CN109382136A - Gaseous hydrocarbon steam converts upper section catalyst and preparation method - Google Patents
Gaseous hydrocarbon steam converts upper section catalyst and preparation method Download PDFInfo
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- CN109382136A CN109382136A CN201710652492.6A CN201710652492A CN109382136A CN 109382136 A CN109382136 A CN 109382136A CN 201710652492 A CN201710652492 A CN 201710652492A CN 109382136 A CN109382136 A CN 109382136A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- 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
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- 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
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Abstract
The invention belongs to hydrocarbon steam conversion technical fields, and in particular to a kind of gaseous hydrocarbon steam conversion upper section catalyst and preparation method.The catalyst, using nickel and rare earth as active component, in catalyst, the content of NiO is 5~25wt.%, and rare-earth oxide content is 0.3~15wt.%；Using co-impregnation in supported on carriers active component nickel and rare earth；Support preparation method are as follows: (1) FCC catalyst gives up agent processing: FCC catalyst agent of giving up being roasted in air atmosphere, crushes, be sieved, obtain powder；(2) prepared by carrier: powder, magnesia, anti-carbon auxiliary agent, pore creating material, lubricant and binder being mixed, ball milling, kneading, granulation, extrusion forming, obtains raw ring, maintenance, drying, roasting obtain carrier.Catalyst of the present invention has good anti-carbon nature energy, mechanical strength and activity of conversion, is used for hydrogen making or oxo-synthesis gas with lower section catalyst cooperation；Preparation method, it is simple process, at low cost.
Description
Technical field
The invention belongs to hydrocarbon steam conversion technical fields, and in particular to a kind of gaseous hydrocarbon steam conversion upper section catalyst and
Preparation method.
Background technique
Hydrocarbon steam conversion is the hydrogen production process that Petrochemical Enterprises generally use both at home and abroad at present.
The hydrocarbon steam conversion past is external due to being sharply increased for light naphtha price using naphtha as primary raw material
As much as possible using relatively inexpensive gaseous hydrocarbons such as natural gases as hydrogen feedstock, to reduce hydrogen cost.But for state
Interior most of oil-refining chemical enterprises for lacking natural gas resource, still using LPG, propane, naphtha etc. as hydrogen feedstock.With
The progress of hydrogen producing technology and being continuously increased for hydrogen demand amount, the relatively inexpensive refinery gas resource in refinery are increasingly taken seriously.
A variety of different refinery gas are pocessed respectively, individually or and liquefied hydrocarbon together as hydrogen feedstock, such hydrogen manufacturing dress
It sets and is also increasing year by year.Using light hydrocarbons such as refinery gas as raw material, not only have plant hydrogen production cost reduces by a relatively large margin,
Simultaneously but also the operating conditions of reburner have clear improvement.It is mainly manifested in the significant drop of carbon deposit tendency of light hydrocarbon feedstock
Low, the operational safety of commercial plant is improved.The new feature and existing catalyst occurred based on current hydrogen feedstock is existed
The deficiency shown in terms of refinery gas hydrocarbon steam conversion, ZL 102451696 disclose one kind and produce for hydrocarbon steam conversion
The catalyst of hydrogen or carbonylation synthesis solid/liquid/gas reactions, results of industrial application is good, but catalyst production cost is higher.
Oil plant catalytic cracking (FCC) catalyst is the maximum a kind of catalyst of application amount in oil refining process, as FCC is advised
The increase of mould, the dosage that gives up is per year over 100000 tons, this is not only economic problems, and more important is environmental issues.FCC gives up agent master
It will be by Al2O3、SiO2, clay and BaCO3It being mixed with and obtains, the useless agent activity of the type is low, also contain a certain amount of heavy metal,
How it is handled, is always insider's one of project of interest.Currently, more fruitful method is by useless agent portion
Divide and recycle, reduce the amount of discard processing, method mainly includes by magnetic separation technique reuse, is used as cement substitution material
Material, as flame retardant agent and microorganism growth inhibitor and again crystallization are at catalyst etc..But these types of processing mode is deposited
In following defect: 1, processing cost is high；2, it is few to consume useless dosage.Landfill is the mode for most saving expense, but can be brought to environment
Significant damage.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of gaseous hydrocarbon steam to convert upper section catalyst, tool
There are good anti-carbon nature energy, mechanical strength and activity of conversion, is used for hydrogen making or oxo-synthesis gas with lower section catalyst cooperation；
The present invention also provides preparation method, simple process, preparation cost are low.
