once urging by the first methanator in a manner of adverse current, cross-flow or cocurrent for the net synthesis gas
Agent bed.
7. according to claim 1 prepare the method rich in methane gas by synthesis gas, it is characterised in that in step (1),
(H in the methanation unstripped gas2-CO2)/(CO+CO2) molar ratio is 2.8-3.5.
8. according to claim 1 prepare the method rich in methane gas by synthesis gas, it is characterised in that in step (4),
The way of contact of the gas stream one and Part III catalyst is adverse current, cross-flow or cocurrent.
9. according to claim 1 prepare the method rich in methane gas by synthesis gas, it is characterised in that first first
Alkanizing catalyst is coccoid catalyst, and the particle size range of the coccoid catalyst is 0.1-200mm.
10. according to claim 9 prepare the method rich in methane gas by synthesis gas, it is characterised in that described first
Methanation catalyst is made of active component, carrier, binding agent and modified additive, wherein, active component, carrier, binding agent and
The percetage by weight of modified additive is respectively 5-90%, 6-64%, 3-45% and 10-6~2%.
11. according to claim 10 prepare the method rich in methane gas by synthesis gas, it is characterised in that the work
Property component be selected from least one of group formed by Ni, Mo, Fe, Co, Ru, Pt, Pd and Rh.
12. according to claim 10 prepare the method rich in methane gas by synthesis gas, it is characterised in that the modification
Auxiliary agent is selected from forms at least one of group by rare earth element, transition metal and major element.
13. according to claim 12 prepare the method rich in methane gas by synthesis gas, it is characterised in that the rare earth
Element is La, Ce, Pr, Nd and Sm, and the transition metal is Zr, Y, Nb, Cr, Ti, Zn, Cu, Mn, Os and Ir, the master
Race's element is Si, Al, Mg, K and Rb.
14. according to claim 1 prepare the method rich in methane gas by synthesis gas, it is characterised in that step (3)
In, the percetage by weight that the Part I catalyst, Part II catalyst and Part III catalyst account for total amount is followed successively by
20-60%, 0-20% and 30-80%.
15. according to claim 1 prepare the method rich in methane gas by synthesis gas, it is characterised in that step (3)
In, the regeneration reactor is selected from fixed bed reactors, moving-burden bed reactor, fluidized-bed reactor and entrained-flow reactor institute group
Into at least one of group, it is serially connected between the regeneration reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610950692.5A CN107987907B (en) | 2016-10-26 | 2016-10-26 | Method for preparing methane-rich gas from synthesis gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610950692.5A CN107987907B (en) | 2016-10-26 | 2016-10-26 | Method for preparing methane-rich gas from synthesis gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107987907A true CN107987907A (en) | 2018-05-04 |
| CN107987907B CN107987907B (en) | 2020-07-10 |
Family
ID=62029527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610950692.5A Active CN107987907B (en) | 2016-10-26 | 2016-10-26 | Method for preparing methane-rich gas from synthesis gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107987907B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110903870A (en) * | 2018-09-18 | 2020-03-24 | 中国石油化工股份有限公司 | Process for preparing methane by single pass of coal-based synthesis gas in slurry bed |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2781195A1 (en) * | 2009-11-18 | 2011-05-26 | G4 Insights Inc. | Method and system for biomass hydrogasification |
| CN104226318A (en) * | 2014-09-29 | 2014-12-24 | 西南化工研究设计院有限公司 | High-space-velocity honeycombed methanation catalyst and preparation method thereof |
| CN204198706U (en) * | 2014-11-05 | 2015-03-11 | 中国华能集团清洁能源技术研究院有限公司 | A kind of methanation device of producing synthesis gas from coal preparing natural gas |
| CN204247177U (en) * | 2014-11-24 | 2015-04-08 | 成都赛普瑞兴科技有限公司 | A kind of thermal insulation-isothermal methanation reactor |
