CN104549284A - Gaseous hydrocarbon self-heating conversion catalyst and preparation method thereof - Google Patents
Gaseous hydrocarbon self-heating conversion catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of gaseous hydrocarbon conversion catalysts, and relates to a catalyst for the field of synthesis gas produced by gaseous hydrocarbon self-heating conversion or hydrogen production and a preparation method of the catalyst. According to the catalyst disclosed by the invention, nickel is used as an active component; SiO2 at free state and 3Al2O3*2SiO2 of a mullite structure are used as carriers; MgO and/or a rare earth metal oxide are used as auxiliaries. The preparation method comprises the following steps: adopting a pulping method or a dry mixing method to prepare a semi-finished product, and then molding and baking the semi-finished product to obtain the finished product catalyst. The catalyst is high in anti-carbon deposition performance, good in strength and strength stability, and good in reactive metal dispersion effect, effectively avoids the reactive metal crystal grain aggregation in the using process, ensures the activity stability of the catalyst, and facilitates large-scale industrial production.
Description
Technical field
The invention belongs to gaseous hydrocarbons catalyst technical field, relate to a kind of Catalysts and its preparation method for the Autothermal reforming preparing synthetic gas of gaseous hydrocarbon or hydrogen preparation field.
Background technology
Along with the minimizing day by day of world petroleum resource, comprise refinery gas, natural gas, casing-head gas the development and utilization of various gaseous hydrocarbons be more and more subject to people's attention.Gaseous hydrocarbon contains hydrogen, methane, ethane, propane and butane etc. according to kind difference.The hydrogen manufacturing of current industrial application gaseous hydrocarbon or preparing synthetic gas generally adopt steam reforming direct translation method.The method is strong endothermic process, requires to carry out under pressure 1.5MPa ~ 3.0MPa, temperature 850 DEG C ~ 900 DEG C conditions, and for preventing catalyst carbon deposition, need high steam/hydrocarbons ratio, energy consumption is high, the H of generation
2with the mol ratio of CO up to 3, be unfavorable for subsequent technique.
The nineties in 20th century starts, the Autothermal reforming process for preparing synthetic gas of gaseous hydrocarbon becomes study hotspot, and this technique is a kind of new technology partial oxidation and adiabatic steam-reforming combined, and methyl hydride combustion releases a large amount of heat for steam reformation, self heat supply of realization response device, reaches adiabatic operation.Gaseous hydrocarbons can be synthesis gas (CO+H by the party's indirect reformer method owned by France
2).Synthesis gas is industrially of many uses, and can be used in synthetic liquid fuel, methyl alcohol, formic acid, methyl esters, dicarbaldehyde etc., is important industrial chemicals.
Compared with traditional steam transforming technique, Autothermal reforming technique has the following advantages:
(1) H in product
2/ CO ratio can adjust, can according to follow-up chemical process needs, by CH in feed change gas
4, O
2and H
2the ratio of O can obtain multiple different H
2the synthesis gas of/CO.
(2) Autothermal reforming technique is exothermic reaction, and carry out in adiabatic reactor, do not need external heat, reduce fuel consumption, thermal discharge is little, and energy consumption is low; Reactor volume is little, can reduce floor space; Eliminate heating furnace, significantly can reduce plant investment.
(3) autothermal reaction carries out at a higher temperature, and reaction speed is fast, and can operate under higher space velocity, efficiency is high.
At present, hydro carbons self-heating Auto-thermal reforming process at home chemical fertilizer industry has carried out commercial Application, and application is comparatively successful, but is raw materials usedly confined to natural gas.But it is very difficult for will ensuring reliable natural gas supply to a lot of oil plant.In this case, consider that the gaseous hydrocarbons such as abundant refinery gas are very necessary as the unstripped gas of Autothermal reforming technique, but the composition of refinery gas is comparatively complicated, and often fluctuates.
Be directed to this, in conjunction with the feature of autothermal reaction technique, be necessary that exploitation one is applicable to gaseous hydrocarbon self-heating conversion catalyst, to meet the particular/special requirement of autothermal reaction to high activity of catalyst, high strength and strength stability, good anti-carbon performance and high temperature sintering resistant performance.
