CN106554830A - Producing synthesis gas from coal prepares the technique for substituting natural gas - Google Patents
Producing synthesis gas from coal prepares the technique for substituting natural gas Download PDFInfo
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Abstract
The present invention relates to a kind of producing synthesis gas from coal prepares the technique for substituting natural gas, belong to coal clean gas field.Described producing synthesis gas from coal prepares the technique for substituting natural gas, including the reaction of at least two-stage methanation in presence of sulfur and at least one-level sulfur-tolerant water gas shift, technical process is that producing synthesis gas from coal first carries out one-level methanation in presence of sulfur reaction, sulfur-tolerant water gas shift is carried out again, two grades of methanation in presence of sulfur reactions are carried out finally, obtain substituting natural gas, solve the problems, such as that technique present in current natural gas from coal technology matches somebody with somebody big hydrogen amount, available gas waste and reaction depth shallow.The present invention is not required to additionally with hydrogen, and the condensed water in process gas is recyclable to be used again, H in producing synthesis gas from coal2And carbonaceous gas is obtained sufficiently utilization, and the mesohigh steam of by-product high added value, comprehensive energy consumption and operating cost are substantially reduced, and the impurity compound conversion ratio such as organic sulfur, hydrogen cyanide and tar reaches more than 99.5%, with preferably economical and environmentally friendly benefit.
Description
Technical field
The present invention relates to a kind of producing synthesis gas from coal prepares the technique for substituting natural gas, belong to coal clean gas field.
Background technology
Chinese Resources structure is oil-poor to lack gas, but coal resource is quite enriched.In recent years with economic fast development, natural gas conduct
A kind of energy of clean and effective, in the consumption of the energy, shared ratio increases sharply, and the demand of current domestic natural gas is much
More than quantity delivered, external degree of dependence on inport is greatly increased, therefore natural gas from coal technology not only can meet growing city
Field demand, and the energy security to China, energy-saving and emission-reduction have great importance.
Although the technology of natural gas from coal is mature on the whole, many production problems are exposed in commercial Application, and due to raw material
The kind of coal is different, and the gasification process of employing is different, and the CO contents in the unstripped gas for producing that gasify height differs, subsequent conversion
And methanation process is also different, each section of reacting furnace bed temperature is also not quite similar.Common process is carried out again using first transformed
Methanation is standby to substitute natural gas, or adopts multistage methanation circulation dilution technique gas to reduce wherein CO contents to control reaction
The full methanation process of temperature, compares the first technique, although without allocating substantial amounts of hydrogen into, but due to by synthesis technique gas
H2With the restriction of the ratio and reaction balance of CO, a portion CO need to be through the hydrogen needed for transformationreation preparation methanation
Gas, produces substantial amounts of CO2, cause the waste of available gas, and due to transformationreation depth it is shallower, reaction liberated heat compared with
Low, the impurity such as hydrogen cyanide, organic sulfur class organic compound and tar for carrying in causing process gas is not enough under middle cryogenic conditions
With complete hydrogenation or hydrolysis, subsequent purification unit load is caused to increase, or even pollution environment.Using multistage methanation pyroreaction
Although to the organic compounds such as organic sulfur hydrogenation effect substantially, need to allocate substantial amounts of hydrogen into, repeatedly circulation and multistage reaction is caused
Energy consumption is larger.
Therefore, carry out producing synthesis gas from coal and prepare the research for substituting natural gas new technology, solve the various problems that presently, there are, reduce
System energy consumption, maintains device stable operation, is current coal gas technique major issue urgently to be resolved hurrily, with important reality meaning
Justice.
The content of the invention
It is an object of the invention to provide a kind of producing synthesis gas from coal prepares the technique for substituting natural gas, current natural gas from coal skill is solved
The problem that technique present in art is big with hydrogen amount, available gas are wasted and reaction depth is shallow.Be not required to additionally match somebody with somebody hydrogen, process gas
In condensed water can recycle, available gas are fully used, byproduct steam, comprehensive energy consumption and operating cost drop significantly
The characteristics of low, impurity high conversion rate.
Producing synthesis gas from coal of the present invention prepares the technique for substituting natural gas, including the reaction of at least two-stage methanation in presence of sulfur and at least
One-level sulfur-tolerant water gas shift, technical process are that producing synthesis gas from coal first carries out one-level methanation in presence of sulfur reaction, then to carry out sulphur-resistant conversion anti-
Should, two grades of methanation in presence of sulfur reactions are finally carried out, obtains substituting natural gas.