Gaseous hydrocarbon steam of the present invention converts upper section catalyst, using nickel and rare earth as active component, in catalyst,
The content of NiO is 5~25wt.%, and rare-earth oxide content is 0.3~15wt.%；It is born on carrier using co-impregnation
Carry active component nickel and rare earth；
The carrier is prepared with the following method:
(1) the useless agent processing of FCC catalyst:
FCC catalyst agent of giving up is roasted in air atmosphere, crushes, be sieved, obtain powder；
(2) prepared by carrier:
Powder, magnesia, anti-carbon auxiliary agent, pore creating material, lubricant and binder are mixed, mixing quality ratio is 100:25
Then~200:20~100:1~5:1~5:30~120 carries out ball milling, kneading, granulation, extrusion forming, obtain raw ring, conserve,
Drying, roasting, obtain carrier.
In the catalyst, the content of NiO is 8~17wt.%, and rare-earth oxide content is 0.5~12wt.%.
In catalyst of the present invention, the content of NiO is 5~25wt.%, preferably 8~17wt.%；The oxide of rare earth metal
Content is 0.3~15wt.%, preferably 0.5~12wt.%；The oxide content summation of alkaline-earth metal is 4~50wt.%, wherein
The content of magnesia is 4~30wt.%, preferably 12~25wt.%；Surplus is carrier.
By carrier total amount be 100% in terms of, in carrier contain 10~30% cement, 5~20% kaliophilite, surplus be aluminium,
Silicon.
0.18~0.22mL/g of Kong Rongwei of the carrier, hole are greater than 220N/ to breaking strength.The water suction of the carrier
Rate is 18~22%.
In step (1), the useless agent of FCC catalyst is the useless agent of the catalyst of ultrastable preparation.
As the Al of carrier component in FCC catalyst2O3And SiO2Content may be up to 95% (w) Zuo You, and catalyst is through too long
Phase uses, and microstructure is relatively stable.In addition, contain part of nickel in useless agent, this is just to be prepared steam using FCC agent of giving up as raw material and turned
Change catalyst and provides possibility.Meanwhile steam reforming catalysts are prepared as raw material can not only reduce its preparation using FCC agent of giving up
Cost, improve competitive strength, the agent that can also give up for from a wealth of sources, low-cost FCC search out one and relatively effective utilize way
Diameter is alleviated the useless agent of FCC and is handled to immense pressure caused by ecological environment.
In step (1), maturing temperature is 500~700 DEG C, and calcining time is 2~10h.Maturing temperature is preferably 600 DEG C,
Calcining time is preferably 3~4h.
In step (1), be sieved for 280~320 meshes, preferably cross 320 meshes.
In step (2), magnesia is the mixture of one or both of light magnesium oxide or heavy-burned magnesia.
In step (2), anti-carbon auxiliary agent is artificial synthesized kaliophilite.Pore creating material be graphite, stearic acid, stearate, nitric acid,
γ-Al2O3, one or more of cellulose or plant fiber, preferably graphite and plant fiber.Lubricant is graphite, stearic acid
Or stearate, preferred graphite.Binder is pure clinker aggregate portland cement, preferably 525 cement or 625 cement.
It in step (2), conserves to be soaked in water and conserving, soaking time is 24~36h.
In step (2), the breaking strength of raw ring is greater than 80N/, preferably greater than 100N/ after maintenance.
In step (2), maturing temperature is 1200~1300 DEG C, and calcining time is 2~6 hours.
The described gaseous hydrocarbon steam conversion upper section catalyst the preparation method is as follows:
Using co-impregnation in supported on carriers active component nickel and rare earth, dip time is 0.5~6 hour, after drying,
400~700 DEG C at a temperature of decompose 1~6 hour, then repeat dipping, drying, decompose primary, obtain finished catalyst.
Carrier of the invention can detecte out magnesium alumino metasilicate salt component (cordierite) through XRD analysis.
2 seed types of catalyst pores distribution point of the invention: in the hole of 10~15nm, quantity accounts for total pore volume for a kind of pore-size
Long-pending 35~45%, a kind of pore-size account for the 15~25% of total hole volume in the macropore of 150~200nm.
The appearance of catalyst of the present invention is Raschig ring, four orifice rings, seven apertures in the human head ring etc., with existing industrialized hydrocarbon steam conversion
Catalyst geometry is consistent, and size is similar.
