CN107043089B - A kind of technique of the equipressure ammonia synthesis co-production containing carbon chemicals - Google Patents
A kind of technique of the equipressure ammonia synthesis co-production containing carbon chemicals Download PDFInfo
- Publication number
- CN107043089B CN107043089B CN201710357642.0A CN201710357642A CN107043089B CN 107043089 B CN107043089 B CN 107043089B CN 201710357642 A CN201710357642 A CN 201710357642A CN 107043089 B CN107043089 B CN 107043089B
- Authority
- CN
- China
- Prior art keywords
- ammonia
- ruthenium
- gas
- based catalyst
- technique
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention provides a kind of isobaric technique of the ammonia synthesis co-production containing carbon chemicals, the joint production process is converted by successively carrying out purification and CO to carbon raw material gas, CO therein is promoted to be converted into synthetic oil, low-carbon alcohols and/or low-carbon alkene, carbon utilization efficiency greatly improved, and can be produced according to market demand flexible modulation, improve the economic benefit of ammonia enterprise；It separates the above-mentioned tail gas containing after carbon chemicals and through decarburization and mentions hydrogen again and obtain hydrogen, it is mixed with specific quantity nitrogen as syngas for synthetic ammonia, successively ammonia synthesis reaction is carried out under the different technology conditions existing for the first ruthenium-based catalyst and the second ruthenium-based catalyst, the conversion ratio and ammonia yield of hydrogen nitrogen greatly improved in the cooperation of successive two-stage reaction, so that the ammonia net value in working off one's feeling vent one's spleen reaches 20.3~22.5%, not only high income and fluctuation it is small, have good prospects for commercial application.
Description
Technical field
The invention belongs to synthesize ammonia technical field, and in particular to a kind of work of the equipressure ammonia synthesis co-production containing carbon chemicals
Skill.
Background technique
Ammonia is important inorganic chemical product, finds nitrogen and hydrogen in high temperature and pressure from German chemist Haber in 1902
And can be directly since chemical combination ammonification in the presence of catalyst, ammonia synthesis industry is developing progressively as mainstay of the national economy industry.
It is industrially the boosting ammonia synthesis technology of 15MPa or more synthesis pressure, the technique using wider Large Scale Ammonia synthetic technology at present
The advantages of be that synthesis pressure is higher, unreacted reactant circulating consumption is small, and convenient for the separation of ammonia, but correspondingly there is also because of Material synthesis
Atmospheric pressure is lower and needs to be equipped with powerful synthesic gas compressor and circulator, and then leads to that equipment investment is big, power consumption is high
Defect.
Within the scope of the world today, the development trend for synthesizing ammonia is that atmospheric pressure processed gradually rises, synthesis pressure gradually decreases,
So that gas processed and synthesis are being carried out close under equal pressure, the isobaric ammonia synthesis of realization that is to say, to reduce energy consumption and simplification
Process flow.In recent years, as the exploitation of low-temp low-pressure ammonia synthesis catalyst and synthetic tower, ammonia separation technology are continuously improved,
The industrial applications of isobaric ammonia synthesis have become possibility.
Chinese patent literature CN102815721A discloses a kind of low pressure ammonia synthesis, and this method uses pure ruthenium-based catalytic
Agent or iron, ruthenium catalyst combination, temperature is 300~425 DEG C, pressure is 5~10MPa, H-N ratio is 0.5~1.46, raw material
Gas air speed is 3000~15000h-1Under conditions of produce ammonia.The raw material that above-mentioned technology is 0.5~1.46 by using H-N ratio
Gas, so that synthetic tower is worked off one's feeling vent one's spleen without being recirculated back to synthetic tower but being directly entered and mention hydrogen production device after ammonia separation, and ammino
It is carried out at 5~10MPa at pressure, the use of gas compressor and circulator can be omitted, to effectively reduce compression power consumption
And equipment investment.However, the synthetic tower of above-mentioned technology work off one's feeling vent one's spleen in ammonia density it is lower and fluctuation it is larger, be 9~19%, cause
The production capacity of the technique is low, economic benefit is bad, to restrict its industrial application.
In addition, at this stage the middle-size and small-size ammonia enterprise in China due to higher cost the low phenomenon of the generally existing utilization of capacity,
Therefore the technological improvement and product adjustment for how carrying out middle-size and small-size ammonia enterprise have important practical significance.From the point of view of policy angle,
Although Modern Coal-based Chemical project is gradually tightened by government, traditional coal chemical industry technological transformation upgrading is encouraged, government issues since 2012
A series of policies and regulations of cloth encourage coal poly-generation, oven gas LNG, synthesis ammonia tradition coal chemical industry technological transformation upgrading etc..And mesh
Preceding ammonia synthesis process is with only the hydrogen in synthesis gas, without making full use of other gas components such as CO, although China
Combined production of methanol ammonia synthesis process technology with independent intellectual property rights is developed, but coal base connection alcohol production capacity in 2012 is up to 11,100,000
Ton/year, the 21.5% of methanol aggregated capacity is accounted for, in addition in recent years, China's methanol aggregated capacity is seriously superfluous, therefore there is an urgent need to
Exploitation synthetic ammonia coproducing it is other containing carbon chemicals to solve the problems, such as that the middle-size and small-size ammonia enterprise utilization of capacity is low and methanol excess capacity.
Summary of the invention
It is an object of the present invention to overcome the outlet ammonia density of existing low pressure ammonia synthesis technology lower and fluctuate compared with
Big defect, it is another object of the present invention to overcome the problems, such as that the existing middle-size and small-size ammonia enterprise utilization of capacity is low and methanol excess capacity, into
And provide a kind of isobaric technique of the ammonia synthesis co-production containing carbon chemicals that ammonia yield can be improved.
