CN108774554A - Loop-free full methanation integrated technique and system - Google Patents
Loop-free full methanation integrated technique and system Download PDFInfo
- Publication number
- CN108774554A CN108774554A CN201810896982.5A CN201810896982A CN108774554A CN 108774554 A CN108774554 A CN 108774554A CN 201810896982 A CN201810896982 A CN 201810896982A CN 108774554 A CN108774554 A CN 108774554A
- Authority
- CN
- China
- Prior art keywords
- methanation
- gas
- reaction
- unit
- multistage
- 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
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 148
- 239000007789 gas Substances 0.000 claims abstract description 112
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000012495 reaction gas Substances 0.000 claims abstract description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 18
- 239000011593 sulfur Substances 0.000 claims abstract description 18
- 238000000746 purification Methods 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 37
- 239000001257 hydrogen Substances 0.000 claims description 37
- 229910052799 carbon Inorganic materials 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- 230000009466 transformation Effects 0.000 claims description 26
- 238000000844 transformation Methods 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000003245 coal Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000002309 gasification Methods 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003034 coal gas Substances 0.000 claims description 4
- 230000003247 decreasing effect Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 238000005804 alkylation reaction Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 206010054949 Metaplasia Diseases 0.000 abstract 1
- 230000015689 metaplastic ossification Effects 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 125000001741 organic sulfur group Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of loop-free full methanation integrated technique and system, technical solution is to include the following steps：Raw gas after oil removing, dedusting is divided into two strands, the reaction gas that methane contents on dry basis is 10-20mol% is obtained after one raw gas is transformed, methanation in presence of sulfur reacts and purification, is subsequently sent to concatenated multistage methanation reaction unit and is carried out the synthetic natural gas that methanation reaction obtains methane contents on dry basis more than 95mol%；Gas is purified after another strand of raw gas is purified, the purified gas is further divided into the entrance reaction gas that multiply mixes multistage methanation reaction unit respectively, participates in follow-up methanation reaction.Present invention process is simple, it is easily operated, without product gas cycle, production cost is low, methane concentration is high, present system is simple in structure, easily controllable, and operating cost is low, is suitable for large-scale methane metaplasia produces.
Description
Technical field
The present invention relates to a kind of methanation process and systems.
Background technology
The energy resource structure feature in China is " rich coal, oil-poor, few gas ", and as coal production and consumption big country, urgently
It needs to find a kind of clean, efficient, acceptable trans-utilization mode of cost.By exploring and using for reference domestic and foreign experience for many years,
Develop the clean coal utilizations modes such as coal gas, can both realize the clean utilization of coal resources, reduce environmental pollution, can also subtract
Light natural gas is to external interdependency, guarantee Chinese energy safety.
In traditional natural gas from coal technique, raw gas first passes around transformationreation and adjusts H:Cmoleratio in 3.0-
Between 3.05, subsequently enters methanation unit and methanation reaction occurs.Reaction principle is as follows：
The characteristics of methanation reaction is strongly exothermic, and high-concentration carbon monoxide reacts the thermal insulation of generation in adiabatic reactor
Wen Sheng great, if not adopting an effective measure, it will equipment overtemperature and sintering of catalyst is caused to inactivate.Traditional process route uses
Portioned product gas recycles, and enters high-temperature methanation reactor after being mixed with unstripped gas, by diluting an oxidation in raw material indirectly
Concentration of carbon controls reactor outlet temperature.The Datang gram flag of commercialized running at present, Xinjiang celebrating China, Inner Mongol remittance can be adopted
Reactor outlet temperature is controlled with setting circulation loop method.But primary high-temperature methanation can be caused anti-after setting circulation loop
Device gas inlet amount is answered to increase, loaded catalyst and equipment investment increase, and further limit the enlargement of unit scale.
Meanwhile the flow also needs to increase recycle compressor, plant maintenance and operating cost increase.Domestic natural gas from coal technique
Related patents also use the outlet temperature of the method control high-temperature methanation reactor of circulation loop mostly
(CN201210029444, CN201110268668, CN201510161040.9) also has using the side such as vapor charge dilution
Method designs the report (CN201410598644, CN201410631615.4) without circulation loop methanation process.But it is steamed using water
It needs additionally to add steam in the scheme of gas charge dilution, needs steam control system, there are a large amount of inertia vapor anti-
It answers in device and reacts, increase system investments.Therefore so far, the more perfect technological means of neither one solves above-mentioned technology
Problem.
