CN101191066B - Iron catalyst for preparing hydrocarbon from synthetic gas and preparation method thereof - Google Patents
Iron catalyst for preparing hydrocarbon from synthetic gas and preparation method thereof Download PDFInfo
- Publication number
- CN101191066B CN101191066B CN 200610144217 CN200610144217A CN101191066B CN 101191066 B CN101191066 B CN 101191066B CN 200610144217 CN200610144217 CN 200610144217 CN 200610144217 A CN200610144217 A CN 200610144217A CN 101191066 B CN101191066 B CN 101191066B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- alloy
- iron
- potassium
- alkali
- 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
Landscapes
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses an iron catalyst used for hydrocarbon preparation by synthesis gas. The weight ratio of compositions of the catalyst is that: Fe: Mn: La: Al: K=100: (5-100): (0.1-10): (0.1-20): (0.1-20). The catalyst is obtained by quickly solidifying the alloy molten material formed by iron with the weight percentage of 20 to 50, aluminum with the weight percentage of 50 to 80, manganese with the weight percentage of 1 to 20 as well as lanthanum with the weight percentage of 0.1 to 10 with the cooling rate of 106 DEG C/s, extracting and scrubbing the quick solidified alloy through aqueousslkali, and loading the potassium on the body of the frame iron by the method of dipping of the potassium compound. The catalyst has high activity and high selectivity of C5+ hydrocarbon and low carbon hydrocarbon.
Description
Technical field
The present invention relates to a kind of is raw material iron catalyst of preparing hydro carbons through Fischer-Tropsch synthesis and preparation method thereof with the synthesis gas.
Background technology
Fischer-Tropsch synthesis be find the twenties in last century by synthesis gas (H
2+ CO) a kind of method of synthetic liquid fuel since the fifties in last century, has realized the heavy industrialization with the coal based synthetic gas synthetic liquid fuel successively in South Africa.In recent years; Along with the world energy sources structure changes to coal, natural gas and oil alliance type from single petroleum-based energy structural type; And the raising day by day of global environmental requirement; With natural gas and coal based synthetic gas be the Fischer-Tropsch of raw material synthetic have do not rely on oil, product cleaning advantages such as (not sulfur-bearing, nitrogen, aromatic hydrocarbon), caused the attention of countries in the world in recent years.
What Fischer-Tropsch synthesized normal employing is ferrum-based catalyst, and synthesis gas reacts in being equipped with the fixed bed of ferrum-based catalyst, fluid bed or paste state bed reactor, generates needed hydrocarbon products, comprises gasoline, diesel oil, wax and naphtha, low-carbon alkene etc.Be the transformation efficiency of raising synthesis gas, the type of reactor that hydrocarbon products selectivity and adaptation are adopted, new iron-based Study of Catalyst is being carried out always.
At present, the preparation method of Fe-base catalyst for Fischer-Tropsch syuthesis has formed several different methods such as the precipitation method, fusion method, sintering process, mull technique, infusion process.Many documents and Patent publish the ferrum-based catalyst of multiple employing fusion method and precipitation method preparations.For example Satterfield and Huff are at Hydrocarbon Processing (1990; 2:59～68) once to the performance of molten iron, Kalakkad, Shroff at Appl.Catal. (1995; 133:335～350) and Jager, Espinoza at Catal.Today (1995; 23:17～28) to performance, Itoh and the Nagano etc. of precipitated iron at Appl.Catal., (1993,96:125～134) have all been carried out a large amount of research respectively to the performance of ultra-fine iron catalyst.Comprehensive these results find that fused iron catalyst is low and difficult bigger raising because of surface area, thereby the fischer-tropsch reaction activity is lower; Precipitated iron and ultra-fine iron catalyst are then poor because of anti-wear performance, so the active high life is short.Meanwhile, research shows, uses the sedimentation type catalyst to exist Fischer-Tropsch product wax to separate difficult problem with catalyst granules, thereby has influenced further industrialization.