For this purpose, the present invention realizes the technical solution of above-mentioned purpose are as follows:
A kind of technique of the equipressure ammonia synthesis co-production containing carbon chemicals, includes the following steps:
S1, purified treatment is carried out to carbon raw material gas to reduce sulphur therein and arsenic content；
S2, the purified gas that step S1 is obtained is sent into reactor to carry out CO conversion reaction, reaction product is after separation
It obtains containing carbon chemicals, residual exhaust successively obtains hydrogen through decarburization and after mentioning hydrogen；
S3, by the obtained hydrogen of step S2 and nitrogen using volume ratio (1.65~2.45): 1 ratio mix after as synthesizing
Ammonia unstripped gas reacts under the conditions of existing for the first ruthenium-based catalyst；
The reaction gas that S4, step S3 are obtained is pressure is 5~7.5MPa, temperature is 360~430 DEG C, volume space velocity is
6000~12000h-1And second ruthenium-based catalyst it is existing under the conditions of react；
Second ruthenium-based catalyst is using the product of roasting of the magnalium hydrotalcite of N doping as carrier, in the product of roasting
Spinel containing 30~60v%；
After ammonia separation, the gaseous mixture of the ammonia and unreacted hydrogen, nitrogen do not isolated follows the reaction gas that S5, step S4 are obtained
Ring is into step S3 for matching production of raw-material gas for synthetic ammonia.
The carbon raw material gas is one of coal based synthetic gas, biology base synthesis gas, natural gas, coal bed gas, shale gas
Or it is a variety of.
Purified treatment of the invention is to be required according to the purification of subsequent workshop section to control the index of harmful substance, specifically such as
Under: F- T synthesis unit requires sulphur and arsenic total content in purified gas to be less than 0.1ppm, CO+CO2In 10ppm under total content；It is low
Carbon alcohol synthesis unit requires the sulfur content in purified gas to be less than 0.05ppm, and arsenic total content is less than 0.05ppm；Low-carbon alkene synthesis
Unit requires the sulfur content in purified gas to be less than 0.2ppm, and arsenic total content is less than 0.1ppm.
Step S1 first carries out reforming of methane on Ni-Ce to the carbon raw material gas, then purifies to the gas after reformation
Processing.
The CO conversion reaction is one of Fischer-Tropsch synthesis, low-carbon alcohols processed reaction, reaction for preparing light olefins or more
Kind.
Tail gas described in step S2 first carries out carrying out decarburization again after CO transformation.
The reaction pressure of step S3 is 5.5~7.5MPa, temperature is 380~435 DEG C, the volume of the syngas for synthetic ammonia
Air speed is 6000~10000h-1；
First ruthenium-based catalyst on the basis of carried by active carbon body weight comprising Ru:2~7wt%, Ba+Mg+Ln:3~
8wt%, K:6~18wt%.
First ruthenium-based catalyst and the second ruthenium-based catalyst are loaded on respectively in different ammonia convertors；Or
First ruthenium-based catalyst and the second ruthenium-based catalyst are loaded in same ammonia convertor.
In second ruthenium-based catalyst, the doping of nitrogen be in mass magnalium hydrotalcite quality 1~
10%；The molar ratio of magnesium and aluminium is (0.6~2.9) in the magnalium hydrotalcite: 1.
The preparation method of the carrier of second ruthenium-based catalyst includes:
Nitrogenous precursor is dissolved in water to be made into containing nitrogen solution, using infusion process by the nitrogenous solution loadings in the magnalium
On hydrotalcite, then heating is allowed to drying, and roasts 0.5~2h at 190~200 DEG C to get the magnalium water of the N doping
Talcum；Wherein, the nitrogenous precursor is urea, ammonium hydroxide or hydrazine hydrate；It is described roasting be in nitrogen and/or ammonia atmosphere into
Capable；
The magnalium hydrotalcite of the N doping is warming up to 600~650 DEG C with the rate of 5~15 DEG C/min and keeps the temperature roasting
1~3h is then warming up to 700~720 DEG C again with the rate of 1~5 DEG C/min and keeps the temperature 0.5~1h of roasting, and product of roasting is
The carrier.
The active component ruthenium of second ruthenium-based catalyst is calculated as the carrier matter of second ruthenium-based catalyst with its quality
The 2~8% of amount.
Second ruthenium-based catalyst further includes auxiliary agent samarium, in mass, the content of samarium be the carrier quality 1~
10%；
Second ruthenium-based catalyst further includes auxiliary agent tantalum, in mass, the content of tantalum be the carrier quality 0.1~
6%.
The preparation method of second ruthenium-based catalyst includes:
Potassium floutaramite and sulfuric acid are heated to 400 DEG C or more, are then diluted with water so that hydrolysis occurs, hydration oxygen is generated
Change tantalum precipitating；The precipitating and the carrier are mediated to obtain semi-finished product, then the semi-finished product are impregnated in mixed containing samarium and ruthenium
It closes in solution, after drying up to second ruthenium-based catalyst.
Above-mentioned technical proposal of the invention has the advantages that
1, isobaric technique of the ammonia synthesis co-production containing carbon chemicals of the present invention, by carbon raw material gas successively into
Row purification and CO conversion processing, promote the CO in carbon raw material gas to be converted into synthetic oil, low-carbon alcohols and/or low-carbon alkene, substantially
The utilization efficiency of carbon is improved, and can be produced according to market demand flexible modulation, is conducive to the economic benefit for improving ammonia enterprise, effectively
It solves the problems, such as that the middle-size and small-size ammonia enterprise utilization of capacity is low, while also overcoming the deficiency of methanol excess capacity, meet country to cleaning
It produces, the requirement of energy-saving and emission-reduction.Furthermore joint production process of the invention also reduces the depth requirements of transformation, reduce synthesis ammonia
The overall investment of device, to reduce the production cost of synthesis ammonia.
Joint production process of the invention is made in ammonia synthesis process by using the product of roasting of the magnalium hydrotalcite of N doping
For the carrier of the second ruthenium-based catalyst, the presence of Spinel (content is 30~60v%) can be improved catalyst in carrier
Anti-hydration energy, and remaining metal composite oxide solid solution part then can ensure that catalyst still and have sufficiently large ratio table
Area, uniform pore structure and pore radius are distributed in macropore range, and the nitrogen adulterated in carrier in addition can not only increase
The electron density of carrier surface and basic activated site, and the 2p track of nitrogen-atoms can also be miscellaneous with the generation of the 4d track of ruthenium atom
Change, such that active component ruthenium is stronger, is carried on carrier to more, so that the low-temp low-pressure that catalyst can be improved is living
The conversion ratio and ammonia yield of hydrogen nitrogen greatly improved in property, the cooperation of front and back stages ammonia synthesis reaction in addition, technique of the invention,
So that the ammonia net value in working off one's feeling vent one's spleen reaches 20.3~22.5%, not only high income and fluctuation is small, before there is good industrial application
Scape.
