CN106984336A - Applied to the sulfur resistant catalyst and its preparation method of synthesis gas methanation and application - Google Patents
Applied to the sulfur resistant catalyst and its preparation method of synthesis gas methanation and application Download PDFInfo
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- CN106984336A CN106984336A CN201710238838.8A CN201710238838A CN106984336A CN 106984336 A CN106984336 A CN 106984336A CN 201710238838 A CN201710238838 A CN 201710238838A CN 106984336 A CN106984336 A CN 106984336A
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- catalyst
- methanation
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
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- 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
Abstract
A kind of sulfur resistant catalyst applied to synthesis gas methanation is that the quality group of catalyst turns into using Mo as active component：Mo 60~70wt%, S 23~35wt%, Al 3~6wt%, 1~4.5wt% of auxiliary agent.The present invention has catalytic performance good, the high advantage of the selectivity of methane.
Description
Technical field
The invention belongs to a kind of applied to sulfur resistant catalyst of synthesis gas methanation and its preparation method and application.
Background technology
Natural gas is as a kind of low-carbon, efficient, cleaning the energy, and proportion will increasingly in disposable energy resource consumption
Greatly.The few gas of the rich coal of the energy resource structure of China, and natural gas demand was increased year by year since 2000 with 16% speed, this makes
Obtain China's natural gas insufficiency of supply-demand year by year to expand, external dependence degree rapid increase.Actively development natural gas from coal, can not only drop
The potential risk that low inlet natural gas market is brought to China, meets the growing market demand, and to the energy of China
Also there is strategic importance in terms of safety, energy-saving and emission-reduction.
Natural gas from coal is that high-carbon energy is converted into hydrogen-rich, the effective way of low-carbon energy by raw material of coal.It passes through
By coal pressure gasification, produced gas to obtain suitable H/C ratios, then leads to through steps such as water-gas shift, acid gas removals
Cross methanation process and prepare the natural gas rich in methane.
Methanation is the core technology of natural gas from coal.At present, the dominant catalyst of industrial methanation is nickel catalyst
Agent, nickel-base catalyst shows very high catalytic activity in methanation reaction.But contain a certain amount of H in coal gas2S, H2S exists
There is unshared electronics pair, the easily strong coordinate bond that electronically forms with Ni metal d tracks, reduction catalysis on electronic structure
The reaction molecular absorption on agent surface and dissociation rate, so as to cause catalyst poisoning, lose methanation activity.In addition, Ni-based urge
Agent has strict requirements to H/C ratios, general to be carried out using nickel-base catalyst in methanation, needs to become by steam first
Change, sulfur removal technology modulation H/C ratios, methanation is then carried out again.Classical sulfur removal technology is that low-temp methanol is washed at present, this technology
First by the coal gas of high temperature desulfurization in -40 DEG C of methanol solution produced after coal gasification, temperature is then increased to 300~400
DEG C carry out methanation.Process of the temperature from -40 DEG C to 300~400 DEG C, greatly wastes energy, adds cost.If energy
Enough develop a kind of sulfur resistant catalyst so that the technological process of gas pressing methanation is changed into:Coal pressure gasification → direct methanation
→ sulphur removing → gas cooling → product gas.This will be such that water-gas shift and methanation process is realized in same reacting furnace, so that
The coal gas of high temperature after coal gasification is directly carried out methanation, without carrying out thick desulfurization and fine de-sulfur, need not also become in advance
Change.Further, since methanation reaction is deduction son reaction, sulfur removal technology is placed on after methanation process so that gas treatment
Amount is significantly reduced, can reduce low-temp methanol and the technical load such as wash, it is to avoid unstripped gas first drops before and after acid gas removal step
The energy dissipation for heating up and causing after temperature, while also eliminating water-gas shift process, reduces equipment investment and operating cost.