Invention content
The purpose of the present invention is to solve above-mentioned technical problem, provide it is a kind of it is simple for process, easily operated, without product
Gas cycle, production cost is low, methane concentration is high, suitable for the loop-free full methanation integrated technique of large-scale production.
The present invention also provides a kind of integrated systems of loop-free full methanation simple in structure, that operation is low with cost of investment
System.
Raw gas after present invention process oil removing, dedusting is divided into two strands, one raw gas is transformed, methanation in presence of sulfur is anti-
Should with obtained after purification the reaction gas that methane contents on dry basis is 10-20mol% be sent into concatenated multistage methanation reaction unit into
Row methanation reaction obtains the synthetic natural gas that methane concentration is more than 95mol%；It is purified after another strand of raw gas is purified
Gas, the purified gas is further divided into the entrance reaction gas at different levels that multiply mixes multistage methanation reaction unit respectively, after participation
Continuous methanation reaction.The method for being mixed into purified gas by share split, control enter first order methanation reaction unit entrance reaction gas
Hydrogen carbon modulus ratio in 16-18, and the hydrogen carbon modulus ratio of concatenated multistage methanation reaction unit entrance reaction gas is passed step by step
Subtract, until the hydrogen carbon modulus ratio of afterbody methanation reaction unit entrance reaction gas is 2.6-3.2.
The hydrogen carbon modulus of the next stage methanation reaction unit entrance reaction gas compares upper level methanation reaction unit
The hydrogen carbon modulus ratio of entrance reaction gas reduces 2-3.
The tolerance of one raw gas accounts for the 60-90mol% of raw gas total amount, and the tolerance of another strand of raw gas accounts for slightly
The 10-40mol% of coal gas total amount.
The raw gas is product gas or oven gas, pyrolysis from dry coal powder gasification or coal-water slurry gasification
One kind in gas.
The shift step includes Two Stages reaction, and one-stage transfor-mation reaction member entrance is controlled by filling into water vapour
Liquid to steam ratio controls between 0.2-0.8, and two-dimensional transform changes the control of reaction member entrance liquid to steam ratio between 0.2-0.8；Described one
200-230 DEG C of the inlet temperature of grade transformationreation unit, 420-450 DEG C of outlet temperature；The entrance of two-dimensional transform device reaction member
200-230 DEG C of temperature, 350-400 DEG C of outlet temperature.
In the methanation in presence of sulfur reaction step, the catalyst of filling is molybdenum base catalyst for methanation in presence of sulfur, controls resistant to sulfur
250-300 DEG C of methanation reaction unit inlet temperature, 500-550 DEG C of outlet temperature.
The multistage methanation reaction unit includes concatenated multistage high-temperature methanation reaction member and multistage low temperature methane
Change reaction member, the purified gas is further divided into multiply and mixes all multistage high-temperature methanation reaction member and whole or portion respectively
Divide in the entrance reaction gas of multistage low temperature methanation reaction unit.
The outlet temperature of the high-temperature methanation reaction member is controlled at 550-700 DEG C；The low temperature methanation unit
Outlet temperature controls between 300-460 DEG C.
The loop-free full methanation integrated system of the present invention, including sequentially connected converter unit, methanation in presence of sulfur are anti-
Unit, the first clean unit and multistage methanation reaction unit are answered, further includes having the second clean unit, second purification is single
The gas access of member is connect with the gas access of the converter unit, and the gas vent of second clean unit is respectively through valve
Each gas access of the multistage methanation reaction unit of door connection.
The multistage methanation reaction unit includes concatenated multistage high-temperature methanation reaction member and multistage low temperature methane
Change reaction member.
The converter unit includes one-stage transfor-mation reaction member and two-dimensional transform reaction member.
The inlet of the one-stage transfor-mation reaction member and two-dimensional transform reaction member is additionally provided with steam and fills into mouth.