Recently, open to the patent of the skeletal iron catalyst of this process.USP6265451 and USP6277895 disclosed be used for fischer-tropsch synthesis process contain the auxiliary agent skeletal iron catalyst.This catalyst is made up of iron, 0-6.1 (weight) % copper, 0-8.2 (weight) % manganese and 0-4.9 (weight) % potassium and the surplus aluminium of 72-91 (weight) %.Its preparation process comprises at first utilizes the preparation of water method of quenching to contain the alloy presoma beyond the potassium; Handle most aluminium suction filtration is fallen through alkali lye then; And then adopting the alcoholic solution of the potassium that is fit to that potassium is supported on the upper skeleton iron catalyst main body, the catalyst that contains auxiliary agent after the drying is through the hydrogen activation processing.This contains the auxiliary agent skeletal iron catalyst and has higher H
2+ CO activity of conversion, middle cut selectivity, abrasion resistance and under the gravitational settling condition with easy separation performance of product wax etc.
The highest cooling velocity that molten alloy can reach in the conventional quenching cooling medium is about 10
2-10
3K/S, alloy have defectives such as crystal grain is thick, segregation is serious.And adopt sudden refrigeration technique, also be flash set technology, the cooling velocity in the time of can significantly improving melt solidifying; Promptly improve the heat transfer rate of melt and cooling medium; Make the nucleation time of melt extremely short, have little time near equilibrium melting point, to solidify, and can only solidify away under the equalization point.The alloy that obtains is a metastable state, is showing unique character aspect electronic effect, magnetic property, mechanical strength and the chemical property.
Summary of the invention
The objective of the invention is to propose a kind of catalytic efficiency high be used for the synthetic iron catalyst of Fischer-Tropsch, and the sudden cold preparation method of this catalyst has been proposed.
The present invention provides a kind of catalyst that is used for preparing hydrocarbon from synthetic gas; The composition of this catalyst consists of than expression with element wt: Fe: Mn: La: Al: K=100: (5-100): (0.1-10): (0.1-20): (0.1-20); Preferred group becomes Fe: Mn: La: Al: K=100: (10-50): (0.2-5): (0.2-10): (0.2-10), more preferably consist of Fe: Mn: La: Al: K=100: (10-20): (0.5-3): (0.5-5): (0.5-5).
Iron catalyst specific area provided by the invention can reach 5-100m
2/ g has the skeleton structure of porous.
The present invention also provides above-mentioned Preparation of catalysts method, it is characterized in that iron by 20 to 50 weight %, and the aluminium of 50 to 80 weight %, the manganese of 1 to 20 weight %, the fused mass of the alloy that the lanthanum of 0.1 to 10 weight % is formed is with greater than 10
6℃/s, be preferably greater than 10
7℃/the above cooldown rate of s solidifies fast, should quick-setting alloy through aqueous slkali extracting processing extracting most aluminium out, and then potassium is supported on the main body of skeleton iron with infusion method.
Among the preparation method provided by the invention, can adopt atwirl single roller or two roller cooling molten alloy.
Among the preparation method provided by the invention; The purpose of alkali extracting is to take out aluminium to handle, and most of aluminium in the alloy is reacted with aqueous slkali and extracts out, and detailed process is: it is in the alkali lye of 2-40 weight % that quick-setting alloy is under agitation added 10-100 ℃, alkali concn; Aluminium and alkali lye in the alloy are fully reacted; Obtain black solid, wherein the reactant ingredient proportion is 1 in weight alloy, and the consumption of alkali is 1-10.