Compared with prior art, the present invention having the following beneficial effects:
1, the support material of catalyst of the present invention greatly reduces catalysis using from a wealth of sources, the low-cost useless agent of FCC
Agent preparation cost also searches out one compared with effective way for FCC agent comprehensive utilization of giving up, FCC is effectively relieved and gives up agent to ecological environment
Caused by immense pressure, with good economic efficiency and social benefit.
2, gaseous hydrocarbon steam conversion upper section catalyst prepared by the present invention has good physical and chemical performance, and mechanical strength is good,
The crushing strength of catalyst is up to 220N/ or more.
3, catalyst of the invention uses potash as anti-carbon component, and therefore, anti-carbon nature can be urged with common binding type
Agent is close；In addition, potash carrier be sintered before be added, after high temperature sintering, mechanical strength, activity of conversion with it is common pre-
Sintered catalyst is close, is better than cement binding type catalyst.
4, gaseous hydrocarbon steam of the invention conversion upper section catalyst is suitable for 450~630 DEG C of reburner inlet temperature, outlet
700~950 DEG C of temperature；Convert carbon space velocity < 2000h-1；Steam/hydrocarbons ratio 2.5~7.0；The hydrogen of 1.5~4.0MPa of pressure, carbonyl processed
The upper section catalyst of base synthesis gas process condition is used for hydrogen making or oxo-synthesis gas with lower section catalyst cooperation.The conversion
Catalyst activity is stablized, and is converted to armatine alkane and meets technique requirement.
5, preparation method of the present invention, simple process, preparation cost are low.
Detailed description of the invention
Fig. 1 is small pressurized activity rating device figure；
In figure: 1- oil-measuring pump；2- water metering pump；3- vaporizer；4- mixer；5- tubular reactor；6- condenser；7-
Separator；8- voltage-stablizer；9- wet flow indicator.
Specific embodiment
Below with reference to embodiment, the present invention will be further described.
The useless agent of FCC used in the examples is the useless agent of the catalyst of ultrastable preparation.
Embodiment 1
FCC agent of giving up is roasted in air atmosphere, maturing temperature is 700 DEG C, calcining time 2h, by the useless agent after roasting
It crushed 320 meshes, referred to as raw material I.
Embodiment 2
FCC agent of giving up is roasted in air atmosphere, maturing temperature 500, calcining time 10h.By the useless agent after roasting
It crushed 280 meshes, referred to as raw material II.
Embodiment 3
FCC agent of giving up is roasted in air atmosphere, maturing temperature 600, calcining time 4h.By the useless agent powder after roasting
Broken 320 mesh of mistake, referred to as raw material II I.
Embodiment 4
Take raw material I 55kg, artificial synthesized kaliophilite 20kg, graphite 2kg, plant fiber 0.5kg, 525 cement 16kg, weight
Matter magnesia 14kg mixing and ball milling, adds water to mediate, and is granulated, and compression moulding obtains raw ring a, is conserved 24 hours with bubble, raw after maintenance
The breaking strength of ring a 110N/.It is sintered 3 hours at a temperature of 1250 ± 10 DEG C, obtains and be pre-sintered carrier a, carrier after roasting
The water absorption rate of a is 21%, and it is 21.2mL/g that mercury injection method, which measures carrier hole to hold, and hole is to breaking strength 225N/.
It is dissolved in water with 110kg nickel nitrate, 12kg lanthanum nitrate and is configured to 100L solution, above-mentioned carrier a is immersed into the solution
In, it is taken out after 2 hours, dries 4 hours at 100 DEG C, decomposed 2 hours at 450 DEG C.Repeated impregnations, are decomposed once, just at drying
Catalyst A is made.
Embodiment 5
Take raw material I 55kg, artificial synthesized kaliophilite 20kg, graphite 2kg, plant fiber 0.5kg, 625 cement 16kg, weight
Matter magnesia 14kg mixing and ball milling, adds water to mediate, and is granulated, and compression moulding obtains raw ring b, is conserved 24 hours with bubble, raw after maintenance
The breaking strength of ring b 92N/.It is sintered 3 hours at a temperature of 1215 ± 15 DEG C, obtains and be pre-sintered carrier b, carrier b after roasting
Water absorption rate 18.5%, it is 18.9mL/g that mercury injection method, which measures carrier hole to hold, and hole is to breaking strength 247N/.
