CN1231326A - Preparation of pulpous state highly-dispersed iron-base coal liquidation catalyst - Google Patents
Preparation of pulpous state highly-dispersed iron-base coal liquidation catalyst Download PDFInfo
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- CN1231326A CN1231326A CN 99103015 CN99103015A CN1231326A CN 1231326 A CN1231326 A CN 1231326A CN 99103015 CN99103015 CN 99103015 CN 99103015 A CN99103015 A CN 99103015A CN 1231326 A CN1231326 A CN 1231326A
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Abstract
The preparation method of coal direct liquification catalyst includes the following steps: producing amorphous Fe(OH)3 or Fe(OH)2 micro-size particles by mixing molysile solution with ammonia water under the condition of high-speed stirring; high-speed centrifugal dehydration to form aquagel; mixing the above-mentioned obtained material with a proper quantity of coal powder and liquification solvent and dispersing so as to obtain the paste ferrous catalyst in which the particle size of ferrous primary particle is about 30-80 nm. In 0.1 t/d continuous coal liquification equipment when the added quantity of iron in the catalyst is 0.5 wt% of dry basis coal, the output rate of distilled oil is up to 57.53%. Its catalytic activity is higher than that of natural pyrite and Japanese synthetic iron sulfide.
Description
From the industrialized target of coal liquefaction, the metal that uses in the catalyzer at first will have catalytic activity, and secondly stock number will be enriched, and manufacturing cost is cheap, and pollution-free.Therefore as abandoning property catalyzer, cheap iron ore and various iron containing compounds become the main flow of exploitation catalyst for coal liquefaction.For many years, at home and abroad in the coal liquefaction craft, (as red mud, main component is Fe to use natural pyrite and various melting waste slag usually
2O
3).Its particle generally several microns to tens of micron, though add-on up to 3% of butt coal owing to disperse badly, catalytic efficiency is restricted.Studies show that the finer particles of catalyzer is disperseed well more in coal slurry, catalytic efficiency is high more.Use the high dispersive Ultra-fine Particle Catalysts, not only can improve oily yield, can also reduce add-on.The entrained oil branch also can descend in liquefied residue and the residue like this, can reach and improve technological operation, reduces the multiple effect of product cost and minimizing environmental pollution.Yet only reduce the particle diameter of catalyzer by mechanical mill, reaching micron order has been the limit.For example in sika island 150t/d gelatin liquefaction pilot plant, two sections case of wet attrition technologies of the natural pyrite of use are state-of-the-art in the world equipment, and the average particle size that it grinds out is the 0.7-0.8 micron.
In order further to reduce the particle diameter of ferrum-based catalyst, the various countries scientist has developed the method for a variety of synthetic, wherein mainly contain following several: 1. in the liquefaction reaction system, directly add organometallic compounds such as oil-soluble iron naphthenate or iron carbonyl, in reaction system, generate metallic sulfide (the Yoon WangL.etal of high dispersive on the spot with promotor S, Fuel, 1997,76 (5): 397).2. Japanese New Energy Development Organization (NEDO) is presided over the synthetic iron sulphide catalyzer (SIS) of exploitation, adopts drying process technology to make FeSO
4With S roasting together, reaction generates FeS
2, product cut size is tens of microns.Reach several micron particle through further grinding, its liquefying activity is higher than natural pyrite (inner exchanging data).3. handle feed coals with various molysite aqueous solutions, and and alkaline reaction such as ammoniacal liquor generate ironic hydroxide, make its high dispersing on the coal dust surface, promptly so-called coal absorption (or dipping) type catalyzer.The for example AIP that is used for the NEDOL liquefaction process and the AWIP catalyzer of Mitsui Ship-building Company exploitation, their catalytic activity has all surpassed Japanese synthetic iron sulphide.(Tsukui Yutaka, etal, Proc.of5th China Japan Symposium on Coal and Cl Chemistry, Huang Shan, May13-16,1996) 4. in all sorts of ways earlier make particle diameter at the ultra-fine ferrum-based catalyst of nano level (1nm-100nm) (as Fe (OH)
3, Fe (OH)
2, FeOOH and Fe
2O
3Particle etc.) join in the liquefaction reaction system, generate high reactivity iron sulphide (Pyrrhotite), Fe with the S reaction again
1-xS.Used preparation method has laser cracking process (Eklund, P.C.etal, ACS Div.Fuel Chem.Preprint, 1992,37 (4): 1781), reversed phase micelle microemulsion method (Anthony Martino, etal, Energy and Fuels, 1289) and modal alkali lye and iron salt solutions neutral precipitator method or the like 1994 (8):.Among in the end a kind of preparation method, the Fe (OH) that can obtain precipitation
3Or Fe (OH)
2With use behind the particle drying and dehydratings such as FeOOH, perhaps further use H
2SO
4Handling also, roasting is converted into superpower acid type particle (Fe
2O
3/ SO
4 2-) re-use (Vivek R.Pradhan, etal, Energy and Fuels, 1991,5 (3): 497).
Although reported the preparation method of various synthetic ferrum-based catalysts, because some preparation method's cost is higher, for example microemulsion method is wanted the organic solvent and the tensio-active agent of consume expensive.Some preparation method's scale is difficult to amplify, and is not suitable for suitability for industrialized production, for example the laser cracking process.Other methods such as synthetic FeS
2Granularity bigger than normal, activity is restricted or the like.Therefore, have in the still alkali lye of industrialization potentiality most and the precipitator method of iron salt solutions.Yet, do not adopt special measure to be difficult to prepare the ultrafine particle of high dispersive by the precipitin reaction of routine merely.One of reason is that the precipitin reaction condition is difficult to control, and having is exactly the Fe (OH) that produces precipitation again
3And Fe (OH)
2During Deng particle drying and dehydrating or roasting become Fe
2O
3Process in, particle diameter is can hurried change big.The coal adsorptive type catalyzer of Mitsui Ship-building Company is just in order to prevent that this phenomenon from developing.They are 10% raw material coal dust and FeSO
4Solution mixes, because molysite is adsorbed on coal grain surface by dispersion, and when adding ammoniacal liquor again or containing the ammonia process waste water reaction, the Fe that is produced (OH)
2Particle (if atmospheric oxidation has part FeOOH) just is not easy to assemble grows up, even also be not easy to reunite in the drying and dehydrating process, so coal adsorptive type catalyzer has reached very high activity.Except Japan, USDOE PETC also did similarly research, and different with the Mitsui shipbuilding is, whole feed coals that they use liquefaction all immerse iron salt solutions and react (A.V.Cugini etal, Catalysis Today, 1994,19:395).But for suitability for industrialized production, handle tens thousand of tons raw material coal dust every day, and it is not too easy that so large-scale mixing, drying etc. operate.
The purpose of this invention is to provide a kind of primary particle particle diameter and be dispersed in pulpous state iron-base coal liquidation catalyst in coal dust and the liquefaction solvent mixed system in nanometer range, its catalytic activity height, preparation technology is simple, and stable operation is easy to amplify.
Pulpous state highly-dispersed iron-base catalyzer of the present invention has following character: 1. the ferrum-based catalyst particle consists of amorphous Fe (OH)
3Or Fe (OH)
2With the FeOOH mixture.2. the primary particle particle diameter is in the 30-80nm scope.3. particle shape almost spherical.4. iron content 1-5% in the slurried catalyst, butt coal 15-25%, liquefaction solvent 40-65%, all the other are water etc.5. to be dispersed in the liquefaction solvent be in the middle of the w/o type emulsification system of external phase for iron-based particle, coal dust etc., long-term stability.
The preparation method of pulpous state ferrum-based catalyst of the present invention carries out as follows: 1. in the ammoniacal liquor of high-speed stirring, disposable impouring iron salt solutions prepares Fe (OH)
3Or Fe (OH)
2Precipitate with FeOOH.The pH value of reaction end is controlled at 8-13, preferably 9-10.2. by the centrifugal above-mentioned reaction product of supercentrifuge, obtain the iron-based hydrogel.3. in high speed dispersor, iron-based hydrogel and an amount of coal dust and liquefaction solvent are mixed together dispersion, can obtain slurry exquisiteness, in stable condition high dispersive ferrum-based catalyst.
According to the inventive method, molysite preferably uses iron nitrate, ferric sulfate or ferrous sulfate.Because the hydrochloride severe corrosion equipment preferably need not.When using ferrous salt, in suitable substance P H environment, part Fe (OH)
2Can oxidation by air form FeOOH.But no matter be Fe (OH)
3, Fe (OH)
2Or the FeOOH of any crystal formation, they all will have the more Fe of the indefinite stoicheiometry of high catalytic activity with promotor S generation in the liquefaction reaction system
1-xS.
Another characteristics of the present invention are in high pH value environment, by violent stirring the precipitin reaction of molysite to be finished in a short period of time, thereby avoided causing that because of long-time dropwise reaction liquid precipitation particles is grown up and size distribution is wide.
Can be by the supercentrifuge dehydration the by product ammonium nitrate of the overwhelming majority or sulfuric acid amine Separation and Recovery, the precipitation particles of having avoided simultaneously causing because of drying and dehydrating is reunited.
At last, disperse hydrogel and an amount of raw material coal dust and the solvent high speed shear of putting together extremely important.By the electron microscopy observation of 100,000 multiplying powers, between 30-80nm, their most coagulations are loose Particle Cluster to the primary particle particle diameter in the hydrogel greatly.Along with time lengthening, interparticle distance can further diminish in the hydrogel, and particle itself also can be grown up because of ageing.Therefore the best approach for the treatment of water gel be not place no matter, it more or not heat drying, but promptly they are distributed in the external phase that oil-based solvent constitutes, by cutting the effect of cutting at a high speed, Particle Cluster in the hydrogel is spread out, be suspended in equably in the middle of the w/o type emulsification system, the existence of solvent and coal dust can prevent the reunion again of catalyst particle.
In addition, in preparation process, can also join promotor S and synergy elements Mo, Co, Ni etc. in the system that iron-based hydrogel, coal dust and liquefaction solvent form, carry out high speed shear and disperse, make compound pulpous state ferrum-based catalyst.
Embodiment 1
Get nine water Fe (NO
3)
32.42 kilogram adds 10.56 liters of tap water dissolvings, other gets 1.92 liters of strong aquas and joins in 22.08 liters of tap water, under high-speed stirring, and the above-mentioned Fe (NO of disposable impouring
3)
3Solution continues after adding to stir for 10 seconds, and it is 9.50 that reaction finishes back PH.By supercentrifuge the Fe (OH) that makes
3Centrifugal 3.67 kilograms of the hydrogels that obtain of suspension.In the container that 7.2 kilograms of liquefaction solvents are housed, add above-mentioned hydrogel, start high speed dispersor,, hydrogel is dispersed into fragment than under the slow speed.Under the high speed shear effect, add 3.4 kilograms of raw material coal dusts (3.36 kilograms of dry coals) then in batches, promptly obtain 14.24 kilograms of pulpous state ferrum-based catalyst products after disperseing through 10-15 minute.
Catalyzer of the present invention is applied on the 0.1t/d gelatin liquefaction continuous apparatus turns round, use Yilan two exploiting field coals, Japanese HAO liquefaction solvent, 450 ℃ of temperature of reaction, pressure 17.0MPa, coal-water fluid concentration 40%, reaction time 1 hour carries out once by test.
Dissimilar catalyzer obtains following result:
| Catalyzer | Add-on (wt%, butt coal) | Distilled oil yield (wt%, daf base coal) |
| The synthetic iron sulphide of Japan | Fe+S=3.0 (wherein Fe=1.4) | ????58.24 |
| China's XiLin pyrite | Raw ore=3.0 (wherein Fe=1.06) | ????54.92 |
| Catalyzer of the present invention | Fe+S=1.07 (wherein Fe=0.5) | ????57.53 |
This shows that catalyzer of the present invention is roughly the same with the oily yield of the synthetic iron sulphide of Japan, but but much less of the former add-on illustrates that catalytic activity is higher.Embodiment 2
Preparation method such as embodiment 1.The SULPHUR POWDER that adds 0.384 kilogram in iron-based hydrogel and coal dust and liquefaction solvent blending dispersion can obtain a kind of compound pulpous state ferrum-based catalyst.In the 0.5L autoclave, use the Yilan coal, Japanese HAO liquefaction solvent, the iron level that adds catalyzer is 0.5% of a butt feed coal, H
2First pressing 10.0MPa, 450 ℃ of temperature of reaction, residence time 60min, reaction product analytical results show, THF transformation efficiency 99.4%, extraction oil yield (HS) 67.0%.
In the foregoing description, Fe (OH)
3The particle photo uses the transmission electron microscope (TEM) of 100K multiplying power to take, and material phase analysis adopts XRD scanning.
Claims (5)
1. pulpous state highly-dispersed iron-base coal liquidation catalyst, it is characterized by: (1) ferrum-based catalyst particle consists of amorphous Fe (OH)
3Or Fe (OH)
2With the FeOOH mixture.(2) the primary particle particle diameter is in the 30-80nm scope.(3) particle shape almost spherical.(4) in the slurried catalyst except iron containing compounds, still comprise coal dust, coal liquefaction solvent and water etc.It is in the middle of the w/o type emulsification system of external phase that iron-based particle and coal dust are dispersed in the liquefaction solvent, long-term stability.
2. a method of making the described pulpous state highly-dispersed iron-base coal liquidation catalyst of claim 1 is characterized in that carrying out as follows.
(1) in the ammoniacal liquor of high-speed stirring, disposable impouring iron salt solutions, preparation Fe (OH)
3Or Fe (OH)
2With the FeOOH precipitation, the reaction end pH value is controlled to be 8-13.
(2) by the centrifugal above-mentioned reaction product of supercentrifuge, obtain the iron-based hydrogel.
(3) in high speed dispersor, iron-based hydrogel and an amount of coal dust and liquefaction solvent are mixed together dispersion, obtain catalyzer of the present invention.
3. according to the described slurried catalyst of claim 1, it is characterized in that iron content is the 1-5% of total catalyst weight, the butt feed coal of 15-25% and the liquefaction solvent of 40-65% are still arranged in addition, all the other are water etc.Each component is that the shearing by high-speed dispersion equipment disperses to become stable w/o type emulsification system.
4. in accordance with the method for claim 2, it is characterized in that the molysite that uses is iron nitrate, ferric sulfate or ferrous sulfate.
5. in accordance with the method for claim 2, it is characterized in that in high speed dispersor, in blending dispersion iron-based hydrogel, coal dust and the liquefaction solvent, can also adding promotor S and some synergy elements Mo, Co, Ni etc. and carrying out blending dispersion together and make compound pulpous state highly-dispersed iron-base catalyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99103015 CN1109734C (en) | 1999-03-19 | 1999-03-19 | Preparation of pulpous state highly-dispersed iron-base coal liquidation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99103015 CN1109734C (en) | 1999-03-19 | 1999-03-19 | Preparation of pulpous state highly-dispersed iron-base coal liquidation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1231326A true CN1231326A (en) | 1999-10-13 |
| CN1109734C CN1109734C (en) | 2003-05-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99103015 Expired - Lifetime CN1109734C (en) | 1999-03-19 | 1999-03-19 | Preparation of pulpous state highly-dispersed iron-base coal liquidation catalyst |
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Cited By (6)
| 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 |
| CN101353586B (en) * | 2007-07-25 | 2012-03-21 | 汉能科技有限公司 | Coal direct liquefaction method |
| CN103160357A (en) * | 2011-12-12 | 2013-06-19 | 北京时地人机电设备有限公司销售分公司 | Coal-fired catalyst |
| CN104785272A (en) * | 2015-04-20 | 2015-07-22 | 神华集团有限责任公司 | Iron-based catalyst and preparation method thereof |
| CN107774146A (en) * | 2016-08-24 | 2018-03-09 | 北京华石联合能源科技发展有限公司 | A kind of equipment and application for being used to prepare catalyst slurry |
| CN109126796A (en) * | 2018-09-05 | 2019-01-04 | 煤炭科学技术研究院有限公司 | Nano-dispersed type catalyst and preparation method thereof for coal Direct Hydrogenation liquefaction |
-
1999
- 1999-03-19 CN CN 99103015 patent/CN1109734C/en not_active Expired - Lifetime
Cited By (9)
| 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 |
| CN101353586B (en) * | 2007-07-25 | 2012-03-21 | 汉能科技有限公司 | Coal direct liquefaction method |
| CN103160357A (en) * | 2011-12-12 | 2013-06-19 | 北京时地人机电设备有限公司销售分公司 | Coal-fired catalyst |
| CN103160357B (en) * | 2011-12-12 | 2015-10-28 | 北京时地人机电设备有限公司销售分公司 | Coal combustion catalyst |
| CN104785272A (en) * | 2015-04-20 | 2015-07-22 | 神华集团有限责任公司 | Iron-based catalyst and preparation method thereof |
| CN107774146A (en) * | 2016-08-24 | 2018-03-09 | 北京华石联合能源科技发展有限公司 | A kind of equipment and application for being used to prepare catalyst slurry |
| CN107774146B (en) * | 2016-08-24 | 2020-05-05 | 北京华石联合能源科技发展有限公司 | Equipment for preparing catalyst slurry and application |
| CN109126796A (en) * | 2018-09-05 | 2019-01-04 | 煤炭科学技术研究院有限公司 | Nano-dispersed type catalyst and preparation method thereof for coal Direct Hydrogenation liquefaction |
| CN109126796B (en) * | 2018-09-05 | 2021-10-29 | 煤炭科学技术研究院有限公司 | Nano-dispersion catalyst for direct coal hydrogenation liquefaction and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1109734C (en) | 2003-05-28 |
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Granted publication date: 20030528 |