Chinese patent CN200810046536 discloses a kind of natural gas intermittent conversion town gas catalyst, and with kaolin and aluminium oxide for raw material, after the honed sieve of mechanical ball, spin is shaped; Under 1300 DEG C of conditions, 4hr is calcined, i.e. obtained SiO after drying and processing
2, Al
2o
3composite oxide carrier, then impregnated activated component.Carrier is mainly α-Al mutually
2o
3and Al
6si
2o
13, account for 80wt% ~ 95wt%; Active component is NiO, accounts for 5wt% ~ 20wt%; Auxiliary agent is selected from Al
2o
3, one or more in rare earth oxide.This invention does not relate to Autothermal reforming field.
US Patent No. 4790929 uses kaolin roasting at 1150 ~ 1350 DEG C to be converted into mullite and free silicon dioxide, cross with alkaline aqueous solution and filter all or silica free at least partially, then dry, the carrier obtained is mainly containing mullite, also have a small amount of free silicon dioxide, the mol ratio of alumina catalyst support/silica is 0.50 ~ 1.65.On carrier by infusion process load be selected from cobalt, nickel, molybdenum, tungsten one or more remove heavy metal as active component for heavy hydrocarbon, or Supported Pt Nanoparticles or palladium are used for catalytic cracking of hydrocarbon reaction etc.This invention relates generally to the preparation of carrier, does not relate to Autothermal reforming field.
Summary of the invention
The object of this invention is to provide a kind of gaseous hydrocarbon self-heating conversion catalyst being applicable to the Autothermal reforming preparing synthetic gas of gaseous hydrocarbon or hydrogen preparation field, provide the preparation method that it is conducive to large-scale industrial production simultaneously.
Gaseous hydrocarbon self-heating conversion catalyst of the present invention, comprises carrier, active component and auxiliary agent, containing free state SiO in described carrier
2;
Described catalyst is nickel-silicon-aluminium System Catalyst, and active component is nickel, and carrier is free state SiO
2with the 3Al of mullite structure
2o
32SiO
2, auxiliary agent is that in the oxide of MgO, rare earth element, one or more arbitrary proportion mixes; The mass fraction of each component is:
Nickel content: count 15 ~ 25 parts with NiO;
Carrier: amount to 75 ~ 90 parts, wherein 3Al
2o
32SiO
2content is 60 ~ 76 parts, and all the other are free state SiO
2, free state SiO
2content is 12.5% ~ 16% in the catalyst;
Auxiliary agent: 2 ~ 8 parts.
Gaseous hydrocarbon self-heating conversion catalyst preparation method of the present invention, comprises the following steps:
(1) pretreatment of raw material: select containing SiO
2and Al
2o
3material is raw material, adds NaOH solution mixing, adds thermal response, filter, washs and obtain alkali modification raw material after drying;
(2) preparation of catalyst: adopt beating method or dry pigmentation Kaolinite Preparation of Catalyst semi-finished product, shaping, roasting, obtains finished catalyst.
Described contains SiO
2and Al
2o
3material is one or more the arbitrary proportion mixing that raw material is selected from the natural or Prof. Du Yucang mineral such as kaolin, bauxite;
Described NaOH solution mass fraction is 10 ~ 25%, and addition is as the criterion with whole dipped raw materials of modification that needs;
Described NaOH solution mass fraction preferably 15 ~ 20%, addition is as the criterion with whole dipped raw materials of modification that needs;
Heating reaction temperature described in step (1) is 70 ~ 100 DEG C, and the reaction time is 2 ~ 6h;
Heating reaction temperature described in step (1) preferably 80 ~ 90 DEG C, the reaction time is 3 ~ 4h;
Beating method step is: active component predecessor, auxiliary agent precursor solution is soluble in water, adds alkali modification raw material, and making beating, dries to obtain semi-finished product; Dry pigmentation step is: by mechanical ball milling after alkali modification raw material, active component predecessor, the mixing of adjuvant component predecessor, obtain catalyst semi-finished product.