It is dissolved in water with 110kg nickel nitrate, 12kg lanthanum nitrate and is configured to 100L solution, above-mentioned carrier b is immersed into the solution
In, it is taken out after 2 hours, dries 4 hours at 100 DEG C, decomposed 2 hours at 450 DEG C.Repeated impregnations, are decomposed once, just at drying
Catalyst B is made.
Embodiment 6
Take raw material II 60kg, artificial synthesized kaliophilite 18kg, graphite 2kg, plant fiber 0.5kg, 525 cement 18kg, weight
Matter magnesia 17kg mixing and ball milling, adds water to mediate, and is granulated, and compression moulding obtains raw ring c, is conserved 36 hours with bubble, raw after maintenance
The breaking strength of ring c 85N/.It is sintered 4 hours at a temperature of 1285 ± 15 DEG C, obtains and be pre-sintered carrier c, carrier c after roasting
Water absorption rate 19.9%, it is 20.6mL/g that mercury injection method, which measures carrier hole to hold, and hole is to breaking strength 234N/.
It is dissolved in water with 100kg nickel nitrate, 10kg lanthanum nitrate and is configured to 100L solution, above-mentioned carrier c is immersed into the solution
In, it is taken out after 2 hours, dries 4 hours at 100 DEG C, decomposed 3 hours at 550 DEG C.Repeated impregnations, are decomposed once, just at drying
Catalyst C is made.
Embodiment 7
Take raw material II I 58kg, artificial synthesized kaliophilite 21kg, graphite 2kg, plant fiber 0.5kg, 625 cement 18kg,
Heavy-burned magnesia 16kg mixing and ball milling, adds water to mediate, and is granulated, and compression moulding obtains raw ring d, is conserved 36 hours with bubble, after maintenance
Breaking strength 103N/ of raw ring d.It is sintered 4 hours at a temperature of 1275 ± 15 DEG C, obtains and be pre-sintered carrier d, roast rear bearing
The water absorption rate of body d is 20.7%, and it is 21.1mL/g that mercury injection method, which measures carrier hole to hold, and hole is to breaking strength 229N/.
It is dissolved in water with 100kg nickel nitrate, 10kg lanthanum nitrate and is configured to 100L solution, above-mentioned carrier d is immersed into the solution
In, it is taken out after 4 hours, dries 4 hours at 100 DEG C, decomposed 3 hours at 550 DEG C.Repeated impregnations, are decomposed once, just at drying
Catalyst D is made.
Embodiment 8
Take each 20kg of raw material I, II, III, artificial synthesized kaliophilite 18kg, graphite 2kg, plant fiber 0.5kg, 525 cement
17kg, heavy-burned magnesia 15kg mixing and ball milling, adds water to mediate, and is granulated, and compression moulding obtains raw ring e, is conserved 24 hours with bubble,
Breaking strength 109N/ of raw ring e after maintenance.It is sintered 5 hours at a temperature of 1225 ± 10 DEG C, obtains and be pre-sintered carrier e, roasting
The water absorption rate of carrier e is 21.9% after burning, and it is 22.1mL/g that mercury injection method, which measures carrier hole to hold, and hole is to breaking strength 231N/.
It is dissolved in water with 120kg nickel nitrate, 12kg lanthanum nitrate and is configured to 100L solution, above-mentioned carrier e is immersed into the solution
In, it is taken out after 4 hours, dries 4 hours at 100 DEG C, decomposed 4 hours at 500 DEG C.Repeated impregnations, are decomposed once, just at drying
Catalyst E is made.
Comparative example 1
Take the catalyst A of above-mentioned 102451696 embodiment 1 of catalyst sample A, B, C, D, E, ZL, industrial catalyst Z into
Row characterization and evaluation.
Evaluation condition:
No. six solvent naphthas.
Condition 1
Complete 700 DEG C of bed temperature, pressure 0.5MPa, H2O/H2=10, hydrogen air speed 400h-1, thermal aging time is 50 hours.
Condition 2
Temperature: 480 DEG C of entrance, 700 DEG C are exported.
Pressure: 3.0MPa.
H2/ C:2.0.
Carbon space velocity: 10000h-1。
Reaction time: 100 hours.
Evaluation result is listed in table 1.