Research shows that catalyst with base of molybdenum has good sulfur tolerance, strong carbon accumulation resisting ability, high Water gas shift/WGS
Can, can as methanation catalyst.Patent CN1033580A1 and CN85109423 disclose a kind of be used for by synthesis gas
The catalyst for methanation in presence of sulfur of methane processed, its main active component is vanadium, molybdenum or tungsten, and accelerator is nickel and/or cobalt, and carrier is porous
CeO2Or ZrO2Although the catalyst can reach 80~88% CO conversion ratios at 500 DEG C, methane selectively is only
30~50%；Patent US4833112 discloses a kind of cerium oxide carrying molybdenum oxide catalyst produced for methanation.It will oxidation
Molybdenum, which is supported on cerium oxide, carries out methanation, but cerium oxide is smaller than surface and expensive, is commonly used as the second component
To improve the performance of catalyst；The A of patent CN 103191720 disclose a kind of methanation in presence of sulfur catalysis of magnesium aluminate spinel load
The preparation method of agent, it is prepared for magnesium by coprecipitation, deposition-precipitation method, infusion process, kneading method or sol-gal process technique
Aluminate carrier, using Mo as active component, but its reaction temperature is 650 DEG C, and higher reaction temperature easily causes activearm
Point distillation and make catalyst inactivation.
Above-mentioned patent preferably improves catalysis by adding Mo as the second component, the optimization of carrier and preparation method
The performance and its stability of agent, but preparation process is relative complex.
The content of the invention
An object of the present invention is to provide a kind of preparation process simply, and good with catalytic performance, the selectivity of methane
It is high applied to sulfur resistant catalyst of synthesis gas methanation and its preparation method and application.
The catalyst for methanation in presence of sulfur of the present invention, using Mo as active component, it is characterised in that the quality group of catalyst turns into：
Mo 60~70wt%, S 23~35wt%, Al 3~6wt%, 1~4.5wt% of auxiliary agent.
Auxiliary agent as described above is the one or more in Fe, Ce, Pt, Ni.
The specific preparation process of catalyst for methanation in presence of sulfur of the present invention is as follows：
(1) preparation of Mo-Al alloy powders：It is 3~9 μm of molybdenum powders, 4~10 μm of aluminium powders and 4~10 μm of promoter metal powder by granularity
Well mixed, the mass fraction for controlling each composition is：Mo 45~59wt%, Al 40~55wt%, 1~5wt% of metal promoter；
Alloy powder, which is warming up to 1400~1600 DEG C, melts it, and with 1~1.5*106K/s speed is cooled under nitrogen protection
Room temperature, is then ground to 80~120 mesh standby；
(2) sulfidation of catalyst：Alloy powder prepared by step (1) is 3~9%H in volume composition2With 91~97%
H2350~550 DEG C of 4~6h of vulcanization, obtain catalyst precursor in S atmosphere；
(3) preparation of sulfur resistant catalyst：Catalyst precursor and solid sodium hydroxide prepared by step (2) is mixed, and controls hydrogen
The quality of sodium oxide molybdena is 1~1.5 times of alloyed powder；3~5 times of distilled water of alloyed powder volume is added drop-wise to mixture dropwise, and
With 80~100r/min magnetic agitations；It is placed on simultaneously in water-bath, it is 0~5 DEG C to control bath temperature；After completion of dropwise addition
Suspension 20~40min of ultrasound under conditions of 40~80kHZ, 40~70 DEG C, purpose catalysis is obtained through distilled water cleaning
Agent.
As the mode of heating of step (1) described melting is：High-temperature heating, one kind in laser heating and microwave heating.
The catalyst for synthesis gas methanation is applied to fixed bed methanation reaction system, and its reaction condition is：
Reaction temperature is 400~550 DEG C；Reaction pressure is 1.0~3.0 MPa；Air speed is 7000~10000 mL/ (gh)；Sulphur contains
Measure as 1000~4000ppm；Unstripped gas H2/ CO volume ratios are 3.1~3.5.
