CN1025158C - Hydrocarbon steam conversion catalyst containing lanthanum-aluminum modified alumina carrier - Google Patents
Hydrocarbon steam conversion catalyst containing lanthanum-aluminum modified alumina carrier Download PDFInfo
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- CN1025158C CN1025158C CN89106847A CN89106847A CN1025158C CN 1025158 C CN1025158 C CN 1025158C CN 89106847 A CN89106847 A CN 89106847A CN 89106847 A CN89106847 A CN 89106847A CN 1025158 C CN1025158 C CN 1025158C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 10
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 7
- UZQSJWBBQOJUOT-UHFFFAOYSA-N alumane;lanthanum Chemical compound [AlH3].[La] UZQSJWBBQOJUOT-UHFFFAOYSA-N 0.000 title 1
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 14
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 238000000629 steam reforming Methods 0.000 claims abstract description 6
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003607 modifier Substances 0.000 claims abstract description 5
- 239000011148 porous material Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 21
- 230000004048 modification Effects 0.000 claims description 13
- 238000012986 modification Methods 0.000 claims description 13
- 239000004411 aluminium Substances 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 3
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 23
- 230000000694 effects Effects 0.000 description 14
- 229910052759 nickel Inorganic materials 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- -1 lanthanum aluminate Chemical class 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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
Landscapes
- Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
A hydrocarbon steam reforming catalyst having the composition and properties: NiO8-13% (wt), la2O30.5-3%(wt)，a-Al2O384-90% (wt), specific surface: 3-5m2The pore volume of more than 50NM is more than 80 percent, the carrier alumina is modified by a mixed oxide of lanthanum and aluminum as a modifier, and is impregnated by 0.49-0.5mol of impregnation liquid containing lanthanum nitrate, so that the obtained catalyst has particularly high-temperature steam sintering resistance and is particularly suitable for being used as a lower-stage conversion catalyst.
Description
The present invention be a kind of be the steam reforming catalysts of raw material with the hydro carbons.Be applied in synthetic ammonia, hydrogen manufacturing and the synthesizing methanol industry.
Technical background:
It is the workshop section of energy consumption maximum in the synthetic ammonia process that the primary reformer hydrocarbon steam transforms.Along with the development of ammonia synthesis process, the appearance in succession of various new energy-saving process is strengthened the process conditions of primary reformer day by day.Improve constantly as air speed, pressure, steam/hydrocarbons ratio is more and more lower, and the raw material hydrocarbon cut is heavy and assorted or the like, and these all require reforming catalyst to have higher activity, anti-carbon nature, hydrothermal stability and intensity.And these performances are conflicting often.Now can be described as the compromise thing of contradiction, all have some shortcomings more or less with catalyst.For example, the binding type catalyst anti-carbon nature that contains potassium can be good, but activity and strength retrogression are fast.Coprecipitated sintered catalyst is active high, but easy hydration and anti-process conditions fluctuation ability.The outstanding advantage of presintering immersion-type catalyst is an intensity and active high, but activity stability is relatively poor.(seeing performance comparison table 1 hereinafter for details).Therefore along with the development of synthetic ammonia and process for making hydrogen, need develop the higher steam reforming catalysts of activity, anti-carbon nature, stability and intensity.Goal of the invention:
According to above-mentioned analysis, the objective of the invention is to solve the hydrothermal stability problem of its bulk structure or surperficial phase structure, to improve intensity, the activity and stable of catalyst under service condition for overcoming the existing shortcoming that exists with catalyst.Thereby improve the ability of the anti-process conditions fluctuation of catalyst, prolong its service life.
Summary of the invention:
Now use the pluses and minuses of catalyst from analyzing three classes, we think the key issue that steam reforming catalysts exists is how further to improve the old and feeble speed that the hydrothermal stability of catalyst (stability that comprises surface and bulk structure) reduces the every performance of catalyst, with the ability that improves the fluctuation of anti-process conditions with increase the service life, and the approach more likely that addresses this problem is to adopt the substep processing method, promptly earlier make the intensity height with high-temperature sintering process, good hydrothermal stability, the pottery carrier that pore structure is suitable, then through the surface modification of carrier, soak active component again, just may make the catalyst of skeleton and surface-stable.