The problem of for background technology, inventor carry out further investigation discovery, exist for high-concentration carbon monoxide
The big problem of the adiabatic temperature rise of generation, the hydrogen carbon modulus ratio of the inlet gas of methanation reaction unit are reacted in adiabatic reactor
Control it is particularly important, can not only have the heating problem for inhibiting methanation reaction, control anti-by the control of hydrogen carbon modulus ratio
Device outlet temperature is answered, without circulation loop is arranged, plant investment is reduced, simplifies operating process.And make high temperature first
Alkylation reaction carries out under hydrogen-rich atmosphere, and catalyst is not easy carbon deposit, extends catalyst service life；To realize methanation reaction
The control of the hydrogen carbon modulus ratio of the inlet gas of unit is designed as follows under the premise of not using product gas to recycle：(1)
Raw gas is divided into two strands, one carries out routine variations and pre- methanation, purification process, and another stock is used as carbon containing after then purifying
In the multistage methanation reaction unit of raw material incorporation, so as to simply adjust the hydrogen into methanation reaction unitary gas
Carbon modulus ratio；Preferably, the tolerance of one raw gas typically constitutes from the 60-90% of raw gas total amount, and another burst of tolerance accounts for raw gas
The 10-40% of total amount, another burst of raw gas tolerance can excessively influence the hydrogen-carbon ratio of system, very few to be unfavorable for making full use of synthesis
Effective gas in gas.(2) since methanation reaction unit is usually plural serial stage, inventor limits second burst of tolerance point
Mix the gas access of multistage methanation reaction unit respectively for multiply, further, with the progress of methanation reaction, every grade
Methanation content gradually increases in the synthesis gas of methanation reaction unit outlet, thus the reaction of methanation reaction unit at different levels
Depth also differs, and second strand of raw gas is according at different levels to the incorporation of every grade of methanation reaction unit inlet gas
The hydrogen carbon modulus ratio of methanation reaction unit inlet gas requires to control, and in the present invention, limits and enters first order methanation
The hydrogen carbon modulus ratio of reaction member inlet gas is in 16-18, and the hydrogen carbon of concatenated multistage methanation reaction unit inlet gas
Modulus ratio is successively decreased step by step, until the hydrogen carbon modulus ratio of afterbody methanation reaction unit inlet gas is 2.6-3.2, every grade
After methanation reaction, methanation content gradually rises in synthesis gas, passes through the realization of successively decreasing step by step of hydrogen carbon modulus ratio in gas
The complete conversion of effective gas in reaction gas.Preferably, total hydrogen carbon in conversion gas and second strand of raw gas after first burst of transformation
Modulus ratio is between 2.99-3.05.
First strand of raw gas is first converted, and the purpose of transformation is to be rich in the methanation for having hydrogen in order to obtain
Unstripped gas, level-one or Two Stages may be used in transformation, can be by filling into water vapour control according to need when using Two Stages
Between 0.2-0.8, two-dimensional transform device is reacted into mouthful liquid to steam ratio control and exists for one-stage transfor-mation reactor inlet liquid to steam ratio control processed
Between 0.2-0.8；200-230 DEG C of the inlet temperature of the one-stage transfor-mation reactor, 420-450 DEG C of outlet temperature；Two level becomes
200-230 DEG C of the inlet temperature of parallel operation reactor, 350-400 DEG C of outlet temperature.
Conversion gas after transformation is directly entered methanation in presence of sulfur unit and carries out pre- methanation processing, contains by transformation
Carbon dioxide reduces carbonomonoxide concentration indirectly, can improve methane content in synthesis gas after pre- methanation processing, reduce follow-up
React load.It is preferred that using molybdenum base catalyst for methanation in presence of sulfur, reaction condition is hydrogen-rich atmosphere, and CO conversion is more than
99%, 250-300 DEG C of reactor inlet temperature, 500-550 DEG C of outlet temperature.
The present invention controls reactor outlet temperature by adjusting carbon monoxide content in methanation reaction unit inlet gas
Degree, by the way that purified gas share split is mixed the control realized in synthesis gas to methanation reaction unit entrance carbon monoxide content, no
It needs that circulation loop is arranged, does not need recycle compressor, reduce plant investment, simplify operating process；Methanation reaction is in hydrogen-rich
It is carried out under atmosphere, catalyst is not easy carbon deposit, extends catalyst service life；For transformation, methanation in presence of sulfur, high/low temperature methane
Changing unit can be according to unstripped gas composition and each reactor outlet temperature requirement, the quantity and entrance object of each reactor of flexible configuration
Parameter is flowed, gas product can reach index request, and present invention process is suitable for a variety of raw gas, is applicable to processing and comes from
One kind in the product gas or oven gas of dry coal powder gasification or coal-water slurry gasification, pyrolysis gas.
Description of the drawings
Fig. 1 is present invention process flow chart；
Fig. 2 is present system figure.