Said aqueous slkali can be the solution of inorganic base or organic base, preferably the aqueous solution of alkali metal hydroxide, more preferably NaOH or KOH.The concentration and the consumption of aqueous slkali have no particular limits, and can confirm the preferred 40-90 of alkali liquid temperature ℃, preferred 30-120min of extracting time according to the alkali treatment condition that desired catalyst is formed and prior art is used; The preferred 10-30% of alkali concn; The reactant ingredient proportion is 1 in weight alloy, and the consumption of alkali is preferably 1.5-4.Alloy to neutral, supports the main body of skeleton iron with infusion method with potassium with room temperature-100 ℃, preferred 60-100 ℃ distilled water washing again after the alkali lye extracting is handled, deionized water washs, and absolute ethyl alcohol is replaced water and catalyst is kept in the absolute ethyl alcohol.
Said quick-setting alloy is before alkali lye is handled, and preferably the particle of alloy being pulverized is about 10-10000 micron, preferred 20-5000 micron.
Among the preparation method provided by the invention, the compound of the said potassium that is used to soak can be potassium hydroxide, potash, saleratus, potassium chloride, potassium nitrate.
Iron catalyst provided by the invention need not activation or only needs simple activation promptly to have very high Fischer-Tropsch synthesis activity, and the gained catalyst possesses by H
2Transform to generate the greater activity of multiple desirable hydrocarbon product reaction with the CO unstripped gas and in operation good abrasion resistance, and the unlikely grain graininess that is broken into below the micron order.And because the higher characteristics of density of catalyst system therefor separate with hydrocarbon product through gravitational settling easily, therefore, the fischer-tropsch synthesis process of the suitable especially paste state bed reactor of this catalyst.
In addition; Catalyst provided by the invention can be used for synthetic continuously reactor; Generally comprising any conventional hydrogenation reactor. this type reactor example comprises, but is not limited to plug flow reactor, CSTR, fixed bed type reactor, fluid bed or magnetic stablizing bed form.
Iron catalyst provided by the invention, cheap, preparation is simple, have high activity and C
5+The high selectivity of above hydrocarbon and low-carbon alkene.This catalyst also possesses the high strength property of fused iron catalyst, has avoided precipitated iron catalyst to be prone to the weakness of loss, makes that its FT activity is very stable; Simultaneously, a certain amount of active hydrogen is dissolved in the iron catalyst skeleton, is suitable for the carrying out of hydrogenation reaction.
The specific embodiment
Following embodiment will further specify method provided by the invention, but therefore not limit content of the present invention.
Owing to the cooling velocity of molten alloy can't directly be measured, generally the rotating speed through the copper roller measures indirectly, the following formula of foundation:
Wherein, Δ T be between molten alloy and the copper roller temperature difference; κ is the thermal conductivity factor of alloy; y
cIt is the zero dimension constant; L is the thickness of alloy strip.
Tenor adopts plasma emission spectrometry (ICP) to measure, and the BET specific area adopts low-temperature nitrogen adsorption method to measure.
Embodiment 1
500g iron, 50g manganese, 5g lanthanum and 500g aluminium are joined in the graphite crucible; It is heated to fusion more than 1300 ℃ in coreless induction furnace, makes its alloying, utilizing inert gas or hydrogen that this alloy liquid is sprayed onto a rotating speed from the crucible nozzle then is on 670 rev/mins the copper roller; Logical cooling water in the copper roller; Alloy liquid forms the flakey band through throwing away along copper roller tangent line after the cooling fast, and cooling velocity is about 2 * 10
7℃/s, the flakey linishing obtains the particle diameter scope at 200-1000 micron foundry alloy.
The 50g foundry alloy is slowly joined in the there-necked flask that fills 500 grams, 25% sodium hydrate aqueous solution, control its temperature and be 70 ℃ and constant temperature and stirred 1 hour.After stopping heating and stirring, decantation liquid, use 60 ℃ distilled water wash to the pH value be 7, obtain black solid.It is in 10% the solution of potassium carbonate that above-mentioned black solid is dropped into 100 ml concns, and slowly magnetic agitation is 1 hour, with absolute ethyl alcohol the water in the solution is replaced.Obtained catalyst is numbered catalyst-1, and the composition and the specific area of catalyst-1 are seen table 1.