2, isobaric technique of the ammonia synthesis co-production containing carbon chemicals of the present invention also contains in second ruthenium-based catalyst
There are samarium and tantalum as auxiliary agent, tantalum energy activating nitrogen gas dissociates, and samarium can play the role of that hydrogen is inhibited to poison, both is combined with
Conducive to the synthesis of ammonia.
3, isobaric technique of the ammonia synthesis co-production containing carbon chemicals of the present invention passes through magnesium in control magnalium hydrotalcite
Molar ratio with aluminium is (0.6~2.9): 1, so that the content of magnesia and aluminium oxide in its product of roasting is in suitable model
In enclosing, the biggish specific surface area of carrier not only ensure that, but also can prevent carrier from being inhibited by hydrogen, to be conducive to improve catalyst
Performance.
4, isobaric technique of the ammonia synthesis co-production containing carbon chemicals of the present invention, passes through strict control support precursor
Roasting condition, it can be ensured that in product of roasting have suitable Spinel, to reach the mesh for taking into account specific surface area and stability
's.
5, isobaric technique of the ammonia synthesis co-production containing carbon chemicals of the present invention, used second ruthenium-based catalytic
Agent is not necessarily to reduction step in the preparation, and need to can only be restored ruthenium source using syngas for synthetic ammonia in catalyst use process
For nanometer ruthenium particle, the preparation step of catalyst is on the one hand simplified, improves preparation efficiency, on the other hand but also the present invention
Catalyst preparation, transport and storage in stability it is more preferable.
Specific embodiment
Technical solution of the present invention will be clearly and completely described below, it is clear that described embodiment is this hair
Bright a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
Every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.
In the following embodiments, wt% indicates that mass percentage, v% indicate volumn concentration.
Each process conditions in following embodiments specifically:
The reaction condition of reforming of methane on Ni-Ce technique are as follows: normal pressure, 560 DEG C, volume space velocity 2300h-1, using Ni- oxygen
Change Al catalysts.
The process conditions of Fischer-Tropsch synthesis are as follows: 5MPa, 220 DEG C, volume space velocity 5000h-1, H2/ CO=1.95 (V/V),
Using Co/SiO2Catalyst.
The process conditions of low-carbon alcohols reaction processed are as follows: 10.4MPa, 280 DEG C, volume space velocity 7200h-1, H2/ CO=1.05 (V/
V), using MoS2Catalyst.
The process conditions of reaction for preparing light olefins are as follows: 1.5MPa, 420 DEG C, volume space velocity 1200h-1, H2/ CO=1.9 (V/
V), using Fe-Mn/MgO catalyst.
The process conditions of CO conversion reaction are as follows: 380 DEG C, water-gas ratio molar ratio is 2.
The process conditions of decarburization are as follows: become owner of that wash the poor methanol temperature of tower be -55 DEG C, out COS+H2S in the main gas for washing tower
≤ 0.1ppm, CO2≤3v%, the water content in poor methanol are less than 1v%, and total sulfur content is less than 100ppm, hot recycling tower backflash
Middle ammonia is less than 5g/L, out Crouse's gas hydrogen sulfide concentration >=25v% of workshop section.
Mention the main Con trolling index of hydrogen are as follows: H2>=99.9v%, CH4≤ 0.1v%, CO+CO2≤ 20ppm, out unit temp
40 DEG C, device pressure 2.4MPa out.
Embodiment 1
A kind of method for preparing the second ruthenium-based catalyst is present embodiments provided, is included the following steps:
(1) 20g urea is dissolved in 100g water and is made into containing nitrogen solution, using equi-volume impregnating by the nitrogenous solution loadings
In on the magnalium hydrotalcite that magnalium molar ratio is 0.6, the heat drying at 100 DEG C, and being roasted in 190 DEG C of nitrogen atmosphere
2h obtains the magnalium hydrotalcite of N doping, and the doping of nitrogen is the 5.5% of magnalium hydrotalcite quality in mass；
(2) magnalium hydrotalcite of above-mentioned N doping is warming up to 630 DEG C with the rate of 15 DEG C/min and keeps the temperature roasting 1h, and
700 DEG C are warming up to the rate of 3 DEG C/min again afterwards and keeps the temperature roasting 0.75h, and product of roasting is catalyst carrier, wherein containing
The Spinel of 30v%；
(3) potassium floutaramite and sulfuric acid are heated to 400 DEG C or more, are then diluted with water so that hydrolysis occurs, generate water
Close tantalum oxide precipitating；It mediates the precipitating and said catalyst carrier, sesbania powder and suitable quantity of water to obtain semi-finished product；
(4) samaric nitrate and acetylacetone,2,4-pentanedione ruthenium (III) are dissolved in water and alcohol mixed solvent, obtain the mixing containing samarium and ruthenium
Above-mentioned semi-finished product are impregnated in the mixed solution, dry afterwards for 24 hours by solution, obtain the second ruthenium-based catalyst.
After measured, the catalyst of the present embodiment is 2wt% containing ruthenium, samarium 5.5wt%, tantalum in terms of 100% by the quality of its carrier
1wt%.
Embodiment 2
A kind of method for preparing the second ruthenium-based catalyst is present embodiments provided, is included the following steps:
(1) 15ml ammonium hydroxide is dissolved in 90ml water and is made into containing nitrogen solution, born this containing nitrogen solution using equi-volume impregnating
It is loaded on the magnalium hydrotalcite that magnalium molar ratio is 1.7, the heat drying at 80 DEG C, and is roasted in 200 DEG C of ammonia atmosphere
0.5h obtains the magnalium hydrotalcite of N doping, and the doping of nitrogen is the 8% of magnalium hydrotalcite quality in mass；
(2) magnalium hydrotalcite of above-mentioned N doping is warming up to 600 DEG C with the rate of 10 DEG C/min and keeps the temperature roasting 3h, and
710 DEG C are warming up to the rate of 5 DEG C/min again afterwards and keeps the temperature roasting 0.5h, and product of roasting is catalyst carrier, after measured should
Containing the Spinel of 45v% in carrier, pore radius is distributed within the scope of 5~21nm；
(3) potassium floutaramite and sulfuric acid are heated to 400 DEG C or more, are then diluted with water so that hydrolysis occurs, generate water
Close tantalum oxide precipitating；It mediates the precipitating and said catalyst carrier, sesbania powder and suitable quantity of water to obtain semi-finished product；
(4) by samaric nitrate and the potassium ruthenate mixed solution soluble in water obtained containing samarium and ruthenium, above-mentioned semi-finished product are impregnated in
It in the mixed solution, is dried after 10h, obtains the second ruthenium-based catalyst.