Wherein, R101- one-stage transfor-mations reaction member；R102- two-dimensional transform reaction members；S101- converts gas-liquid separation
Tank；S102- methanation knockout drums；S103- product knockout drums；R201- methanation in presence of sulfur reaction members；A101-
One clean unit；The second clean units of A102-；R301- high-temperature methanation reaction members；The reaction of R302- high-temperature methanations is single
Member；R303- high-temperature methanation reaction members；R304- high-temperature methanation reaction members；R305- low temperature methanation reaction units；
R306- low temperature methanation reaction units；R307- low temperature methanation reaction units.
Specific implementation mode
Explanation is further explained to present system below in conjunction with the accompanying drawings：
The loop-free full methanation integrated system of the present invention include sequentially connected one-stage transfor-mation reaction member R101,
Convert knockout drum S101, two-dimensional transform reaction member R102, methanation in presence of sulfur reaction member R301, the first clean unit；
A101 and multistage methanation reaction unit, the multistage methanation reaction unit include concatenated multistage high-temperature methanation reaction
Unit R 301, R302, R303, R304 and multistage low temperature methanation reaction unit R 305, R306, R307, wherein the present embodiment
In, also it is in series with methanation knockout drum S102 and product knockout drum before and after low temperature methanation reaction unit R 307
S103, to realize gas-liquid separation；
Further include thering is the gas access of the second clean unit A102, the second clean unit A102 to become with the level-one
The gas access connection of reaction member R101 is changed, the gas vent of the second clean unit member A102 is connected through valve respectively
Each gas access of multistage methanation reaction unit.In the present embodiment, the gas vent point of the second clean unit A102
Multistage high-temperature methanation reaction member R301, R302, R303, R304 and multistage low temperature methanation reaction are not connected to through valve
The gas access of unit R 305.
The one-stage transfor-mation reaction member R101, two-dimensional transform reaction member R102 and high-temperature methanation reaction member
It is additionally provided with steam at the gas access of R301 and fills into mouth.
Technological process is as shown in Figure 1, the raw gas after dedusting, oil removing (forms H2- 17.98mol%, CO-
52.47mol%, CO2- 7.45mol%, CH4- 0, N2- 0.8mol%, H2O-20.8mol%, C2H6- 0, H2S-0.43mol%,
COS-0.01mol%, Ar-0.06mol%, O2-0；168 DEG C of temperature, pressure 3.9MPa, flow 30776.7kmol/h) it is divided into
Two strands, first strand of raw gas enters one-stage transfor-mation reaction member R101 and two-dimensional transform reaction member R102, and tolerance accounts for rough coal
The 60-90% of gas total amount controls one-stage transfor-mation reaction member R101 entrances and two-dimensional transform reaction member by filling into water vapour
The liquid to steam ratio of R102 entrances is between 0.2-0.8.
200-230 DEG C of one-stage transfor-mation reaction member R101 inlet temperatures, 420-450 DEG C of outlet temperature, two-dimensional transform reaction
200-230 DEG C of 102 inlet temperature of unit R, 350-400 DEG C of outlet temperature.Conversion gas after transformation is directly entered methanation in presence of sulfur
Methanation reaction occurs for reaction member R201, loads molybdenum base catalyst for methanation in presence of sulfur in reactor, reaction condition is hydrogen rich gas
Atmosphere, CO conversion is more than 99%, 250-300 DEG C of reactor inlet temperature, 500-550 DEG C of outlet temperature,；Reaction gas
The hydrogen sulfide removed through the first clean unit A101, carbonyl sulfur, after the sulfur impurities such as organic sulfur, methane contents on dry basis in reaction gas
For 10-20mol%, hydrogen contents on dry basis is 70-90%.Another strand of raw gas first removes devulcanization through the second clean unit A102
Hydrogen, carbonyl sulfur are purified gas after the impurity such as organic sulfur, are separated into multiply and mix methanation reactions at different levels respectively as carbon source
In the reaction gas of unit entrance, participates in follow-up methanation reaction and generate methane.