Carrier: the used carrier of steam reforming catalysts of the present invention is aluminum contained compounds such as aluminium oxide or aluminate, and adopting α-Al203 is the carrier best results, makes by common method.Must carry out surface modification to the carrier that makes then, just might make body phase (skeleton) structure and surface texture the high steam partial pressure of high temperature stable catalyst all.The material that is suitable for doing modifier has rare earth, alkaline earth, Tu's oxide.The mixed oxide of rare earth and Tu preferably.Especially the mixed oxide of lanthanum and aluminium.Initiation material as the aluminium oxide of modifier is an aluminum nitrate, obtains γ-AL203 when adding thermal decomposition, and the different in kind with the α-AL203 of body under lower temperature (500-800 ℃), just can generate lanthanum aluminate with lanthana.Adding method employing dipping/or preferably adopt dipping one precipitation method.After enclosing the skim lanthanum aluminate on α-AL203 surface, formed smooth surface became more coarse when high temperature sintering originally.Therefore the specific surface of carrier has increased about 20% after the modification.When after soaking active component again on this thin layer lanthanum aluminate surface, the not only Stability Analysis of Structures of lanthanum aluminate layer own, and the active component nickel on soaking had significant peptizaiton, being evenly distributed of nickel, from the transmission electron microscope image, to compare with carrier is unmodified, crystal grain obviously reduces.And suppress the agglomeration of nickel crystallite under the high steam partial pressure of high temperature.Catalyst composition of the present invention and physico-chemical parameter are as follows:
Form (WT%)
NiO 8-13%
La
2O
30.5-3%
α-Al
2O
384-90%
Specific surface 3-5m
2/ G
Pore volume more than aperture: the 50NM is greater than 80%
Side pressure strength: greater than the 40kg/cm height
Water absorption rate: 20-25%
The catalyst and the industrial used several catalyst that make by the present invention carry out performance comparison, and it mainly the results are shown in table 1.Wherein, " old and feeble sample " is meant is accelerating on the old and feeble device, the sample that takes out after handling 30 hours under the following condition:
H2O/H2=10, hydrogen air speed=500hr
-1
Temperature t=800 ℃ pressure P=0.5MPa
Can find out from table 1 data, the sample MA that makes by the present invention, and now with several catalyst relatively, its performance has obvious advantage, the old and feeble speed of properties of sample after the high steam partial pressure of high temperature is handled especially is more significantly less than used several catalyst.This shows that the catalyst of making by the present invention has extra high hydrothermal stability.(active few intensity that descends descends few, and it is low that nickel crystallite increases rate.）
Example 1
(1) takes by weighing SILVER REAGENT nickel nitrate (Ni(NO3)
26H2O) 593.3 grams are put into the 500ML beaker, add an amount of deionized water and make it dissolving, follow in the shift-in 500ML volumetric flask, be diluted to graduation mark promptly join solution (1).Take by weighing 300 gram Raschig ring carriers, put in the beaker that fills 250ML solution (1), rock a little, at room temperature left standstill 1 hour.Put into oven for drying after taking-up drains, move into muffle furnace again, after decomposing 3 hours under 500 ℃, be cooled to room temperature naturally.Above-mentioned dipping and roasting process repeat once again, just make sample A, to contrast sample as the basis.
(2) get 92.6 gram SILVER REAGENT lanthanum nitrates, be made into 500ML solution by last method.Raschig ring carrier 500 grams are immersed in this solution, at room temperature flooded 90 minutes, taking-up drains, in baking oven,, move into muffle furnace again, reduce to room temperature then 800 ℃ of roastings 3 hours in 120 ℃ of bakings 3 hours, soak nickel by (1) method again, just make the catalyst B of carrying the modification of herbal classic lanthanum.