After measured, the catalyst of the present embodiment is 5wt% containing ruthenium, samarium 6wt%, tantalum in terms of 100% by the quality of its carrier
3wt%, potassium 6wt%.
Embodiment 3
A kind of method for preparing the second ruthenium-based catalyst is present embodiments provided, is included the following steps:
(1) 12ml hydrazine hydrate is dissolved in 100ml water and is made into containing nitrogen solution, this is contained by nitrogen solution using equi-volume impregnating
It is carried on the magnalium hydrotalcite that magnalium molar ratio is 2.5, the heat drying at 90 DEG C, and is roasted in 200 DEG C of ammonia atmosphere
1h is burnt, the magnalium hydrotalcite of N doping is obtained, the doping of nitrogen is the 10% of magnalium hydrotalcite quality in mass；
(2) magnalium hydrotalcite of above-mentioned N doping is warming up to 650 DEG C with the rate of 5 DEG C/min and keeps the temperature roasting 2h, and
720 DEG C are warming up to the rate of 1 DEG C/min again afterwards and keeps the temperature roasting 0.5h, and product of roasting is catalyst carrier, wherein containing
The Spinel of 37v%；
(3) potassium floutaramite and sulfuric acid are heated to 400 DEG C or more, are then diluted with water so that hydrolysis occurs, generate water
Close tantalum oxide precipitating；It mediates the precipitating and said catalyst carrier, sesbania powder and suitable quantity of water to obtain semi-finished product；
(4) samaric nitrate and acetylacetone,2,4-pentanedione ruthenium (III) are dissolved in water and acetone mixed solvent, obtain the mixing containing samarium and ruthenium
Above-mentioned semi-finished product are impregnated in the mixed solution, dry after 14h by solution, obtain the second ruthenium-based catalyst.
After measured, the catalyst of the present embodiment is 6wt% containing ruthenium, samarium 1wt%, tantalum in terms of 100% by the quality of its carrier
2wt%.
Embodiment 4
A kind of method for preparing the second ruthenium-based catalyst is present embodiments provided, is included the following steps:
(1) 18g urea is dissolved in 95g water and is made into containing nitrogen solution, using equi-volume impregnating by the nitrogenous solution loadings
In on the magnalium hydrotalcite that magnalium molar ratio is 2.9, the heat drying at 90 DEG C, and being roasted in 190 DEG C of nitrogen atmosphere
1.5h obtains the magnalium hydrotalcite of N doping, and the doping of nitrogen is the 1% of magnalium hydrotalcite quality in mass；
(2) magnalium hydrotalcite of above-mentioned N doping is warming up to 650 DEG C with the rate of 8 DEG C/min and keeps the temperature roasting 3h, and
700 DEG C are warming up to the rate of 2 DEG C/min again afterwards and keeps the temperature roasting 1h, and product of roasting is catalyst carrier, wherein containing 60v%
Spinel；
(3) potassium floutaramite and sulfuric acid are heated to 400 DEG C or more, are then diluted with water so that hydrolysis occurs, generate water
Close tantalum oxide precipitating；It mediates the precipitating and said catalyst carrier, sesbania powder and suitable quantity of water to obtain semi-finished product；
(4) samaric nitrate and acetylacetone,2,4-pentanedione ruthenium (III) are dissolved in water and alcohol mixed solvent, obtain the mixing containing samarium and ruthenium
Above-mentioned semi-finished product are impregnated in the mixed solution, dry after 18h by solution, obtain the second ruthenium-based catalyst.
After measured, the catalyst of the present embodiment is 4wt% containing ruthenium, samarium 3wt%, tantalum in terms of 100% by the quality of its carrier
0.1wt%.
Embodiment 5
A kind of method for preparing the second ruthenium-based catalyst is present embodiments provided, is included the following steps:
(1) 20g urea is dissolved in 100g water and is made into containing nitrogen solution, using equi-volume impregnating by the nitrogenous solution loadings
In on the magnalium hydrotalcite that magnalium molar ratio is 2, the heat drying at 100 DEG C, and roast 1h in 200 DEG C of nitrogen atmosphere,
The magnalium hydrotalcite of N doping is obtained, the doping of nitrogen is the 7% of magnalium hydrotalcite quality in mass；
(2) magnalium hydrotalcite of above-mentioned N doping is warming up to 650 DEG C with the rate of 12 DEG C/min and keeps the temperature roasting 0.5h,
710 DEG C then are warming up to the rate of 4 DEG C/min again and keeps the temperature roasting 0.5h, and product of roasting is catalyst carrier, wherein containing
The Spinel of 52v%；
(3) potassium floutaramite and sulfuric acid are heated to 400 DEG C or more, are then diluted with water so that hydrolysis occurs, generate water
Close tantalum oxide precipitating；It mediates the precipitating and said catalyst carrier, sesbania powder and suitable quantity of water to obtain semi-finished product；
(4) samaric nitrate and acetylacetone,2,4-pentanedione ruthenium (III) are dissolved in water and alcohol mixed solvent, obtain the mixing containing samarium and ruthenium
Above-mentioned semi-finished product are impregnated in the mixed solution, dry afterwards for 24 hours, obtain ruthenium-based ammonia synthetic catalyst by solution.
After measured, the catalyst of the present embodiment is 8wt% containing ruthenium, samarium 4wt%, tantalum in terms of 100% by the quality of its carrier
5wt%.