The reaction gas that per share purified gas is drawn with upper level methanation reaction unit in proportion mixes, and mainly passes through control
Carbon monoxide content controls high-temperature methanation reaction member outlet temperature between 600-700 DEG C in mixed reaction gas,
The high-temperature methanation reaction member quantity is 4-10, and particular number is made of raw gas and high-temperature methanation reactor goes out
Mouth temperature determines, if hydrogen content is more in raw gas, while the setting of high-temperature methanation reaction member outlet temperature is higher, then
The quantity of high-temperature methanation reactor can be reduced accordingly.It is connected using four high-temperature methanation reaction members in the present embodiment,
The control of carbon monoxide contents on dry basis is in 2-15mol% in entrance reaction gas；Control enters first order high-temperature methanation reaction member
The hydrogen carbon modulus ratio of R301 entrance reaction gas is in 16-18, and concatenated multistage high-temperature methanation reaction member and multistage low temperature
The hydrogen carbon modulus ratio of methanation reaction unit entrance reaction gas is successively decreased step by step, until afterbody methanation reaction unit entrance
The hydrogen carbon modulus ratio of reaction gas is 2.6-3.2.Preferably, the hydrogen carbon of the next stage methanation reaction unit entrance reaction gas
The hydrogen carbon modulus ratio that modulus compares upper level methanation reaction unit entrance reaction gas reduces 2-3.In the present embodiment, consider into
Hydrogen carbon modulus ratio has met control and has required in mouth reaction gas, and last two-stage low temperature methanation reaction unit R 306, R307 are practical
And it is not incorporated into purified gas (another strand of raw gas), when actual motion, those skilled in the art can be according to measuring and calculating
Hydrogen carbon modulus ratio select in the entrance reaction gas of each grade low-temp methanation reaction unit whether all or part of incorporation purified gas with
And specific mixed ratio, it can specifically be required according to the hydrogen carbon modulus ratio of design to control.
The moisture that transformation and methanation generate can be arranged as required to knockout drum and be removed water.In order to ensure an oxygen
Change carbon completion and be converted into methane, the present invention has connected 3 low temperature methanation reaction unit Rs 305, R306, R307 simultaneously, goes out
Mouth temperature control synthesizes between 300-460 DEG C, and before entering afterbody low temperature methanation reaction unit R 307
Gas removes partial moisture through supercooling, separation, then enters back into afterbody low temperature methanation reaction unit R 307, ensures one
Carbon oxide conversion rate is more than 99.9%.Total hydrogen carbon mould in synthesis gas and second strand of raw gas after first burst of transformation of the present invention
Number ratio is between 2.99-3.05.After above-mentioned reaction process, the group of produced synthetic natural gas becomes H2- 0.5mol%, CO-0,
CO2- 1.2mol%, CH4- 96.7, N2- 1.1mol%, H2O-0.3mol%, Ar-0.06mol%；40 DEG C of temperature, pressure
2.3MPa, flow 5594.66kmol/h.
It is recycled without product gas in present invention process, low energy consumption, equipment investment and operating cost are low, is suitable for extensive first
Alkanisation produces.
Claims (13)
1. a kind of loop-free full methanation integrated technique, which is characterized in that include the following steps：It is thick after oil removing, dedusting
Coal gas is divided into two strands, and it is 10- that methane contents on dry basis is obtained after one raw gas is transformed, methanation in presence of sulfur reacts and purification
The reaction gas of 20mol% is subsequently sent to concatenated multistage methanation reaction unit and carries out methanation reaction and obtain methane butt containing
Synthetic natural gas of the amount more than 95mol%；Gas is purified after another strand of raw gas is purified, the purified gas is further divided into multiply
In the entrance reaction gas for mixing multistage methanation reaction unit respectively, follow-up methanation reaction is participated in.
2. loop-free full methanation integrated technique as described in claim 1, which is characterized in that be mixed into purification by share split
The method of gas, control into first order methanation reaction unit entrance reaction gas hydrogen carbon modulus ratio in 16-18, and it is concatenated more
The hydrogen carbon modulus ratio of grade methanation reaction unit entrance reaction gas is successively decreased step by step, until afterbody methanation reaction unit entrance
The hydrogen carbon modulus ratio of reaction gas is 2.6-3.2.
3. loop-free full methanation integrated technique as claimed in claim 2, which is characterized in that the next stage methanation
The hydrogen carbon modulus ratio that the hydrogen carbon modulus of reaction member entrance reaction gas compares upper level methanation reaction unit entrance reaction gas subtracts
Few 2-3.
4. loop-free full methanation integrated technique as described in claim 1, which is characterized in that one raw gas
Tolerance accounts for the 60-90mol% of raw gas total amount, and the tolerance of another strand of raw gas accounts for the 10-40mol% of raw gas total amount.
