CN1226466A - Manufacture of catalyst for coal liquefaction - Google Patents
Manufacture of catalyst for coal liquefaction Download PDFInfo
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- CN1226466A CN1226466A CN98126944A CN98126944A CN1226466A CN 1226466 A CN1226466 A CN 1226466A CN 98126944 A CN98126944 A CN 98126944A CN 98126944 A CN98126944 A CN 98126944A CN 1226466 A CN1226466 A CN 1226466A
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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
- 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
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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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
- 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
- Y02P20/584—Recycling of catalysts
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Abstract
To provide a producing method of a coal liquefaction catalyst in which the catalytically active mineral material can be recovered from the reaction residue by an ammonia water iron precipitation method (AWIP) and can be reused while clogging of plant with the residue, etc., is prevented. In the coal liquefaction process to liquefy coal by the reaction of coal 6 and hydrogen 9 in the presence of an ion-sulfur coal liquefaction catalyst and to distill the obtd. reaction liquid to recover the coal liquefaction oil 12, 14, sulfuric acid 15 is added to a catalyst material comprising the residue 13 containing an iron component obtd. by distillation. The obth. iron sulfate soln. 16 is reacted with ammonia water 10 in the presence of a coal slurry 8 prepared by dispersing fine particles of coal in a solvent so as to obtain a coal slurry 7 containing coal with deposition of the catalyst comprising the catalyst with iron highly dispersed to be used for the iron-sulfur coal liquefaction catalyst.
Description
The invention relates to the manufacture method of catalyst for coal liquefaction, more particularly, the invention relates to the manufacture method of the catalyst for coal liquefaction (coal of attached catalyst) that on fine coal, adheres to Fe-series catalyst.
At present, the most of petroleum resources that rely on of the energy in the world, in order to effectively utilize petroleum resources, substitute energy as oil, people research and develop liquidation of coal technology such as brown coal, sub-bituminous coal and bituminous coal, now know, use iron-sulphur series catalysts can obtain oil engine (mainly be transportation with) with the high liquefied coal coil of added values such as fuel.
Coal liquefaction craft in the past generally is made up of liquefaction operation and liquefaction oil distillation process.Described liquefaction operation is, fine coal is sneaked in the solvent (normally recycling the part of liquefied coal coil), add liquefaction and make coal slurry with catalyzer, under the hydrogen concurrent conditions with this coal slurry at 400-600 ℃ (preferably 450-550 ℃), 150-300kg/cm
2The state of-G kept about 1 hour down, made gelatin liquefaction; Described distillation process generally is with the resultant of reaction air distillation, and underpressure distillation then is fractionated into each boiling point composition, obtains the high liquefied coal coil of added value.
For above-mentioned Fe-series catalyst technology, how reducing manufacturing cost is to need one of important topic of studying from now on.
Through studies confirm that of the inventor, { ammonia/iron precipitator method (AWIP method) } iron that the water generation reaction that contains ammonia that use obtains in liquefaction process easily obtains is that dispersed catalysts (using the coal of form as attached catalyst) has practical value on industrialness is implemented.
Promptly, the mixed liquefied method that the AWIP method can be suitable for the coal of attached catalyst (will be liquefied and mix with certain proportion with the coal of attached catalyst with coal, make the method for coal slurry), the water generation reaction that contains ammonia that is used for the catalyzer manufacturing can be self-supporting, the catalytic amount that use is equivalent to the 1/4-1/5 of synthetic iron sulphide catalyzer (hereinafter to be referred as SIS) in the past can demonstrate equal liquefaction performance, and can be widely used in brown coal, sub-bituminous coal and bituminous coal etc. is coal widely, height when oil yield ratio uses iron sulphide catalyzer (CIS), the blending ratio of adhering to coal in the mixed liquefied method can 5% (weight) or below, have the performance of above-mentioned various excellences.
First purpose of the present invention is, can not effectively utilize this shortcoming of residue (containing catalyst substrate) that reclaims behind the liquefied coal coil at above-mentioned any method of using high-dispersion iron catalyst in the past, the method that above-mentioned residue can be reused for gelatin liquefaction is provided.
Second purpose of the present invention is, provides by above-mentioned that to utilize method can reclaim the base material with catalytic activity contained in the coal simultaneously again from above-mentioned residue be the method for iron, manganese etc.
The 3rd purpose of the present invention is, provides can remove reclaiming, when recycling catalyst substrate, separating out because of solid, is deposited in the recovery method of the catalyst substrate of the calcium that causes line clogging in the device.
The manufacture method that is intended to realize the catalyst for coal liquefaction of the present invention of above-mentioned purpose comprises: making liquefaction with coal slurry and H-H reaction in the presence of iron-sulphur is catalyst for coal liquefaction, make the liquefaction operation of gelatin liquefaction, and distill the resultant of reaction that this liquefaction operation obtains, reclaim the distillation process of liquefied coal coil, it is characterized in that, sulfuric acid is sneaked in the catalyst substrate that the residue that contains ferrous components that obtained by above-mentioned distillation constitutes, under the condition that dust coal is scattered in the coal slurry existence that forms in water or the solvent, make the reaction of resulting ferric sulfate aqueous solution and ammoniacal liquor, obtaining containing by above-mentioned iron-sulphur is that the iron that uses in the catalyst for coal liquefaction is the coal slurry that catalyzer that dispersed catalysts constitutes adheres to coal.
Be used to reclaim the sulfuric acid of above-mentioned catalyst substrate, the hydrogen sulfide of association is raw material synthetic sulfuric acid in the time of can using with gelatin liquefaction.
The kind of employed dust coal can be any coal that brown coal, sub-bituminous coal, bituminous coal etc. used in ammonia/iron precipitator method (AWIP method) in the past.Preferably about 100 orders of the particle diameter of dust coal or following.
Catalyzer adheres to the coal slurry that uses in the operation and has no particular limits, and preferably share above-mentioned catalyzer simultaneously and adheres to the coal slurry that uses in the operation and the coal slurry of gelatin liquefaction reaction raw materials.The coal-water fluid concentration of gelatin liquefaction reaction raw materials can be normal content in the past 40% (weight) or more than, the high density about 50% (weight) preferably.
Employed above-mentioned ammoniacal liquor has no particular limits, and can use the by product that is obtained by the gelatin liquefaction operation promptly to contain the generation water of ammoniacal liquor.
Operable above-mentioned solvent has no particular limits so long as not have the solvent of obstruction to get final product to gelatin liquefaction reaction and in sneaking into resulting liquefied coal coil the time, preferentially selects the solvent that is got by liquefied coal coil for use.In this occasion, in order to reduce the working pressure of gelatin liquefaction reaction process, and in the coal slurry preheater, prevent from the condensation reaction that causes owing to thermolysis to improve the liquefaction yield, can be with the solvent hydrogenation that gets by liquefied coal coil.
Above-mentioned iron-sulphur is the sulphur that uses in the catalyst for coal liquefaction, same for example can coal slurry with the above-mentioned gelatin liquefaction raw material of monomeric form weight feed in.
Contain the coal slurry that above-mentioned catalyzer adheres to coal, in order to sneak into ammoniacal liquor in that dust coal is scattered in the presence of the coal slurry that forms in water or the solvent, ferric sulfate aqueous solution reaction with reclaiming in the distillation residue by above-mentioned liquefied coal coil must separate moisture (dehydration) as required.
The method of separating moisture from above-mentioned coal slurry can adopt methods such as filtration, pressurizing and dehydrating.
Attached to the iron in the catalyzer on the above-mentioned dust coal, through identifying that its main component is an ironic hydroxide.
Distillation to above-mentioned liquefied coal coil has no particular limits, and in the occasion of a part of using liquefied coal coil as above-mentioned solvent, preferably uses the heavy ingredient in the gained liquefied coal coil, and its mode without limits.
Fig. 1 is the summary description figure of the coal liquefaction craft whole process of one embodiment of the invention.
Fig. 2 is the summary description figure of the catalyst for coal liquefaction manufacture method of one embodiment of the invention.
Fig. 3 is the summary description figure of the catalyst for coal liquefaction manufacture method of another embodiment of the invention.
Fig. 4 is the summary description figure of an example of expression catalyst substrate recovery process of the present invention.
Fig. 5 is with the catalyzer addition of the catalyzer of embodiment 1 of the inventive method and use known method and the column diagram that the liquefied coal coil yield compares.
Narrate with reference to the accompanying drawings an embodiment of the invention, specifically describe the present invention.
The manufacture method of the catalyst for coal liquefaction of Fig. 1 outline explanation the present embodiment. Coal liquefaction craft shown in Figure 1 adheres to operation 5 by coal slurry manufacturing process 1, liquefaction reaction operation 2, distillation process 3, catalyst substrate recovery process 4, catalyst and solvent hydrogenation process 14 (the solvent hydrogenation process can omit sometimes) consists of.
Coal slurry manufacturing process 1 is, base feed dust coal 6, catalyst adhere to the coal that contains attached catalyst of preparation in the operation 5 in the mixing channel that is equipped with the mixer (not shown) coal slurry 7 and sulphur (not shown) are made coal slurry 8. Do like this so that the coal concentration in the coal slurry 8 remains on 40-50% (weight), catalyst concn calculates with Fe+S and remains on 0.4-1% (weight).
With the coal slurry 8 that catalyst adheres to coal that contains of making in the preheater (not shown) heating coal slurry manufacturing process 1, it is supplied with liquefaction reaction operation 2. Liquefaction reaction operation 2 is by remaining on 450-480 ℃, 150-300kg/cm2High pressure reaction assembly (not shown) under the-G condition consists of, and one side is supplied with hydrogen 9, and one side is carried out liquefaction reaction. The ammonia that liquefaction reaction generates is discharged with moisture, will generate the water generation reaction 10 that contains ammoniacal liquor after the cooling1Take out, with this water generation reaction 101The ammoniacal liquor that adheres to operation 5 as the supply catalyst uses.
Liquefied coal coil 11 after liquefaction reaction operation 2 finishes is separated into liquefaction oil 12, liquefaction oil residue 13 and water generation reaction (containing ammoniacal liquor) 10 in distillation process 32(symbol 10 expressions 10 hereinafter1With 102The interflow). Above-mentioned liquefaction oil 12, a part is as the solvent 12 of making coal slurry 8 usefulness1, being back to catalyst and adhering to operation 5, remainder is as goods 122Discharge.
The liquefaction oil residue 13 that reclaims is supplied to catalyst substrate recovery process 4, in this operation, add sulfuric acid 15, making the major part in the liquefaction oil residue 13 is to make iron (catalyst substrate) form ferric sulfate aqueous solution 16 to be reclaimed, and remainder separates, reclaims with sludge 18 as pitch 17.
Adhere in the operation 5 at catalyst, adhere to the coal slurry 8 of coal manufacturing usefulness except supplying with catalyst by coal slurry manufacturing process 1, also supply with ferric sulfate aqueous solution 16, water generation reaction (containing ammoniacal liquor) 10, the solvent 12 of above-mentioned recovery1, and the ferric sulfate (FeSO that uses as catalyst substrate in supply and when starting4-7H
2O) 19, make ferric sulfate aqueous solution 16 and water generation reaction (containing ammoniacal liquor) 10 reactions, make ferric sulfate be transformed into iron hydroxide and be attached on the dust coal surface of coal slurry 8, obtain containing the coal slurry 7 that catalyst adheres to coal. Symbol 20 shown in Fig. 1 is to adhere to the Separation of Water that operation 5 is discharged by catalyst.
In above-mentioned ferric sulfate aqueous solution 16, make the mineral composition of the catalytic active components such as manganese contained in the raw material dust coal 6 form sulfate, can be reclaimed equally with ferrous components. In addition, calcium forms calcium sulfate, can separate from above-mentioned sludge 18, reclaim.
Electron micrograph and chemical analysis show, is attached with particle take γ alkali formula iron hydroxide as main component on the dust coal surface in the coal slurry 7 that catalyst adheres to coal contained of above-mentioned preparation, confirms that having obtained desired catalyst adheres to coal.
The solvent hydrogenation process 14 that dots among Fig. 1 is that supply hydrogen 9 makes solvent 121Hydrogenation, to reduce the operation of the operating pressure in the Coal liquefaction operation, this operation is not requisite operation in the coal liquefaction.
Below, with reference to Fig. 2, further specify catalyst by concrete example and adhere to coal manufacturing process 5. In Fig. 2, with coal slurry 8 (also can be dust coal 6), water generation reaction (containing ammoniacal liquor) 10, the solvent 12 of coal slurry manufacturing process 1 (Fig. 1) supply1, ferric sulfate aqueous solution 16 and new ferric sulfate 19 supplies in the mixing channel 22 with agitator, one side stirs, one side makes and keeps pH6.5-8.5 in the groove and they are reacted, and obtaining dust coal surface in mud, to be attached with ferric sulfate and the reaction product that contains the water generation reaction of ammoniacal liquor be that the catalyst of iron hydroxide adheres to coal.
Electron microscope and chemico-analytic result confirm, through above-mentioned ferric sulfate and the reaction that contains the water generation reaction of ammoniacal liquor, separate out iron hydroxide with the particle diameter of 50-100nm on the dust coal surface in mud.
With solid-liquid separating machine 23 catalyst that contains that obtains in the above-mentioned mixing channel 22 is adhered to the coal slurry separated component dried up 20 of coal and contains the coal slurry 7 that catalyst adheres to coal. Symbol 24 shown in Fig. 2 is to carry to contain catalyst and adhere to the coal slurry of coal and the pipeline of water solution mixture.
Catalyst shown in Fig. 3 adheres to coal manufacturing process 5, is another object lesson that uses pressurizing and dehydrating device 25, represents with prosign with parts identical among Fig. 2, omits explanation. In Fig. 3, will be with the solvent 12 of vapor heated solvent heater 26 heating1, with coal slurry 7 that containing of carrying by pipeline 24, catalyst adhered to coal with separate before the mixture of Separation of Water 20 supply in the pressurizing and dehydrating device 24, emit from the bottom of device and contain the coal slurry 7 that catalyst adheres to coal, discharge Separation of Water 20 from cat head.
Below, by a concrete example above-mentioned catalyst substrate recovery process 4 is described with reference to Fig. 4.Among Fig. 4, liquefied coal coil described in above-mentioned Fig. 1 11 is supplied with vacuum still 27, will supply with a water cooler 29 by 330-350 ℃ the liquefaction oil residue 13 (Fig. 1) that residue discharge line 28 is discharged, water coolant becomes steam, carry out recovery of heat, be cooled to 180-250 ℃.Above-mentioned recovery of heat as water vapour is an example, the invention is not restricted to this.Contain in this once cooled liquefaction oil residue 13 that a spot of oil distillate and pitch divide and feed coal in mineral composition such as contained iron, aluminium, manganese, magnesium, titanium, phosphorus, sulphur and unreacted coal (inertia ature of coal) and be main catalyst substrate of adding with the Fe-series catalyst.
The aqueous sulfuric acid 15 of these once cooled liquefaction oil residues 13 (Fig. 1) and concentration 10-20% is supplied with in the catalyst substrate separator tank 31 of catalyst substrate recovery process 4, mineral composition in the oil phase and catalyst substrate are transferred to aqueous phase as sulfate solution, supply to the bituminization device 33 through vent pipe 30 with the bottom of pitch fractions from catalyst substrate separator tank 31, become pH6.5-8.5 by sneaking into alkali lye 34, through directly being cooled to about about 150 ℃, meanwhile above-mentioned pitch fractions is owing to the difference of wettability forms micropartical, thereby formation contains the mud of above-mentioned mineral composition (catalyst substrate) and unconverted coal.
The water slurry that contains the pitch fractions of above-mentioned corpusculed and catalyst substrate etc., vent pipe 36 via bottom land supplies in the recooler 37, further is cooled to 40-70 ℃ (preferably 55-65 ℃), and calcium sulfate is separated out, form sludge, separate with flotation machine 38.For recycling catalyst substrate, reclaiming and recycle the present invention of the mineral composition that is expected catalytic activity in the coal simultaneously, it is very important with aforesaid method calcium and other mineral composition and catalyst substrate being separated, and can alleviate lime carbonate like this and separate out deposition and blocking pipe in the pipeline of reaction process.
As mentioned above, calcium component is separated out after, above-mentioned residue is supplied with in the floatation device 38 (omit air and be blown into pipe etc.), above-mentioned micropartical pitch fractions is separated into blister 39 and screen underflow 40.The pitch fractions that contains 80-85% (weight) in the blister 39 is supplied with bitumen recovery machine 41 with it, and liquid is taken off in separation becomes blister parting liquid (being above-mentioned ferric sulfate aqueous solution) 16 and pitch 17.
In addition, liquid is taken off in 43 separation of above-mentioned screen underflow 40 process sludge separating machines, becomes the sludge 18 of ash content and unconverted coal formation and the sludge parting liquid that is made of above-mentioned ferric sulfate aqueous solution 16.Sludge 18 is handled after can washing as required etc.Ferric sulfate aqueous solution 16 by blister parting liquid and sludge parting liquid constitute adheres in the operation 5 with the above-mentioned catalyzer that supplies to equally, recycles as catalyst substrate.
As mentioned above, the manufacture method of catalyst for coal liquefaction of the present invention can reclaim that the contained mineral composition with catalytic activity is recycled in catalyst substrate when carrying out gelatin liquefaction and the coal, thereby can guarantee economy.And owing to can effectively remove the composition that calcium etc. can not recycle, thereby can guarantee operational stability.
Regard to the result that brown coal, sub-bituminous coal and bituminous coal explanation preparation catalyzer adhere to coal down.The above-mentioned various coals and the analytical results that use in the present embodiment are shown in Table 1.
Table 1
In Fig. 5, various liquidation of coal oil yields are compared according to the addition of each catalyzer and sulphur/iron ratio.As shown in Figure 5, use oily yield that the AWIP method of the inventive method obtains and (in the gelatin liquefaction circulating solvent, main component is FeS with ball mill etc. with pulverizing among other the SIS (synthetic iron sulphide catalyzer), NP oil
2Natural pyrite micro mist broken), NP pulverizes the gelatin liquefaction yield that (natural pyrite and coal are mixed pulverizing), SIS pulverize (will synthesize iron sulphide catalyzer and coal mix pulverize) the whole bag of tricks altogether altogether and compares, and just can obtain the result equal or higher with them with less catalyzer addition.
Embodiment 2
Table 2
| Coal | The ash content total amount | Ash composition (wt%) d.b. | |||||||||||
| (wt％)d.b. | ?SiO 2 | ?FeO 3 | ?Al 2O 3 | ?CaO | ??MgO | ?P 2O 5 | ?TiO 2 | ??MnO | ??Na 2O | ??K 2O | ?SO 2 | Add up to | |
| Sub-bituminous coal C | ???5.2 | ?37.00 | ?12.40 | ?16.70 | ?14.70 | ??5.80 | ?0.60 | ?0.80 | ??0.10 | ??0.80 | ??0.90 | ?7.90 | ?97.70 |
According to the relation of contained ash composition and vitriolic theoretical consumption in the coal of the sub-bituminous coal C shown in the table 2, be about 0.45g with respect to raw coal (d.b.) 100g as the theoretical yield of the catalyst substrate of Fe.In addition, adhere to coal as catalyzer, in Fe+S if 0.6-0.7% (weight) just much of that.In contrast to this, according to test-results, as Fe, the rate of recovery is about 95%, as FeSO
4, yield is 1.16% (weight), reclaiming the needed sulfuric acid consumption of catalyst substrate is 2.5g.
The NH of sub-bituminous coal C
3Growing amount actual measurement difficulty very, thereby press the following formula reckoning.Promptly in table 1, suppose that all N all are converted into NH
3,
The N amount is 100 * (1-0.045) * 0.016 ≈ 1.53g
Needed sulfuric acid amount is
Therefore, can be by reclaiming the sulfuric acid amount that catalyst substrate consumed in the residue by NH
3Fully neutralization in addition, divides insufficient occasion at alkali, can be from outside supply alkali, and give and reclaim as the byproduct of sulphur.
The effect of invention
As mentioned above, catalyst for coal liquefaction manufacture method of the present invention in this catalyst for coal liquefaction manufacture process, is adhered to the needed raw material of coal for the manufacturing catalyst and can be utilized the water generation reaction that contains ammonia, and the iron that can reclaim in the residue divides, and is used as catalyst substrate. And, compare with other existing method, can obtain equal or above liquefied coal coil yield with less catalytic amount, can expect to have high economy.
In addition, can effectively remove calcium and divide, the obstruction of pipeline and reaction unit when preventing from recycling catalyst substrate.
Claims (6)
1. the manufacture method of catalyst for coal liquefaction, it is included in iron-sulphur is to make liquefaction coal slurry and H-H reaction under catalyst for coal liquefaction exists, make the liquefaction operation of gelatin liquefaction, and distill the resultant of reaction that this liquefaction operation obtains, reclaim the distillation process of liquefied coal coil, it is characterized in that, sulfuric acid is sneaked in the catalyst substrate that the residue that contains ferrous components that obtained by above-mentioned distillation constitutes, under dust coal being scattered in the condition that the coal slurry that forms in water or the solvent exists resulting ferric sulfate aqueous solution and ammoniacal liquor are reacted, obtaining containing by above-mentioned iron-sulphur is that the iron that uses in the catalyst for coal liquefaction is the coal slurry that catalyzer that dispersed catalysts constitutes adheres to coal.
2. the manufacture method of the described catalyst for coal liquefaction of claim 1 is characterized in that, the water generation reaction that contains ammonia that obtains with above-mentioned gelatin liquefaction operation or solvent hydrogenation process replaces above-mentioned ammoniacal liquor.
3. the manufacture method of claim 1 or 2 described catalyst for coal liquefaction is characterized in that, described solvent is a liquefied coal coil.
4. the manufacture method of claim 1,2 or 3 described catalyst for coal liquefaction is characterized in that, uses above-mentioned gelatin liquefaction coal slurry as described coal slurry of sneaking into ferric sulfate aqueous solution.
5. the manufacture method of claim 1,2,3 or 4 described catalyst for coal liquefaction is characterized in that, reclaims in described ferric sulfate aqueous solution as vitriol with mineral compositions such as iron contained in the coal, manganese being liquefied.
6. the manufacture method of claim 1,2,3,4 or 5 described catalyst for coal liquefaction, it is characterized in that, add sulfuric acid, make the water after the interpolation remain on pH6-8, temperature 40-70 ℃, making is liquefied divides with calcium contained in the coal and to form calcium sulfate, reclaims, is separated in the sludge from above-mentioned containing the residue that iron divides.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32720/1998 | 1998-02-16 | ||
| JP32720/98 | 1998-02-16 | ||
| JP03272098A JP3981456B2 (en) | 1998-02-16 | 1998-02-16 | Method for producing coal liquefaction catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1226466A true CN1226466A (en) | 1999-08-25 |
| CN1117632C CN1117632C (en) | 2003-08-13 |
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ID=12366688
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98126944A Expired - Fee Related CN1117632C (en) | 1998-02-16 | 1998-12-21 | Manufacture of catalyst for coal liquefaction |
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| Country | Link |
|---|---|
| JP (1) | JP3981456B2 (en) |
| CN (1) | CN1117632C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298029C (en) * | 2003-03-26 | 2007-01-31 | 中国电子科技集团公司第五十五研究所 | RF desk-top silicon diode electrophoretic depositional glass conformal passivation film manufacture |
| CN100361743C (en) * | 2003-02-03 | 2008-01-16 | 三井造船株式会社 | Method for preparing highly active catalyst for coal liquefaction |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4909457B2 (en) * | 2000-07-06 | 2012-04-04 | 三井造船株式会社 | Method for producing catalyst composition for iron hydroxide coal liquefaction |
| CN104014351A (en) * | 2014-06-13 | 2014-09-03 | 煤炭科学研究总院 | Solid acid catalyst for directly liquefying lignite and preparation method thereof |
-
1998
- 1998-02-16 JP JP03272098A patent/JP3981456B2/en not_active Expired - Lifetime
- 1998-12-21 CN CN98126944A patent/CN1117632C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100361743C (en) * | 2003-02-03 | 2008-01-16 | 三井造船株式会社 | Method for preparing highly active catalyst for coal liquefaction |
| CN1298029C (en) * | 2003-03-26 | 2007-01-31 | 中国电子科技集团公司第五十五研究所 | RF desk-top silicon diode electrophoretic depositional glass conformal passivation film manufacture |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3981456B2 (en) | 2007-09-26 |
| CN1117632C (en) | 2003-08-13 |
| JPH11226427A (en) | 1999-08-24 |
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