The mass ratio of the raw material of alkali modification, active component and auxiliary agent is 75 ~ 90: 10 ~ 25: 2 ~ 8; Active component is in NiO, and auxiliary agent is in MgO or rare-earth oxide;
Described active component predecessor is that in nickel nitrate, nickel oxalate, one or both arbitrary proportion mixes;
Described auxiliary agent predecessor is the arbitrary proportion of one or more mixing in magnesium nitrate, magnesium oxalate, rare-earth oxalate, rare earth nitrades;
Forming method, for getting 100 parts of semi-finished product, adds lubricant 3 ~ 6 parts, ball milling mixing 15 ~ 30min, and rear taking-up adds 5 ~ 15 parts of deionized waters, compressing after mixing;
Lubricant is selected from any one or a few arbitrary proportion mixing in graphite, paraffin, stearate;
Forming shape is sheet or the cellular specially-shaped annular of two sphere seven apertures in the human heads; Sheet, particle diameter is 3.5 ~ 6mm, is highly 3.5 ~ 6mm; The cellular specially-shaped annular of two sphere seven apertures in the human heads, external diameter is 10 ~ 16mm, internal diameter 0.5 ~ 2.0mm, hole count 7, is highly 8 ~ 11mm;
Sintering temperature is 800 ~ 1200 DEG C, and roasting time is 4 ~ 9h;
Sintering temperature preferably 900 ~ 1150 DEG C, roasting time is 6 ~ 8h.
The present invention compared with prior art has following beneficial effect:
(1) its carrier of gaseous hydrocarbon self-heating conversion catalyst described in through alkali modification process, and adds MgO and/or rare-earth oxide as auxiliary agent, makes carrier meta-alkalescence, thus improves the anti-carbon performance of catalyst;
(2) catalyst is through high-temperature roasting process, forms mullite as dominant phase, has good intensity and strength stability;
(3) common carrier is made with porous silicon, increase active metal decentralization, improving catalyst activity surface adopts beating method or dry pigmentation preparation technology both can ensure catalyst activity, active metal crystal grain in use procedure can be avoided again to assemble, ensure catalyst activity stability, be conducive to large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is pressurization activity rating device schematic flow sheet.
In figure: 1, water measuring pump; 2, methane, oxygen bottle; 3, vaporizer; 4, blender; 5, tubular reactor; 6, condenser; 7, separator; 8, voltage-stablizer; 9, wet flow indicator.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
Get calcined kaolin (aluminium oxide 35.21%, silica 55.31%, impurity≤2%, lower with) add mass fraction 15%NaOH solution and keep 70 DEG C to soak 4h, filtration washing is to without Na
+exist, 120 DEG C of oven dry, are crushed to 280 orders.
Take nickel nitrate 58.4g, magnesium nitrate 12.8g, be dissolved in 85g water, joined by the aqueous solution in above-mentioned alkaline-modified kaolin 82.5g, mixing making beating, puts into baking oven 120 DEG C of dry 12h, obtains semi-finished product A1 by slurry.
Embodiment 2
Get calcined kaolin to add mass fraction 15%NaOH solution and keep 70 DEG C to soak 4h, filtration washing is to without Na
+exist, 120 DEG C of oven dry, are crushed to 280 orders.
Take nickel nitrate 66.2g, magnesium nitrate 38.4g, be dissolved in 90g water, joined by the aqueous solution in above-mentioned alkaline-modified kaolin 88g, mixing making beating, puts into baking oven 120 DEG C of dry 12h, obtains semi-finished product A2 by slurry.
Embodiment 3
Get calcined kaolin to add mass fraction 17%NaOH solution and keep 75 DEG C to soak 4h, filtration washing is to without Na
+exist, 120 DEG C of oven dry, are crushed to 280 orders.
Take nickel nitrate 77.8g, magnesium nitrate 19.2g, be dissolved in 100g water, joined by the aqueous solution in above-mentioned alkaline-modified kaolin 95g, mixing making beating, puts into baking oven 120 DEG C of dry 12h, obtains semi-finished product A3 by slurry.
Embodiment 4
Get calcined kaolin to add mass fraction 20%NaOH solution and keep 90 DEG C to soak 3h, filtration washing is to without Na
+exist, 120 DEG C of oven dry, are crushed to 280 orders.
Take nickel nitrate 97.3g, magnesium nitrate 25.6g, be dissolved in 100g water, joined by the aqueous solution in above-mentioned alkaline-modified kaolin 98g, mixing making beating, puts into baking oven 120 DEG C of dry 12h, obtains semi-finished product A4 by slurry.