5. loop-free full methanation integrated technique according to any one of claims 1-4, which is characterized in that the rough coal
Gas is one kind in product gas or oven gas, pyrolysis gas from dry coal powder gasification or coal-water slurry gasification.
6. loop-free full methanation integrated technique according to any one of claims 1-4, which is characterized in that the transformation
Step includes Two Stages reaction, and the control of one-stage transfor-mation reaction member entrance liquid to steam ratio is controlled in 0.2- by filling into water vapour
Between 0.8, two-dimensional transform reaction member entrance liquid to steam ratio controls between 0.2-0.8；The one-stage transfor-mation reaction member enters
200-230 DEG C of temperature of mouth, 420-450 DEG C of outlet temperature；200-230 DEG C of the inlet temperature of two-dimensional transform unitary reactor, outlet
350-400 DEG C of temperature.
7. loop-free full methanation integrated technique according to any one of claims 1-4, which is characterized in that the resistant to sulfur
In methanation reaction step, the catalyst of filling is molybdenum base catalyst for methanation in presence of sulfur, and control methanation in presence of sulfur reaction member enters
250-300 DEG C of temperature of mouth, 500-550 DEG C of outlet temperature.
8. loop-free full methanation integrated technique according to any one of claims 1-4, which is characterized in that the multistage
Methanation reaction unit includes concatenated multistage high-temperature methanation reaction member and multistage low temperature methanation reaction unit, described net
Change gas and is further divided into that multiply mix all multistage high-temperature methanation reaction members respectively and all or part of multistage low temperature methanation is anti-
In the entrance reaction gas for answering unit.
9. loop-free full methanation integrated technique according to any one of claims 8, which is characterized in that the high-temperature methanation reaction
The outlet temperature of unit is controlled at 600-700 DEG C；The low temperature methanation unit outlet temperature control 300-460 DEG C it
Between.
10. a kind of loop-free full methanation integrated system, including the reaction of sequentially connected converter unit, methanation in presence of sulfur are single
Member, the first clean unit and multistage methanation reaction unit, which is characterized in that further include having the second clean unit, described second
The gas access of clean unit is connect with the gas access of the converter unit, the gas vent difference of second clean unit
Each gas access of multistage methanation reaction unit is connected through valve.
11. loop-free full methanation integrated system as claimed in claim 10, which is characterized in that the multistage methanation
Reaction member includes concatenated multistage high-temperature methanation reaction member and multistage low temperature methanation reaction unit, second purification
The gas vent of unit connects each gas feed of multistage high-temperature methanation reaction member and multistage low temperature first through valve respectively
All or part of gas feed of alkylation reaction unit.
12. the loop-free full methanation integrated system as described in claim 10 or 11, which is characterized in that the transformation is single
Member includes one-stage transfor-mation reaction member and two-dimensional transform reaction member.
13. loop-free full methanation integrated system as claimed in claim 12, which is characterized in that the one-stage transfor-mation is anti-
It answers the inlet of unit and two-dimensional transform reaction member to be additionally provided with steam and fills into mouth.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810896982.5A CN108774554B (en) | 2018-08-08 | 2018-08-08 | Circulating-free complete methanation integrated process and system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810896982.5A CN108774554B (en) | 2018-08-08 | 2018-08-08 | Circulating-free complete methanation integrated process and system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108774554A true CN108774554A (en) | 2018-11-09 |
| CN108774554B CN108774554B (en) | 2023-10-27 |
Family
ID=64028530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810896982.5A Active CN108774554B (en) | 2018-08-08 | 2018-08-08 | Circulating-free complete methanation integrated process and system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108774554B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1443735A (en) * | 1972-09-08 | 1976-07-21 | Parsons Co Ralph M | Production of substitute natural gas |
| CN102660339A (en) * | 2012-04-27 | 2012-09-12 | 阳光凯迪新能源集团有限公司 | Gas-steam efficient cogeneration process and system based on biomass gasification and methanation |