The present invention compared with prior art, the advantage is that：
(1) present invention is prepared for the alloyed powder of sulfur resistant catalyst by the method for melting.It is living in catalyst in methanation reaction
Property component content directly affect the catalytic performance of catalyst, can effectively be controlled by the method for melting active in catalyst
The content of component.With conventionally by dipping process change active component content compared with, melting method can larger raising urge
The effective content of active component in agent；
(2) present invention prepares MoS in catalyst for methanation in presence of sulfur, unsupported catalyst for methanation in presence of sulfur by sulfidation2Urge
Agent active component content is high, active site density is big, with higher CO methanation activities;
(3) gas after pressurized gasification directly can be carried out methanation by sulfur resistant catalyst prepared by the present invention, by sulphur-resistant conversion
It is merged into methanation in presence of sulfur in same synthetic tower, reduces sulphur-resistant conversion device unit, reduce industrial cost；Simultaneously by gas
The cleaning procedure of body has been placed on after methanation process so that the treating capacity of gas is substantially reduced, and is reduced low-temp methanol and is washed work
The load of section.
Embodiment
Herein below is only several typical embodiments of the present invention, it is impossible to limit the scope of the present invention with this.I.e. generally according to this
The equivalent changes and modifications that patent application the scope of the claims is done, should all still fall within the range of patent of the present invention covers.
Embodiment 1
(1) preparation of Mo-Al alloy powders：It is 3~6 μm of molybdenum powders 5.8g, 4~6 μm of aluminium powder 4.1g and 4~6 μm of iron gold by granularity
Belong to powder 0.1g to be well mixed；Alloy powder is warming up into 1400 DEG C to be melted, and with 1*106K/s is cooled down under nitrogen protection
To room temperature, and it is standby to be ground to 90 mesh；
(2) sulfidation of catalyst：Alloy powder prepared by (1) is 3%H in volume composition2/97%H2350 in S atmosphere
DEG C vulcanization 5h；
(3) preparation of sulfur resistant catalyst：By (2) prepare catalyst precursor and solid sodium hydroxide mix, sodium hydroxide with
The mass ratio 1 of alloyed powder:1；3 times of the distilled water that volume is alloyed powder is added drop-wise to mixture and with 80/min magnetic force dropwise
Stirring；It is placed on simultaneously in water-bath, it is 0 DEG C to control bath temperature；Suspension after completion of dropwise addition in 50kHz, 60 DEG C
Under the conditions of ultrasound 30min, deionized water cyclic washing produces catalyst for methanation in presence of sulfur into neutrality, saves it in standby in water
With.Detected through ICP, the quality group of catalyst turns into Mo 67.6wt%, S 25.6wt%, Al 3.7wt%, Fe 3.1wt%.
Sulfur resistant catalyst manufactured in the present embodiment is applied in fixed bed methanator, actual conditions and result
See attached list 1.
Embodiment 2
(1) preparation of Mo-Al alloy powders：It is 3~6 μm of molybdenum powders 5.6g, 4~6 μm of aluminium powder 4.3g and 6~8 μm of nickel gold by granularity
Belong to powder 0.1g to be well mixed；Alloy powder is warming up into 1400 DEG C to be melted, and with 1*106K/s is cooled down under nitrogen protection
To room temperature, and it is standby to be ground to 100 mesh；
(2) sulfidation of catalyst：Alloy powder prepared by (1) is 5%H in volume composition2/95%H2450 in S atmosphere
DEG C vulcanization 5h；
(3) preparation of sulfur resistant catalyst：By (2) prepare catalyst precursor and solid sodium hydroxide mix and incite somebody to action, hydroxide
The mass ratio 1.1 of sodium and alloyed powder:1；3 times of the distilled water that volume is alloyed powder is added drop-wise to mixture and with 90/ dropwise
Min magnetic agitations；It is placed on simultaneously in water-bath, it is 3 DEG C to control bath temperature；Suspension after completion of dropwise addition exists
60kHz, ultrasound 30min under conditions of 50 DEG C, deionized water cyclic washing produces catalyst for methanation in presence of sulfur into neutrality, by it
It is stored in standby in water.Detected through ICP, the quality group of product catalyst turns into Mo 66.4wt%, S 27.3wt%, Al
4.4wt%, Ni 1.9wt%.