Example 2
Get 90.6 gram SILVER REAGENT lanthanum nitrates and 127.5 gram aluminum nitrates, be made into 500ML solution, then by routine 1(2) method makes the catalyst C of carrier through the modification of lanthanum aluminium.
Example 3
Get 92.6 gram SILVER REAGENT lanthanum nitrates, 127.5 gram aluminum nitrates and 52.7 gram industrial urea, be made into 500ML solution.Add 500 gram Raschig ring carriers then, at room temperature flooded 90 minutes.After taking-up drains, put into the crucible of adding a cover, in baking oven,, make solution in the hole, decompose precipitation in 110 ℃ of heating 14 hours.Again in the shift-in muffle furnace, by routine 1(2) method roasting and soak nickel, just make the catalyst D that carrier is carried out the modification of lanthanum aluminium with the dipping-precipitation method.
Above-mentioned sample is at H2O/H2=10, accelerate old and feeble 30 hours under T=800 ℃ the condition after, little anti--measure its activity of conversion on the chromatogram arrangement.Condition determination is as follows:
Unstripped gas: the casing-head gas after desulfurization (sulfur content＜0.2PPM)
CH4 content 85%, total carbon 110%
Carbon space velocity: 6.67 seconds
-1
H2O/C：4
H2O/H2：10
Pressure: normal pressure, 500 ℃ of temperature
Catalytic amount: the 200mg(50-60 order)
If reaction pair CH4 is a first order reaction, then represent catalyst activity with rate constant K, K can try to achieve from following formula:
The K=(carbon space velocity) * in[1/(1-X)]
X is the conversion ratio that the hydrocarbon conversion becomes the oxide of carbon in the formula, promptly
X＝ (CO＋CO
2)/(ΣC) ×100%
Now record and the results are shown in table 2
(table is seen the literary composition back)
Table 2 is the result show, α-AL203 carrier is through the lanthanum aluminium modification of lanthanum modification, the modification of lanthanum aluminium or the employing dipping-precipitation method, all can improve the hydrothermally stable of catalyst, the activity of conversion that makes the sample after the high steam partial pressure of process high temperature is handled is apparently higher than not having modification sample A, the growth rate of nickel crystallite also obviously reduces, and the said sequence enhancing is pressed in this effect.
In order to confirm that further catalyst of the present invention has excellent activity and stable, we are with sample A, and B and IC146-1, four samples of RKNR drop into the middle part (about 5 meters) of pilot scale conversion tube together.Liquid air speed at light oil: 1.75h
-1, H2O/C=3, temperature: enter the mouth 480 ℃, export 780 ℃, running is 700 hours under the condition of pressure 3MPa, takes out sample analysis then, and the result is as follows.This shows that the sample D by the present invention makes really has very high stability.
(table is seen the literary composition back)
Sample activity of conversion K nickel crystallite size nm
A 0.186 46.4
D 0.279 40.6
IC146-1 0.065 56.4
RKNR 0.193 54.9
The every performance comparison of table 1. catalyst
Sample activity of conversion K nickel crystallite size (nm) side pressure strength kg/cm height
The old and feeble sample of the fresh sample of the old and feeble sample of the fresh sample of the old and feeble sample of the fresh sample of product
MA 1.163 0.715 30.8 34.4 45 46 of the present invention
C11-9 1.070 0.497 39.3 45.4 47 39
C11-2S 0.439 0.149 43.0 50.8 29 18
1C146-1 0.651 0.065 40.2 49.0 41 22
1C146-4 1.107 0.209 42.1 50.8 42 25
RKNR 1.261 0.516 33.5 48.5 28 19
Table 2. is accelerated the activity and the nickel crystallite size of old and feeble front and back sample
Sample activity of conversion K second
-1Nickel crystallite size (nm)
The old and feeble sample of the fresh sample of the old and feeble sample of the fresh sample of product
A 1.153 0.499 30.8 45.4
B 1.160 0.575 31.2 42.0
C 1.128 0.650 31.2 36.1
D 1.148 0.714 30.8 34.1
Claims (4)
1, a kind of hydrocarbon steam conversion catalyst, its composition and character are as follows:
Nio 8-13wt%
La
2O
30.5-3wt%
α-Al
2O
384-90wt%
Specific area 3-5m
2/ g
Pore volume＞80% that aperture 50NM is above
Described alumina support is through the mixed oxide modification of modifier lanthanum-oxides or lanthanum and aluminium, and wherein said modification is handled employing 0.49-0.5mol lanthanum nitrate or handled with the mixed impregnant liquor of 0.68mol aluminum nitrate.