Wherein, preferred technical scheme is as follows：
Described producing synthesis gas from coal prepares the technique of replacement natural gas and comprises the following steps：
(1) one-level methanation in presence of sulfur reaction：
Producing synthesis gas from coal Jing one-level separator remove impurity and cooling after, then Jing first-class heat exchangers with pass through one-level mesohigh used heat
After one-level methanation in presence of sulfur reactor outlet gas heat exchange after boiler by-product mesohigh steam, react into one-level methanation in presence of sulfur
Device carries out one-level methanation in presence of sulfur reaction；
(2) sulfur-tolerant water gas shift：
One-level methanation in presence of sulfur reactor outlet gas Jing after one-level mesohigh waste heat boiler by-product mesohigh steam, with remove impurity
After being exchanged heat with the producing synthesis gas from coal after cooling, transformationreation is carried out into sulfur-tolerant water gas shift device；
(3) two grades of methanation in presence of sulfur reactions：
Sulfur-tolerant water gas shift device exit gas Jing after the cooling heat exchange of two grades of mesolow waste heat boilers, two grades of separators continue cooling,
Enter Jing secondary heat exchanger with two grades of methanation in presence of sulfur reactor outlet gas after three-level mesohigh waste heat boiler byproduct steam again
After row heat exchange, two grades of methanation in presence of sulfur reactions are carried out into two grades of methanation in presence of sulfur reactors；Two grades of methanation in presence of sulfur reactors go out
Gas Jing after the cooling of three-level mesohigh waste heat boiler, then Jing secondary heat exchangers with pass through two grades of mesolow waste heat boilers and two grades of water
Sulfur-tolerant water gas shift device exit gas after separator cooling heat exchange is exchanged heat, and finally gives replacement natural gas.
Producing synthesis gas from coal in step (1) Jing after one-level separator removes impurity and cooling, by first-class heat exchanger and Jing one-levels
One-level methanation in presence of sulfur reactor outlet gas after mesohigh waste heat boiler by-product mesohigh steam exchange heat to 200-260 DEG C, one-level
Methanation in presence of sulfur inside reactor bed temperature is 260-760 DEG C, and in one-level methanation in presence of sulfur reactor outlet gas, CO's is dry
Base volume content≤40%, methane butt volume content >=20%, organic sulfur conversion rate ＞ 99.0%.
In step (2) one-level methanation in presence of sulfur reactor outlet gas with remove impurity and lower the temperature after producing synthesis gas from coal exchange heat to
230-280 DEG C, then sulfur-tolerant water gas shift device is entered with after one-level separator, the cold water mix of two grades of separator recyclings
Sulfur-tolerant water gas shift is carried out, sulfur-tolerant water gas shift device bed temperature is 280-480 DEG C, CO in sulfur-tolerant water gas shift device exit gas
Butt volume content≤1.0%, methane butt volume content >=14%, organic sulfur conversion rate ＞ 99.5%.
Bis- grades of mesolow waste heat boilers of sulfur-tolerant water gas shift device exit gas Jing cooling heat exchange in step (3), two grades of separators after
After continuous cooling, by the outlet of secondary heat exchanger and two grades of methanation in presence of sulfur reactors Jing after the cooling of three-level mesohigh waste heat boiler
To 220-270 DEG C, two grades of methanation in presence of sulfur inside reactor bed temperatures are 270-700 DEG C to gas converting heat, two grades of methanation in presence of sulfur
Butt volume content≤0.1% of CO in reactor outlet gas, methane butt volume content >=90%, organic sulfur conversion rate ＞
99.5%.
Wherein：
(1) technique of the present invention, is adapted to sulfur-bearing, CO and H2Producing synthesis gas from coal raw material, the butt body of wherein CO
Product content is 20-45%, and preferably 25-40%, feed pressure are 2.0-6.0MPa, preferably 3.0-4.0MPa.
(2) technique of the present invention, (H in sulfur-tolerant water gas shift device exit gas2-CO2) and (CO+CO2) butt volume
Than for 3.0 ± 0.3, preferably 3.0 ± 0.1.
(4) after technique of the present invention, one-level separator and two grades of separator adjustment WGRs, Outlet Gas Temperature is
100-170 DEG C, preferably 120-150 DEG C.