Sulfur resistant catalyst manufactured in the present embodiment is applied in synthesis gas fixed bed methane reaction, actual conditions and
As a result 1 is seen attached list.
Embodiment 3
(1) preparation of Mo-Al alloy powders：It is 6~9 μm of molybdenum powders 5.4g, 8~10 μm of aluminium powder 4.3g and 6~8 μm of cerium gold by granularity
Belong to powder 0.3g to be well mixed；Alloy powder is warming up into 1500 DEG C to be melted, and with 1.2*106K/s is cold under nitrogen protection
But room temperature is arrived, and it is standby to be ground to 100 mesh；
(2) sulfidation of catalyst：Alloy powder prepared by (1) constitutes 7%H in volume2/93%H2450 DEG C in S atmosphere
Vulcanize 3h；
(3) preparation of sulfur resistant catalyst：By (2) prepare catalyst precursor and solid sodium hydroxide mix and incite somebody to action, hydroxide
The mass ratio 1.2 of sodium and alloyed powder:1；By 4 times of the distilled water that volume is alloyed powder be added drop-wise to dropwise mixture and with
100r/min magnetic agitations；It is placed on simultaneously in water-bath, it is 5 DEG C to control bath temperature；Suspension after completion of dropwise addition exists
70kHz, ultrasound 40min under conditions of 50 DEG C, deionized water cyclic washing produces catalyst for methanation in presence of sulfur into neutrality, by it
It is stored in standby in water.Detected through ICP, the quality group of product catalyst turns into Mo 62.3wt%, S 30.1wt%, Al
3.2wt%, Ce 4.4wt%.
Progress of the sulfur resistant catalyst manufactured in the present embodiment in synthesis gas fixed bed methane reaction is applied, actual conditions
And result sees attached list 1.
Embodiment 4
(1) preparation of Mo-Al alloy powders：It is 3~6 μm of molybdenum powders 5.0g, 6~8 μm of aluminium powder 4.5g and 8~10 μm of platinums by granularity
Belong to powder 0.5g to be well mixed；Alloy powder is warming up into 1500 DEG C to be melted, and with 1.2*106K/s is cold under nitrogen protection
But room temperature is arrived, and it is standby to be ground to 90 mesh；
(2) sulfidation of catalyst：Alloy powder prepared by (1) is 9%H in volume composition2/91%H2550 in S atmosphere
DEG C vulcanization 3h；
(3) preparation of sulfur resistant catalyst：By (2) prepare catalyst precursor and solid sodium hydroxide mix and incite somebody to action, hydroxide
The mass ratio 1.3 of sodium and alloyed powder:1；4 times of the distilled water that volume is alloyed powder is added drop-wise in mixing and ice-water bath is maintained at
In；Mixture is added drop-wise to dropwise and with 80r/min magnetic agitations；It is placed on simultaneously in water-bath, it is 2 to control bath temperature
℃；Suspension after the completion of dropwise addition ultrasound 40min under conditions of 60kHz, 60 DEG C, deionized water cyclic washing is into neutrality, i.e.,
Catalyst for methanation in presence of sulfur is obtained, is saved it in standby in water.Detected through ICP, the quality group of product catalyst turns into Mo
60.4wt%, S 31.4wt%, Al 5.7wt%, Pt 2.5wt%.
Progress of the sulfur resistant catalyst manufactured in the present embodiment in synthesis gas fixed bed methane reaction is applied, actual conditions
And result sees attached list 1.