Embodiment 6
The preparation method of ruthenium-based ammonia synthetic catalyst provided in this embodiment includes the following steps:
(1) 20g urea is dissolved in 100g water and is made into containing nitrogen solution, using equi-volume impregnating by the nitrogenous solution loadings
In on the magnalium hydrotalcite that magnalium molar ratio is 2.2, the heat drying at 100 DEG C, and being roasted in 190 DEG C of nitrogen atmosphere
2h obtains the magnalium hydrotalcite of N doping, and the doping of nitrogen is the 3.6% of magnalium hydrotalcite quality in mass；
(2) magnalium hydrotalcite of above-mentioned N doping is warming up to 630 DEG C with the rate of 11 DEG C/min and keeps the temperature roasting
0.75h is then warming up to 720 DEG C again with the rate of 5 DEG C/min and keeps the temperature roasting 0.75h, and product of roasting is catalyst carrier,
Wherein containing the Spinel of 40v%；
(3) potassium floutaramite and sulfuric acid are heated to 400 DEG C or more, are then diluted with water so that hydrolysis occurs, generate water
Close tantalum oxide precipitating；It mediates the precipitating and said catalyst carrier, sesbania powder and suitable quantity of water to obtain semi-finished product；
(4) samaric nitrate and potassium ruthenate are dissolved in water and alcohol mixed solvent, obtain the mixed solution containing samarium and ruthenium, it will be upper
It states semi-finished product to be impregnated in the mixed solution, dries afterwards for 24 hours, obtain ruthenium-based ammonia synthetic catalyst.
After measured, the catalyst of the present embodiment is 7wt% containing ruthenium, samarium 10wt%, tantalum in terms of 100% by the quality of its carrier
6wt%, potassium 8wt%.
Embodiment 7
Equipressure technique of the ammonia synthesis co-production containing carbon chemicals provided in this embodiment includes the following steps:
S1, using natural gas as carbon raw material gas, first carry out methane portion oxidation and reform that H is made2/ CO=3's (V/V)
Synthesis gas, into purification section, the total content of sulphur and arsenic is 0.08ppm, CO+CO in purifying column gas out2Total content is 7ppm；
S2, step S1 purified gas enter in Fischer-Tropsch synthesis device and reacted, reaction product is by isolated hard
Wax, soft wax, heavy oil, light oil and liquefied petroleum gas, the CO gas conversion per pass through Fischer-Tropsch reaction is complete, without carrying out CO transformation；
The hydrogen in hydrogen technique extraction tail gas is then mentioned using PSA；
The ratio of S3, the resulting hydrogen of step S2 and the nitrogen (oxygen≤10ppm) from space division workshop section 1.95:1 by volume
Example, which is uniformly mixed, is used as syngas for synthetic ammonia, its pressure is adjusted to be sent into after 5.5MPa is filled with the of the first ruthenium-based catalyst
It in one ammonia convertor, and is 7000h in 435 DEG C, gas volume air speed-1Under conditions of carry out level-one ammonia synthesis reaction；
The group of first ruthenium-based catalyst becomes, on the basis of its carried by active carbon body weight, Ru:4.5wt%, Ba:4wt%,
Mg:1.4wt%, La:0.1wt%, K:17wt%；
S4, the reaction gas feeding that step S3 is obtained is filled with the second ruthenium-based catalyst made from the embodiment of the present invention 2
In second ammonia convertor, pressure is 6MPa, temperature is 360 DEG C, gas volume air speed is 10000h-1Under conditions of second level occurs
Ammonia synthesis reaction；
S5, it reaction gas that step S4 is obtained is sent into ammonia condensing tower carries out ammonia separation, collect liquefied ammonia, and do not isolate
The gaseous mixture of ammonia and unreacted hydrogen, nitrogen is recycled in step S3 for production of raw-material gas for synthetic ammonia.
Embodiment 8
Equipressure technique of the ammonia synthesis co-production containing carbon chemicals provided in this embodiment includes the following steps:
S1, the H come out from Shell crushed coal pressurized-gasification furnace2The synthesis gas of/CO=1.2 (V/V), needs not move through transformation
Workshop section is directly entered purification section, and sulfur content is less than 0.04ppm, arsenic content 0.03ppm in purifying column gas out；
S2, step S1, which are purified gas and enter in low-carbon alcohols reactor, to be reacted, and reaction product passes through isolated first
Alcohol, ethyl alcohol, propyl alcohol, butanol and amylalcohol；Tail gas, which enters CO conversion section, makes unreacted CO be converted into CO2, using Shandong surprise low temperature
Methanol cleaning process removes CO2, CO in scrubbing tower outlet2≤ 0.3v%, then hydrogen technique is mentioned using PSA, hydrogen is made；
The ratio of S3, the resulting hydrogen of step S2 and the nitrogen (oxygen≤10ppm) from space division workshop section 2.45:1 by volume
Example, which is uniformly mixed, is used as syngas for synthetic ammonia, its pressure is adjusted to be sent into after 6.5MPa is filled with and 7 phase of the embodiment of the present invention
It in the first ammonia convertor with the first ruthenium-based catalyst of composition, and is 9000h in 380 DEG C, gas volume air speed-1Under conditions of
Carry out level-one ammonia synthesis reaction；
S4, the reaction gas feeding that step S3 is obtained is filled with the second ruthenium-based catalyst made from the embodiment of the present invention 2
In second ammonia convertor, pressure is 7.5MPa, temperature is 400 DEG C, gas volume air speed is 8000h-1Under conditions of occur it is anti-
It answers；
S5, it reaction gas that step S4 is obtained is sent into ammonia condensing tower carries out ammonia separation, collect liquefied ammonia, and do not isolate
The gaseous mixture of ammonia and unreacted hydrogen, nitrogen is recycled in step S3 for production of raw-material gas for synthetic ammonia.