Beneficial effects of the present invention are as follows：
The present invention need not additionally match somebody with somebody hydrogen, and the condensed water in process gas can be recycled, and substep methanation and transformationreation are arranged in pairs or groups
H in producing synthesis gas from coal can be made2And carbonaceous gas is fully utilized, and the mesohigh steam of by-product high added value, comprehensive energy
Consumption and operating cost substantially reduce, while in present invention process gas the conversion ratio of organic sulfur, hydrogen cyanide and tar reach 99.5% with
On, solve current producing synthesis gas from coal prepare substitute in natural gas technique with hydrogen amount is big, available gas are wasted and reaction depth is shallow and
Organic sulfur, hydrogen cyanide, the not tractable difficult problem of tar class impurity compound, with preferably economical and environmentally friendly benefit.
Description of the drawings
Fig. 1 is the process chart of the present invention.
In figure：1st, producing synthesis gas from coal；2nd, one-level separator；3rd, first-class heat exchanger；4th, one-level methanation in presence of sulfur reactor；
5th, one-level mesohigh waste heat boiler；6th, sulfur-tolerant water gas shift device；7th, two grades of mesolow waste heat boilers；8th, two grades of separators；
9th, secondary heat exchanger；10th, two grades of methanation in presence of sulfur reactors；11st, three-level mesohigh waste heat boiler；12nd, substitute natural gas.
Specific embodiment
With reference to embodiments the present invention is described further.
Embodiment 1
(1) in certain natural gas from coal device, the CO butts volume content of producing synthesis gas from coal is 40%, hydrogen butt volume content
For 38%, feed pressure is 6.0MPa, and Jing one-levels separator removes impurity and is cooled to 120 DEG C of dehydrations, then Jing one-levels exchange heat
Device and one-level methanation in presence of sulfur reactor outlet gas after one-level mesohigh waste heat boiler by-product mesohigh steam exchange heat to
220 DEG C, into one-level methanation in presence of sulfur reactor, bed hot(test)-spot temperature is 750 DEG C, one-level methanation in presence of sulfur reactor outlet gas
In body, the butt volume content of CO is 38%, the butt volume content 20% of methane, and organic sulfur conversion rate is 99.1%.
(2) gas from one-level methanation in presence of sulfur reactor out first passes through one-level mesohigh waste heat boiler by-product mesohigh steam
Afterwards, then with removing impurity and being cooled to 120 DEG C of producing synthesis gas from coal exchanged heat, adjustment temperature to after 250 DEG C, then with one-level
The cold water mix that separator and two grades of separators are recycled, adjusts the aqueous vapor ratio needed for sulfur-tolerant water gas shift, after mixing
Transformationreation is carried out into sulfur-tolerant water gas shift device, bed hot(test)-spot temperature is 450 DEG C, CO in sulfur-tolerant water gas shift device exit gas
Butt volume content be 1.0%, (H2-CO2)/(CO+CO2) butt volume ratio be 2.9, the butt volume content of methane
For 15%, organic sulfur conversion rate is 99.5%.
(3) bis- grades of mesolow waste heat boiler cooling heat exchange of the gas Jing from sulfur-tolerant water gas shift device out and two grades of separators are adjusted
After whole WGR, process gas temperature to 110 DEG C, then by secondary heat exchanger with Jing three-level mesohigh waste heat boiler cooling heat exchange after
The heat exchange of two grades of methanation in presence of sulfur reactor outlet gas, make process gas temperature rise to 230 DEG C, into two grades of methanation in presence of sulfur
Reactor carries out two grades of methanation in presence of sulfur reactions, and bed hot(test)-spot temperature is 700 DEG C, two grades of methanation in presence of sulfur reactor outlet gas
The butt volume content of middle CO is 0.08%, and the butt volume content of methane is 91%, and organic sulfur conversion rate is 99.7%.
Embodiment 2
(1) in certain natural gas from coal device, the CO butts volume content of producing synthesis gas from coal is 29%, and hydrogen butt volume content is
48%, feed pressure is 3.8MPa, and Jing one-levels separator removes impurity and is cooled to 150 DEG C of dehydrations, then Jing first-class heat exchangers
Exchange heat to 260 with the one-level methanation in presence of sulfur reactor outlet gas after one-level mesohigh waste heat boiler by-product mesohigh steam
DEG C, into one-level methanation in presence of sulfur reactor, bed hot(test)-spot temperature is 760 DEG C, one-level methanation in presence of sulfur reactor outlet gas
The butt volume content of middle CO is 22%, the butt volume content 34% of methane, and organic sulfur conversion rate is 99.3%.