The gained catalyst is transferred in the fixed bed reactors under absolute ethyl alcohol protection, is applied to that the Fischer-Tropsch synthesis condition is on this catalyst: air speed is 2000h
-1, 2: 1 H
2, CO mol ratio, 270 ℃ reaction temperature and the reaction pressure of 2MPa.The catalyst activity evaluation result is listed in the table 2.
Embodiment 2
500g iron, 50g manganese, 5g lanthanum and 700g aluminium are joined in the graphite crucible; It is heated to fusion more than 1300 ℃ in coreless induction furnace, makes its alloying, utilizing inert gas or hydrogen that this alloy liquid is sprayed onto a rotating speed from the crucible nozzle then is on 670 rev/mins the lanthanum roller; Logical cooling water in the copper roller; Alloy liquid forms the flakey band through throwing away along copper roller tangent line after the cooling fast, and cooling velocity is about 2 * 10
7℃/s, the flakey linishing obtains the particle diameter scope at 200-1000 micron foundry alloy.
The 50g foundry alloy is slowly joined in the there-necked flask that fills 500 grams, 25% sodium hydrate aqueous solution, control its temperature and be 70 ℃ and constant temperature and stirred 1 hour.After stopping heating and stirring, decantation liquid, use 60 ℃ distilled water wash to the pH value be 7, obtain black solid.It is in 10% the solution of potassium carbonate that above-mentioned black solid is dropped into 100 ml concns, and slowly magnetic agitation is 1 hour, with absolute ethyl alcohol the water in the solution is replaced.Obtained catalyst is numbered catalyst-2, and the composition and the specific area of catalyst-2 are seen table 1.
The Fischer-Tropsch synthesis condition is identical with embodiment 1.The catalyst activity evaluation result is listed in table 2.
Embodiment 3
500g iron, 100g manganese, 5g lanthanum and 700g aluminium are joined in the graphite crucible; It is heated to fusion more than 1300 ℃ in coreless induction furnace, makes its alloying, utilizing inert gas or hydrogen that this alloy liquid is sprayed onto a rotating speed from the crucible nozzle then is on 670 rev/mins the lanthanum roller; Logical cooling water in the copper roller; Alloy liquid forms the flakey band through throwing away along copper roller tangent line after the cooling fast, and cooling velocity is about 2 * 10
7℃/s, the flakey linishing obtains the particle diameter scope at 200-1000 micron foundry alloy.
The 50g foundry alloy is slowly joined in the there-necked flask that fills 500 grams, 25% sodium hydrate aqueous solution, control its temperature and be 70 ℃ and constant temperature and stirred 1 hour.After stopping heating and stirring, decantation liquid, use 60 ℃ distilled water wash to the pH value be 7, obtain black solid.It is in 10% the solution of potassium carbonate that above-mentioned black solid is dropped into 100 ml concns, and slowly magnetic agitation is 1 hour, with absolute ethyl alcohol the water in the solution is replaced.Obtained catalyst is numbered catalyst-3, and the composition and the specific area of catalyst-3 are seen table 1.
The Fischer-Tropsch synthesis condition is identical with enforcement 1 example.The catalyst activity evaluation result is listed in table 2.
Embodiment 4
500g iron, 50g manganese, 10g lanthanum and 700g aluminium are joined in the graphite crucible; It is heated to fusion more than 1300 ℃ in coreless induction furnace, makes its alloying, utilizing inert gas or hydrogen that this alloy liquid is sprayed onto a rotating speed from the crucible nozzle then is on 670 rev/mins the lanthanum roller; Logical cooling water in the copper roller; Alloy liquid forms the flakey band through throwing away along copper roller tangent line after the cooling fast, and cooling velocity is about 2 * 10
7℃/s, the flakey linishing obtains the particle diameter scope at 200-1000 micron foundry alloy.