Embodiment 9
Equipressure technique of the ammonia synthesis co-production containing carbon chemicals provided in this embodiment includes the following steps:
S1, the H come out from texaco coal-water slurry gasification furnace2The synthesis gas of/CO=2 (V/V), needs not move through conversion section
It is directly entered purification section, sulfur content is 0.15ppm, arsenic content 0.09ppm in purifying column gas out；
S2, step S1, which are purified gas and enter in low carbon olefin hydrocarbon reactor, to be reacted, and reaction product is by isolated
Ethylene, propylene, butylene；Tail gas, which enters CO conversion section, makes unreacted CO be converted into CO2, using Shandong surprise low-temp methanol washing process
Remove CO2, CO in scrubbing tower outlet2≤ 0.5v%, then hydrogen technique is mentioned using PSA, hydrogen is made；
The ratio of S3, the resulting hydrogen of step S2 and the nitrogen (oxygen≤10ppm) from space division workshop section 1.65:1 by volume
Example, which is uniformly mixed, is used as syngas for synthetic ammonia, its pressure is adjusted to be sent into after 7.5MPa is filled with and 7 phase of the embodiment of the present invention
It in the first ammonia convertor with the first ruthenium-based catalyst of composition, and is 6000h in 400 DEG C, gas volume air speed-1Under conditions of
Carry out level-one ammonia synthesis reaction；
S4, the reaction gas feeding that step S3 is obtained is filled with the second ruthenium-based catalyst made from the embodiment of the present invention 2
In second ammonia convertor, pressure is 7.5MPa, temperature is 380 DEG C, gas volume air speed is 9000h-1Under conditions of occur it is anti-
It answers；
S5, it reaction gas that step S4 is obtained is sent into ammonia condensing tower carries out ammonia separation, collect liquefied ammonia, and do not isolate
The gaseous mixture of ammonia and unreacted hydrogen, nitrogen is recycled in step S3 for production of raw-material gas for synthetic ammonia.
Embodiment 10
Equipressure technique of the ammonia synthesis co-production containing carbon chemicals provided in this embodiment includes the following steps:
S1, hydrogen is made using method identical with the embodiment of the present invention 9, by hydrogen and the nitrogen from space division workshop section
(oxygen≤10ppm) by volume 2.05:1 ratio be uniformly mixed be used as syngas for synthetic ammonia, its pressure is adjusted to 6.5MPa
Be sent into afterwards be filled with in the first ammonia convertor of the first ruthenium-based catalyst of 7 same composition of the embodiment of the present invention, and 400
DEG C, gas volume air speed be 8000h-1Under conditions of carry out level-one ammonia synthesis reaction；
S2, the reaction gas feeding that step S1 is obtained is filled with the second ruthenium-based catalyst made from the embodiment of the present invention 2
In second ammonia convertor, pressure is 7MPa, temperature is 400 DEG C, gas volume air speed is 12000h-1Under conditions of occur it is anti-
It answers；
S3, it reaction gas that step S2 is obtained is sent into ammonia condensing tower carries out ammonia separation, collect liquefied ammonia, and do not isolate
The gaseous mixture of ammonia and unreacted hydrogen, nitrogen is recycled in step S1 for production of raw-material gas for synthetic ammonia.
Embodiment 11
Equipressure technique of the ammonia synthesis co-production containing carbon chemicals provided in this embodiment includes the following steps:
S1, hydrogen is made using method identical with the embodiment of the present invention 9, by hydrogen and the nitrogen from space division workshop section
(oxygen≤10ppm) by volume 1.65:1 ratio be uniformly mixed be used as syngas for synthetic ammonia, after its pressure is adjusted to 7MPa
Feeding be filled with in the first ammonia convertor of the first ruthenium-based catalyst of 7 same composition of the embodiment of the present invention, and 410 DEG C,
Gas volume air speed is 10000h-1Under conditions of carry out level-one ammonia synthesis reaction；
S2, the reaction gas feeding that step S1 is obtained is filled with the second ruthenium-based catalyst made from the embodiment of the present invention 2
In second ammonia convertor, pressure is 5MPa, temperature is 430 DEG C, gas volume air speed is 6000h-1Under conditions of react；
S3, it reaction gas that step S2 is obtained is sent into ammonia condensing tower carries out ammonia separation, collect liquefied ammonia, and do not isolate
The gaseous mixture of ammonia and unreacted hydrogen, nitrogen is recycled in step S1 for production of raw-material gas for synthetic ammonia.
Comparative example 1
The preparation method for the second ruthenium-based catalyst that this comparative example provides includes the following steps:
(1) 15ml ammonium hydroxide is dissolved in 90ml water and is made into containing nitrogen solution, born this containing nitrogen solution using equi-volume impregnating
It is loaded on the magnalium hydrotalcite that magnalium molar ratio is 1.7, the heat drying at 80 DEG C, and is roasted in 200 DEG C of ammonia atmosphere
0.5h obtains the magnalium hydrotalcite of N doping, and the doping of nitrogen is the 8% of magnalium hydrotalcite quality in mass；
(2) magnalium hydrotalcite of above-mentioned N doping is placed directly within to 710 DEG C of Muffle kiln roasting 0.5h, product of roasting is
The composite oxides of N doping, wherein being free of Spinel；
(3) according to method identical with the embodiment of the present invention 2 on above-mentioned product of roasting load active component and auxiliary agent, system
Obtain ruthenium-based ammonia synthetic catalyst.
After measured, the catalyst of this comparative example is 3wt% containing ruthenium, samarium 3.8wt%, tantalum in terms of 100% by the quality of its carrier
2.1wt%, potassium 4.2wt%.
Comparative example 2
The second ruthenium-based catalyst that this comparative example provides, the preparation method of carrier is in the embodiment of the present invention 2, herein not
It repeats again；Potassium ruthenate is carried on carrier using equi-volume impregnating, then dries and just obtains ruthenium-based ammonia synthetic catalyst.
After measured, the catalyst of this comparative example is 5wt% containing ruthenium, potassium 6wt% in terms of 100% by the quality of its carrier.
Comparative example 3
Isobaric technique of the ammonia synthesis co-production containing carbon chemicals that this comparative example provides includes the following steps:
S1, syngas for synthetic ammonia is obtained using method identical with the embodiment of the present invention 10, its pressure is adjusted to 7MPa
It is sent into and is filled with the second ammonia convertor of the second ruthenium-based catalyst of 2 same composition of the embodiment of the present invention afterwards, be in temperature
400 DEG C, gas volume air speed be 12000h-1Under conditions of react；
S2, it reaction gas that step S1 is obtained is sent into ammonia condensing tower carries out ammonia separation, collect liquefied ammonia, and do not isolate
The gaseous mixture of ammonia and unreacted hydrogen, nitrogen is recycled in step S1 for production of raw-material gas for synthetic ammonia.
Experimental example 1
Using BET specific surface area test method to the ratio table of catalyst carrier made from above-described embodiment 1-6 and comparative example 1
Area, pore volume and average pore size are determined, and the results are shown in Table 1.
Specific surface area, pore volume and the average pore size of each carrier of table 1
Experimental example 2
Second ruthenium-based catalyst made from the above embodiment of the present invention 1-6 and comparative example 1-2 carries out ammonia synthesis active testing,
Test process is as follows: the catalyst of above-mentioned equivalent is loaded on respectively in stainless steel high pressure ammonia convertor, reaction gas is mixed for hydrogen nitrogen
Gas is closed, hydrogen nitrogen volume ratio is 3:1, air speed 10000h-1, reaction pressure 6MPa, reaction temperature are 350 DEG C, measurement outlet
Ammonia density.It is corresponding that test result is as follows shown in table 2:
The activity rating of each catalyst of table 2
| Catalyst | It exports ammonia density (v%) |
| Embodiment 1 | 19.9 |
| Embodiment 2 | 23.3 |
| Embodiment 3 | 22.0 |
| Embodiment 4 | 21.7 |
| Embodiment 5 | 22.8 |
| Embodiment 6 | 23.1 |
| Comparative example 1 | 11.6 |
| Comparative example 2 | 14.2 |
Experimental example 3
It is dense that hydrogen in the working off one's feeling vent one's spleen of the second ammonia convertor in above-described embodiment 7-11 and comparative example 3, nitrogen and ammonia are measured respectively
Degree, and hydrogen conversion ratio, the conversion rate of nitrogen being calculated in ammonia net value and syngas for synthetic ammonia, the results are shown in Table 3.
Ammonia net value, the hydrogen conversion rate of nitrogen of each technique of table 3
| Ammonia net value (v%) | Conversion rate of nitrogen (%) | Hydrogen conversion ratio (%) | |
| Embodiment 7 | 20.3% | 87.2% | 90.5% |
| Embodiment 8 | 21.4% | 88.0% | 90.9% |
| Embodiment 9 | 20.8% | 88.6% | 91.3% |
| Embodiment 10 | 22.5% | 89.1% | 91.6% |
| Embodiment 11 | 21.9% | 88.0% | 90.4% |
| Comparative example 3 | 15.2% | 80.3% | 80.8% |
Experimental example 4
It measures in above-described embodiment 7-11 and is separated containing the CO concentration in the tail gas after carbon chemicals respectively, and according to carbon containing original
CO concentration calculation in material gas obtains CO conversion ratio, and the results are shown in Table 4.
The CO conversion ratio of each technique of table 4
| CO conversion ratio (%) | |
| Embodiment 7 | 92.4% |
| Embodiment 8 | 92.8% |
| Embodiment 9 | 93.6% |
| Embodiment 10 | 93.8% |
| Embodiment 11 | 92.2% |
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (9)
1. a kind of technique of the equipressure ammonia synthesis co-production containing carbon chemicals, which comprises the steps of:
S1, purified treatment is carried out to carbon raw material gas to reduce sulphur therein and arsenic content；
S2, the purified gas for obtaining step S1 are sent into reactor to carry out CO conversion reaction, and reaction product obtains after separation
Containing carbon chemicals, residual exhaust successively obtains hydrogen through decarburization and after mentioning hydrogen；
S3, by the obtained hydrogen of step S2 and nitrogen using volume ratio (1.65~2.45): 1 ratio mix after as synthesis ammonia original
Expect gas, reacts under the conditions of existing for the first ruthenium-based catalyst；
The reaction gas that S4, step S3 are obtained pressure is 5~7.5MPa, temperature is 360~430 DEG C, volume space velocity be 6000~
12000h-1And second ruthenium-based catalyst it is existing under the conditions of react；
Second ruthenium-based catalyst contains in the product of roasting using the product of roasting of the magnalium hydrotalcite of N doping as carrier
The Spinel of 30~60v%；
After ammonia separation, the gaseous mixture of the ammonia and unreacted hydrogen, nitrogen do not isolated is recycled to the reaction gas that S5, step S4 are obtained
For matching production of raw-material gas for synthetic ammonia in step S3；
Wherein, the carbon raw material gas is one of coal based synthetic gas, biology base synthesis gas, natural gas, coal bed gas, shale gas
Or it is a variety of.
2. technique of the equipressure ammonia synthesis co-production containing carbon chemicals according to claim 1, which is characterized in that step S1 is first
Reforming of methane on Ni-Ce is carried out to the carbon raw material gas, then purified treatment is carried out to the gas after reformation.
3. technique of the equipressure ammonia synthesis co-production containing carbon chemicals according to claim 1 or 2, which is characterized in that described
CO conversion reaction is one of Fischer-Tropsch synthesis, low-carbon alcohols processed reaction, reaction for preparing light olefins or a variety of.
4. technique of the equipressure ammonia synthesis co-production containing carbon chemicals according to claim 1 or 2, which is characterized in that step
Tail gas described in S2 first carries out carrying out decarburization again after CO transformation.
5. technique of the equipressure ammonia synthesis co-production containing carbon chemicals according to claim 1 or 2, which is characterized in that step
The reaction pressure of S3 is 5.5~7.5MPa, temperature is 380~435 DEG C, the volume space velocity of the syngas for synthetic ammonia is 6000~
10000h-1；
First ruthenium-based catalyst on the basis of carried by active carbon body weight comprising Ru:2~7wt%, Ba+Mg+Ln:3~
8wt%, K:6~18wt%.
6. technique of the equipressure ammonia synthesis co-production containing carbon chemicals according to claim 1 or 2, which is characterized in that described
First ruthenium-based catalyst and the second ruthenium-based catalyst are loaded on respectively in different ammonia convertors；Or
First ruthenium-based catalyst and the second ruthenium-based catalyst are loaded in same ammonia convertor.
7. technique of the equipressure ammonia synthesis co-production containing carbon chemicals according to claim 1 or 2, which is characterized in that in institute
It states in the second ruthenium-based catalyst, the doping of nitrogen is the 1~10% of magnalium hydrotalcite quality in mass；The magnalium water
The molar ratio of magnesium and aluminium is (0.6~2.9) in talcum: 1.