Embodiment 5
(1) preparation of Mo-Al alloy powders：It is 6~9 μm of molybdenum powder 4.8g, 6~8 μm of aluminium powder 5.1g, 4~6 μm of ferrous metals by granularity
Powder 0.1g and 6~8 μm of nickel metal powder 0.1g are well mixed；Alloy powder is warming up into 1600 DEG C to be melted, and with 1.5*
106K/s is cooled to room temperature under nitrogen protection, and it is standby to be ground to 120 mesh；
(2) sulfidation of catalyst：Alloy powder prepared by (1) is 6%H in volume composition2/94%H2350 in S atmosphere
DEG C vulcanization 5h；
(3) preparation of sulfur resistant catalyst：By (2) prepare catalyst precursor and solid sodium hydroxide mix and incite somebody to action, hydroxide
The mass ratio 1.4 of sodium and alloyed powder:1；5 times of the distilled water that volume is alloyed powder is added drop-wise in mixing and ice-water bath is maintained at
In；Mixture is added drop-wise to dropwise and with 90r/min magnetic agitations；It is placed on simultaneously in water-bath, it is 4 to control bath temperature
℃；Suspension after the completion of dropwise addition ultrasound 30min under conditions of 80kHz, 50 DEG C, deionized water cyclic washing is into neutrality, i.e.,
Catalyst for methanation in presence of sulfur is obtained, is saved it in standby in water.Detected through ICP, the quality group of product catalyst turns into Mo
60.1wt%, S 34.3wt%, Al 4.4wt%, Ni 0.8wt%, Fe 0.4wt%.
Progress of the sulfur resistant catalyst manufactured in the present embodiment in synthesis gas fixed bed methane reaction is applied, actual conditions
And result sees attached list 1.
Embodiment 6
(1) preparation of Mo-Al alloy powders：It is 6~9 μm of molybdenum powder 4.5g, 8~10 μm of aluminium powder 5.3g, 8~10 μm of platinum by granularity
Metal powder 0.2g and 4~6 μm of Fe metal powders 0.1g are well mixed；Alloy powder is warming up into 1600 DEG C to be melted, and with
1.5*106K/s is cooled to room temperature under nitrogen protection, and it is standby to be ground to 120 mesh；
(2) sulfidation of catalyst：Alloy powder prepared by (1) is 8%H in volume composition2/92%H2550 in S atmosphere
DEG C vulcanization 3h；
(3) preparation of sulfur resistant catalyst：By (2) prepare catalyst precursor and solid sodium hydroxide mix and incite somebody to action, hydroxide
The mass ratio 1.5 of sodium and alloyed powder:1；By 5 times of the distilled water that volume is alloyed powder be added drop-wise to dropwise mixture and with
100r/min magnetic agitations；It is placed on simultaneously in water-bath, it is 0 DEG C to control bath temperature；Suspension after completion of dropwise addition exists
70kHz, ultrasound 40min under conditions of 50 DEG C, deionized water cyclic washing produces catalyst for methanation in presence of sulfur into neutrality, by it
It is stored in standby in water.Detected through ICP, the quality group of product catalyst turns into Mo 69.5wt%, S 24.2wt%, Al
3.8wt%, Pt 1.4wt%, Fe1.1wt%.
Progress of the sulfur resistant catalyst manufactured in the present embodiment in synthesis gas fixed bed methane reaction is applied, actual conditions
And result sees attached list 1.
Subordinate list 1
Claims (5)
1. a kind of sulfur resistant catalyst applied to synthesis gas methanation, it is characterised in that catalyst for methanation in presence of sulfur, using Mo as work
Property component, it is characterised in that the quality group of catalyst turns into：Mo 60~70wt%, S 3~6wt% of 23~35wt%, Al, auxiliary agent 1
~4.5wt%.
2. a kind of sulfur resistant catalyst applied to synthesis gas methanation as claimed in claim 1, it is characterised in that described helps
Agent is the one or more in Fe, Ce, Pt and Ni.