The 50g foundry alloy is slowly joined in the there-necked flask that fills 500 grams, 25% sodium hydrate aqueous solution, control its temperature and be 70 ℃ and constant temperature and stirred 1 hour.After stopping heating and stirring, decantation liquid, use 60 ℃ distilled water wash to the pH value be 7, obtain black solid.It is in 10% the solution of potassium carbonate that above-mentioned black solid is dropped into 100 ml concns, and slowly magnetic agitation is 1 hour, with absolute ethyl alcohol the water in the solution is replaced.Obtained catalyst is numbered catalyst-4, and the composition and the specific area of catalyst-4 are seen table 1.
The Fischer-Tropsch synthesis condition is identical with enforcement 1 example.The catalyst activity evaluation result is listed in table 2.
Embodiment 5
500g iron, 50g manganese, 5g lanthanum and 700g aluminium are joined in the graphite crucible; It is heated to fusion more than 1300 ℃ in coreless induction furnace, makes its alloying, utilizing inert gas or hydrogen that this alloy liquid is sprayed onto a rotating speed from the crucible nozzle then is on 670 rev/mins the lanthanum roller; Logical cooling water in the copper roller; Alloy liquid forms the flakey band through throwing away along copper roller tangent line after the cooling fast, and cooling velocity is about 2 * 10
7℃/s, the flakey linishing obtains the particle diameter scope at 200-1000 micron foundry alloy.
The 50g foundry alloy is slowly joined in the there-necked flask that fills 500 grams, 25% sodium hydrate aqueous solution, control its temperature and be 70 ℃ and constant temperature and stirred 1 hour.After stopping heating and stirring, decantation liquid, use 60 ℃ distilled water wash to the pH value be 7, obtain black solid.It is in 20% the solution of potassium carbonate that above-mentioned black solid is dropped into 100 ml concns, and slowly magnetic agitation is 1 hour, with absolute ethyl alcohol the water in the solution is replaced.Obtained catalyst is numbered catalyst-5, and the composition and the specific area of catalyst-5 are seen table 1.
The Fischer-Tropsch synthesis condition is identical with embodiment 1.The catalyst activity evaluation result is listed in table 2.
Embodiment 6
500g iron, 50g manganese, 5g lanthanum and 700g aluminium are joined in the graphite crucible; It is heated to fusion more than 1300 ℃ in coreless induction furnace, makes its alloying, utilizing inert gas or hydrogen that this alloy liquid is sprayed onto a rotating speed from the crucible nozzle then is on 1000 rev/mins the lanthanum roller; Logical cooling water in the copper roller; Alloy liquid forms the flakey band through throwing away along copper roller tangent line after the cooling fast, and cooling velocity is about 3 * 10
7℃/s, the flakey linishing obtains the particle diameter scope at 200-1000 micron foundry alloy.
The 50g foundry alloy is slowly joined in the there-necked flask that fills 500 grams, 25% sodium hydrate aqueous solution, control its temperature and be 70 ℃ and constant temperature and stirred 1 hour.After stopping heating and stirring, decantation liquid, use 60 ℃ distilled water wash to the pH value be 7, obtain black solid.It is in 10% the solution of potassium carbonate that above-mentioned black solid is dropped into 100 ml concns, and slowly magnetic agitation is 1 hour, with absolute ethyl alcohol the water in the solution is replaced.Obtained catalyst is numbered catalyst-6, and the composition and the specific area of catalyst-6 are seen table 1.
The Fischer-Tropsch synthesis condition is identical with embodiment 1.The catalyst activity evaluation result is listed in table 2.