(2) gas from one-level methanation in presence of sulfur reactor out first passes through one-level mesohigh waste heat boiler by-product mesohigh steam
Afterwards, then with removing impurity and being cooled to 150 DEG C of producing synthesis gas from coal exchanged heat, adjustment temperature to after 270 DEG C, then with one-level
The cold water mix that separator and two grades of separators are recycled, adjusts the aqueous vapor ratio needed for sulfur-tolerant water gas shift, after mixing
Transformationreation is carried out into sulfur-tolerant water gas shift device, bed hot(test)-spot temperature is 420 DEG C, CO in sulfur-tolerant water gas shift device exit gas
Butt volume content be 0.8%, (H2-CO2)/(CO+CO2) volume ratio be 3.1, the butt volume content of methane is 28%,
Organic sulfur conversion rate is 99.5%.
(3) bis- grades of mesolow waste heat boiler cooling heat exchange of the gas Jing from sulfur-tolerant water gas shift device out and two grades of separators are adjusted
After whole WGR, process gas temperature to 120 DEG C, then by secondary heat exchanger with Jing three-level mesohigh waste heat boiler cooling heat exchange after
The heat exchange of two grades of methanation in presence of sulfur reactor outlet gas, make process gas temperature rise to 230 DEG C, into two grades of methanation in presence of sulfur
Reactor carries out two grades of methanation in presence of sulfur reactions, and bed hot(test)-spot temperature is 680 DEG C, two grades of methanation in presence of sulfur reactor outlet gas
The butt volume content of middle CO is 0.06%, and the butt volume content of methane is 90%, and organic sulfur conversion rate is 99.6%.
Embodiment 3
(1) in certain natural gas from coal device, the CO butts volume content of producing synthesis gas from coal is 45%, and hydrogen butt volume content is
36%, feed pressure is 4.0MPa, and Jing one-levels separator removes impurity and is cooled to 100 DEG C of dehydrations, then Jing first-class heat exchangers
Exchange heat to 240 with the one-level methanation in presence of sulfur reactor outlet gas after one-level mesohigh waste heat boiler by-product mesohigh steam
DEG C, into one-level methanation in presence of sulfur reactor, bed hot(test)-spot temperature is 740 DEG C, one-level methanation in presence of sulfur reactor outlet gas
The butt volume content of middle CO is 40%, the butt volume content 24% of methane, and organic sulfur conversion rate is 99.2%.
(2) gas from one-level methanation in presence of sulfur reactor out first passes through one-level mesohigh waste heat boiler by-product mesohigh steam
Afterwards, then with removing impurity and being cooled to 100 DEG C of producing synthesis gas from coal exchanged heat, adjustment temperature to after 280 DEG C, then with one-level
A small amount of cold water mix that the cold water and outside of separator and two grades of separator recyclings is allocated into, adjusts sulfur-tolerant water gas shift institute
The aqueous vapor ratio for needing, carries out sulfur-tolerant water gas shift into sulfur-tolerant water gas shift device after mixing, and bed hot(test)-spot temperature is 480 DEG C, resistance to
In sulphur shift-converter exit gas, the butt volume content of CO is 0.6%, (H2-CO2)/(CO+CO2) butt volume
It is 17% than the butt volume content for 3.3, methane, organic sulfur conversion rate is 99.8%.
(3) bis- grades of mesolow waste heat boiler cooling heat exchange of the gas Jing from sulfur-tolerant water gas shift device out and two grades of separators are adjusted
After whole WGR, process gas temperature to 170 DEG C, then by secondary heat exchanger with Jing three-level mesohigh waste heat boiler cooling heat exchange after
Two grades of methanation in presence of sulfur reactor outlet gas exchanged heat, make process gas temperature rise to 230 DEG C, into two grades of resistant to sulfur first
Alkylation reactors carry out two grades of methanation in presence of sulfur reactions, and bed hot(test)-spot temperature is 700 DEG C, two grades of methanation in presence of sulfur reactor outlets
In gas, the butt volume content of CO is 0.04%, and the butt volume content of methane is 92%, and organic sulfur conversion rate is 99.8%.