8. technique of the equipressure ammonia synthesis co-production containing carbon chemicals according to claim 1 or 2, which is characterized in that described
The preparation method of the carrier of second ruthenium-based catalyst includes:
Nitrogenous precursor is dissolved in water to be made into containing nitrogen solution, using infusion process by the nitrogenous solution loadings in the magnalium neatly
Shi Shang, then heating is allowed to drying, and roasts 0.5~2h at 190~200 DEG C to get the magnalium hydrotalcite of the N doping；
Wherein, the nitrogenous precursor is urea, ammonium hydroxide or hydrazine hydrate；The roasting is carried out in nitrogen and/or ammonia atmosphere；
By the magnalium hydrotalcite of the N doping with the rate of 5~15 DEG C/min be warming up to 600~650 DEG C and keep the temperature roasting 1~
3h is then warming up to 700~720 DEG C again with the rate of 1~5 DEG C/min and keeps the temperature 0.5~1h of roasting, and product of roasting is described
Carrier.
9. technique of the equipressure ammonia synthesis co-production containing carbon chemicals according to claim 1 or 2, which is characterized in that described
The active component ruthenium of second ruthenium-based catalyst is calculated as the 2~8% of the carrier quality of second ruthenium-based catalyst with its quality；
Second ruthenium-based catalyst further includes auxiliary agent samarium, and in mass, the content of samarium is the 1~10% of the carrier quality；
Second ruthenium-based catalyst further includes auxiliary agent tantalum, and in mass, the content of tantalum is the 0.1~6% of the carrier quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710357642.0A CN107043089B (en) | 2017-05-19 | 2017-05-19 | A kind of technique of the equipressure ammonia synthesis co-production containing carbon chemicals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710357642.0A CN107043089B (en) | 2017-05-19 | 2017-05-19 | A kind of technique of the equipressure ammonia synthesis co-production containing carbon chemicals |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107043089A CN107043089A (en) | 2017-08-15 |
| CN107043089B true CN107043089B (en) | 2019-06-04 |
Family
ID=59546522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710357642.0A Active CN107043089B (en) | 2017-05-19 | 2017-05-19 | A kind of technique of the equipressure ammonia synthesis co-production containing carbon chemicals |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107043089B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110038615A (en) * | 2019-05-21 | 2019-07-23 | 福州大学 | A kind of preparation method of the activated carbon supported metal ruthenium catalyst of Nitrogen element |
| CN114477089B (en) * | 2020-10-26 | 2023-10-27 | 中国石油化工股份有限公司 | Method for removing trace CO at low temperature |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080039313A1 (en) * | 2004-04-26 | 2008-02-14 | William Jones | Process for the Preparation of a Metal-Containing Composition |
| CN104785255A (en) * | 2015-04-21 | 2015-07-22 | 福州大学 | Ruthenium ammonia synthesis catalyst by using N-doped active carbon as carrier and preparation of ruthenium ammonia synthesis catalyst |
| CN104888774B (en) * | 2015-06-15 | 2017-04-12 | 福州大学 | Rare earth element-doped hydrotalcite-like precursor loading ruthenium ammonia synthetic catalyst |
| CN105384147A (en) * | 2015-11-04 | 2016-03-09 | 中国科学院山西煤炭化学研究所 | Ammonia-synthesis and carbon-containing-chemical combinative production technology |
| CN105883851B (en) * | 2016-04-07 | 2017-11-07 | 河南中鸿集团煤化有限公司 | A kind of Novel gasification and pyrolysis coupling coal gas multi-production process |
| CN106513030B (en) * | 2016-12-12 | 2019-06-11 | 福州大学 | Using nitrogen-dopped activated carbon as ruthenium-based ammonia synthetic catalyst of carrier and preparation method thereof |
-
2017
- 2017-05-19 CN CN201710357642.0A patent/CN107043089B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107043089A (en) | 2017-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109759064B (en) | Co @ C/biomass catalyst and preparation method and application thereof | |
| CN102125849B (en) | Method for preparing synthetic methane catalyst and catalyst precursor | |
| CN104028270A (en) | Methanation catalyst and preparation method thereof | |
| CN103566936A (en) | Preparation method of catalyst for carbon dioxide reforming of methane to produce synthesis gas | |
| CN102600860A (en) | Catalyst suitable for complete methanation of middle-low-temperature synthetic gas and preparation method thereof | |
| CN107043089B (en) | A kind of technique of the equipressure ammonia synthesis co-production containing carbon chemicals | |
| CN104984769B (en) | A kind of method of synthesizing gas by reforming methane with co 2 carbon base catalyst | |
| CN100569365C (en) | Gaseous hydrocarbon low temperature insulation transformation catalyst and reaction process thereof | |
| CN110721690B (en) | Ni-Fe bimetal multifunctional catalyst for biological oil steam reforming hydrogen production | |
| CN102259004B (en) | Catalyst used in coal natural gas methanation reactor and preparation method thereof | |
| CN104001538A (en) | Nickel-loaded SBA-15 catalyst modified by cerium dioxide and preparation method and application of nickel-loaded SBA-15 catalyst modified by cerium dioxide | |
| CN103706228B (en) | A kind of pre-reduction type manganese fimily desulfurizing agent and preparation method thereof | |
| CN103157475B (en) | For the Catalysts and its preparation method of coke-stove gas tri-reforming | |
| CN101703934A (en) | Natural gas catalyst manufactured by coal and manufacturing method thereof | |
| CN115196590B (en) | Process for co-production of hydrogen by capturing carbon in blast furnace gas | |
| CN103551182A (en) | Catalyst for splitting decomposition of biomass tar and preparation method thereof | |
| CN107055571B (en) | A kind of gaseous hydrocarbon using after self-heating recapitalization is the isobaric Ammonia Process of raw material | |
| CN114768859B (en) | Nickel-silicon catalyst suitable for methane dry reforming and preparation method thereof | |
| CN107537536B (en) | Sulfur-tolerant methanation catalyst, preparation method and application thereof | |
| CN113083371B (en) | Phosphotungstic acid loaded iron-based MOF material and preparation and application thereof | |
| CN114522691A (en) | Preparation method of composite metal oxide for organic sulfur catalytic hydrolysis | |
| CN105582969B (en) | Catalyst for methanation in presence of sulfur and preparation method | |
| CN107188196B (en) | A kind of equipressure ammonia synthesis technology | |
| CN106311352A (en) | Preparation method of catalyst carrier for preparing natural gas from coke-oven gas | |
| CN110586028A (en) | Desulfurizing agent and preparation method and application thereof |
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 |