Table conversion in 1 100 hours exports evaluation result
Claims (10)
1. a kind of gaseous hydrocarbon steam converts upper section catalyst, it is characterised in that: the catalyst is urged using nickel and rare earth as active component
In agent, the content of NiO is 5~25wt.%, and rare-earth oxide content is 0.3~15wt.%；Existed using co-impregnation
Supported on carriers active component nickel and rare earth；
The carrier is prepared with the following method:
(1) the useless agent processing of FCC catalyst:
FCC catalyst agent of giving up is roasted in air atmosphere, crushes, be sieved, obtain powder；
(2) prepared by carrier:
By powder, magnesia, anti-carbon auxiliary agent, pore creating material, lubricant and binder mix, mixing quality ratio be 100:25~
Then 200:20~100:1~5:1~5:30~120 carries out ball milling, kneading, granulation, extrusion forming, obtain raw ring, and maintenance is dried
Dry, roasting, obtains carrier.
2. gaseous hydrocarbon steam according to claim 1 converts upper section catalyst, it is characterised in that: in the catalyst, NiO
Content be 8~17wt.%, rare-earth oxide content be 0.5~12wt.%.
3. gaseous hydrocarbon steam according to claim 1 converts upper section catalyst, it is characterised in that: the Kong Rongwei of the carrier
0.18~0.22mL/g, hole are greater than 220N/ to breaking strength.
4. gaseous hydrocarbon steam according to claim 1 converts upper section catalyst, it is characterised in that: in step (1), FCC is urged
The useless agent of agent is the useless agent of the catalyst of ultrastable preparation；The binder is pure clinker aggregate portland cement.
5. gaseous hydrocarbon steam according to claim 1 converts upper section catalyst, it is characterised in that: in step (1), roasting temperature
Degree is 500~700 DEG C, and calcining time is 2~10h.
6. gaseous hydrocarbon steam according to claim 1 converts upper section catalyst, it is characterised in that: in step (1), being sieved is
Cross 280~320 meshes.
7. gaseous hydrocarbon steam according to claim 1 converts upper section catalyst, it is characterised in that: in step (2), conserve and be
Be soaked in water maintenance, and soaking time is 24~36h.
8. gaseous hydrocarbon steam according to claim 1 converts upper section catalyst, it is characterised in that: in step (2), after maintenance
The breaking strength of raw ring is greater than 80N/.
9. gaseous hydrocarbon steam according to claim 1 converts upper section catalyst, it is characterised in that: in step (2), roasting temperature
Degree is 1200~1300 DEG C, and calcining time is 2~6 hours.
10. a kind of preparation method of any gaseous hydrocarbon steam conversion upper section catalyst of claim 1-9, feature exist
In: using co-impregnation in supported on carriers active component nickel and rare earth, dip time is 0.5~6 hour, after drying, 400
It is decomposed 1~6 hour at a temperature of~700 DEG C, then repeats dipping, drying, decomposes once, obtain finished catalyst.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301666A (en) * | 1999-12-29 | 2001-07-04 | 中国石化集团齐鲁石油化工公司 | Steam preconversion catalyst for hydrocarbon |
| CN101543783A (en) * | 2008-03-27 | 2009-09-30 | 中国石油化工股份有限公司 | Suspension bed hydrocracking catalyst and preparation method and application thereof |
| CN102451696A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Catalyst for reaction of hydrogen preparation or carbonyl synthesis gas preparation by hydrocarbon steam conversion |
| CN104549284A (en) * | 2013-10-15 | 2015-04-29 | 中国石油化工股份有限公司 | Gaseous hydrocarbon self-heating conversion catalyst and preparation method thereof |
| CN105561990A (en) * | 2014-10-09 | 2016-05-11 | 中国石油化工股份有限公司 | Hydrocarbon steam conversion catalyst and preparation method thereof |
-
2017
- 2017-08-02 CN CN201710652492.6A patent/CN109382136B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301666A (en) * | 1999-12-29 | 2001-07-04 | 中国石化集团齐鲁石油化工公司 | Steam preconversion catalyst for hydrocarbon |
| CN101543783A (en) * | 2008-03-27 | 2009-09-30 | 中国石油化工股份有限公司 | Suspension bed hydrocracking catalyst and preparation method and application thereof |
| CN102451696A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Catalyst for reaction of hydrogen preparation or carbonyl synthesis gas preparation by hydrocarbon steam conversion |
| CN104549284A (en) * | 2013-10-15 | 2015-04-29 | 中国石油化工股份有限公司 | Gaseous hydrocarbon self-heating conversion catalyst and preparation method thereof |
| CN105561990A (en) * | 2014-10-09 | 2016-05-11 | 中国石油化工股份有限公司 | Hydrocarbon steam conversion catalyst and preparation method thereof |
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