3. a kind of preparation method of sulfur resistant catalyst applied to synthesis gas methanation as claimed in claim 1 or 2, its feature
It is to comprise the following steps：
(1) preparation of Mo-Al alloy powders：It is 3~9 μm of molybdenum powders, 4~10 μm of aluminium powders and 4~10 μm of promoter metal powder by granularity
Well mixed, the content mass fraction for controlling each composition is：Mo 40~55wt% of 45~59wt%, Al, metal promoter 1~
5wt% ；Alloy powder, which is warming up to 1400~1600 DEG C, melts it, and with 1~1.5*106K/s speed is under nitrogen protection
Room temperature is cooled to, 80~120 mesh are then ground to standby；
(2) sulfidation of catalyst：Alloy powder prepared by step (1) is 3~9%H in volume composition2With 91~97%H2S
Atmosphere in 350~550 DEG C vulcanization 4~6h, obtain catalyst precursor；
(3) preparation of sulfur resistant catalyst：Catalyst precursor and solid sodium hydroxide prepared by step (2) is mixed, and controls hydrogen
The quality of sodium oxide molybdena is 1~1.5 times of alloyed powder；By 3~5 times of the distillation of alloyed powder volume be added drop-wise to dropwise mixture and with
80~100r/min magnetic agitations；It is placed on simultaneously in water-bath, it is 0~5 DEG C to control bath temperature；It is outstanding after completion of dropwise addition
Turbid liquid 20~40min of ultrasound under conditions of 40~80kHZ, 40~70 DEG C, purpose catalyst is obtained through distilled water cleaning.
4. a kind of preparation method of sulfur resistant catalyst applied to synthesis gas methanation as claimed in claim 3, its feature exists
In step (1) described melting mode of heating for high-temperature heating, laser heating or microwave heating in one kind.
5. a kind of application of sulfur resistant catalyst applied to synthesis gas methanation as claimed in claim 1 or 2, it is characterised in that
Made catalyst is applied to fixed bed methanation reaction system, and its reaction condition is：Reaction temperature is 400~550 DEG C；Reaction
Pressure is 1.0~3.0 MPa；Air speed is 7000~10000 mL/ (gh)；Sulfur content is 1000~4000ppm；Unstripped gas
H2/ CO volume ratios are 3.1~3.5.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140147344A1 (en) * | 2011-02-17 | 2014-05-29 | Phillips 66 Company | MoS2 CATALYST SYSTEM FOR THE CONVERSION OF SUGAR ALCOHOL TO HYDROCARBONS |
| CN105013472A (en) * | 2015-06-16 | 2015-11-04 | 中国科学院山西煤炭化学研究所 | Sulfur-tolerant catalyst suitable for high concentration CO methanation, preparation method and applications thereof |
| CN105582969A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Sulfur-tolerant methanation catalyst and preparation method thereof |
| CN105597788A (en) * | 2016-03-10 | 2016-05-25 | 赛鼎工程有限公司 | Sulfur-tolerant catalyst for synthesized gas methanation and preparation method and application of sulfur-tolerant catalyst |
-
2017
- 2017-04-13 CN CN201710238838.8A patent/CN106984336A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140147344A1 (en) * | 2011-02-17 | 2014-05-29 | Phillips 66 Company | MoS2 CATALYST SYSTEM FOR THE CONVERSION OF SUGAR ALCOHOL TO HYDROCARBONS |
| CN105582969A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Sulfur-tolerant methanation catalyst and preparation method thereof |
| CN105013472A (en) * | 2015-06-16 | 2015-11-04 | 中国科学院山西煤炭化学研究所 | Sulfur-tolerant catalyst suitable for high concentration CO methanation, preparation method and applications thereof |
| CN105597788A (en) * | 2016-03-10 | 2016-05-25 | 赛鼎工程有限公司 | Sulfur-tolerant catalyst for synthesized gas methanation and preparation method and application of sulfur-tolerant catalyst |
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