Embodiment 4
(1) in certain natural gas from coal device, the CO butts volume content of producing synthesis gas from coal is 32%, hydrogen butt volume content
46%, feed pressure is 3.0MPa, and Jing one-levels separator removes impurity and is cooled to 130 DEG C of dehydrations, then Jing first-class heat exchangers
Exchange heat to 260 with the one-level methanation in presence of sulfur reactor outlet gas after one-level mesohigh waste heat boiler by-product mesohigh steam
DEG C, into one-level methanation in presence of sulfur reactor, bed hot(test)-spot temperature is 760 DEG C, one-level methanation in presence of sulfur reactor outlet gas
The butt volume content of middle CO is 27%, the butt volume content 23% of methane, and organic sulfur conversion rate is 99.4%.
(2) gas from one-level methanation in presence of sulfur reactor out first passes through one-level mesohigh waste heat boiler by-product mesohigh steam
Afterwards, then with removing impurity and being cooled to 130 DEG C of producing synthesis gas from coal exchanged heat, adjustment temperature to after 240 DEG C, then with one-level
The cold water mix that separator and two grades of separators are recycled, adjusts the aqueous vapor ratio needed for sulfur-tolerant water gas shift, after mixing
Sulfur-tolerant water gas shift is carried out into sulfur-tolerant water gas shift device, bed hot(test)-spot temperature is 460 DEG C, sulfur-tolerant water gas shift device exit gas
The butt volume content of middle CO is 0.7%, (H2-CO2)/(CO+CO2) butt volume ratio be 3.0, the butt of methane
Volume content is 18%, and organic sulfur conversion rate is 99.6%.
(3) bis- grades of mesolow waste heat boiler cooling heat exchange of the gas Jing from sulfur-tolerant water gas shift device out and two grades of separators are adjusted
After whole WGR, process gas temperature lowers the temperature two grade exchange heat after with Jing three-level waste heat boiler to 150 DEG C, then by secondary heat exchanger
Methanation in presence of sulfur reactor outlet gas are exchanged heat, and make process gas temperature rise to 260 DEG C, anti-into two grades of methanation in presence of sulfur
Device is answered to carry out two grades of methanation in presence of sulfur reactions, bed hot(test)-spot temperature is 680 DEG C, in two grades of methanation in presence of sulfur reactor outlet gas
The butt volume content of CO is 0.06%, and the butt volume content of methane is 91%, and organic sulfur conversion rate is 99.7%.
Claims (10)
1. a kind of producing synthesis gas from coal prepares the technique for substituting natural gas, it is characterised in that：React including at least two-stage methanation in presence of sulfur
At least one-level sulfur-tolerant water gas shift, technical process is that producing synthesis gas from coal first carries out one-level methanation in presence of sulfur reaction, then carries out resistant to sulfur
Transformationreation, finally carries out two grades of methanation in presence of sulfur reactions, obtains substituting natural gas.
2. producing synthesis gas from coal according to claim 1 prepares the technique for substituting natural gas, it is characterised in that：Including following step
Suddenly：
(1) one-level methanation in presence of sulfur reaction：
Producing synthesis gas from coal Jing one-level separator remove impurity and cooling after, then Jing first-class heat exchangers with pass through one-level mesohigh used heat
After one-level methanation in presence of sulfur reactor outlet gas heat exchange after boiler by-product mesohigh steam, react into one-level methanation in presence of sulfur
Device carries out one-level methanation in presence of sulfur reaction；
(2) sulfur-tolerant water gas shift：
One-level methanation in presence of sulfur reactor outlet gas Jing after one-level mesohigh waste heat boiler by-product mesohigh steam, with remove impurity
After being exchanged heat with the producing synthesis gas from coal after cooling, sulfur-tolerant water gas shift is carried out into sulfur-tolerant water gas shift device；
(3) two grades of methanation in presence of sulfur reactions：
Sulfur-tolerant water gas shift device exit gas Jing after the cooling heat exchange of two grades of mesolow waste heat boilers, two grades of separators continue cooling,
Enter Jing secondary heat exchanger with two grades of methanation in presence of sulfur reactor outlet gas after three-level mesohigh waste heat boiler byproduct steam again
After row heat exchange, two grades of methanation in presence of sulfur reactions are carried out into two grades of methanation in presence of sulfur reactors, two grades of methanation in presence of sulfur reactors go out
Gas Jing after the cooling of three-level mesohigh waste heat boiler, then Jing secondary heat exchangers with pass through two grades of mesolow waste heat boilers and two grades of water
Sulfur-tolerant water gas shift device exit gas after separator cooling heat exchange is exchanged heat, and finally gives replacement natural gas.