2, catalyst according to claim 1, its spy is being that support modification adopts the dipper precipitation method, precipitating reagent adopts urea.
3, catalyst according to claim 1 is characterized in that described modifier is the mixed oxide of lanthanum and aluminium.
4, claim 1 or 2 described catalyst can be used as the lower section catalyst of hydro carbons (gaseous state, liquid state) for the steam-reforming stove of raw material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN89106847A CN1025158C (en) | 1989-10-28 | 1989-10-28 | Hydrocarbon steam conversion catalyst containing lanthanum-aluminum modified alumina carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN89106847A CN1025158C (en) | 1989-10-28 | 1989-10-28 | Hydrocarbon steam conversion catalyst containing lanthanum-aluminum modified alumina carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1042696A CN1042696A (en) | 1990-06-06 |
| CN1025158C true CN1025158C (en) | 1994-06-29 |
Family
ID=4856920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89106847A Expired - Lifetime CN1025158C (en) | 1989-10-28 | 1989-10-28 | Hydrocarbon steam conversion catalyst containing lanthanum-aluminum modified alumina carrier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1025158C (en) |
Cited By (1)
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|---|---|---|---|---|
| CN101108350B (en) * | 2006-07-18 | 2010-05-12 | 中国石油天然气股份有限公司 | Hydrocarbon steam conversion catalyst and preparation method thereof |
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| CN100415369C (en) * | 2004-08-04 | 2008-09-03 | 中国石油化工股份有限公司 | Coarse octyl alcohol liquid phase hydrogenation refining catalyst and hydrogenation reaction technique thereof |
| CN1305566C (en) * | 2004-08-20 | 2007-03-21 | 上海舜华新能源系统有限公司 | Integral catalyst for preparation hydrogen by methyl alcohot reformation and its preparation method |
| JP5261801B2 (en) * | 2006-09-20 | 2013-08-14 | 中国石油化工股▲分▼有限公司 | Nickel catalysts for selective hydrogenation |
| DE102007046297B4 (en) * | 2007-09-27 | 2016-12-22 | Süd-Chemie Ip Gmbh & Co. Kg | New catalyst design and manufacturing method for steam reforming catalysts |
| CN102019183B (en) * | 2009-09-22 | 2013-07-24 | 中国石油化工股份有限公司 | Catalyst for producing hydrogen from hydrocarbon steam conversion or carboxyl syngas reaction |
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| CN103894237B (en) * | 2012-12-28 | 2016-05-18 | 中国石油化工股份有限公司 | A kind of catalyst for partially oxidizing conversion protective agent and application thereof |
| CN104549275B (en) * | 2013-10-12 | 2018-06-15 | 王颖华 | Transient metal doped solid catalyst, preparation method and the method for handling water |
| CN104475115A (en) * | 2014-11-20 | 2015-04-01 | 西南化工研究设计院有限公司 | Gaseous hydrocarbon pre-conversion catalyst and preparation method thereof |
| CN114100616B (en) * | 2020-08-31 | 2023-10-20 | 中国石油化工股份有限公司 | Hydrocarbon steam conversion catalyst and its preparation method |
-
1989
- 1989-10-28 CN CN89106847A patent/CN1025158C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101108350B (en) * | 2006-07-18 | 2010-05-12 | 中国石油天然气股份有限公司 | Hydrocarbon steam conversion catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1042696A (en) | 1990-06-06 |
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