Embodiment 5
Get calcined kaolin to add mass fraction 20%NaOH solution and keep 70 DEG C to soak 4h, filtration washing is to without Na
+exist, 120 DEG C of oven dry, are crushed to 280 orders.
Take nickel nitrate 89.5g, magnesium nitrate 51.2g, be dissolved in 100g water, joined by the aqueous solution in above-mentioned alkaline-modified kaolin 94.5g, mixing making beating, puts into baking oven 120 DEG C of dry 12h, obtains semi-finished product A5 by slurry.
Implement 6
Get calcined kaolin to add mass fraction 20%NaOH solution and keep 80 DEG C to soak 4h, filtration washing is to without Na
+exist, 120 DEG C of oven dry, are crushed to 280 orders.
Take nickel nitrate 58g, magnesium nitrate 13g, after drying, mixing is put into ball mill and is milled to 90wt% and crosses 280 mesh sieves, takes kaolin 83g and above-mentioned mixing of materials ball milling 6h, obtains semi-finished product A6.
Embodiment 7
Get calcined kaolin to add mass fraction 15%NaOH solution and keep 70 DEG C to soak 4h, filtration washing is to without Na
+exist, 120 DEG C of oven dry, are crushed to 280 orders.
Take nickel nitrate 66g, magnesium nitrate 38g, after drying, mixing is put into ball mill and is milled to 90wt% and crosses 280 mesh sieves, takes kaolin 90g and above-mentioned mixing of materials ball milling 6h, obtains semi-finished product A7.
Embodiment 8
Get calcined kaolin to add mass fraction 15%NaOH solution and keep 75 DEG C to soak 4h, filtration washing is to without Na
+exist, 120 DEG C of oven dry, are crushed to 280 orders.
Take nickel nitrate 77.8g, magnesium nitrate 19.5g, after drying, mixing is put into ball mill and is milled to 90wt% and crosses 280 mesh sieves, takes kaolin 98g and above-mentioned mixing of materials ball milling 8h, obtains semi-finished product A8.
Embodiment 9
Get calcined kaolin to add mass fraction 17%NaOH solution and keep 70 DEG C to soak 4h, filtration washing is to without Na
+exist, 120 DEG C of oven dry, are crushed to 280 orders.
Take nickel nitrate 97.3g, magnesium nitrate 25.6g, after drying, mixing is put into ball mill and is milled to 90wt% and crosses 280 mesh sieves, takes kaolin 98g and above-mentioned mixing of materials ball milling 7h, obtains semi-finished product A8.
Embodiment 10
Get calcined kaolin to add mass fraction 20%NaOH solution and keep 80 DEG C to soak 3h, filtration washing is to without Na
+exist, 120 DEG C of oven dry, are crushed to 280 orders.
Take nickel nitrate 89.5g, magnesium nitrate 51.2g, after drying, mixing is put into ball mill and is milled to 90wt% and crosses 280 mesh sieves, takes kaolin 93g and above-mentioned mixing of materials ball milling 8h, obtains semi-finished product A10.
Embodiment 11
Semi-finished product prepared by Example 1-10, add graphite by semi-finished product weight 5%, and it is compressing to add suitable quantity of water, and shape is two cellular specially-shaped annulars of sphere seven apertures in the human head.1100 DEG C of roasting 8h, obtain finished catalyst B1-B10.
Catalyst physical and chemical performance prepared by above-described embodiment 1-11 is as described in Table 1:
Table 1 gaseous hydrocarbon Natural Transformation catalyst physical and chemical performance
For investigating catalyst performance of the present invention, the evaluating apparatus shown in Fig. 1 is adopted to evaluate catalyst.
Evaluating unstripped gas used is casing-head gas after desulfurization, and its component is as shown in table 2.
Table 2 raw material casing-head gas composition (%, v/v)
Evaluating catalyst condition
Process gas is analyzed: Shimadzu GC-8A chromatogram, column length 2m, and fill TDX-01, column temperature 45 DEG C, gasifies 100 DEG C, detector 100 DEG C, flow velocity 35mL/min.
Table 3 evaluating catalyst result
From above-mentioned experimental data, the catalyst of preparation has good activity of conversion.The equal particle of the catalyst unloaded after conversion is complete, and color is even, without Carbon Deposit Phenomenon, illustrates that catalyst has good anti-carbon nature energy.
For detecting intensity and the strength stability of catalyst, measuring the sample strength after the fresh sample of catalyst and heat run respectively, the catalyst phosphorus content before and after running is also detected, draw the clean coke content of running rear catalyst, the results are shown in table 4.The method of heat run is that Temperature fall to room temperature, then surveys intensity, to detect the strength stability of catalyst by catalyst granules in Muffle furnace after 800 DEG C of roasting 3h.
Table 4 catalyst strength, anti-carbon nature result
| Sample number into spectrum | Fresh sample intensity | Intensity after heat run | Strength retention ratio, % | Clean coke content after running, % |
| B1 | 386 | 289 | 77.07 | -0.12 |
| B2 | 375 | 302 | 76.26 | -0.43 |
| B3 | 396 | 274 | 78.06 | -0.07 |
| B4 | 351 | 302 | 82.51 | -0.57 |
| B5 | 366 | 265 | 69.37 | -0.13 |
| B6 | 382 | 322 | 80.70 | -0.28 |
| B7 | 399 | 325 | 93.93 | -0.33 |
| B8 | 346 | 312 | 83.20 | -0.21 |
| B9 | 375 | 296 | 77.69 | -0.42 |
| B10 | 381 | 336 | 88.19 | -0.37 |
As can be seen from Table 4, catalyst has good intensity and strength stability, fully can meet the requirement of autothermal process to catalyst.In addition, the clean coke content after catalyst runs is negative value, further illustrates catalyst of the present invention and has good coking resistivity.
Comparative example 1
According to enforcement 1 scheme, get calcined kaolin (aluminium oxide 35.21%, silica 55.31%, impurity≤2%) add the 25%NaOH solution being different from embodiment 1 and keep 70 DEG C to soak 12h, filtration washing is to without Na
+exist, 120 DEG C of oven dry, are crushed to 280 orders.
Take nickel nitrate 58.4g, magnesium nitrate 12.8g, be dissolved in 85g water, joined by the aqueous solution in above-mentioned alkaline-modified kaolin 82.5g, mixing making beating, puts into baking oven 120 DEG C of dry 12h, obtains semi-finished product C1 by slurry.Get real semi-finished product C1, add graphite by semi-finished product weight 5%, it is compressing to add suitable quantity of water, and shape is two cellular specially-shaped annulars of sphere seven apertures in the human head.1100 DEG C of roasting 8h, obtain finished catalyst D1.
Comparative example 2
By changing concentration and the soak time of NaOH solution in embodiment 1, obtain different content free state SiO
2catalyst D2, D3.
Gained catalyst B 1 and D1, D2, D3, adopt transmission electron microscope to carry out nickel crystallite comparative analysis, the results are shown in table 5; Carry out active comparative evaluation, the results are shown in table 6.
Table 5 catalyst TEM Data Comparison
Table 6 catalyst activity comparative evaluation data
Can be found out by table 5, appropriate free state SiO in catalyst
2existence can improve the decentralization of active metal Ni, and be conducive to the agglomeration improving active metal.Can be found out by table 6, containing appropriate free state SiO
2catalyst comparatively containing a small amount of SiO
2catalyst, its activity improves a lot.
Claims (10)
1. a gaseous hydrocarbon self-heating conversion catalyst, comprises carrier, active component and auxiliary agent, it is characterized in that, containing free state SiO in carrier
2.
2. gaseous hydrocarbon self-heating conversion catalyst according to claim 1, is characterized in that, this catalyst is nickel-silicon-aluminium System Catalyst, and active component is nickel, and carrier is free state SiO
2with the 3Al of mullite structure
2o
32SiO
2, auxiliary agent be selected from MgO, rare earth oxide one or more.
3. gaseous hydrocarbon self-heating conversion catalyst according to claim 2, is characterized in that, the mass fraction of each component is:
Nickel: count 15 ~ 25 parts with NiO;
Carrier: 75 ~ 90 parts, wherein 3Al
2o
32SiO
2content is 60 ~ 76 parts, and all the other are free state SiO
2, free state SiO
2mass percentage is 12.5% ~ 16% in the catalyst;
Auxiliary agent: 2 ~ 8 parts.
4. a preparation method for the arbitrary described gaseous hydrocarbon self-heating conversion catalyst of claim 1-3, is characterized in that, comprise the following steps:
(1) pretreatment of raw material: select containing SiO
2and Al
2o
3material is raw material, joins NaOH solution and soaks, add thermal response, and filtration, washing, drying, ball mill grinding obtain alkali modification raw material;
(2) preparation of catalyst: adopt beating method or dry pigmentation Kaolinite Preparation of Catalyst semi-finished product, shaping, roasting, obtains finished catalyst.
5. the preparation method of gaseous hydrocarbon self-heating conversion catalyst according to claim 4, is characterized in that, described raw material is the mixture of kaolin, one or more arbitrary proportions of bauxite.
6. the preparation method of gaseous hydrocarbon self-heating conversion catalyst according to claim 5, is characterized in that, beating method step is: active component predecessor, auxiliary agent precursor solution is soluble in water, adds alkali modification raw material, and making beating, dries to obtain semi-finished product; Dry pigmentation step is: by mechanical ball milling after alkali modification raw material, active component predecessor, the mixing of adjuvant component predecessor, obtain catalyst semi-finished product.
7. gaseous hydrocarbon self-heating conversion catalyst preparation method according to claim 6, is characterized in that, forming method is for getting 100 parts of semi-finished product, add lubricant 3 ~ 6 parts, ball milling mixing 15 ~ 30min, rear taking-up adds 5 ~ 15 parts of deionized waters, compressing after mixing.
8. gaseous hydrocarbon self-heating conversion catalyst preparation method according to claim 6, is characterized in that, alkali modification raw material, active component and auxiliary agent mass ratio are 75 ~ 90: 10 ~ 25: 2 ~ 8, and wherein active component is with oxide basis, and auxiliary agent is with oxide basis.
9. gaseous hydrocarbon self-heating conversion catalyst preparation method according to claim 4, is characterized in that, described active component predecessor is that in nickel nitrate, nickel oxalate, one or both arbitrary proportion mixes; Described auxiliary agent predecessor is the arbitrary proportion of one or more mixing in magnesium nitrate, magnesium oxalate, rare-earth oxalate, rare earth nitrades.
10. gaseous hydrocarbon self-heating conversion catalyst preparation method according to claim 4, is characterized in that, sintering temperature is 800 ~ 1200 DEG C, and roasting time is 4 ~ 9h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109382136A (en) * | 2017-08-02 | 2019-02-26 | 中国石油化工股份有限公司 | Gaseous hydrocarbon steam converts upper section catalyst and preparation method |
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|---|---|---|---|---|
| US4790929A (en) * | 1983-06-20 | 1988-12-13 | Engelhard Corporation | Hydrotreating process using porous mullite |
| US6066589A (en) * | 1997-05-19 | 2000-05-23 | Sud Chemie Mt. S.R.L. | Hydrogenation catalysts |
| CN1876234A (en) * | 2005-06-06 | 2006-12-13 | 中国石油化工股份有限公司 | Gaseous hydrocarbon low temperature insulation transformation catalyst and its reaction process |
| CN102008962A (en) * | 2009-09-07 | 2011-04-13 | 中国石油化工股份有限公司 | Hydrocarbon pre-converting catalyst for large-scale energy-saving hydrogen production technology |
-
2013
- 2013-10-15 CN CN201310479967.8A patent/CN104549284B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4790929A (en) * | 1983-06-20 | 1988-12-13 | Engelhard Corporation | Hydrotreating process using porous mullite |
| US6066589A (en) * | 1997-05-19 | 2000-05-23 | Sud Chemie Mt. S.R.L. | Hydrogenation catalysts |
| CN1876234A (en) * | 2005-06-06 | 2006-12-13 | 中国石油化工股份有限公司 | Gaseous hydrocarbon low temperature insulation transformation catalyst and its reaction process |
| CN102008962A (en) * | 2009-09-07 | 2011-04-13 | 中国石油化工股份有限公司 | Hydrocarbon pre-converting catalyst for large-scale energy-saving hydrogen production technology |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109382136A (en) * | 2017-08-02 | 2019-02-26 | 中国石油化工股份有限公司 | Gaseous hydrocarbon steam converts upper section catalyst and preparation method |
| CN109382136B (en) * | 2017-08-02 | 2022-04-08 | 中国石油化工股份有限公司 | Gaseous hydrocarbon steam conversion upper-section catalyst and preparation method thereof |
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