Table 1
| Catalyst | Specific area (m 2/g) | Catalyst is formed (weight ratio) |
| Catalyst-1 | 48 | 100Fe/10.1Mn/0.7La/6.6Al/0.6K |
| Catalyst-2 | 55 | 100Fe/9.6Mn/0.9La/3.2Al/0.8K |
| Catalyst-3 | 59 | 100Fe/20.4Mn/0.8La/3.5Al/0.7K |
| Catalyst-4 | 57 | 100Fe/11.0Mn/1.7La/3.1Al/0.8K |
| Catalyst-5 | 58 | 100Fe/9.4Mn/0.8La/3.0Al/1.5K |
| Catalyst-6 | 60 | 100Fe/12.0Mn/0.9La/2.8Al/0.8K |
Table 2
Claims (9)
1. iron catalyst that is used for preparing hydrocarbon from synthetic gas; It is characterized in that this catalyst is formed is expressed as with the element wt ratio: Fe: Mn: La: Al: K=100: (5-100): (0.1-10): (0.1-20): (0.1-20), the fused mass of the alloy that this catalyst is made up of iron, aluminium, manganese, lanthanum is with greater than 10
6℃/the above cooldown rate of s solidifies fast, and quick-setting alloy is handled and washing through the aqueous slkali extracting, potassium compound is supported potassium with the method for soaking to obtain on the main body of skeleton iron again.
2. according to the described catalyst of claim 1, it is characterized in that composition is expressed as with the element wt ratio: Fe: Mn: La: Al: K=100: (10-50): (0.2-5): (0.2-10): (0.2-10).
3. according to the described catalyst of claim 2, it is characterized in that composition is expressed as with the element wt ratio: Fe: Mn: La: Al: K=100: (10-20): (0.5-3): (0.5-5): (0.5-5).
4. according to the described catalyst of claim 1, the specific area that it is characterized in that catalyst is 5-100m
2/ g.
5. according to the iron catalyst of claim 1, it is characterized in that said quick curing adopts atwirl single roller or two roller cooling molten alloy.
6. according to the iron catalyst of claim 1; It is characterized in that said alkali extractive process is that quick-setting alloy is under agitation added 10-100 ℃; Alkali concn is in the alkali lye of 2-40 weight %, and aluminium and alkali lye in the alloy are fully reacted, and obtains black solid; Wherein the reactant ingredient proportion is 1 in weight alloy, and the consumption of alkali is 1-10.
7. according to the iron catalyst of claim 1, it is characterized in that before the aqueous slkali extracting is handled that alloy is crushed to size and is the 10-10000 micron.
8. according to the iron catalyst of claim 1, it is characterized in that wherein said reactant ingredient proportion is 1 in weight alloy, the consumption of alkali is 1.5-4.
9. according to the iron catalyst of claim 1, it is characterized in that the compound of described potassium is selected from potassium hydroxide, potash, saleratus, potassium chloride or potassium nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610144217 CN101191066B (en) | 2006-11-30 | 2006-11-30 | Iron catalyst for preparing hydrocarbon from synthetic gas and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610144217 CN101191066B (en) | 2006-11-30 | 2006-11-30 | Iron catalyst for preparing hydrocarbon from synthetic gas and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101191066A CN101191066A (en) | 2008-06-04 |
| CN101191066B true CN101191066B (en) | 2012-12-12 |
Family
ID=39486271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610144217 Active CN101191066B (en) | 2006-11-30 | 2006-11-30 | Iron catalyst for preparing hydrocarbon from synthetic gas and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101191066B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073726A (en) * | 1991-12-24 | 1993-06-30 | 中国石油化工总公司石油化工科学研究院 | Large specific surface amorphous alloy and preparation thereof |
| CN1495148A (en) * | 2002-08-21 | 2004-05-12 | 碳氢技术公司 | Adjuvant-containing skeleton iron catalyst for Fischer-Tropsch synthesis process and its preparation method |
| CN1562470A (en) * | 2004-04-08 | 2005-01-12 | 复旦大学 | Nickel base catalyst of burst cooling framework in use for preparing hydrogen peroxide by adding hydrogen to 2-ethyl-anthraquinone |