| CN204848758U (en) * | 2015-03-27 | 2015-12-09 | 中国昆仑工程公司 | Remove bed methyl alcohol system hydrocarbon system all |
| WO2016081956A1 (en) * | 2014-11-20 | 2016-05-26 | Sasol Technology Proprietary Limited | Fischer-tropsch synthesis |
-
2016
- 2016-10-26 CN CN201610950692.5A patent/CN107987907B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2781195A1 (en) * | 2009-11-18 | 2011-05-26 | G4 Insights Inc. | Method and system for biomass hydrogasification |
| CN104226318A (en) * | 2014-09-29 | 2014-12-24 | 西南化工研究设计院有限公司 | High-space-velocity honeycombed methanation catalyst and preparation method thereof |
| CN204198706U (en) * | 2014-11-05 | 2015-03-11 | 中国华能集团清洁能源技术研究院有限公司 | A kind of methanation device of producing synthesis gas from coal preparing natural gas |
| WO2016081956A1 (en) * | 2014-11-20 | 2016-05-26 | Sasol Technology Proprietary Limited | Fischer-tropsch synthesis |
| CN204247177U (en) * | 2014-11-24 | 2015-04-08 | 成都赛普瑞兴科技有限公司 | A kind of thermal insulation-isothermal methanation reactor |
| CN204848758U (en) * | 2015-03-27 | 2015-12-09 | 中国昆仑工程公司 | Remove bed methyl alcohol system hydrocarbon system all |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110903870A (en) * | 2018-09-18 | 2020-03-24 | 中国石油化工股份有限公司 | Process for preparing methane by single pass of coal-based synthesis gas in slurry bed |
| CN110903870B (en) * | 2018-09-18 | 2021-08-20 | 中国石油化工股份有限公司 | Process for preparing methane by single pass of coal-based synthesis gas in slurry bed |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107987907B (en) | 2020-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hossain et al. | Chemical-looping combustion (CLC) for inherent CO2 separations—a review | |
| JP6479677B2 (en) | Parallel production of hydrogen, carbon monoxide and carbon-containing products | |
| CN101817716B (en) | Method and device for catalyzing methanation of synthesis gas | |
| CN101979476B (en) | Process for synthesizing natural gas by methanation of coal synthesis gas | |
| CN102782161A (en) | Blast furnace operation method, iron mill operation method, and method for utilizing a gas containing carbon oxides | |
| CN103373706B (en) | A kind of methane reforming hydrogen production process and device | |
| CN102695669A (en) | Water gas shift reaction process | |
| CN104001457B (en) | A kind of methanation fluidized-bed reactor | |
| CN102010759A (en) | Method and device for producing hydrogen-rich gases by catalyzing and gasifying solid fuels | |
| CN104998654B (en) | The method of nickel-base catalyst and preparation method thereof and methane catalytic decomposition production hydrogen | |
| CN102585947A (en) | Method and device for preparing methane-containing gas by using coal | |
| Tian et al. | Evaluation of a hierarchically-structured CuO@ TiO2-Al2O3 oxygen carrier for chemical looping with oxygen uncoupling | |
| CN103242921A (en) | Technology for preparing natural gas from synthetic gas | |
| CN107987907A (en) | It is a kind of that the method rich in methane gas is prepared by synthesis gas | |
| CN102441353A (en) | Device and method for synthesizing chloroethylene by using acetylene method | |
| CN204848257U (en) | Device of methane catalytic cracking production hydrogen | |
| CN103896209B (en) | A kind of method of being produced synthetic gas by coal, Sweet natural gas and carbonic acid gas catalytic reforming | |
| CN101274872B (en) | Fluidizer and technique for preparing ethylene by ethanol dehydration | |
| CN101830434A (en) | Method for producing synthetic gas by natural gas conversion | |
| CN107987906A (en) | A kind of method for producing methane | |
| CN107983268B (en) | A method of by producing firedamp by syngas | |
| CN104341259B (en) | A kind of catalyzing methanation of synthesis gas method and device | |
| CN102259037A (en) | Process for continuously regenerating catalyst for liquefied gas aromatization and liquefied gas cracking | |
| CN2934206Y (en) | Methane catalyzed partial oxidation produced synthetic gas circulating fluidized bed device | |
| CN202570115U (en) | Radial reactor for moving bed |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |