CN100361743C - Method for preparing highly active catalyst for coal liquefaction - Google Patents
Method for preparing highly active catalyst for coal liquefaction Download PDFInfo
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- CN100361743C CN100361743C CNB2004800033777A CN200480003377A CN100361743C CN 100361743 C CN100361743 C CN 100361743C CN B2004800033777 A CNB2004800033777 A CN B2004800033777A CN 200480003377 A CN200480003377 A CN 200480003377A CN 100361743 C CN100361743 C CN 100361743C
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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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/086—Characterised by the catalyst used
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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Abstract
A method for preparing a highly active catalyst for coal liquefaction, which comprises a catalyst component formation step (1) of reacting ferrous sulfate as a law material for the catalyst with ammonia in an aqueous solution, to form iron hydroxide, a dewatering-drying step (2) of subjecting the iron hydroxide formed in the step (1) to dewatering and drying, and an activation step (3) of pulverizing the dewatered and dried iron hydroxide together with a coal (a part of the raw material coal to be liquefied) in a dry pulverizer, to thereby convert the dried iron hydroxide to a fine powder and allow the powder to adhere on the surface of the coal in a highly dispersed state. The preparation method allows the use of the ammonia water formed in the step (5) as the ammonia in the above catalyst component formation step, and also allows the use of oxygen or an oxygen-containing gas, such as air, as a raw material of the catalyst together with the above ferrous sulfate and the use of the resultant iron oxyhydroxide as an intermediate material.
Description
Technical field
The present invention relates to the manufacture method of highly active catalyst for coal liquefaction, in more detail, relate to and make that to make iron be catalyst for coal liquefaction composition high degree of dispersion, and attached to the manufacture method of the highly active catalyst for coal liquefaction on the carrier that constitutes by micro mist shape coal.
Background technology
For a long time, obtain in that coal is carried out hydrogenation carrying out technological development aspect the direct coal liquefaction method of liquid fuel always, it is generally acknowledged that its most important technology essential factor is to improve the activity of catalyst for coal liquefaction (hydrogenation of coal catalyst).As catalyst for coal liquefaction, desired key element is the yield height of oil, and in generating oil the yield height of matter oil in the shared lightweight, low price, and catalyst consumption is few.The catalyst of these key elements is satisfied in exploitation comprehensively, be realize that direct coal liquefaction method is business-like must obligato technical research problem.
It is generally acknowledged that in the past noble metal series catalysts such as molybdenum, nickel, cobalt are highly active, but its price is very high, and when being used for catalyst of direct coal liquefaction, cost recovery that is used for using repeatedly and poisoning regeneration cost are too high, so practicality is lower.
On the other hand, though the catalytic activity of Fe-series catalyst is poorer than the noble metal series catalysts,,, researching and developing it as business-like catalyst from can disposable viewpoint considering usually from its low price always.
But as Fe-series catalyst, making with the most use is the catalyst that derives from natural pyrite natural materials such as (iron sulfide), though the low price of these catalyst itself, but in order further to improve its catalytic activity, usually how to pulverize the particle diameter of catalyst very little as the exploitation problem.
As the method for dwindling this catalyst particle size, open the spy and to have announced in the flat 6-99071 communique by iron sulfide or iron oxide are reached capacity and proceed again after the particle diameter to pulverize, obtain the situation of high activity catalyst for coal liquefaction.And the red soil that has obtained when also having enumerated various ores, refined aluminum as the raw material of aforesaid compound, the regulus that produces when making iron and steel have also been enumerated the situation as the Dry-crusher of available pulverizer respectively.
But the pulverizing cost of method shown in the above-mentioned communique is very high, certain limit is also arranged aspect active improving, so catalyst consumption is many, so the residue of coal liquefaction (dead catalyst) amount is many, exists the high problem of residue cost of handling.
As making this Fe-series catalyst particle diameter become very little, and improve active method, developed ammonia/iron precipitation method Fe-series catalyst synthetic methods such as (AWIP methods).The AWIP method is in the coal existence or does not have under the condition of coal, and ferric sulfate and ammonia, oxygen, carbonic acid etc. are reacted in the aqueous solution, separates out iron hydroxide, FeO (OH), ferric carbonate etc., generates the catalyst component (catalyst precarsor) of fine (several～tens nanometers).Under the coal existence condition, the catalyst component high degree of dispersion of generation is attached to the surface of coal, and the result can obtain highly active catalytic effect with little amount of catalyst, reduces the cost that catalyst is pulverized etc.
Catalyst component in the aqueous reaction solution that obtains by catalyst component generation/dispersion step, in can dehydration/drying process below as dry body separation and Extraction, and and feed coal, fusion Sulfur (co-catalyst) etc. offer the liquefaction reaction operation with the slurries form together, one side is blown into hydrogen, and one side is carried out liquefaction reaction.
But in business-like extensive coal liquefaction craft flow process, (wet type) makes catalyst component (catalyst precarsor) high degree of dispersion and attached to the method on the coal in the aqueous solution, the equipment operation cost and the unit scale that the coal of attached catalyst are dehydrated operation all will become excessive, therefore the catalyst generating apparatus also will become huge, exist the shortcoming that equipment and operating cost increase.
Under the condition that does not have coal to exist, generate this catalyst component (catalyst precarsor), as separating catalyst, the equipment of its extracting method and operating cost are low to be an advantage, but consider from the catalytic activity aspect, originally very fine catalyst component (catalyst precarsor) can cause secondary aggregation, form the particle diameter of several microns sizes, thus exist can not get resembling aforementioned under the coal existence condition highly active shortcoming the gained catalyst component.
The spy opens in the flat 3-131683 communique on the other hand, thereby as making the Fe-series catalyst high degree of dispersion improve the method for catalytic activity, the case of wet attrition of coal and solvent (oil) and Fe-series catalyst being carried out together machinery is disclosed, make it form slurries, add the sulphur of molten condition in these slurries, mixed hydrogenation makes the method for coal liquefaction.
Open the spy and to disclose in the flat 11-76823 communique being crushed to average grain diameter at the comminuted coal below 20 microns with pulverize iron compound and mix with 1/3～3 weight rate, and make its dispersion remain on slurry catalyst in the oil, the gross weight of said mixture is 60～40 weight % of slurry catalyst overall weight in this slurry catalyst, and remaining is an oil.Also enumerated iron sulfide as aforementioned iron compound.
But in the method that these Te Kaiping 3-131683 communiques and the flat 11-76823 communique of Te Kai are introduced, because is oleophobic property with iron sulfide (pyrite), iron hydroxide, FeO oleophobic property inorganic constituents such as (OH) as the Fe-series catalyst (separating catalyst) of principal component, so in organic solvent (oil), carry out in the method for case of wet attrition with coal, its wetability is bad, if so make particle diameter become very fine, in solvent (oil), carry out high degree of dispersion certain limit is arranged, improve active aspect, be difficult to obtain tremendous progress.
Disclosure of the Invention
The objective of the invention is to solve relevant Fe-series catalyst above-mentioned shortcoming technically in the past comprehensively, provide low-cost and improving the manufacture method that can obtain the highly active catalyst for coal liquefaction of tremendous progress aspect active.
In order to achieve the above object, the manufacture method of highly active catalyst for coal liquefaction of the present invention is to generate operation by catalyst component, dehydrate operation and catalyst activation procedure, it is that ferrous sulfate and ammonia are reacted in the aqueous solution that aforementioned catalyst component generates operation, generate the operation of iron hydroxide, the aforementioned operation that dehydrates is the operation that the aforementioned iron hydroxide that generates is dehydrated, aforementioned catalyst activation procedure is that the coal of aforementioned iron hydroxide through dehydrating and part liquefaction raw material is pulverized in Dry-crusher together, make aforementioned iron hydroxide form the micro mist shape, and high degree of dispersion is attached to the operation on coal surface.
Aforementioned catalyst component generates operation, preferably reactant liquor is stirred, and makes whole reaction system keep uniform state, obtain 1 moles of hydrogen iron oxide, and needed ammonia amount is that 1.6 times of iron are more than the mole.Reaction temperature is usually at 20～80 ℃, preferred about 40～60 ℃.
Be not particularly limited for employed method in aforementioned dehydration/drying process, but dewatering can use filtration under diminished pressure machine etc.For drying, because in can catalyst activation procedure (dry type pulverizing process) after this, utilize the heat that is produced when pulverizing that catalyst is carried out drying, so there is no need to be dried to the state of bone dry, as long as moisture is reached below 75%, preferably reach below 30% and get final product through dehydration/drying.As the drying means that can adopt, can enumerate slurry dried machine etc.
Generate in the operation at aforementioned catalyst component, when making ferrous sulfate and ammonia react, if one side is blown into oxygen or contains the gas of aerobic in aqueous solution, one side is reacted ferrous sulfate and ammonia, then can when generating iron hydroxide, generate FeO (OH).As oxygen-containing gas, can use air.
Supply source for employed ammonia in the aforementioned catalyst component generation operation is not particularly limited, and can use the technical process draining that is dissolved with the accessory substance ammonia that is generated by the coal liquefaction reaction.If take this method, by dissolving and be present in the ferric carbonate that by-product carbonic acid ion in the technical process draining can generate catalyst component.
The catalyst activation procedure comes down to the dry type pulverizing process, operable pulverizer is to carry out the fine grinding mode of dry type, in addition be not particularly limited, but preferably simultaneously making catalyst component contact the regular hour one side with coal in crushing process pulverizes simultaneously, for example be 5～180 minutes, preferred 10～60 minutes this time of contact, preferably adopts ball mill.In the dry type pulverizing process, also can utilize the heat that produces when pulverizing that catalyst and coal are carried out drying simultaneously.
The simple declaration of accompanying drawing
Fig. 1 is to making the manufacturing process of highly active catalyst for coal liquefaction and the process chart that coal liquefaction operation ordinary circumstance is described with one embodiment of the invention.
Fig. 2 is the flow chart of flow-type small liquid experimental rig of liquefaction reaction operation 5 details of presentation graphs 1.
Fig. 3 is to the process chart by to use iron in the past be the catalyst for coal liquefaction comparative example that carries out coal liquefaction describes the ordinary circumstance of coal liquefaction operation.
Fig. 4 is to the total recovery of the oil that obtains with embodiment of the present invention shown in Figure 1 and the curve map that compares with the total recovery of the oil of comparative example shown in Figure 3.
Fig. 5 is to hydrogen consumption that obtains with embodiment of the present invention shown in Figure 1 and the curve map that compares with the hydrogen consumption of comparative example shown in Figure 3.
Fig. 6 be to obtain with embodiment of the present invention shown in Figure 1 light in matter oil yield and the curve map that compares with the oily yield of matter in comparative example shown in Figure 3 light.
Fig. 7 is to gas production rate that obtains with embodiment of the present invention shown in Figure 1 and the curve map that compares with the gas production rate of comparative example shown in Figure 3.
The preferred plan that carries out an invention
Following with reference to embodiment of accompanying drawing displaying that this specification added, specify situation of the present invention.
According to operation shown in Figure 1, carry out the manufacturing and the catalytic performance test of the highly active catalyst for coal liquefaction (following high activated catalyst or the MA catalyst of simply being called) of the present embodiment.Be that MA catalyst manufacturing process is made of catalyst component generation operation 1, dehydration/drying process 2 and activation procedure 3.Catalyst (not illustrating among the figure) the catalytic performance test that gained is carried on the dust coal is undertaken by the coal liquefaction reaction test, therefore after aforementioned MA catalyst manufacturing process, liquefaction reaction operation 5 (Fig. 1) is set.
Used device is the batch reactor that has 2 liter capacity of mixer and air-diffuser in the catalyst component generation operation 1.In Fig. 1, dehydration/drying process 2 and activation procedure 3 usefulness square frame frames are got up and illustrate that the part of coal (x% of total amount) that is provided provides in this square frame, expression is sometimes when design apparatus, dehydration/drying process 2 and activation procedure 3 are regarded as an operation, and the coal that expression is used for activating is a part that is used for all coals of coal liquefaction reaction.
In the present embodiment, offer in the catalyst raw material of catalyst component generation operation 1, except ferrous sulfate (FeSO
4) outside, also use air (oxygen-containing gas), generate the essential ammonia (NH that uses in the catalyst component in addition
4) what adopt is the technical process draining of by-product in the liquefaction reaction operation 5.When coal used in the liquefaction reaction is the coal of Shenhua, the analysis result to the technical process draining is shown in table 1.
Table 1
The analysis example of coal liquefaction craft process draining
| NH 4 | 29,000mg/l(ppm) |
| Fe | 5.5mg/l(ppm) |
| S 2 | 3,600mg/l(ppm) |
| CO 3 | 33,000mg/l(ppm) |
| pH(℃) | 9,0(26.4) |
Table 1 shows, contains the necessary ammonia of a large amount of generation catalyst components in the technical process draining, from technical process displacement and its NH
4The comprehensive analyse shows (ammonia) of catalyst addition in concentration, the coal liquefaction (Fe amount) is self-sufficient.But also can recognize in the technical process draining, except aforementioned ammonia, also contain the carbonate (CO that can generate catalyst component
3).
Dehydration/drying process 2 is to be extracted in catalyst components such as the iron hydroxide of separating out in the reacting solution, FeO (0H), ferric carbonate (i.e. dehydration) from reactant liquor, and makes its dry operation, and aforementioned dehydration can adopt the filtration under diminished pressure machine to carry out.Drying can adopt vacuum desiccator to carry out.
For make catalyst carrier with high dispersion state attached on the coal particle, dewater as previously mentioned/when dry, the content of moisture is reached below 75%, preferably reach below 30%; Simultaneously employed coal is dewatered/drying too, its moisture is reached below 75%, preferably reach below 30%.
Activation procedure 3 is dry type pulverizing process, when operation is managed, make the particle diameter of the catalyst component of high degree of dispersion attached to its surperficial coal, and for example reaching average grain diameter is about 30～40 microns.Catalyst component can carry out secondary aggregation in dehydration/drying process 2, so also must decompose pulverizing to catalyst component.So in activation procedure 3, for by coal and catalyst component both sides are all pulverized, and the two is mixed, make catalyst component fully and high degree of dispersion attached to the coal surface, preferably make the two stop in the crushed zone 5～180 minutes, more preferably stop about 10～60 minutes, consider that from this point ball mill is desirable Dry-crusher.In activation procedure (dry type pulverizing process) 3, also can utilize the heat that produces when pulverizing simultaneously simultaneously, catalyst and coal are carried out the part drying.
The ratio of the coal that is used to activate, be 1～40% of liquefaction coal total amount, be preferably about 3～15%, simultaneously the amount of catalyst, with iron (Fe) is 0.05～1.5wt%, the preferred 0.2～0.6wt% that standard is equivalent to liquefaction coal total amount (daf (dryash free) standard, just pure coal standard).
Though be used for the ratio of coal of aforementioned activation and catalytic amount as previously mentioned, composition, the proterties of looking liquefaction coal are also different, so must select best value according to the liquefaction coal raw material.Therefore preferably as a reference, determined according to actual conditions with aforementioned general standard.
After the coal of activated attached catalyst taken out from pulverizer, adjust in the grooves (not illustrating among the figure) with solvent (can use the circulating solvent that from liquefied coal coil, reclaims), most of liquefaction feed coal that in activation, not have a use at slurries, add co-catalyst sulphur (S) as required and mix, make the slurries shape.Here because coal is oil loving originally, thus be easy to high degree of dispersion in solvent (oil), so high degree of dispersion at the catalyst on coal surface also high degree of dispersion in slurries, so in the liquefaction reaction operation of its back, can obtain highly active catalytic performance.
(embodiment)
The reactor that is used for liquefaction reaction operation 5, use capacity are 0.01 ton/day flow-type small liquid experimental rig.The ordinary circumstance of used flow-type small liquid experimental rig is shown in Fig. 2.Symbol C1 shown in Fig. 2 is a hydrogen gas compressor, GM1 is a wet gas meter, H1 is the slurries preheater, RC is a force cell, LTV1 and LTV2 are pressure relief valve, NR1 and NR2 are check valve, nV1 and nV2 are needle-valves, P1 is a slurry circulating pump, P2 is high pressure slurries measuring pumps, PCV1 and PCV2 are pressure-regulating valves, R1 is a reactor, V1 is the slurries measuring tanks, V2 is an accumulator, V3 is the High Temperature Gas liquid/gas separator, V4 is thick oily dump tank, V5 is the low temperature gas-liquid separator, V6 is the spraying separator.
The slurries quantity delivered is adjusted by high pressure slurries measuring pump P2, and the quantity delivered of hydrogen is by the flow control valve interlock that does not illustrate among hydrogen gas compressor C1 and the figure is regulated.Needle-valve nV1 and nV2 are used for discharging on a small quantity gradually liquid.This flow-type small liquid experimental rig is designed to can be used as continuous reaction apparatus to be used.
Main liquefaction reaction condition used in the present embodiment is shown in table 2.
Table 2
The experimental condition of small-sized flow-type liquefaction test device
| Use coal: the coal of Shenhua |
| Use solvent: liquefied coal coil |
| Liquefaction reaction pressure: 18.7Mpa |
| Liquefaction reaction temperature: 455 ℃ |
| The concentration of coal: 45wt% |
| The time of staying: 1.2～1.8hr |
[comparative example]
The catalyst, the natural pyrite catalyst in past (N.P. catalyst) and the separating catalyst in the past that use the ammonia under the coal existence condition/iron precipitation method (AWIP method) in the past to obtain have as a comparative example carried out the coal liquefaction test.
Among Fig. 3, use the coal liquefaction test of the catalyst that obtains by the AWIP method to constitute by catalyst component generation/dispersion step 10, dehydration/drying process 11 and liquefaction reaction operation 12.In the catalyst component generation/dispersion step 10, provide ferric sulfate as the catalyst raw material, provide coal as catalyst carrier, provide accessory substance ammoniacal liquor (not illustrating among the figure) in the liquefaction reaction operation 12 as the ammonia composition, under agitation solids fraction to be carried out micro mist broken for one side in the aqueous solution, one side is reacted ferric sulfate and ammonia, make the iron hydroxide high degree of dispersion that generates on the coal surface, generate catalyst component (particle diameter is the catalyst precarsor that several～tens nanometers constitute: do not illustrate among the figure).
Separating catalyst is to make generating under the identical condition of operation 1 and dehydration/drying process 2 with the catalyst of aforementioned MA catalyst.What simultaneously natural pyrite adopted is broken through micro mist, makes its particle diameter reach the following material of a few μ m, uses the reaction condition identical with reaction condition shown in the table 2 to carry out the coal liquefaction test respectively.Compare with the coal liquefaction result of the test and the comparative example coal liquefaction result of the test of gas production rate (Fig. 7) several respects previous embodiments.
From interpretation of result shown in Fig. 4～7 as can be known, compare with natural pyrite catalyst (N.P. catalyst) and separating catalyst, the MA catalyst consumption of the present embodiment is few, and catalytic activity is much higher, compare with the AWIP catalyst, also can obtain higher activity.The total amount of catalyst addition (wt%) expression Fe+S shown in the Figure 4 and 5, in MA catalyst, AWIP catalyst, separating catalyst, the atomic ratio of Fe/S is 1.5.
Just can think the oily yield (Fig. 4) of MA catalyst, particularly light in the yield height (Fig. 6) of matter oil content, the consumption of hydrogen many (Fig. 5) can be used for hydrogen generating gently matter oil content more selectively.Can think aspect gas production rate (Fig. 7) simultaneously, the MA catalyst is lower than other catalyst, help to increase substantially the economy of coal liquefaction, MA catalyst of the present invention is excellent especially highly active catalyst for coal liquefaction in Fe-series catalyst up to now, and this point is very clear and definite.
Industrial applicibility
In sum, highly active catalyst for coal liquefaction manufacture method of the present invention is to make the oleophobic property catalyst components such as iron hydroxide, FeO (OH), ferric carbonate as separating catalyst, through generation, dehydration, drying, stop simultaneously certain hour with the part liquefaction feed coal for supported catalyst through Dry-crusher again, jointly pulverize, obtain making aforementioned separating catalyst high degree of dispersion and be carried on catalyst on the dust coal, thus can obtain in coal liquefaction complete oily yield, hydrogen consumption, light in oily yield, gas production rate aspect all than ammonia/iron precipitation method (AWIP method) etc. in the past the catalyst excellence the coal liquefaction characteristic of Duoing.
Claims (6)
1. the manufacture method of highly active catalyst for coal liquefaction, it is to generate operation by catalyst component, dehydrate that operation and catalyst activation procedure constitute, it is that ferrous sulfate and ammonia are reacted in the aqueous solution that aforementioned catalyst component generates operation, generate the operation of iron hydroxide, the aforementioned operation that dehydrates is the operation that the aforementioned iron hydroxide that generates is dehydrated, aforementioned catalyst activation procedure is by in Dry-crusher the coal of the raw material that liquefies through an aforementioned iron hydroxide that dehydrates and a part being pulverized together simultaneously, make aforementioned iron hydroxide form the micro mist shape, and high degree of dispersion is attached to the operation on the surface of coal.
2. according to the manufacture method of the highly active catalyst for coal liquefaction described in the claim 1, wherein, generate in the operation at aforementioned catalyst component, one side is blown into the gas that contains aerobic in aqueous solution, one side makes ferrous sulfate and ammonia react, in the iron hydroxide that generates as reaction product, generate FeO (OH).
3. according to the manufacture method of the highly active catalyst for coal liquefaction described in the claim 1, wherein, generate in the operation at aforementioned catalyst component, one side is blown into oxygen in aqueous solution, one side makes ferrous sulfate and ammonia react, in the iron hydroxide that generates as reaction product, generate FeO (OH).
4. according to the manufacture method of the highly active catalyst for coal liquefaction described in any one of the claim 1～3, wherein, as the supply source that generates employed ammonia in the operation at aforementioned catalyst component, use the technical process draining that is dissolved with by the ammonia of coal liquefaction reaction by-product.
5. according to the manufacture method of the highly active catalyst for coal liquefaction described in any one of the claim 1～3, wherein, the aforementioned Dry-crusher in aforementioned catalyst activation procedure adopts ball mill.
6. according to the manufacture method of the highly active catalyst for coal liquefaction described in the claim 4, wherein, the aforementioned Dry-crusher in aforementioned catalyst activation procedure adopts ball mill.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP025720/2003 | 2003-02-03 | ||
| JP2003025720A JP4149280B2 (en) | 2003-02-03 | 2003-02-03 | Method for producing coal liquefied highly active catalyst |
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| CN1744947A CN1744947A (en) | 2006-03-08 |
| CN100361743C true CN100361743C (en) | 2008-01-16 |
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| JP (1) | JP4149280B2 (en) |
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| CN101302455B (en) * | 2008-05-22 | 2012-06-20 | 煤炭科学研究总院 | Method for plasticizing lower-grade metamorphic bituminous |
| CN105363450B (en) * | 2014-09-01 | 2018-01-19 | 中科合成油技术有限公司 | A kind of ferrum-based catalyst of carbon raw material hydrogenation liquefaction and its preparation method and application |
| CN105233829B (en) * | 2015-11-18 | 2017-11-21 | 陕西延长石油（集团）有限责任公司 | A kind of iron slag prepares the method and its application of hydrocracking catalyst |
| CN108970614B (en) * | 2018-08-01 | 2021-05-18 | 国家能源投资集团有限责任公司 | Iron-based catalyst, preparation method and application thereof |
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- 2003-02-03 JP JP2003025720A patent/JP4149280B2/en not_active Expired - Fee Related
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- 2004-01-28 WO PCT/JP2004/000758 patent/WO2004069405A1/en active Application Filing
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| JPH03131683A (en) * | 1989-10-16 | 1991-06-05 | Nippon Katsutan Ekika Kk | Liquefaction of coal |
| JPH0699071A (en) * | 1992-09-18 | 1994-04-12 | Nippon Koole Oil Kk | Catalyst for hydrogenation liquefaction of coal |
| AU8171094A (en) * | 1994-01-13 | 1995-09-28 | New Energy And Industrial Technology Development Organization | Process of coal liquefaction |
| JPH0867880A (en) * | 1994-08-29 | 1996-03-12 | Agency Of Ind Science & Technol | Liquefaction of coal using impregnation type iron catalyst |
| CN1226466A (en) * | 1998-02-16 | 1999-08-25 | 三井造船株式会社 | Manufacture of catalyst for coal liquefaction |
| CN1242415A (en) * | 1998-07-20 | 2000-01-26 | 中国科学院山西煤炭化学研究所 | Method for direct liquefaction of coal using FeSOX as presoma of catalyst therefor |
| JP2000254509A (en) * | 1999-03-05 | 2000-09-19 | Mitsui Eng & Shipbuild Co Ltd | Production of iron hydroxide type coal liquefying catalyst composition |
| CN1231326A (en) * | 1999-03-19 | 1999-10-13 | 煤炭科学研究总院北京煤化学研究所 | Preparation of pulpous state highly-dispersed iron-base coal liquidation catalyst |
| JP2002018287A (en) * | 2000-07-06 | 2002-01-22 | Mitsui Eng & Shipbuild Co Ltd | Iron hydroxide type coal liquefying catalyst composition and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4149280B2 (en) | 2008-09-10 |
| WO2004069405A1 (en) | 2004-08-19 |
| JP2004261635A (en) | 2004-09-24 |
| CN1744947A (en) | 2006-03-08 |
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