3. producing synthesis gas from coal according to claim 1 prepares the technique for substituting natural gas, it is characterised in that：Producing synthesis gas from coal
The butt volume content of middle CO is 20-45%, and feed pressure is 2.0-6.0MPa.
4. producing synthesis gas from coal according to claim 2 prepares the technique for substituting natural gas, it is characterised in that：Step (1)
Middle producing synthesis gas from coal Outlet Gas Temperature Jing after one-level separator adjustment WGR is 100-170 DEG C, then Jing first-class heat exchangers with it is logical
The one-level methanation in presence of sulfur reactor outlet gas crossed after one-level mesohigh waste heat boiler by-product mesohigh steam exchange heat to 200-260
DEG C, one-level methanation in presence of sulfur inside reactor bed temperature is 260-760 DEG C.
5. the producing synthesis gas from coal according to claim 2 or 4 prepares the technique for substituting natural gas, it is characterised in that：Step (1)
Butt volume content≤40% of CO in middle one-level methanation in presence of sulfur reactor outlet gas, the butt volume content of methane >=
20%, organic sulfur conversion rate ＞ 99.0%.
6. producing synthesis gas from coal according to claim 2 prepares the technique for substituting natural gas, it is characterised in that：Step (2)
Middle one-level methanation in presence of sulfur reactor outlet gas Jing after one-level mesohigh waste heat boiler by-product mesohigh steam, with remove impurity and
Producing synthesis gas from coal after cooling exchanges heat to 230-280 DEG C and enters sulfur-tolerant water gas shift device, on cobalt molybdenum system transformation catalyst carries out resistant to sulfur
Transformationreation, inside sulfur-tolerant water gas shift device, bed temperature is 280-480 DEG C.
7. the producing synthesis gas from coal according to claim 2 or 6 prepares the technique for substituting natural gas, it is characterised in that：Step (2)
(H in middle sulfur-tolerant water gas shift device exit gas2-CO2) and (CO+CO2) butt volume ratio be the dry of 3.0 ± 0.3, CO
Base volume content≤1.0%, butt volume content >=14% of methane, organic sulfur conversion rate ＞ 99.5%.
8. the producing synthesis gas from coal according to claim 2 or 6 prepares the technique for substituting natural gas, it is characterised in that：Step (2)
Middle one-level methanation in presence of sulfur reactor outlet gas Jing after one-level mesohigh waste heat boiler by-product mesohigh steam, with remove impurity and
Producing synthesis gas from coal after cooling is exchanged heat, then the cold water mix recycled with one-level separator, two grades of separators, and one
Rising carries out sulfur-tolerant water gas shift into sulfur-tolerant water gas shift device.
9. producing synthesis gas from coal according to claim 2 prepares the technique for substituting natural gas, it is characterised in that：Step (3)
Bis- grades of mesolow waste heat boiler cooling heat exchange of middle sulfur-tolerant water gas shift device exit gas Jing, but bis- grades of separators of Jing adjust WGR
Temperature is changed into 100-170 DEG C afterwards, then by secondary heat exchanger and two grades of methanation in presence of sulfur Jing after the cooling of three-level mesohigh waste heat boiler
Reactor outlet gas exchange heat to 220-270 DEG C, and two grades of methanation in presence of sulfur inside reactor bed temperatures are 270-700 DEG C.
10. producing synthesis gas from coal according to claim 2 prepares the technique for substituting natural gas, it is characterised in that：Step (3)
In in two grades of methanation in presence of sulfur reactor outlet gas CO butt volume content≤0.1%, the butt volume content of methane >=
90%, organic sulfur conversion rate ＞ 99.5%.
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| CN109810739A (en) * | 2019-03-01 | 2019-05-28 | 新地能源工程技术有限公司 | A kind of resistant to sulfur process for synthesizing methane and device |
| CN110877895A (en) * | 2019-08-08 | 2020-03-13 | 中石化宁波工程有限公司 | Integrated process for hydrogen-making sulfur-tolerant shift methanation matched with coal in refinery plant |
| 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 |
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| CN110877895A (en) * | 2019-08-08 | 2020-03-13 | 中石化宁波工程有限公司 | Integrated process for hydrogen-making sulfur-tolerant shift methanation matched with coal in refinery plant |
| CN110877895B (en) * | 2019-08-08 | 2023-03-14 | 中石化宁波工程有限公司 | Integrated process for hydrogen-making sulfur-tolerant shift methanation of coal matched with refinery |
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Application publication date: 20170405 |