| CN102776043A (en) * | 2012-07-30 | 2012-11-14 | 西南化工研究设计院有限公司 | Circulating method for preparing natural gas by multi-stage methanation of semi-coke tail gas |
| CN102952597A (en) * | 2012-10-16 | 2013-03-06 | 大连瑞克科技有限公司 | Circulation-free process of synthesizing natural gas |
| CN103289769A (en) * | 2013-05-27 | 2013-09-11 | 中国寰球工程公司 | Method without circulation loop for producing synthetic natural gas by complete methanation of synthesis gas |
| CN104194851A (en) * | 2014-08-19 | 2014-12-10 | 赛鼎工程有限公司 | Technique for synthesizing natural gas from coke oven gas by sulfur-resistant methanation |
| CN105925328A (en) * | 2016-05-06 | 2016-09-07 | 青岛联信催化材料有限公司 | Production technology for preparing natural gas from high CO-content raw gas through sulfur-tolerant shift conversion and methanation |
| CN208803040U (en) * | 2018-08-08 | 2019-04-30 | 中国五环工程有限公司 | Loop-free full methanation integrated system |
-
2018
- 2018-08-08 CN CN201810896982.5A patent/CN108774554B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1443735A (en) * | 1972-09-08 | 1976-07-21 | Parsons Co Ralph M | Production of substitute natural gas |
| CN102660339A (en) * | 2012-04-27 | 2012-09-12 | 阳光凯迪新能源集团有限公司 | Gas-steam efficient cogeneration process and system based on biomass gasification and methanation |
| CN102776043A (en) * | 2012-07-30 | 2012-11-14 | 西南化工研究设计院有限公司 | Circulating method for preparing natural gas by multi-stage methanation of semi-coke tail gas |
| CN102952597A (en) * | 2012-10-16 | 2013-03-06 | 大连瑞克科技有限公司 | Circulation-free process of synthesizing natural gas |
| CN103289769A (en) * | 2013-05-27 | 2013-09-11 | 中国寰球工程公司 | Method without circulation loop for producing synthetic natural gas by complete methanation of synthesis gas |
| CN104194851A (en) * | 2014-08-19 | 2014-12-10 | 赛鼎工程有限公司 | Technique for synthesizing natural gas from coke oven gas by sulfur-resistant methanation |
| CN105925328A (en) * | 2016-05-06 | 2016-09-07 | 青岛联信催化材料有限公司 | Production technology for preparing natural gas from high CO-content raw gas through sulfur-tolerant shift conversion and methanation |
| CN208803040U (en) * | 2018-08-08 | 2019-04-30 | 中国五环工程有限公司 | Loop-free full methanation integrated system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108774554B (en) | 2023-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106629600B (en) | Crude synthesis gas adsoption catalysis process for making hydrogen and its equipment | |
| CN104152201B (en) | Coal syngas circulation gas free methanation technology | |
| CN103449365B (en) | Process for converting high-concentration CO-tolerant sulfur and device thereof | |
| CN205035336U (en) | Resistant sulphur transform process systems of high concentration CO part | |
| CN102229827A (en) | Method for producing synthetic natural gas | |
| CN105883851B (en) | A kind of Novel gasification and pyrolysis coupling coal gas multi-production process | |
| CN110358594A (en) | Water electrolysis hydrogen production and CO2The device and method of methanation synthetic natural gas | |
| CN102041019B (en) | Method for coproducing substitute natural gas through coal liquefaction | |
| CN102876411B (en) | Method and device for producing synthetic natural gas | |
| CN208803040U (en) | Loop-free full methanation integrated system | |
| CN104830391A (en) | Methanation device and process for synthesizing high-quality natural gas produced by coal | |
| CN104119972A (en) | Multifunctional sulfur-resistant methanation transformation process adapting to coal gas | |
| CN106160240B (en) | A kind of system and technique of storage and release electric energy | |
| CN208803039U (en) | Raw gas combined type full methanation system without circulation loop | |
| CN108774554A (en) | Loop-free full methanation integrated technique and system | |
| CN209854029U (en) | Device for preparing methanol from synthesis gas without conversion system | |
| CN103289769A (en) | Method without circulation loop for producing synthetic natural gas by complete methanation of synthesis gas | |
| CN101550053B (en) | New process for producing firedamp by syngas | |
| CN104774662B (en) | It is a kind of that crude synthesis gas is converted into the technique rich in methane gas | |
| CN103013598B (en) | Method and device for producing synthesized natural gas | |
| CN103980091A (en) | System for producing methanol by using coke oven gas | |
| CN106554830A (en) | Producing synthesis gas from coal prepares the technique for substituting natural gas | |
| CN101966472B (en) | Device for reducing catalyst for catalytic synthesis of dimethyl ether by one-step method | |
| CN108865307A (en) | Raw gas combined type full methanation technique and system without circulation loop | |
| CN104058368A (en) | Process and system for producing hydrogen by converting hydrocarbon-containing tail gas |
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 |