| CN1605388A (en) * | 2003-09-08 | 2005-04-13 | 拜尔材料科学股份公司 | Process for the preparation of Raney nickel catalysts and their use in the hydrogenation of organic compounds |
-
2006
- 2006-11-30 CN CN 200610144217 patent/CN101191066B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073726A (en) * | 1991-12-24 | 1993-06-30 | 中国石油化工总公司石油化工科学研究院 | Large specific surface amorphous alloy and preparation thereof |
| CN1495148A (en) * | 2002-08-21 | 2004-05-12 | 碳氢技术公司 | Adjuvant-containing skeleton iron catalyst for Fischer-Tropsch synthesis process and its preparation method |
| CN1605388A (en) * | 2003-09-08 | 2005-04-13 | 拜尔材料科学股份公司 | Process for the preparation of Raney nickel catalysts and their use in the hydrogenation of organic compounds |
| CN1562470A (en) * | 2004-04-08 | 2005-01-12 | 复旦大学 | Nickel base catalyst of burst cooling framework in use for preparing hydrogen peroxide by adding hydrogen to 2-ethyl-anthraquinone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101191066A (en) | 2008-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2751043C (en) | Fischer-tropsch synthesis fe-based catalyst, process of preparation and application thereof | |
| CN101747160B (en) | Method for preparation of methanol, dimethyl ether and low-carbon olefin with synthetic gas | |
| CN107721843B (en) | Method for synthesizing succinic acid by catalytic hydrogenation of acetylene dicarbonylation product | |
| CN101164693B (en) | Iron catalyst, preparation method and its application in synthesizing hydrocarbon reaction | |
| CN101190412B (en) | Fe catalyst for preparing hydrocarbons with synthesis gas and preparation method thereof | |
| CN102441402A (en) | Fischer-Tropsch synthesis catalyst and application thereof | |
| CN104888783A (en) | Methanation catalyst, preparation method and application thereof | |
| CN101993707A (en) | Fischer-Tropsch synthesis method for heavy hydrocarbon | |
| CN106607036A (en) | Oxalate hydrogenation catalyst, preparation method and uses thereof | |
| CN101992097A (en) | Preparation method of iron-based Fischer-Tropsch synthetic catalyst for fluid bed | |
| CN101164692A (en) | Cobalt catalyst, preparation method and application thereof | |
| CN109174091A (en) | A kind of Ru-Rh/C bimetallic catalyst and its preparation method and application | |
| CN104045569B (en) | By the dinitrotoluene (DNT) low-voltage hydrogenation synthesis technique of tolylene diamine and the method for making of catalyzer and catalyzer | |
| CN100594061C (en) | Nickelic Fischer-Tropsch synthetic iron-based catalyst and preparation thereof | |
| CN102091629A (en) | Catalyst for methanation of carbon dioxide | |
| CN101279260B (en) | Iron nickel Fischer-Tropsch synthetic catalyst and preparation thereof | |
| CN101099932B (en) | High-efficient iron-series catalyst and its preparation method | |
| CN107754831B (en) | Amorphous alloy catalyst, preparation method thereof and application thereof in ammonia borane decomposition hydrogen production | |
| CN102041020B (en) | Fluidized bed Tropsch synthesis method for heavy hydrocarbons | |
| CN106810419A (en) | For graphene-supported metal composite in acetic acid preparation of ethanol through hydrogenation catalyst and preparation method thereof | |
| CN101191066B (en) | Iron catalyst for preparing hydrocarbon from synthetic gas and preparation method thereof | |
| JP4937584B2 (en) | Intermetallic compound Ni3Al catalyst for methanol reforming and methanol reforming method using the same | |
| CN103055861B (en) | Copper catalyst and preparation method and application thereof | |
| CN102911693B (en) | Fischer-Tropsch synthesis method by employing mixed catalyst | |
| CN104230641A (en) | Production method of isopropyl benzene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |